Self-cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Correlation of Static Ageing Effects on Automotive Catalysts

This study identifies and analyzes the effect that aging time and temperature have on the CO light-off activity of three-way catalyst samples, aged in a static air (oxidizing) atmosphere. The bench aging time (BAT) equation proposed by the Environmental Protection Agency (EPA), which describes aging as dependent upon time at temperature, was used to calculate a range of oven aging times and temperatures based on a RAT-A engine bench aging cycle.

CO light-off tests carried out on cores aged between 800 and 900 °C have shown that it is the aging temperature that has the greatest effect on catalyst deterioration for static aging testing, with aging time having little effect. These results were in contradiction to the BAT equation, an industry norm for the aging of catalysts. This demonstrates that static aging, whilst showing how temperature affects aging, gives little or no time effects. The results have shown that static aging is not representative of actual aging on a vehicle.

Progressive aging conducted at a temperature of 1000 °C was shown to cause a decrease in catalyst activity as the aging time increased. However, even in these extreme conditions, static aging gave a slower rate of aging with time when compared to engine aging as defined by the BAT equation. Overall, static aging in air has been shown to produce a greater increase in aging due to temperature than predicted by the BAT equation, but less aging due to aging time.

Advanced Ceramic Substrate with Ordered and Designed Micro-Structure for Applications in Automotive Catalysts

This study describes an innovative monolith structure designed for applications in automotive catalysis using an advanced manufacturing approach developed at Imperial College London. The production process combines extrusion with phase inversion of a ceramic-polymer-solvent mixture in order to design highly ordered substrate micro-structures that offer improvements in performance, including reduced PGM loading, reduced catalyst ageing and reduced backpressure.

This study compares the performance of the novel substrate for CO oxidation against commercially available 400 cpsi and 900 cpsi catalysts using gas concentrations and a flow rate equivalent to those experienced by a full catalyst brick when attached to a vehicle. Due to the novel micro-structure, no washcoat was required for the initial testing and 13 g/ft3 of Pd was deposited directly throughout the substrate structure in the absence of a washcoat.

Initial results for CO oxidation indicate that the advanced micro-structure leads to enhanced conversion efficiency. Despite an 79% reduction in metal loading and the absence of a washcoat, the novel substrate sample performs well, with a light-off temperature (LOT) only 15 °C higher than the commercial 400 cpsi sample.

To test the effects of catalyst ageing on light-off temperature, each sample was aged statically at a temperature of 1000 °C, based on the Bench Ageing Time (BAT) equation. The novel substrate performed impressively when compared to the commercial samples, with a variation in light-off temperature of only 3% after 80 equivalent hours of ageing, compared to 12% and 25% for the 400 cpsi and 900 cpsi monoliths, respectively.

Synthesis of , of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs’ catalysts

A series of alpha,beta-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (>= 90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids. 

Tracking smart grid hackers

The next-generation smart grid will rely highly on telecommunications infrastructure for data transfer between various systems. Anywhere we have data transfer in a system is a potential security threat. When we consider the possibility of smart grid data being at the heart of our critical systems infrastructure it is imperative that we do all we can to ensure the confidentiality, availability and integrity of the data. A discussion on security itself is outside the scope of this paper, but if we assume the network to be as secure as possible we must consider what we can do to detect when that security fails, or when the attacks comes from the inside of the network. One way to do this is to setup a hacker-trap, or honeypot. A honeypot is a device or service on a network which appears legitimate, but is in-fact a trap setup to catch breech attempts. This paper identifies the different types of honeypot and describes where each may be used. The authors have setup a test honeypot system which has been live for some time. The test system has been setup to emulate a device on a utility network. The system has had many hits, which are described in detail by the authors. Finally, the authors discuss how larger-scale systems in utilities may benefit from honeypot placement.

Securing the smart grid

The availability of electricity is fundamental to modern society. It is at the top of the list of critical infrastructures and its interruption can have severe consequences. This highly important system is now evolving to become more reliable, efficient, and clean. This evolving infrastructure has become known as the smart grid; and these future smart grid systems will rely heavily on ICT. This infrastructure will require many servers and due to the nature of the grid, many of these systems will be geographically diverse requiring communication links. At the heart of this ICT infrastructure will be security. At each level of the smart grid from smart metering right through to remote sensing and control networks, security will be a key factor for system design consideration. With an increased number of ICT systems in place the security risk also increases. In this paper the authors discuss the changing nature of security in relation to the smart grid by looking at the move from legacy systems to more modern smart grid systems. The potential planes of attack for future smart grid systems are identified, and the general anatomy of a cyber-attack is presented. The authors then introduce the various threat levels of different types of attack and the mitigation techniques that could be put in place for each. Finally, the authors' introduce a Phasor Measurement Unit (PMU) communication system (operated by the authors) that can be used as a test-bed for some of the proposed future security research.

A smart load appliance application using a single compressor fridge-freezer to support grid operations

This paper describes a fridge-freezer smart load model, which responds to external signals from the wholesale electricity market to support grid operations while switching the fridge-freezer on and off to maintain optimum operations for the owner. The key parameters of the model are the appliance dimensions, thermal mass, the fridge and freezer thermal time constants and the compressor power consumption. The model demonstrates that control strategies help to minimise load at times when the grid is under stress from high demand, and shift some load to a lower wholesale price or when there is excess renewable power. Three control strategies are proposed, based on peak shaving and valley filling, price signals and wind availability.

Assessment of Domestic Load Suitable for Smart Consumer Load Participation

This study characterizes the domestic loads suitable to participate in the load participation scheme to make the power system more carbon and economically efficient by shifting the electricity demand profile towards periods when there is plentiful renewable in-feed.

A series of experiments have been performed on a common fridge-freezer, both completely empty and half full. The results presented are ambient temperature, temperature inside the fridge, temperature inside the drawer of the fridge, temperature inside the freezer, thermal time constants, power consumption and electric energy consumed.

The thermal time constants obtained clearly demonstrate the potential of such refrigeration load for Smart Customer Load Participation.

Mechanochemical preparation of Ag catalysts for the n-octane-SCR de-NOx reaction: Structural and reactivity effects

Mechanochemical preparation of Ag/Al2O3 catalysts used for the selective catalytic reduction of NOx using hydrocarbons has been shown to substantially increase the activity of the catalyst in comparison with Ag/Al2O3 prepared by wet impregnation. The effect of using different ball-milling experimental parameters on both the structure of the material as well as the catalyst activity has been investigated and the optimum conditions established. A phase transition from γ- to α-alumina was observed milling at high speeds which was found to result in lower catalyst activities. At lower milling speeds both fracturing and agglomeration of the alumina support can be observed depending on the grinding time. However, due to ball-milling, a general enhancement in the NOx reduction activity was observed for all catalysts compared with the conventionally prepared catalysts irrespective of the reductant used. Transient DRIFTS-MS experiments were performed to investigate the effect of H2 in the absence and presence of water on the SCR reaction over catalysts prepared by both ball milling and wet impregnation. In-situ DRIFTS-MS analysis revealed significant differences in both gas phase and surface species. Most notably, isocyanate species were formed significantly more quickly and at higher surface concentration in the case of the mechanochemically prepared catalyst.

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.

Cationic palladium(II) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide.

Ligated Pd(II) complexes have been studied for the catalytic oxidation of terminal olefins to their corresponding methyl ketones. The method uses aqueous hydrogen peroxide as the terminal oxidant; a sustainable and readily accessible oxidant. The choice of ligand, counterion and solvent all have a significant effect on catalytic performance and we were able to develop systems which perform well for these challenging oxidations.