Optimum coal properties and engineering processes for CO2 geosequestration in Coal

CO2 Geosequestration is seen by many worldwide scientists and engineers as a leading prospective solution to the global warming problem arising from excessive CO2 and other greenhouse gas emissions. CO2 geosequestration in coal seams has two important strategic benefits: the process has an extremely low risk of leakage, due to the adsorbed state of the CO2 and the known reservoir context of essentially-zero leakage into which it is be injected; the second benefit arises from the valuable by-product, clean burning coalbed methane gas. This paper presents the authors’ experience, knowledge and perspective on what coal properties and engineering processes would favour implementing a demonstration or commercial CO2 storage-in-coal project, in Queensland, Australia. As such, it may be considered a template for screening studies to select the optimum coal seam reservoir, and for preliminary studies in designing the injection system and predicting production response to the technology. The paper concludes by examining the current knowledge gaps of CO2 geosequestration in coal, identifying further basic and applied research topics.

A INFLUÊNCIA DAS COMPETÊNCIAS COLETIVAS SOBRE A EFICÁCIA DO ATENDIMENTO AO CLIENTE

O relacionamento de longo prazo é atualmente o elemento-chave para o sucesso das organizações. Com um mercado tão competitivo, as empresas estão desenvolvendo estratégias que melhor possam satisfazer e criar valor para seus clientes. As empresas precisam definir muito bem as suas estratégias com foco na percepção de seus clientes e do mercado. Porém a criação de valor não advém apenas da qualidade de um produto, da tecnologia e da infraestrutura. Ela também tem base em valores intrínsecos como, por exemplo, as competências. Sendo assim, as empresas precisam investir nos profissionais de linha de frente para que eles desenvolvam competências e atendam às necessidades e desejos dos clientes. Este trabalho tem o intuito de demonstrar se as competências coletivas, desenvolvidas a partir da interação social de um grupo podem trazer algum(s) benefício(s) ou não para o atendimento ao cliente em termos de satisfação e criação de valor, promovendo o marketing de relacionamento. Em seu desenvolvimento, foram utilizadas como base as teorias de competência, competências coletivas, gestão do conhecimento, satisfação e criação de valor para o cliente e marketing de relacionamento. Porém, não foi possível encontrar na literatura qualquer relação entre os temas competências coletivas e marketing de relacionamento. Neste contexto, o presente trabalho teve como objetivo geral analisar como o desenvolvimento das competências coletivas de uma equipe de vendas pode influenciar a satisfação do cliente. Especificamente buscou-se a) levantar quais os principais fatores ligados à equipe de vendas que geram satisfação nos clientes; b) analisar como as competências coletivas da equipe de vendas influenciam a satisfação do cliente; c) identificar como se formam competências coletivas em uma equipe de vendas. A partir destes objetivos, o procedimento metodológico de abordagem qualitativa foi orientado pelo método de estudo de caso, com procedimentos de análise de dados de entrevistas, observação direta e levantamento de registros. Foram entrevistadas duas equipes de vendas de uma empresa multinacional no segmento de serviços para análise e proteção de crédito, envolvendo o gerente, três vendedores e um cliente de cada equipe, atendidos por estes vendedores. As observações foram realizadas em duas reuniões de vendas envolvendo vendedores e clientes, e os registros analisados referem-se a metas e número de clientes atendidos no mês. Os resultados evidenciam que as competências coletivas podem influenciar na satisfação do cliente, embora estes só percebam as competências individuais e organizacionais. Mas ficou evidente, por parte de vendedores e gerentes de equipe, que as competências coletivas, além de promover a satisfação do cliente, auxiliam no desenvolvimento e na formação de competências individuais das pessoas na área comercial.

Advances in (poly)phenol research: novel sources, bioavailability, bioaccumulation and bioactivity

In the last decades, increasing scientific evidence has correlated the regular consumption of (poly)phenol-rich foods to a potential reduction of chronic disease incidence and mortality. However, epidemiological evidence on the role of (poly)phenol intake against the risk of some chronic diseases is promising, but not conclusive. In this framework a proper approach to (poly)phenol research is requested, using a step by step strategy. The plant kingdom produces an overwhelming array of structurally diverse secondary metabolites, among which flavonoids and related phenolic and (poly)phenolic compounds constitute one of the most numerous and widely distributed group of natural products. To date, more than 8000 structures have been classified as members of the phytochemical class of (poly)phenol, and among them over 4000 flavonoids have been identified. For this reason, a detailed food (poly)phenolic characterization is essential to identify the compounds that will likely enter the human body upon consumption, to predict the metabolites that will be generated and to unravel the potential effects of phenolic rich food sources on human health. In the first part of this work the attention was focused on the phenolic characterization of fruit and vegetable supplements, considering the increasing attention recently addressed to the so called "nutraceuticals", and on the main coffee industry by-product, namely coffee silverskin. The interest oriented toward (poly)phenols is then extended to their metabolism within the human body, paramount in the framework of their putative health promoting effects. Like all nutrients and non-nutrients, once introduced through the diet, (poly)phenols are subjected to an intense metabolism, able to convert the native compounds into similar conjugated, as well as smaller and deeply modified molecules, which in turn could be further conjugated. Although great strides have been made in the last decades, some steps of the (poly)phenol metabolism remain unclear and are interesting points of research. In the second part of this work the research was focused on a specific bran fraction, namely aleurone, added in feed pellets and in bread to investigate the absorption, metabolism and bioavailability of its phenolic compounds in animal and humans, with a preliminary in vitro step to determine their potential bioaccesibility. This part outlines the best approaches to assess the bioavailability of specific phenolics in several experimental models. The physiological mechanisms explaining the epidemiological and observational data on phenolics and health, are still far from being unraveled or understood in full. Many published results on phenolic actions at cell levels are biased by the fact that aglycones or native compounds have been used, not considering the previously mentioned chemical and biological transformations. In the last part of this thesis work, a new approach in (poly)phenol bioactivity investigation is proposed, consisting of a medium-long term treatment of animals with a (poly)phenol source, in this specific case resveratrol, the detection of its metabolites to determine their possible specific tissue accumulation, and the evaluation of specific parameters and/or mechanism of action at target tissue level. To conclude, this PhD work has contributed to advancing the field, as novel sources of (poly)phenols have been described, the bioavailability of (poly)phenols contained in a novel specific bran fraction used as ingredient has been evaluated in animal and in humans, and, finally, the tissue accumulation of specific (poly)phenol metabolites and the evaluation of specific parameters and/or mechanism of action has been carried out. For these reasons, this PhD work should be considered an example of adequate approach to the investigation of (poly)phenols and of their bioactivity, unavoidable in the process of unequivocally defining their effects on human health.

Ultralong Raman fibre lasers as virtually lossless optical media

By transforming the optical fiber span into an ultralong cavity laser, we experimentally demonstrate quasilossless transmission over long (up to 75 km) distances and virtually zero signal power variation over shorter (up to 20 km) spans, opening the way for the practical implementation of integrable nonlinear systems in optical fiber. As a by-product of our technique, the longest ever laser (to the best of our knowledge) has been implemented, with a cavity length of 75 km. A simple theory of the lossless fiber span, in excellent agreement with the observed results, is presented.

Combined bioreaction and separation in centrifugal fields

The aim of this work has been to investigate the principle of combined centrifugal bioreaction-separation. The production of dextran and fructose by the action of the enzyme dextransucrase on sucrose was employed to elucidate some of the principles of this type of process. Dextran is a valuable pharmaceutical product used mainly as a blood volume expander and blood flow improver whilst fructose is an important dietary product. The development of a single step process capable of the simultaneous biosynthesis of dextran and the separation of the fructose by-product should improve dextran yields whilst reducing capital and processing costs. This thesis shows for the first time that it is possible to conduct successful bioreaction-separations using a rate-zonal centrifugation technique. By layering thin zones of dextrasucrase enzyme onto sucrose gradients and centrifuging, very high molecular weight (MW) dextran-enzyme complexes were formed that rapidly sedimented through the sucrose substrate gradients under the influence of the applied centrifugal field. The low MW fructose by-product sedimented at reduced rates and was thus separated from the enzyme and dextran during the reaction. The MW distribution of dextran recovered from the centrifugal bioreactor was compared with that from a conventional batch bioreactor. The results indicated that the centrifugal bioreactor produced up to 100% more clinical dextran with MWs of between 12 000 and 98 000 at 20% w/w sucrose concentrations than conventional bioreactors. This was due to the removal of acceptor fructose molecules from the sedimenting reaction zone by the action of the centrifugal field. Higher proportions of unwanted lower MW dextran were found in the conventional bioreactor than in the centrifugal bioreactor-separator. The process was studied on a number of alternative centrifugal systems. A zonal rotor fitted with a reorienting gradient core proved most successful for the evaluation of bioreactor performance. Results indicated that viscosity build-up in the reactor must be minimised in order to increase the yields of dextran per unit time and improve product separation. A preliminary attempt at modelling the process has also been made.

Chemical modification of smectite clays

Today, speciality use organoclays are being developed for an increasingly large number of specific applications. Many of these, including use in cosmetics, polishes, greases and paints, require that the material be free from abrasive impurities so that the product retains a smooth `feel'. The traditional `wet' method preparation of organoclays inherently removes abrasives naturally present in the parent mineral clay, but it is time-consuming and expensive. The primary objective of this thesis was to explore the alternative `dry' method (which is both quicker and cheaper but which provides no refining of the parent clay) as a process, and to examine the nature of the organoclays produced, for the production of a wide range of commercially usable organophilic clays in a facile way. Natural Wyoming bentonite contains two quite different types of silicate surface (that of the clay mineral montmorillonite and that of a quartz impurity) that may interact with the cationic surfactant added in the `dry' process production of organoclays. However, it is oil shale, and not the quartz, that is chiefly responsible for the abrasive nature of the material, although air refinement in combination with the controlled milling of the bentonite as a pretreatment may offer a route to its removal. Ion exchange of Wyoming bentonite with a long chain quaternary ammonium salt using the `dry' process affords a partially exchanged, 69-78%, organoclay, with a monolayer formation of ammonium ions in the interlayer. Excess ion pairs are sorbed on the silicate surfaces of both the clay mineral and the quartz impurity phases. Such surface sorption is enhanced by the presence of very finely divided, super paramagnetic, Fe2O3 or Fe(O)(OH) contaminating the surfaces of the major mineral components. The sorbed material is labile to washing, and induces a measurable shielding of the 29Si nuclei in both clay and quartz phases in the MAS NMR experiment, due to an anisotropic magnetic susceptibility effect. XRD data for humidified samples reveal the interlamellar regions to be strongly hydrophobic, with the by-product sodium chloride being expelled to the external surfaces. Many organic cations will exchange onto a clay. The tetracationic cyclophane, and multipurpose receptor, cyclobis(paraquat-p-phenylene) undergoes ion exchange onto Wyoming bentonite to form a pillared clay with a very regular gallery height. The major plane of the cyclophane is normal to the silicate surfaces, thus allowing the cavity to remain available for complexation. A series of group VI substituted o-dimethoxybenzenes were introduced, and shown to participate in host/guest interactions with the cyclophane. Evidence is given which suggests that the binding of the host structure to a clay substrate offers advantages, not only of transportability and usability but of stability, to the charge-transfer complex which may prove useful in a variety of commercial applications. The fundamental relationship between particle size, cation exchange capacity and chemical composition of clays was also examined. For Wyoming bentonite the extent of isomorphous substitution increases with decreasing particle size, causing the CEC to similarly increase, although the isomorphous substitution site: edge site ratio remains invarient throughout the particle size range studied.

The durability of cement bound minestone

The demand for road making materials continues to pressurise the supply of traditional good quality aggregates. Over the years, therefore, consideration has been given to alternative materials including industrial wastes. This thesis is concerned with potential use of Minestone, the by-product of coal mining, for the lower structural layers of pavement construction. Because of their clay like nature, Minestones do not merit consideration for such applications in an unbound state and, therefore, some form of stabilisation is necessary. Previous research has demonstrated that certain cement bound minestones, containing between 5 and 10 per cent cement, satisfy current Department of Transport requirements for use in pavement construction and, furthermore, they are not frost susceptible. However, doubts concerning the durability of cement bound minestones still remain. The thesis includes a review of both the cement and lime stabilisation techniques and also traces the origin and development of the methods used to assess the quality and durability of stabilised materials. An experimental study is described in which cement bound minestone specimens were subjected to a programme of tests which examined compressive strength, resistance to immersion, and resistance to freezing and thawing. The results of the tests were related to the properties of the raw materials. It was discovered that the response to cement stabilisation was governed mainly by the source of the minestone and, to a lesser degree, the cement content. It was also found that resistance in the durability tests was generally improved when the initial moisture content was raised above the optimum value. The result suggest that current methods for assessing cement stabilised materials are not appropriate to cement bound minestones. Alternative methods and criteria, based on volume change and retained strength following immersion and freeze-thaw tests, have been proposed. It is believed that these methods and criteria should also apply to other cement bound materials.

Energy conservation measures on an industrial site

World and UK energy resources and use are reviewed and the role of energy conservation in energy policy identified. In considering various energy conservation measures, a distinction is made between energy intensive and non-intensive industries and also between direct and indirect uses of energy. Particular attention is given to the non-intensive user of energy. Energy use on one such industrial site has been studied to determine the most effective energy saving measures in the short term. Here it is estimated that over 65% of energy is consumed for indirect purposes, mainly for heating and lighting buildings. Emphasis is placed on energy auditing techniques and those energy saving measures requiring greater technical, economic and organisational resources to secure their implementation. Energy auditing techniques include the use of aerial thermography and snow formation surveys to detect heat losses. Qualitative and quantitative interpretations are carried out, but restricted mainly to evaluating building roof heat losses. From the energy auditing exercise, it is confirmed that the intermittent heating of buildings is the largest and most cost effective fuel saving measure. This was implemented on the site and a heat monitoring programme established to verify results. Industrial combined heat and power generation is investigated. A proposal for the site demonstrates that there are several obstacles to its successful implementation. By adopting an alternative financial rationale, a way of overcoming these obstacles is suggested. A useful by-product of the study is the classification of industrial sites according to the nature of industrial energy demand patterns. Finally, energy saving measures implemented on the site are quantlfied using comparative verification methods. Overall fuel savings of 13% are indicated. Cumulative savings in heating fuel amount to 26% over four years although heated area increased by approximately 25%.

Properties of seawater bitterns with regard to liquid-desiccant cooling

This study concerns the properties of the concentrated bittern solutions occurring as by-product from solar salt works, in relation to their potential use as liquid desiccants in cooling systems. Solutions of compositions similar to those of bitterns have been made up in the laboratory, as have concentrated mixtures of MgCl2–MgSO4–H2O. Measurements of vapour pressure have been carried out using an isoteniscope and are reported together with measurements of density and viscosity. Several theoretical models representing these properties are reviewed and compared against the experimental results; the average agreement between theory and experiment is within 5% for vapour pressure and better for the preferred models of the other two properties. Based on these findings, an expression is provided for the equilibrium relative humidity of bitterns as a function of concentration relative to raw seawater. The vapour pressures of bittern solutions are found to be similar to those of solutions containing only magnesium chloride but having the same mass fraction of total salts. Therefore magnesium chloride solution is a reasonable model for bitterns for the purpose of developing the proposed cooling system.

A solar powered liquid-desiccant cooling system for greenhouses

Liquid desiccant systems are of potential interest as a means of cooling greenhouses to temperatures below those achieved by conventional means. However, only very little work has been done on this technology with previous workers focussing on the cooling of human dwellings using expensive desiccants such as lithium salts. In this study we are designing a system for greenhouse cooling based on magnesium chloride desiccant which is an abundant and non-toxic substance. Magnesium chloride is found in seawater, for example, and is a by-product from solar salt works. We have carried out a detailed experimental study of the relevant properties of magnesium rich solutions. In addition we have constructed a test rig that includes the main components of the cooling system, namely a dehumidifier and solar regenerator. The dehumidifier is a cross-flow device that consists of a structured packing made of corrugated cellulose paper sheets with different flute angles and embedded cooling tubes. The regenerator is of the open type with insulated backing and fabric covering to spread the flow of desiccant solution. Alongside these experiments we are developing a mathematical model in gPROMS® that combines and simulates the heat and mass transfer processes in these components. The model can be applied to various geographical locations. Here we report predictions for Havana (Cuba) and Manila (Philippines), where we find that average wet-bulb temperatures can be lowered by 2.2 and 3°C, respectively, during the month of May.

Scaling up question-answering to linked data

Linked Data semantic sources, in particular DBpedia, can be used to answer many user queries. PowerAqua is an open multi-ontology Question Answering (QA) system for the Semantic Web (SW). However, the emergence of Linked Data, characterized by its openness, heterogeneity and scale, introduces a new dimension to the Semantic Web scenario, in which exploiting the relevant information to extract answers for Natural Language (NL) user queries is a major challenge. In this paper we discuss the issues and lessons learned from our experience of integrating PowerAqua as a front-end for DBpedia and a subset of Linked Data sources. As such, we go one step beyond the state of the art on end-users interfaces for Linked Data by introducing mapping and fusion techniques needed to translate a user query by means of multiple sources. Our first informal experiments probe whether, in fact, it is feasible to obtain answers to user queries by composing information across semantic sources and Linked Data, even in its current form, where the strength of Linked Data is more a by-product of its size than its quality. We believe our experiences can be extrapolated to a variety of end-user applications that wish to scale, open up, exploit and re-use what possibly is the greatest wealth of data about everything in the history of Artificial Intelligence. © 2010 Springer-Verlag.

Ultralong raman fiber lasers as virtually lossless optical media

By transforming the optical fiber span into an ultralong cavity laser, we experimentally demonstrate quasilossless transmission over long (up to 75 km) distances and virtually zero signal power variation over shorter (up to 20 km) spans, opening the way for the practical implementation of integrable nonlinear systems in optical fiber. As a by-product of our technique, the longest ever laser (to the best of our knowledge) has been implemented, with a cavity length of 75 km. A simple theory of the lossless fiber span, in excellent agreement with the observed results, is presented. © 2006 The American Physical Society.

Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

New Symmetric (61,16,4) Designs Invariant Under the Dihedral Group of Order 10

∗ This work has been partially supported by the Bulgarian NSF under Contract No. I-506/1995.

Theorem for Series in Three-Parameter Mittag-Leffler Function

Mathematics Subject Classification 2010: 26A33, 33E12.