Evaluation of a simple disposable microband electrode device for amperometric gas sensing

We report a simple and facile methodology for constructing Pt (6.3 mm x 50 mu m) and Cu (6.3 mm x 30 mu m) annular microband electrodes for use in room temperature ionic liquids (RTILs) and propose their use for amperometric gas sensing. The suitability of microband electrodes for use in electrochemical analysis was examined in experiments on two systems. The first system studied to validate the electrochemical responses of the annular microband electrode was decamethylferrocene (DmFc), as a stable internal reference probe commonly used in ionic liquids, in [Pmim][NTf2], where the diffusion coefficients of DmFc and DmFc(+) and the standard electron rate constant for the DmFc/DmFc(+) couple were determined through fitting chronoamperometric and cyclic voltammetric responses with relevant simulations. These values are independently compared with those collected from a commercially available Pt microdisc electrode with excellent agreement. The second system focuses on O-2 reduction in [Pmim][NTf2], which is used as a model for gas sensing. The diffusion coefficients of O-2 and O-2(-) and the electron transfer rate constant were again obtained using chronoamperometry and cyclic voltammetry, along with simulations. Results determined from the microbands are again consistent to those evaluated from the Pt microdisc electrode when compared these results from home-made microband and commercially available microdisc electrodes. These observations indicate that the fabricated annular microband electrodes are suitable for quantitative measurements. Further the successful use of the Cu electrodes in the O-2 system suggests a cheap disposable sensor for gas detection. (C) 2013 Elsevier B.V. All rights reserved.

Mechanism of gas permeation in processed HNBR/nanoclay composites

The influence of the layered silicate clay platelets on the nitrogen permeation properties of hydrogenated nitrile butadiene rubber (HNBR)/nanoclay nanocomposites has been investigated. Nanocomposites of HNBR modified with different percentages of the organoclay are processed through various routes. Commercially available organoclay (CLOISITE 15A) and various silane-coupling agents are used to improve the dispersion of the nanoclay in HNBR. A total of 10 different formulations of nanocomposites are manufactured. The addition of the organoclay has resulted in a significant enhancement of the nitrogen barrier properties of the manufactured nanocomposite. The mechanism of the reduction in the permeability is explained through the changes in the morphology and its bond to the filler. These changes are confirmed through examination of the morphology using x-ray diffraction, transmission electron microscope, and dynamic mechanical thermal analysis. There has been a drastic reduction up to 55.7% in nitrogen permeability. The reduction in gas permeation in HNBR is attributed to uniformly exfoliated clay platelets. Finally, three different permeability models, namely, the Nielsen model, modified Nielsen model, and Cussler model, have also been considered to predict the permeability behavior of nanocomposites with different volume filler fractions. The experimental values of gas permeability have been compared with theoretical models. It is observed that the modified Nielsen model closely matches with the measured permeation behavior. © 2011 Wiley Periodicals, Inc.

Application of colloidal gas aphron suspensions produced from Sapindus mukorossi for arsenic removal from contaminated soil

Colloidal gas aphron dispersions (CGAs) can be described as a system of microbubbles suspended homogenously in a liquid matrix. This work examines the performance of CGAs in comparison to surfactant solutions for washing low levels of arsenic from an iron rich soil. Sodium Dodecyl Sulfate (SDS) and saponin, a biodegradable surfactant, obtained from Sapindus mukorossi or soapnut fruit were used for generating CGAs and solutions for soil washing. Column washing experiments were performed in down-flow and up flow modes at a soil pH of 5 and 6 using varying concentration of SDS and soapnut solutions as well as CGAs. Soapnut CGAs removed more than 70% arsenic while SDS CGAs removed up to 55% arsenic from the soil columns in the soil pH range of 5–6. CGAs and solutions showed comparable performances in all the cases. CGAs were more economical since it contains 35% of air by volume, thereby requiring less surfactant. Micellar solubilization and low pH of soapnut facilitated arsenic desorption from soil column. FT-IR analysis of effluent suggested that soapnut solution did not interact chemically with arsenic thereby facilitating the recovery of soapnut solution by precipitating the arsenic. Damage to soil was minimal arsenic confirmed by metal dissolution from soil surface and SEM micrograph.

A long-term analysis of pumped hydro storage to firm wind power

Although pumped hydro storage is seen as a strategic key asset by grid operators, financing it is complicated in new liberalised markets. It could be argued that the optimum generation portfolio is now determined by the economic viability of generators based on a short to medium term return on investment. This has meant that capital intensive projects such as pumped hydro storage are less attractive for wholesale electricity companies because the payback periods are too long. In tandem a significant amount of wind power has entered the generation mix, which has resulted in operating and planning integration issues due to wind's inherent uncertain, varying spatial and temporal nature. These integration issues can be overcome using fast acting gas peaking plant or energy storage. Most analysis of wind power integration using storage to date has used stochastic optimisation for power system balancing or arbitrage modelling to examine techno-economic viability. In this research a deterministic dynamic programming long term generation expansion model is employed to optimise the generation mix, total system costs and total carbon dioxide emissions, and unlike other studies calculates reserve to firm wind power. The key finding of this study is that the incentive to build capital-intensive pumped hydro storage to firm wind power is limited unless exogenous market costs come very strongly into play. Furthermore it was demonstrated that reserve increases with increasing wind power showing the importance of ancillary services in future power systems. © 2014 Elsevier Ltd. All rights reserved.

Climate change response in Europe: What's the reality? Analysis of adaptation and mitigation plans from 200 urban areas in 11 countries

Urban areas are pivotal to global adaptation and mitigation efforts. But how do cities actually perform in terms of climate change response? This study sheds light on the state of urban climate change adaptation and mitigation planning across Europe. Europe is an excellent test case given its advanced environmental policies and high urbanization. We performed a detailed analysis of 200 large and medium-sized cities across 11 European countries and analysed the cities' climate change adaptation and mitigation plans. We investigate the regional distribution of plans, adaptation and mitigation foci and the extent to which planned greenhouse gas (GHG) reductions contribute to national and international climate objectives. To our knowledge, it is the first study of its kind as it does not rely on self-assessment (questionnaires or social surveys). Our results show that 35 % of European cities studied have no dedicated mitigation plan and 72 % have no adaptation plan. No city has an adaptation plan without a mitigation plan. One quarter of the cities have both an adaptation and a mitigation plan and set quantitative GHG reduction targets, but those vary extensively in scope and ambition. Furthermore, we show that if the planned actions within cities are nationally representative the 11 countries investigated would achieve a 37 % reduction in GHG emissions by 2050, translating into a 27 % reduction in GHG emissions for the EU as a whole. However, the actions would often be insufficient to reach national targets and fall short of the 80 % reduction in GHG emissions recommended to avoid global mean temperature rising by 2 °C above pre-industrial levels. © 2013 Springer Science+Business Media Dordrecht.

Biomass-derived Oxymethylene Ethers as Diesel Additives: A Thermodynamic Analysis

Conversion of biomass for production of liquid fuels can help in reducing the greenhouse gas (GHG) emissions which are predominantly generated by combustion of fossil fuels. Adding oxymethylene ethers (OMEs) in conventional diesel fuel has the potential to reduce soot formation during the combustion in a diesel engine. OMEs are downstream products of syngas, which can be generated by the gasification of biomass. In this research, a thermodynamic analysis has been conducted through development of data intensive process models of all the unit operations involved in production of OMEs from biomass. Based on the developed model, the key process parameters affecting the OMEs production including equivalence ratio, H2/CO ratio, and extra water flow rate were identified. This was followed by development of an optimal process design for high OMEs production. It was found that for a fluidized bed gasifier with heat capacity of 28 MW, the conditions for highest OMEs production are at an air amount of 317 tonne/day, at H2/CO ratio of 2.1, and without extra water injection. At this level, the total OMEs production is 55 tonne/day (13 tonne/day OME3 and 9 tonne/day OME4). This model would further be used in a techno-economic assessment study of the whole biomass conversion chain to determine the most attractive pathways.

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.

Analysis of electric vehicle charging using the traditional generation expansion planning analysis tool WASP-IV

Electric vehicles (EV) are proposed as a measure to reduce greenhouse gas emissions in transport and support increased wind power penetration across modern power systems. Optimal benefits can only be achieved, if EVs are deployed effectively, so that the exhaust emissions are not substituted by additional emissions in the electricity sector, which can be implemented using Smart Grid controls. This research presents the results of an EV roll-out in the all island grid (AIG) in Ireland using the long term generation expansion planning model called the Wien Automatic System Planning IV (WASP-IV) tool to measure carbon dioxide emissions and changes in total energy. The model incorporates all generators and operational requirements while meeting environmental emissions, fuel availability and generator operational and maintenance constraints to optimize economic dispatch and unit commitment power dispatch. In the study three distinct scenarios are investigated base case, peak and off-peak charging to simulate the impacts of EV’s in the AIG up to 2025.

The importance of gas infrastructure in power systems with high wind power penetrations

Gas fired generation currently plays an integral support role ensuring security of supply in power systems with high wind power penetrations due to its technical and economic attributes. However, the increase in variable wind power has affected the gas generation output profile and is pushing the boundaries of the design and operating envelope of gas infrastructure. This paper investigates the mutual dependence and interaction between electricity generation and gas systems through the first comprehensive joined-up, multi-vector energy system analysis for Ireland. Key findings reveal the high vulnerability of the Irish power system to outages on the Irish gas system. It has been shown that the economic operation of the power system can be severely impacted by gas infrastructure outages, resulting in an average system marginal price of up to €167/MWh from €67/MWh in the base case. It has also been shown that gas infrastructure outages pose problems for the location of power system reserve provision, with a 150% increase in provision across a power system transmission bottleneck. Wind forecast error was shown to be a significant cause for concern, resulting in large swings in gas demand requiring key gas infrastructure to operate at close to 100% capacity. These findings are thought to increase in prominence as the installation of wind capacity increases towards 2020, placing further stress on both power and gas systems to maintain security of supply.

A well-to-wheel analysis of electric vehicles in the all-island Single Electricity Market

The European Union has set a target for 10% renewable energy in transport by 2020 to be met using biofuels and electric vehicles. In the case of biofuels, the biofuel must achieve greenhouse gas savings of 35% relative to the fossil fuel replaced. For biofuels, greenhouse gas savings can be calculated using life cycle analysis or the European Union default values. In contrast, all electricity used in transport is considered to be the same, regardless of the source or the type of electric vehicle. However, the choice of the electric vehicle and electricity source will have a major impact on the greenhouse gas saving. In this paper the initial findings of a well-to-wheel analysis of electric vehicle deployment in Northern Ireland are presented. The key finding indicates that electric vehicles require least amount of energy per mile on a well-to-wheel basis, consume the fewest resources, even accommodating inefficient fuel production, in comparison to standard internal combustion engine and hybrid vehicles.

Dynamic Modeling and Interaction of Hybrid Natural Gas and Electricity Supply System in Microgrid

Natural gas (NG) network and electric network are becoming tightly integrated by microturbines in the microgrid. Interactions between these two networks are not well captured by the traditional microturbine (MT) models. To address this issue, two improved models for single-shaft MT and split-shaft MT are proposed in this paper. In addition, dynamic models of the hybrid natural gas and electricity system (HGES) are developed for the analysis of their interactions. Dynamic behaviors of natural gas in pipes are described by partial differential equations (PDEs), while the electric network is described by differential algebraic equations (DAEs). So the overall network is a typical two-time scale dynamic system. Numerical studies indicate that the two-time scale algorithm is faster and can capture the interactions between the two networks. The results also show the HGES with a single-shaft MT is a weakly coupled system in which disturbances in the two networks mainly influence the dc link voltage of the MT, while the split-shaft MT is a strongly coupled system where the impact of an event will affect both networks.

Study on Hybrid Heat-Gas-Power Flow Algorithm for Integrated Community Energy System: 区域综合能源系统电/气/热混合潮流算法研究

With the integration of combined heat and power (CHP) units, air-conditioners and gas boilers, power, gas, and heat systems are becoming tightly linked to each other in the integrated community energy system (ICES). Interactions among the three systems are not well captured by traditional methods. To address this issue, a hybrid power-gas-heat flow calculation method was developed in this paper. In the proposed method, an energy hub model was presented to describe interactions among the three systems incorporating various CHP operating modes. In addition, three operating modes were proposed for the ICES including fully decoupled, partially coupled, and fully coupled. Numerical results indicated that the proposed algorithm can be used in the steady-state analysis of the ICES and reflect interactions among various energy systems.

Studying administrative reforms through textual analysis: the case of Italian central government accounting

This paper contributes to the literature on public-sector reforms by proposing textual analysis as a useful research strategy to explore how reform archetypes and related ideas are deployed in the parliamentary debate and regulations advancing reforms. Public Administration (PA) (Wilson 1887; Weber 1922), New Public Management (NPM) (Hood 1991, 1995; Dunleavy and Hood 1994; Ferlie et al. 1996) and Public Governance (GOV) (Osborne 2010; Rhodes 1997) can be depicted as three different archetypes providing characteristic administrative ideas and concepts (i.e. interpretive schemes) and related tools and practices (i.e. structures and systems) which lead reforms. We use textual analysis to look into more than twenty years of Italian central government accounting reforms and investigate how the three administrative archetypes have evolved, intertwined and replaced each other. Textual analysis proves a useful tool to investigate reform processes and allows highlighting that in neo-Weberian countries, such as Italy, NPM and GOV, far from being revolutionary paradigms, may represent fashionable trends that did not leave significant traces in the practice and rhetoric of reforms. These results also suggest interesting implications for practitioners and policy makers.

TAP Reactor Development and Application in the Kinetic Characterization of Catalysts for Heterogeneously Catalyzed Gas Phase Reactions

This manuscript describes the application and further development of the TAP technique in kinetic characterization of heterogeneous catalysis. The major application of TAP systems is to study mechanisms, kinetics and transport phenomena in heterogeneous catalysis, all of which is made possible by the sub-millisecond time resolution. Furthermore, the kinetic information obtained can be used to gain an insight into the mechanism occurring over the catalyst system. This is advantageous as heterogeneous catalysts with an improved efficiency can be developed as a result. TAP kinetic studies are carried out at low pressure (~1x10-7 mbar) and TAP pulses are sufficiently small (1013-1015 molecules) so as to maintain this low pressure. The use of a small number of molecules in comparison to the total number of active sites means the state of the catalyst remains relatively unchanged. The use of the low intensity pulses also makes the pressure gradient negligible and so allows the TAP reactor system to operate in the Knudsen Diffusion regime, where gas-gas reactions are eliminated. Hence only gas-catalyst reactions are investigated and, by the use of moment analysis of observed exit flow, rate constants of elementary steps of the reaction can be obtained.

In this manuscript, two attempts to further the TAP technique are reported. Firstly, the work undertaken at QUB to attempt to control the number of molecules of condensable reagents that can be pulsed during a TAP pulse experiment is disclosed. Secondly, a collaborative project with SAI Ltd Manchester is discussed in a separate chapter, where technical details and validation of a customised time of flight mass spectrometer (ToF MS) for the QUB TAP-1 system are reported. A collaborative project with Cardiff Catalysis Institute focusing on the study of CO oxidation over hopcalite catalysts is also reported. The analysis of the experimental results has provided an insight into the possible mechanism of the oxidation of CO over these catalysts. A correction function has also been derived which accounts for the adsorption of reactant molecules over inert materials that are used for the reactor packing in TAP experiments. This function was then applied to the selective reduction of O2 in a H2 rich ethene feed, so that more accurate TAP moment based analysis could be conducted.