The reaction path of CO and Fe2O3 in a chemical-looping combustion system

The reaction mechanism of CO and Fe₂O₃ in a chemical-looping combustion (CLC) was studied based on density functional theory (DFT) at B3LYP level in this paper. The structures of all reactants, intermediate, transition structures and products of this reaction had been optimized and characterized. The reaction path was validated by means of the intrinsic reaction coordinate (IRC) approach. The result showed that the reaction was divided into two steps, the adsorbed CO molecule on Fe ₂O₃ surface formed a medium state with one broken Fe-O bond in step1, and in step2, O atom broken here oxidized a subsequent CO molecule in the fuel reactor. Thus, Fe₂O₃ molecule transport O from air to oxide CO continually in the CLC process. The activation energy and rate coefficients of the two steps were also obtained.

The Coal Jetty

A single poem, presented in the section of the anthology devoted to showcasing the collections shortlisted for the Forward Prize for Best Collection.

A Conventional Internal Combustion Engine Versus a Range Extended Electric Vehicle Under the Current Regulatory Regime in the United Kingdom

Transport accounts for 22% of greenhouse gas emissions in the United Kingdom and cars are expected tomore than double by 2050. Car manufacturers are continually aiming for a substantially reduced carbonfootprint through improved fuel efficiency and better powertrain performance due to the strict EuropeanUnion emissions standards. However, road tax, not just fuel efficiency, is a key consideration of consumerswhen purchasing a car. While measures have been taken to reduce emissions through stricter standards, infuture, alternative technologies will be used. Electric vehicles, hybrid vehicles and range extended electricvehicles have been identified as some of these future technologies. In this research a virtual test bed of aconventional internal combustion engine and a range extended electric vehicle family saloon car were builtin AVL’s vehicle and powertrain system level simulation tool, CRUISE, to simulate the New EuropeanDrive Cycle and the results were then soft-linked to a techno-economic model to compare the effectivenessof current support mechanisms over the full life cycle of both cars. The key finding indicates that althoughcarbon emissions are substantially reduced, switching is still not financially the best option for either theconsumer or the government in the long run.

Integrated techno-economic and environmental assessments of sixty scenarios for co-firing biomass with coal and natural gas

Displacement of fossil fuel-based power through biomass co-firing could reduce the greenhouse gas (GHG) emissions from fossil fuels. In this study, data-intensive techno-economic models were developed to evaluate different co-firing technologies as well as the configurations of these technologies. The models were developed to study 60 different scenarios involving various biomass feedstocks (wood chips, wheat straw, and forest residues) co-fired either with coal in a 500 MW subcritical pulverized coal (PC) plant or with natural gas in a 500 MW natural gas combined cycle (NGCC) plant to determine their technical potential and costs, as well as to determine environmental benefits. The results obtained reveal that the fully paid-off coal-fired power plant co-fired with forest residues is the most attractive option, having levelized costs of electricity (LCOE) of $53.12–$54.50/MW h and CO2 abatement costs of $27.41–$31.15/tCO2. When whole forest chips are co-fired with coal in a fully paid-off plant, the LCOE and CO2 abatement costs range from $54.68 to $56.41/MW h and $35.60 to $41.78/tCO2, respectively. The LCOE and CO2 abatement costs for straw range from $54.62 to $57.35/MW h and $35.07 to $38.48/tCO2, respectively.

Contribution of biomass combustion to air pollutant emissions

In Portugal, it was estimated that around 1.95 Mton/year of wood is used in residential wood burning for heating and cooking. Additionally, in the last decades, burnt forest area has also been increasing. These combustions result in high levels of toxic air pollutants and a large perturbation of atmospheric chemistry, interfere with climate and have adverse effects on health. Accurate quantification of the amounts of trace gases and particulate matter emitted from residential wood burning, agriculture and garden waste burning and forest fires on a regional and global basis is essential for various purposes, including: the investigation of several atmospheric processes, the reporting of greenhouse gas emissions, and quantification of the air pollution sources that affect human health at regional scales. In Southern Europe, data on detailed emission factors from biomass burning are rather inexistent. Emission inventories and source apportionment, photochemical and climate change models use default values obtained for US and Northern Europe biofuels. Thus, it is desirable to use more specific locally available data. The objective of this study is to characterise and quantify the contribution of biomass combustion sources to atmospheric trace gases and aerosol concentrations more representative of the national reality. Laboratory (residential wood combustion) and field (agriculture/garden waste burning and experimental wildland fires) sampling experiments were carried out. In the laboratory, after the selection of the most representative wood species and combustion equipment in Portugal, a sampling program to determine gaseous and particulate matter emission rates was set up, including organic and inorganic aerosol composition. In the field, the smoke plumes from agriculture/garden waste and experimental wildland fires were sampled. The results of this study show that the combustion equipment and biofuel type used have an important role in the emission levels and composition. Significant differences between the use of traditional combustion equipment versus modern equipments were also observed. These differences are due to higher combustion efficiency of modern equipment, reflecting the smallest amount of particulate matter, organic carbon and carbon monoxide released. With regard to experimental wildland fires in shrub dominated areas, it was observed that the largest organic fraction in the samples studied was mainly composed by vegetation pyrolysis products. The major organic components in the smoke samples were pyrolysates of vegetation cuticles, mainly comprising steradienes and sterol derivatives, carbohydrates from the breakdown of cellulose, aliphatic lipids from vegetation waxes and methoxyphenols from the lignin thermal degradation. Despite being a banned practice in our country, agriculture/garden waste burning is actually quite common. To assess the particulate matter composition, the smoke from three different agriculture/garden residues have been sampled into 3 different size fractions (PM2.5, PM2.5-10 and PM>10). Despite distribution patterns of organic compounds in particulate matter varied among residues, the amounts of phenolics (polyphenol and guaiacyl derivatives) and organic acids were always predominant over other organic compounds in the organosoluble fraction of smoke. Among biomarkers, levoglucosan, β-sitosterol and phytol were detected in appreciable amounts in the smoke of all agriculture/garden residues. In addition, inositol may be considered as an eventual tracer for the smoke from potato haulm burning. It was shown that the prevailing ambient conditions (such as high humidity in the atmosphere) likely contributed to atmospheric processes (e.g. coagulation and hygroscopic growth), which influenced the particle size characteristics of the smoke tracers, shifting their distribution to larger diameters. An assessment of household biomass consumption was also made through a national scale survey. The information obtained with the survey combined with the databases on emission factors from the laboratory and field tests allowed us to estimate the pollutant amounts emitted in each Portuguese district. In addition to a likely contribution to the improvement of emission inventories, emission factors obtained for tracer compounds in this study can be applied in receptor models to assess the contribution of biomass burning to the levels of atmospheric aerosols and their constituents obtained in monitoring campaigns in Mediterranean Europe.

Application of WRF-Chem to Forecasting PM10 Concentration over Poland

The meteorological and chemical transport model WRF-Chem was implemented to forecast PM10 concentrations over Poland. WRF-Chem version 3.5 was configured with three one way nested domains using the GFS meteorological data and the TNO MACC II emissions. Forecasts, with 48h lead time, were run for a winter and summer period 2014. WRF-Chem in general captures the variability in observed PM10 concentrations, but underestimates some peak concentrations during winter-time. The peaks coincide with either stable atmospheric condition during nighttime in the lower part of the planetary boundary layer or on days with very low surface temperatures. Such episodes lead to increased combustion in residential heating, where hard coal is the main fuel in Poland. This suggests that a key to improvement in the model performance for the peak concentrations is to focus on the simulation of PBL processes and the distribution of emissions with high resolution in WRF-Chem.

Nanoporous carbons from sisal residues and their application in hybrid TiO2/carbon photocatalysts for the removal and degradation of phenol in solution

Tese de doutoramento, Química (Química Tecnológica), Universidade de Lisboa, Faculdade de Ciências, 2016

Modeling radionuclides dispersion and deposition downwind of a coal-fired power plant

In this study the inhalation doses and respective risk are calculated for the population living within a 20 km radius of a coal-fired power plant. The dispersion and deposition of natural radionuclides were simulated by a Gaussian dispersion model estimating the ground level activity concentration. The annual effective dose and total risk were 0.03205 mSv/y and 1.25 x 10-8, respectively. The effective dose is lower than the limit established by the ICRP and the risk is lower than the limit proposed by the U.S. EPA, which means that the considered exposure does not pose any risk for the public health.

Radiation dose rates and exposure associated to Technologically Enhanced Naturally Occurring Radioactive Materials (TENORM) at locations of a Portuguese coal-fired power plant

Coal contains trace quantities of natural radionuclides such as Th-232, U-235, U-238, as well as their radioactive decay products and 40K. These radionuclides can be released as fly ash in atmospheric emissions from coal-fired power plants, dispersed into the environment and deposited on the surrounding top soils. Therefore, the natural radiation background level is enhanced and consequently increase the total dose for the nearby population. A radiation monitoring programme was used to assess the external dose contribution to the natural radiation background, potentially resulting from the dispersion of coal ash in past atmospheric emissions. Radiation measurements were carried out by gamma spectrometry in the vicinity of a Portuguese coal-fired power plant. The radiation monitoring was achieved both on and off site, being the boundary delimited by a 20 km circle centered in the stacks of the coal plant. The measured radionuclides concentrations for the uranium and thorium series ranged from 7.7 to 41.3 Bq/kg for Ra-226 and from 4.7 to 71.6 Bq/kg for Th-232, while K-40 concentrations ranged from 62.3 to 795.1 Bq/kg. The highest values were registered near the power plant and at distances between 6 and 20 km from the stacks, mainly in the prevailing wind direction. The absorbed dose rates were calculated for each sampling location: 13.97-84.00 ηGy/h, while measurements from previous studies carried out in 1993 registered values in the range of 16.6-77.6 ηGy/h. The highest values were registered at locations in the prevailing wind direction (NW-SE). This study has been primarily done to assess the radiation dose rates and exposure to the nearby population in the surroundings of a coal-fired power plant. The results suggest an enhancement or at least an influence in the background radiation due to the coal plant past activities.

Radiological impact associated to Technologically Enhanced Naturally Occurring Radioactive Materials (TENORM) from coal-fired power plants emissions

Certain materials used and produced in a wide range of non-nuclear industries contain enhanced activity concentrations of natural radionuclides. In particular, electricity production from coal is one of the major sources of increased human exposure to naturally occurring radioactive materials. A methodology was developed to assess the radiological impact due to natural radiation background. The developed research was applied to a specific case study, the Sines coal-fired power plant, located in the southwest coastline of Portugal. Gamma radiation measurements were carried out with two different instruments: a sodium iodide scintillation detector counter (SPP2 NF, Saphymo) and a gamma ray spectrometer with energy discrimination (Falcon 5000, Canberra). Two circular survey areas were defined within 20 km of the power plant. Forty relevant measurements points were established within the sampling area: 15 urban and 25 suburban locations. Additionally, ten more measurements points were defined, mostly at the 20-km area. The registered gamma radiation varies from 20 to 98.33 counts per seconds (c.p.s.) corresponding to an external gamma exposure rate variable between 87.70 and 431.19 nGy/h. The highest values were measured at locations near the power plant and those located in an area within the 6 and 20 km from the stacks. In situ gamma radiation measurements with energy discrimination identified natural emitting nuclides as well as their decay products (Pb-212, Pb-2142, Ra-226, Th-232, Ac-228, Th-234, Pa-234, U- 235, etc.). According to the results, an influence from the stacks emissions has been identified both qualitatively and quantitatively. The developed methodology accomplished the lack of data in what concerns to radiation rate in the vicinity of Sines coal-fired power plant and consequently the resulting exposure to the nearby population.

Measurements of environmental background radiation in the surrounding area of a coal-fired power plant

Certain materials used and produced in a wide range of non-nuclear industries contain enhanced activity concentrations of natural radionuclides. In particular, electricity production from coal is one of the major sources of increased exposure to man from enhanced naturally occurring materials. Over the past decades there has been some discussion about the elevated natural background radiation in the area near coal-fired power plants due to high uranium and thorium content present in coal. This work describes the methodology developed to assess the radiological impact due to natural radiation background increasing levels, potentially originated by a coal-fired power plant’s operation. Gamma radiation measurements have been done with two different instruments: a scintillometer (SPP2 NF, Saphymo) and a gamma ray spectrometer with energy discrimination (Falcon 5000, Canberra). A total of 40 relevant sampling points were established at locations within 20 km from the power plant: 15 urban and 25 suburban measured stations. The highest values were measured at the sampling points near to the power plant and those located in the area within the 6 and 20 km from the stacks. This may be explained by the presence of a huge coal pile (1.3 million tons) located near the stacks contributing to the dispersion of unburned coal and, on the other hand, the height of the stacks (225 m) which may influence ash’s dispersion up to a distance of 20 km. In situ gamma radiation measurements with energy discrimination identified natural emitting nuclides as well as their decay products (212Pb, 214Pb, 226Ra 232Th, 228Ac, 234Th 234Pa, 235U, etc.). This work has been primarily done to in order to assess the impact of a coal-fired power plant operation on the background radiation level in the surrounding area. According to the results, an increase or at least an influence has been identified both qualitatively and quantitatively.

Assessment of heavy metals in the surroundings of coal-fired power plant

This paper aims to survey metal concentrations in soils in the vicinity of a coal-firedpower plant located in southwest of Portugal. Two annual sampling campaigns were carried out to measure a hypothetical soil contamination around the coal plant. The sampling area was divided into two subareas, both centered in the emission source, delimited by two concentric circles with radius of 6 km and 20 km. About 40 samplings points were defined in the influence area. Metals measurements were performed with a portable analytical X-ray dispersive energy fluorescence spectrometer identifying about 20 different elements in each sampling point. The most relevant elements measured included As, Cu, Fe, Hg, Pb, Ti and Zn in both sampling areas. Considering the results obtained in the first sampling campaign, arsenic is predominantly higher within the 6-20 km sampling area. The second sampling campaign showed that both sampling areas presented relatively similar metal concentrations except for Fe, Mn, Sr and Zn which concentration is higher within the 6-20 km sampling area. Also, As, Fe, Mn and Ti concentrations decreased significantly from the first to the second sampling campaign and their concentration were predominately higher in the NE-E and E-SE directions.

Particulate matter flux deposition in the vicinity of a coal-fired power plant

This paper describes the methodology adopted to assess local air quality impact in the vicinity of a coal power plant located in the south of Portugal. Two sampling areas were selected to assess the deposition flux of dust fallout and its potential spatial heterogeneity. The sampling area was divided into two subareas: the inner, with higher sampling density and urban and suburban characteristics, inside a 6-km circle centered on the stacks, and an outer subarea, mainly rural, with lower sampling density within a radius of 20 km. Particulate matter deposition was studied in the vicinity of the coal fired power plant during three seasonal sampling campaigns. For the first one, the average annual flux of dust fallout was 22.51 g/(m2 yr), ranging from 4.20 to 65.94 g/(m2 yr); for the second one was 9.47 g/(m2 yr), ranging from 0.78 to 32.72 g/(m2 yr) and for the last one was 38.42 g/(m2 yr), ranging from 1.41 to 117.48 g/(m2 yr). The fallout during the second campaign turned out to be much lower than for others. This was in part due to meteorological local patterns but mostly due to the fact that the power plant was not working at full power during the second sampling campaign.155

Radioactivity levels of 238U and 232Th decay series and related dose rates in the surroundings of a coal power plant using high resolution g-spectrometry

Gamma radiations measurements were carried out in the vicinity of a coal-fired power plant located in the southwest coastline of Portugal. Two different gamma detectors were used to assess the environmental radiation within a circular area of 20 km centred in the coal plant: a scintillometer (SPP2 NF, Saphymo) and a high purity germanium detector (HPGe, Canberra). Fifty urban and suburban measurements locations were established within the defined area and two measurements campaigns were carried out. The results of the total gamma radiation ranged from 20.83 to 98.33 counts per second (c.p.s.) for both measurement campaigns and outdoor doses rates ranged from 77.65 to 366.51 Gy/h. Natural emitting nuclides from the U-238 and Th-232 decay series were identified as well as the natural emitting nuclide K-40. The radionuclide concentration from the uranium and thorium series determined by gamma spectrometry ranged from 0.93 to 73.68 Bq/kg, while for K-40 the concentration ranged from 84.14 to 904.38 Bq/kg. The obtained results were used primarily to define the variability in measured environmental radiation and to determine the coal plant’s influence in the measured radiation levels. The highest values were measured at two locations near the power plant and at locations between the distance of 6 and 20 km away from the stacks, mainly in the prevailing wind direction. The results showed an increase or at least an influence from the coal-fired plant operations, both qualitatively and quantitatively.

Dispersion Modelling of Natural Radionuclides 238U, 232Th and 40K Released from Coal-fired Power Plants Operations

The aim of this work was to simulate the radionuclides dispersion in the surrounding area of a coal-fired power plant, operational during the last 25 years. The dispersion of natural radionuclides (236Ra, 232Th and 40K) was simulated by a Gaussian plume dispersion model with three different stability classes estimating the radionuclides concentration at ground level. Measurements of the environmen-tal activity concentrations were carried out by γ-spectrometry and compared with results from the air dispersion and deposition model which showed that the stabil-ity class D causes the dispersion to longer distances up to 20 km from the stacks.