NaOH and KOH for preparing activated carbons used in energy and environmental applications

Alkaline hydroxides, especially sodium and potassium hydroxides, are multi-million-ton per annum commodities and strong chemical bases that have large scale applications. Some of them are related with their consequent ability to degrade most materials, depending on the temperature used. As an example, these chemicals are involved in the manufacture of pulp and paper, textiles, biodiesels, soaps and detergents, acid gases removal (e.g., SO2) and others, as well as in many organic synthesis processes. Sodium and potassium hydroxides are strong and corrosive bases, but they are also very stable chemicals that can melt without decomposition, NaOH at 318ºC, and KOH at 360ºC. Hence, they can react with most materials, even with relatively inert ones such as carbon materials. Thus, at temperatures higher than 360ºC these melted hydroxides easily react with most types of carbon-containing raw materials (coals, lignocellulosic materials, pitches, etc.), as well as with most pure carbon materials (carbon fibers, carbon nanofibers and carbon nanotubes). This reaction occurs via a solid-liquid redox reaction in which both hydroxides (NaOH or KOH) are converted to the following main products: hydrogen, alkaline metals and alkaline carbonates, as a result of the carbon precursor oxidation. By controlling this reaction, and after a suitable washing process, good quality activated carbons (ACs), a classical type of porous materials, can be prepared. Such carbon activation by hydroxides, known since long time ago, continues to be under research due to the unique properties of the resulting activated carbons. They have promising high porosity developments and interesting pore size distributions. These two properties are important for new applications such as gas storage (e.g., natural gas or hydrogen), capture, storage and transport of carbon dioxide, electricity storage demands (EDLC-supercapacitors-) or pollution control. Because these applications require new and superior quality activated carbons, there is no doubt that among the different existing activating processes, the one based on the chemical reaction between the carbon precursor and the alkaline hydroxide (NaOH or KOH) gives the best activation results. The present article covers different aspects of the activation by hydroxides, including the characteristics of the resulting activated carbons and their performance in some environment-related applications. The following topics are discussed: i) variables of the preparation method, such as the nature of the hydroxide, the type of carbon precursor, the hydroxide/carbon precursor ratio, the mixing procedure of carbon precursor and hydroxide (impregnation of the precursor with a hydroxide solution or mixing both, hydroxide and carbon precursor, as solids), or the temperature and time of the reaction are discussed, analyzing their effect on the resulting porosity; ii) analysis of the main reactions occurring during the activation process, iii) comparative analysis of the porosity development obtained from different activation processes (e.g., CO2, steam, phosphoric acid and hydroxides activation); and iv) performance of the prepared activated carbon materials on a few applications, such as VOC removal, electricity and gas storages.

Using the damage from 2010 Haiti earthquake for calibrating vulnerability models of typical structures in Port-au-Prince (Haiti)

After the 2010 Haiti earthquake, that hits the city of Port-au-Prince, capital city of Haiti, a multidisciplinary working group of specialists (seismologist, geologists, engineers and architects) from different Spanish Universities and also from Haiti, joined effort under the SISMO-HAITI project (financed by the Universidad Politecnica de Madrid), with an objective: Evaluation of seismic hazard and risk in Haiti and its application to the seismic design, urban planning, emergency and resource management. In this paper, as a first step for a structural damage estimation of future earthquakes in the country, a calibration of damage functions has been carried out by means of a two-stage procedure. After compiling a database with observed damage in the city after the earthquake, the exposure model (building stock) has been classified and through an iteratively two-step calibration process, a specific set of damage functions for the country has been proposed. Additionally, Next Generation Attenuation Models (NGA) and Vs30 models have been analysed to choose the most appropriate for the seismic risk estimation in the city. Finally in a next paper, these functions will be used to estimate a seismic risk scenario for a future earthquake.

Solubility, Density, Refractive Index, and Viscosity for the Polyhydric Alcohol + CsBr + H2O Ternary Systems at Different Temperatures

The solubility, density, refractive index, and viscosity data for the ethylene glycol + CsBr + H2O, 1,2-propanediol + CsBr + H2O, and glycerin + CsBr + H2O ternary systems have been determined at (288.15, 298.15, and 308.15) K. In all cases, the solubility of CsBr in aqueous solutions was decreased significantly due to the presence of polyhydric alcohol. The liquid–solid equilibrium experimental data were correlated using the NRTL (nonrandom two-liquid) activity coefficient model, considering nondissociation of the dissolved salt in the liquid phase, and new interaction parameters were estimated. The mean deviations between calculated and experimental compositions were low, showing the good descriptive quality and applicability of the NRTL model. The refractive indices, densities, and viscosities for the unsaturated solutions of the three ternary systems have also been measured at three temperatures. Values for all of the properties were correlated with the salt concentrations and proportions of polyhydric alcohol in the solutions.

De novo synthesis of brominated dioxins and furans

On the basis of laboratory experiments with model mixtures (active carbon + CuBr2 at different loads), this work studies the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) by de novo synthesis. For the different samples, the temperature of the maximum carbon oxidation rate was determined by thermogravimetric analysis, and a kinetic model was proposed for the degradation of the materials in an oxidizing atmosphere (synthetic air). The effect of the addition of different amounts of CuBr2 was studied, finding that its presence accelerates the degradation of the carbonaceous structure in the presence of oxygen. The thermal degradation of the samples in air is satisfactorily described by a first-order single-reaction model. In addition, combustion runs of one of the mixtures (consisting of activated carbon + 50 wt % CuBr2, pyrolyzed at 700 °C) were performed in a quartz horizontal laboratory furnace. The analysis of the emissions and the solid residue proved the formation of brominated dioxins and furans at 300, 400, and 500 °C, with a maximum yield at 300 °C (91.7 ng/g of total PBDD/Fs) and a higher bromination degree with increasing temperature.

Detection and mapping of burnt areas from time series of MODIS-derived NDVI data in a Mediterranean region

Moderate resolution remote sensing data, as provided by MODIS, can be used to detect and map active or past wildfires from daily records of suitable combinations of reflectance bands. The objective of the present work was to develop and test simple algorithms and variations for automatic or semiautomatic detection of burnt areas from time series data of MODIS biweekly vegetation indices for a Mediterranean region. MODIS-derived NDVI 250m time series data for the Valencia region, East Spain, were subjected to a two-step process for the detection of candidate burnt areas, and the results compared with available fire event records from the Valencia Regional Government. For each pixel and date in the data series, a model was fitted to both the previous and posterior time series data. Combining drops between two consecutive points and 1-year average drops, we used discrepancies or jumps between the pre and post models to identify seed pixels, and then delimitated fire scars for each potential wildfire using an extension algorithm from the seed pixels. The resulting maps of the detected burnt areas showed a very good agreement with the perimeters registered in the database of fire records used as reference. Overall accuracies and indices of agreement were very high, and omission and commission errors were similar or lower than in previous studies that used automatic or semiautomatic fire scar detection based on remote sensing. This supports the effectiveness of the method for detecting and mapping burnt areas in the Mediterranean region.

Modulation of the Silica Sol–Gel Composition for the Promotion of Direct Electron Transfer to Encapsulated Cytochrome c

The direct electron transfer between indium–tin oxide electrodes (ITO) and cytochrome c encapsulated in different sol–gel silica networks was studied. Cyt c@silica modified electrodes were synthesized by a two-step encapsulation method mixing a phosphate buffer solution with dissolved cytochrome c and a silica sol prepared by the alcohol-free sol–gel route. These modified electrodes were characterized by cyclic voltammetry, UV–vis spectroscopy, and in situ UV–vis spectroelectrochemistry. The electrochemical response of encapsulated protein is influenced by the terminal groups of the silica pores. Cyt c does not present electrochemical response in conventional silica (hydroxyl terminated) or phenyl terminated silica. Direct electron transfer to encapsulated cytochrome c and ITO electrodes only takes place when the protein is encapsulated in methyl modified silica networks.

Surface growth for molten silicon infiltration into carbon millimeter-sized channels: Lattice–Boltzmann simulations, experiments and models

The process of liquid silicon infiltration is investigated for channels with radii from 0.25 to 0.75 [mm] drilled in compact carbon preforms. The advantage of this setup is that the study of the phenomenon results to be simplified. For comparison purposes, attempts are made in order to work out a framework for evaluating the accuracy of simulations. The approach relies on dimensionless numbers involving the properties of the surface reaction. It turns out that complex hydrodynamic behavior derived from second Newton law can be made consistent with Lattice-Boltzmann simulations. The experiments give clear evidence that the growth of silicon carbide proceeds in two different stages and basic mechanisms are highlighted. Lattice-Boltzmann simulations prove to be an effective tool for the description of the growing phase. Namely, essential experimental constraints can be implemented. As a result, the existing models are useful to gain more insight on the process of reactive infiltration into porous media in the first stage of penetration, i.e. up to pore closure because of surface growth. A way allowing to implement the resistance from chemical reaction in Darcy law is also proposed.

Avaliação do efeito de escala no cálculo da perigosidade de incêndio florestal

Dissertação apresentada à Escola Superior Agrária do Instituto Politécnico de Castelo Branco para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Sistemas de Informação Geográfica - Recursos Agro-Florestais e Ambientais.

Female Labour Force Participation and Economic Development in Southern Mediterranean Countries: What scenarios for 2030? MEDPRO Technical Report No. 19/December 2012

This paper investigates the relationship between female labour force participation rates and economic growth in southern Mediterranean countries. A two-step methodology involving econometric estimations and the use of a general equilibrium model was used for this purpose. The econometric estimations suggest that there is a U-shaped relationship between economic growth and female labour force participation rates and they indicate the presence of region-specific barriers impeding women's entry into the labour force in southern Mediterranean countries. The econometric results were fed into a general equilibrium model, the GEM-E3-MEDPRO, which was used to simulate two alternative assumptions on developments in female labour participation rates in the region up to 2030. The first of these simulated changes in female labour force participation rates arising from income level trends projected for the period 2015–2030 in southern Mediterranean countries. The second assumed the lowering of region-specific barriers which deter female labour force participation. The results of these simulations suggest that lower female labour force participation rates may lead to marginally lower economic growth in the region, while the removal of region-specific barriers to female labour force participation may encourage economic growth. This has important policy implications, suggesting that policies intended to remove such barriers could help to promote the growth of the region's economies.

Trade policy in a dynamic Heckscher-Ohlin model

The Import Substitution Process in Latin Amer ica was an attempt to enhance GDP growth and productivity by rising trade barriers upon capital-intensive products. Our main goal is to analyze how an increase in import tariff on a particular type of good affects the production choices and trade pattern of an economy. We develop an extension of the dynamic Heckscher-Ohlin model – a combination of a static two goods, two-factor Heckscher-Ohlin model and a two-sector growth model – allowing for import tariff. We then calibrate the closed economy model to the US. The results show that the economy will produce less of both consumption and investment goods under autarky for low and high levels of capital stock per worker. We also find that total GDP may be lower under free trade in comparison to autarky.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

(Table1) Sedimentation rates and age-control points form ODP Hole 152-919A

Planktic d18O and d13C records and point count records of biogenic, volcanic, and nonvolcanic terrigenous [ice-rafted debris (IRD)] sediment components from Hole 919A in the Irminger basin, northern North Atlantic provide a comprehensive dataset from which a paleoceanographic reconstruction for the last 630 kyr has been developed. The paleoceanographic evolution of the Irminger basin during this time contains both long-term patterns and significant developmental steps. One long-term pattern observed is the persistent deposition of hematite-stained ice-rafted debris. This record suggests that the modern and late Pleistocene discharges of icebergs from northern redbed regions to the Irminger Sea lie in the low end of the range observed over the last 630 kyr. In addition, Arctic front fluctuations appear to have been the main controlling factor on the long-term accumulation patterns of IRD and planktic biogenic groups. The Hole 919A sediment record also contains a long-term association between felsic volcanic ash abundances and light d18O excursions in both interglacial and glacial stages, which suggests a causal link between deglaciations and explosive Icelandic eruptions. A significant developmental step in the paleoceanographic reconstruction based on benthic evidence was for diminished supply of Denmark Strait Overflow Water (DSOW) beginning at ~380 ka, possibly initiated by the influx of meltwater from broad-scale iceberg discharges along the east Greenland coast. There is also planktic evidence of a two-step cooling of sea surface conditions in the Irminger basin, first at ~338-309 ka and later at ~211-190 ka, after which both glacials and interglacials were colder as the Arctic front migrated southeast of Site 919. In addition to offering these findings, this reconstruction provides a longer-term geologic context for the interpretation of more recent paleoceanographic events and patterns of deposition from this region.

Sedimentation rates calculated on surface sediment samples from different site of the Atlantic and Pacific Oceans (Table 1)

Radiocarbon ages on CaCO3 from deep-sea cores offer constraints on the nature of the CaCO3 dissolution process. The idea is that the toll taken by dissolution on grains within the core top bioturbation zone should be in proportion to their time of residence in this zone. If so, dissolution would shift the mass distribution in favor of younger grains, thereby reducing the mean radiocarbon age for the grain ensemble. We have searched in vain for evidence supporting the existence of such an age reduction. Instead, we find that for water depths of more than 4 km in the tropical Pacific the radiocarbon age increases with the extent of dissolution. We can find no satisfactory steady state explanation and are forced to conclude that this increase must be the result of chemical erosion. The idea is that during the Holocene the rate of dissolution of CaCO3 has exceeded the rain rate of CaCO3. In this circumstance, bioturbation exhumes CaCO3 from the underlying glacial sediment and mixes it with CaCO3 raining from the sea surface.

Improving constraints on the sources and distribution of sea salt aerosols in polar regions

Thesis (Master's)--University of Washington, 2016-06