A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu-ZSM-5

A low temperature, isothermal, gas-phase, recyclable process is described for the partial oxidation of methane to methanol over Cu–ZSM-5. Activation in NO at 150 °C followed by methane reaction and steam extraction (both at 150 °C) allowed direct observation of methanol at the reactor outlet.

Assessing Climate Effects on Railway Earthworks Using MASW

Many parts of the UK’s rail network were constructed in the mid-19th century long before the advent of modern construction standards. Historic levels of low investment, poor maintenance strategies and the deleterious effects of climate change have resulted in critical elements of the rail network being at significant risk of failure. The majority of failures which have occurred over recent years have been triggered by extreme weather events. Advance assessment and remediation of earthworks is, however, significantly less costly than dealing with failures reactively. It is therefore crucial that appropriate approaches for assessment of the stability of earthworks are developed, so that repair work can be better targeted and failures avoided wherever possible. This extended abstract briefly discusses some preliminary results from an ongoing geophysical research project being carried out in order to study the impact of climate or seasonal weather variations on the stability of a century old railway embankment on the Gloucestershire Warwickshire steam railway line in Southern England.

Formation mechanism of levoglucosan and formaldehyde during cellulose pyrolysis

Biomass pyrolysis is an efficient way to transform raw biomass or organic waste materials into useable energy, including liquid, solid, and gaseous materials. Levoglucosan (1,6-anhydro-β-d-glucopyranose) and formaldehyde are two important products in biomass pyrolysis. The formation mechanism of these two products was investigated using the density functional theory (DFT) method based on quantum mechanics. It was found that active anhydroglucose can be obtained from a cellulose homolytic reaction during high-temperature steam gasification of the biomass process. Anhydroglucose undergoes a hydrogen-donor reaction and forms an intermediate, which can transform into the products via three pathways, one (path 1) for the formation of levoglucosan and two (paths 2 and 3) for formaldehyde. A total of six elementary reactions are involved. At a pressure of 1 atm, levoglucosan can be formed at all of the temperatures (450-750 K) considered in this simulation, whereas formaldehyde can be formed only when the temperature is higher than 475 K. Moreover, the energy barrier of levoglucosan formation is lower than that of formaldehyde, which is in agreement with the mechanism proposed in the experiments. © 2011 American Chemical Society.

Development of a Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) Cell for the In Situ Analysis of Co-Electrolysis in a Solid Oxide Cell

Co-electrolysis of carbon dioxide and steam has been shown to be an efficient way to produce syngas, however further optimisation requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the solid oxide cell (SOC) during operation. Whilst electrochemical measurements are currently conducted in situ, many analytical techniques can only be used ex situ and may even be destructive to the cell (e.g. SEM imaging of microstructure). In order to fully understand and characterise co-electrolysis, in situ monitoring of the reactants, products and SOC is necessary. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) is ideal for in situ monitoring of co-electrolysis as both gaseous and adsorbed CO and CO2 species can be detected, however it has previously not been used for this purpose. The challenges of designing an experimental rig which allows optical access alongside electrochemical measurements at high temperature and operates in a dual atmosphere are discussed. The rig developed has thus far been used for symmetric cell testing at temperatures from 450[degree]C to 600[degree]C. Under a CO atmosphere, significant changes in spectra were observed even over a simple Au|10Sc1CeSZ|Au SOC. The changes relate to a combination of CO oxidation, the water gas shift reaction and carbonate formation and decomposition processes, with the dominant process being both potential and temperature dependent.

Evidence reasoning for event inference in smart transport video surveillance

In this paper we present a new event recognition framework, based on the Dempster-Shafer theory of evidence, which combines the evidence from multiple atomic events detected by low-level computer vision analytics. The proposed framework employs evidential network modelling of composite events. This approach can effectively handle the uncertainty of the detected events, whilst inferring high-level events that have semantic meaning with high degrees of belief. Our scheme has been comprehensively evaluated against various scenarios that simulate passenger behaviour on public transport platforms such as buses and trains. The average accuracy rate of our method is 81% in comparison to 76% by a standard rule-based method.

Video Event Recognition by Dempster-Shafer Theory

This paper presents an event recognition framework, based on Dempster-Shafer theory, that combines evidence of events from low-level computer vision analytics. The proposed method employing evidential network modelling of composite events, is able to represent uncertainty of event output from low level video analysis and infer high level events with semantic meaning along with degrees of belief. The method has been evaluated on videos taken of subjects entering and leaving a seated area. This has relevance to a number of transport scenarios, such as onboard buses and trains, and also in train stations and airports. Recognition results of 78% and 100% for four composite events are encouraging.

Density Functional Theory Studies of Ethanol Decomposition on Rh(211)

Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(3)CO -> CH(3) + CO -> CH(2) + CO -> CH + CO -> C + CO and (2) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(2)COH -> CHCOH -> CHCO -> CH + CO -> C + CO. Both pathways have a common intermediate of CH(3)COH, and the key step is the formation of CH(3)CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH(3)COH rather than an oxametallacycle species (-CH(2)CH(2)O- for Rh( 111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial C(alpha)-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.

Rethinking Rice Preparation for Highly Efficient Removal of Inorganic Arsenic Using Percolating Cooking Water

A novel way of cooking rice to maximize the removal of the carcinogen inorganic arsenic (Asi) is presented here. In conventional rice cooking water and grain are in continuous contact, and it is known that the larger the water:rice cooking ratio, the more Asi removed by cooking, suggesting that the Asi in the grain is mobile in water. Experiments were designed where rice is cooked in a continual stream of percolating near boiling water, either low in Asi, or Asi free. This has the advantage of not only exposing grain to large volumes of cooking water, but also physically removes any Asi leached from the grain into the water receiving vessel. The relationship between cooking water volume and Asi removal in conventional rice cooking was demonstrated for the rice types under study. At a water-to-rice cooking ratio of 12:1, 57±5% of Asi could be removed, average of 6 wholegrain and 6 polished rice samples. Two types of percolating technology were tested, one where the cooking water was recycled through condensing boiling water steam and passing the freshly distilled hot water through the grain in a laboratory setting, and one where tap water was used to cook the rice held in an off-the-shelf coffee percolator in a domestic setting. Both approaches proved highly effective in removing Asi from the cooking rice, with up to 85% of Asi removed from individual rice types. For the recycled water experiment 59±8% and 69±10% of Asi was removed, on average, compared to uncooked rice for polished (n=27) and wholegrain (n=13) rice, respectively. For coffee percolation there was no difference between wholegrain and polished rice, and the effectiveness of Asi removal was 49±7% across 6 wholegrain and 6 polished rice samples. The manuscript explores the potential applications and further optimization of this percolating cooking water, high Asi removal, discovery.

Paired associative transcranial alternating current stimulation increases the excitability of corticospinal projections in humans

Many types of non-invasive brain stimulation alter corticospinal excitability (CSE). Paired associative stimulation (PAS) has attracted particular attention as its effects ostensibly adhere to Hebbian principles of neural plasticity. In prototypical form, a single electrical stimulus is directed to a peripheral nerve in close temporal contiguity with transcranial magnetic stimulation delivered to the contralateral primary motor cortex (M1). Repeated pairing of the two discrete stimulus events (i.e. association) over an extended period either increases or decreases the excitability of corticospinal projections from M1, contingent on the interstimulus interval. We studied a novel form of associative stimulation, consisting of brief trains of peripheral afferent stimulation paired with short bursts of high frequency (≥80 Hz) transcranial alternating current stimulation (tACS) over contralateral M1. Elevations in the excitability of corticospinal projections to the forearm were observed for a range of tACS frequency (80, 140 and 250 Hz), current (1, 2 and 3 mA) and duration (500 and 1000 ms) parameters. The effects were at least as reliable as those brought about by PAS or transcranial direct current stimulation. When paired with tACS, muscle tendon vibration also induced elevations of CSE. No such changes were brought about by the tACS or peripheral afferent stimulation alone. In demonstrating that associative effects are expressed when the timing of the peripheral and cortical events is not precisely circumscribed, these findings suggest that multiple cellular pathways may contribute to a long term potentiation-type response. Their relative contributions will differ depending on the nature of the induction protocol that is used.

Generating Isolated Elliptically Polarized Attosecond Pulses Using Bichromatic Counterrotating Circularly Polarized Laser Fields

We theoretically demonstrate the possibility to generate both trains and isolated attosecond pulses with high ellipticity in a practical experimental setup. The scheme uses circularly polarized, counterrotating two-color driving pulses carried at the fundamental and its second harmonic. Using a model Ne atom, we numerically show that highly elliptic attosecond pulses are generated already at the single-atom level. Isolated pulses are produced by using few-cycle drivers with controlled time delay between them.

Evaluation of thermochemical biomass conversion in fluidized bed

Dado o aumento acelerado dos preços dos combustíveis fósseis e as incertezas quanto à sua disponibilidade futura, tem surgido um novo interesse nas tecnologias da biomassa aplicadas à produção de calor, eletricidade ou combustíveis sintéticos. Não obstante, para a conversão termoquímica de uma partícula de biomassa sólida concorrem fenómenos bastante complexos que levam, em primeiro lugar, à secagem do combustível, depois à pirólise e finalmente à combustão ou gasificação propriamente ditas. Uma descrição relativamente incompleta de alguns desses estágios de conversão constitui ainda um obstáculo ao desenvolvimento das tecnologias que importa ultrapassar. Em particular, a presença de elevados conteúdos de matéria volátil na biomassa põe em evidência o interesse prático do estudo da pirólise. A importância da pirólise durante a combustão de biomassa foi evidenciada neste trabalho através de ensaios realizados num reator piloto de leito fluidizado borbulhante. Verificou-se que o processo ocorre em grande parte à superfície do leito com chamas de difusão devido à libertação de voláteis, o que dificulta o controlo da temperatura do reator acima do leito. No caso da gasificação de biomassa a pirólise pode inclusivamente determinar a eficiência química do processo. Isso foi mostrado neste trabalho durante ensaios de gasificação num reator de leito fluidizado de 2MWth, onde um novo método de medição permitiu fechar o balanço de massa ao gasificador e monitorizar o grau de conversão da biomassa. A partir destes resultados tornou-se clara a necessidade de descrever adequadamente a pirólise de biomassa com vista ao projeto e controlo dos processos. Em aplicações de engenharia há particular interesse na estequiometria e propriedades dos principais produtos pirolíticos. Neste trabalho procurou-se responder a esta necessidade, inicialmente através da estruturação de dados bibliográficos sobre rendimentos de carbonizado, líquidos pirolíticos e gases, assim como composições elementares e poderes caloríficos. O resultado traduziu-se num conjunto de parâmetros empíricos de interesse prático que permitiram elucidar o comportamento geral da pirólise de biomassa numa gama ampla de condições operatórias. Para além disso, propôs-se um modelo empírico para a composição dos voláteis que pode ser integrado em modelos compreensivos de reatores desde que os parâmetros usados sejam adequados ao combustível ensaiado. Esta abordagem despoletou um conjunto de ensaios de pirólise com várias biomassas, lenhina e celulose, e temperaturas entre os 600 e 975ºC. Elevadas taxas de aquecimento do combustível foram alcançadas em reatores laboratoriais de leito fluidizado borbulhante e leito fixo, ao passo que um sistema termo-gravimétrico permitiu estudar o efeito de taxas de aquecimento mais baixas. Os resultados mostram que, em condições típicas de processos de combustão e gasificação, a quantidade de voláteis libertada da biomassa é pouco influenciada pela temperatura do reator mas varia bastante entre combustíveis. Uma análise mais aprofundada deste assunto permitiu mostrar que o rendimento de carbonizado está intimamente relacionado com o rácio O/C do combustível original, sendo proposto um modelo simples para descrever esta relação. Embora a quantidade total de voláteis libertada seja estabelecida pela composição da biomassa, a respetiva composição química depende bastante da temperatura do reator. Rendimentos de espécies condensáveis (água e espécies orgânicas), CO2 e hidrocarbonetos leves descrevem um máximo relativamente à temperatura para dar lugar a CO e H2 às temperaturas mais altas. Não obstante, em certas gamas de temperatura, os rendimentos de algumas das principais espécies gasosas (e.g. CO, H2, CH4) estão bem correlacionados entre si, o que permitiu desenvolver modelos empíricos que minimizam o efeito das condições operatórias e, ao mesmo tempo, realçam o efeito do combustível na composição do gás. Em suma, os ensaios de pirólise realizados neste trabalho permitiram constatar que a estequiometria da pirólise de biomassa se relaciona de várias formas com a composição elementar do combustível original o que levanta várias possibilidades para a avaliação e projeto de processos de combustão e gasificação de biomassa.

A new combined joules supercritical rankine cycle exergetic analysis and optimization

The application of a supercritical Rankine cycle in combined cycles does not happen in today’s thermoelectric power stations. Nevertheless, the most recent development in gas turbines, that allows a high efficiency and high exhaust gases temperatures, and the improvement of high pressure and temperature alloys, makes this cycle possible. This study’s intent is to prove the viability of this combined cycle, since it can break the 60% efficiency barrier, which is the plafond in actual power stations. To attain this target, several configurations for this cycle have been simulated, optimized and analyzed [1]. The simulations were done with the computational program IPSEpro [2] and the optimizations were effectuated with software developed for the effect, using the DFP method [3]. In parallel with the optimization that claims the cycle’s efficiency maximization, an exergetic analysis was also made [4] to all the cycle components. In opposite to what happens in subcritical combined cycles, it was demonstrated that in supercritical combined cycles the higher efficiency takes place with a single steam pressure in the heat recovery steam generator (HRSG).

Improved extraction of arabinoxylans from rye bran and production of health beneficial oligosaccharides

Dissertação de mest., Engenharia Biológica, Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2011

The challenge of high cube ISO containers for British rail freight operations

Rail freight activity in Britain has increased by almost 50% in the last ten years, with the movement of deep sea ISO containers between ports and inland terminals being a significant growth sector, with considerable further growth potential. High cube ISO containers have become more prevalent, posing a considerable challenge for rail freight operators since much of the rail network has insufficient loading gauge clearance to carry them on standard wagons. This paper investigates the extent to which rail currently handles high cube container movements to/from ports through the analysis of a representative survey of container trains in 2007. The incidence of high cube containers carried by services on gauge-cleared and non-gauge-cleared routes is identified to assess the extent to which a lack of gauge enhancement affects the movement by rail of high cube containers and to identify the impacts of the lack of gauge clearance on operating efficiency. The paper concludes with an evaluation of the likely consequences of the gauge enhancement schemes for which funding is now committed, assessing the extent to which they will reduce or remove the barriers associated with carrying high cube containers between ports and their hinterlands.

An investigation of container train service provision and load factors in Great Britain

The continued growth in the volume of international trade poses considerable economic and sustainability challenges, particularly as transport routes become more congested and concern grows about the role of transport movements in accelerating climate change. Rail freight plays a major role in the inland transport of containers passing through the main British container ports, and potentially could play a more significant role in the future. However, there is little detailed understanding of the nature of this particular rail market, especially in terms its current operating efficiency. This paper examines container train service provision to/from the four main ports, based on analysis of a representative survey of more than 500 container trains between February and August 2007. The extent to which the existing capacity is utilised is presented, and scenarios by which the number of containers carried could be increased without requiring additional train service provision are modelled, to identify the theoretical potential for greater rail volumes. Finally, the paper identifies the challenges involved in achieving higher load factors, emphasising the importance both of wider supply chain considerations and government policy decision-making.