In-situ Monitoring of Solid Oxide Electrolysis Cells

High temperature co-electrolysis of steam and carbon dioxide using a solid oxide cell (SOC) has been shown to be an efficient route to produce syngas (CO + H-2), which can then be converted to synthetic fuel. Optimization of co-electrolysis requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the SOC during operation. Thermal imaging, Raman spectroscopy and Diffuse Reflectance Infrared Fourier Transform Spectroscopy are being developed to probe in-situ both the reactions occurring during operation and any associated changes within the structure of the electrodes and electrolyte. Here we discuss the challenges in designing experimental apparatus suitable for high temperature operation with optical spectroscopic access to the areas of the SOC that are of interest. In particular, issues with sealing, temperature gradients, signal strength and cell configuration are discussed and final designs are presented. Preliminary results obtained during co-electrolysis operation are also presented.

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.

Austerity and Reform of the Irish Public Administration

The impact of the global financial crisis has been particularly severe in Ireland, and the 2008-14 period has been one defined by considerable state retrenchment. It has, however, also given rise to a period of unprecedented public service reform, and particularly following the election of a government with a strong reforming mandate in 2011. In this paper, the context and content of the reforms are examined along institutional, financial and politico-administrative dimensions respectively. A final section discusses the politics of reform in a time of crisis.

Quango Reform: The Next Steps

The Coalition Government elected in 2010 in the UK pursued a programme of quango reform focusedon reducing the number and expenditure of arm’slength bodies, increasing transparency, improvingaccountability and maximising efficiency and effectiveness. In this article we revisit Flinders andSkelchers’ 2012 article ‘Shrinking the quango state: five challenges in reforming quangos’ to assessprogress to date and consider future challenges. Drawing insights from the UK programme ofquango reform , as well as similar developments in Ireland, we identify five new challenges for governments: ‘regulating’, ‘managing’, ‘reconciling’, ‘co‐ordinating’ and ‘reflecting’.

Space and Place: Lessons from National School Buildings in the North of Ireland

Forms of integrated schooling are currently promoted in post-conflict Northern Ireland, but an earlier attempt to establish secular education in Ireland during the nineteenth and early twentieth centuries – the Irish National Schools system – is often forgotten. A preliminary archaeological study of former National Schools indicated differences in size, placement and external appearance between rural and urban buildings, possibly linked to the expression of divergent cultural and religious traditions in conflict with the reforming principles of the national system. This paper uses archaeological and anthropological perspectives to examine the social and cultural significance of such schools, including the first recorded excavation of an Irish National School, in relation to their past and current significance for education, identity, landscape, place and kinship.

Reconstructing the Social Fabric amid On-going Violence: Attitudes toward Reconciliation and Structural Transformation in Colombia

Given the increase of reconciliation processes initiated amid on-going violence, this study focuses on community reconciliation and its relation to structural transformation, or social reconstruction through reforming unjust institutions and practices that facilitate protracted violent conflict. Drawing lessons from the Caribbean coast of Colombia, mixed method analyses include eight in-depth interviews and 184 surveys. Four key dimensions of reconciliation – truth, justice, mercy, peace – are examined. In the interviews, participants prioritize reconstructing the truth and bringing perpetrators to justice as essential aspects of reconciliation. Notions of mercy and forgiveness are less apparent. For the participants, sustainable peace is dependent on structural transformation to improve livelihoods. These data, however, do not indicate how this understanding of reconciliation may relate to individual participation in reconciliation processes. Complementing the qualitative data, quantitative analyses identify some broad patterns that relate to participation in reconciliation events. Compared to those who did not participate, individuals who engaged in reconciliation initiatives report higher levels of personal experience with violence, live alongside demobilized paramilitaries, are more engaged in civic life, and express greater preference for structural transformation. The paper concludes with policy implications that integrate reconciliation and structural transformation to deepen efforts to rebuild the social fabric amid violence.

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.

Historical Dialogue and Memory in Organisational Transition: the case of the Police in Northern Ireland

During Northern Ireland’s transition towards peace the role of the police as an actor in the conflict has been a key point of contention. As such, the reform of policing has been central to conflict transformation. Within this process, the role of dialogue about what policing had been and could be in the future has been vital. Such institutional post violence change processes have been hugely significant in illustrating both organisational resistance to change and the need for transitions to be powerfully manoeuvred through complex, political, organisational and cultural processes (Buchanan and Badham 1999; Pettigrew 2012). The radical and reforming nature of policing transition (Murphy 2013) has been both organisationally challenging (requiring significant transformational leadership, resourcing and external engagement from wider civic society) and politically unusual. Indeed, in a society emerging from violence the NI police are the only public sector organisation to have engaged structurally and culturally in understanding the point at which their core roles intersected with the ‘management’ of the conflict in NI generally. This paper presents an analysis of the role of historical dialogue in organisational change process, using the RUC / PSNI case. It proposes that historical dialogue is not just an external, societal process but also an internal organisational process and as such, has implications for managing institutional change in societies emerging from conflict. In doing so, it builds theoretical links between literature on conflict transformation and that on organisational memory and empirically explores messaging internal to the RUC before and during the four main periods of organisational change (Murphy 2013), with dialogue aimed at an external audience. It offers an analysis of how historical dialogue itself impacts on and is impacted by the organisational realities of change itself.

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

Despesa e redistribuição na segurança social em Portugal : análise da reforma de 2007

Tese de doutoramento, Ciências Sociais (Sociologia Política), Universidade de Lisboa, Instituto de Ciências Sociais, 2015