Methanol Conversion to Hydrocarbons (MTH) Over H-ITQ-13 (ITH) Zeolite

Product flexibility is key to meeting fluctuating chemicals demands in the future. In this contribution, the methanol to hydrocarbons (MTH) reaction was investigated over two Ge-containing H-ITQ-13 samples, one with needle-like (H-ITQ-13(N), with (Si+Ge)/Al) = 42) and another with plate-like (H-ITQ-13(P), with (Si+Ge)/Al > 100) morphology. The samples were characterised using XRD, BET, SEM/EDS and FTIR spectroscopy, and their MTH performance was compared with the performance of H-ZSM-5 and H-ZSM-22. Similar specific surface areas (413 and 455 m² g^?1 for H-ITQ-13(N) and (P), respectively) and similar acid strength (Δν ~ ?327(?310) cm^?1) was observed for the two H-ITQ-13 samples. Testing of H-ITQ-13(N) at weight hourly space velocity (WHSV) = 2–8 h^?1 at 350–450 °C revealed that C₅₊ alkenes were the main products (35–45 % selectivity at 400 °C), followed by propene and butene. A low but significant selectivity for aromatic products was observed (6–8 % selectivity at 400 °C). Product selectivity was found to be independent of deactivation. The methanol conversion capacity of H-ITQ-13(N) was 120–150 g methanol g^?1 catalyst at 400 °C. Testing H-ITQ-13 at high (30 atm) and ambient pressure, respectively, at 350 °C showed that a high pressure led to enhanced C₅₊ selectivity, but close to a tenfold decrease in methanol conversion capacity. H-ITQ-13(P) was tested at 400 °C and 2 h^?1. It gave lower conversion than H-ITQ-13(N). Furthermore, when compared at the same conversion level, H-ITQ-13(P) gave higher C₅₊ alkene selectivity, lower aromatics selectivity, and a higher propene to ethene ratio than H-ITQ-13(N). The H-ITQ-13 samples yielded a product spectrum intermediate of H-ZSM-22 and H-ZSM-5. The effluent product cut-off of H-ITQ-13 was similar to that of H-ZSM-5 with tetramethylbenzene as the largest significant product, while H-ZSM-22 produced mainly linear and branched alkenes. The lifetime of H-ITQ-13(N) was clearly enhanced compared to H-ZSM-22, but inferior to H-ZSM-5.     

Superelasticity and fatigue in oligocrystalline shape memory alloy microwires

In oligocrystalline shape memory alloys, the total grain boundary area is smaller than the surface area of the specimen, leading to significant effects of free surfaces on the martensitic transformation and related shape memory and superelastic properties. Here we study sample size effects upon the superelastic characteristics of oligocrystalline microwires after one loading cycle and after many. Cu-Zn-Al wires with diameters ranging from ∼100 down to ∼20 μm are fabricated by the Taylor liquid processing technique and characterized through both uniaxial cyclic tensile testing and mechanically constrained thermal cycling. The energy dissipated per superelastic cycle increases with decreasing wire diameter, and this size effect is preserved after extensive cycling despite a significant transient evolution of the superelastic response for early cycles. We also present fatigue and fracture data, indicating that oligocrystalline wires of this normally brittle alloy can exhibit fatigue lifetimes two orders of magnitude improved over conventional polycrystalline Cu-Zn-Al.     

Risk-based rules for crane safety systems

The International Maritime Organisation (IMO) has recommended a method called formal safety assessment (FSA) for future development of rules and regulations. The FSA method has been applied in a pilot research project for development of risk-based rules and functional requirements for systems and components for offshore crane systems. This paper reports some developments in the project. A method for estimating target reliability for the risk-control options (safety functions) by means of the cost/benefit decision criterion has been developed in the project and is presented in this paper. Finally, a structure for risk-based rules is proposed and presented.     

Tuning of Empirical Radio Propagation Models Effect of Location Accuracy

The paper summarises tuning of empirical propagation model RX-level predictions to measurements. An algorithm using least-squares fit of predictions to measurements is discussed. The algorithm uses the Condition number of the resulting equations to control the numerical stability of the calculations. The algorithm has been evaluated using measurements obtained in a drive-test measurement campaign in Helsinki. The results indicate that the algorithm performs well by being able to improve the fit of RX-level predictions to the observations. An aim of the CELLO project has been to evaluate the feasibility of using RX-level location data logged by the network to tune the propagation model. If this is feasible, predicted coverage could be continuously re-tuned based on location data acquired during the normal operation of the network. However, because the location methods that will most likely be available in the network are less accurate than GPS-locations, it is necessary to evaluate the effect of less accurate locations on the tuning. The paper thus evaluates the effect of location accuracy on the tuning results. The evaluation is based on measurements where locations were estimated by different methods. A tentative conclusion is made that the location accuracy provided by the DCM (Database Correlation Method) positioning method [H. Jormakka (ed.), S. Horsmanheimo, J. Lähteenmäki, J. Rissanen, Juuso Pajunen, E. Aarnes, S. Holm, B. Forsberg, “Trial Results” CELLO-WP3-VTT-D30, 2003.] could be sufficient for tuning purposes.     

System failure,innovation policy and patents: Fuel cells and related hydrogen technology in Norway 1990–2002

The empirical focus of this article is technological innovation activities in the emerging field of fuel cells and related hydrogen technology in Norway from 1990 to 2002. In this period, four comparatively large-scale research and development projects and a number of smaller projects aimed at development of fuel cells technology were undertaken, resulting in many inventions that were subsequently patented. Although this creativity may be considered an indication of success, only one of the projects became successful in an innovation perspective. All the large projects were initiated and funded for divergent political and economic reasons. An important reason in the late 1980s was the prospect of using Norway's abundant supply of natural gas in fuel cells for electric power generation. The large R&D projects that attempted to develop fuel cells based on natural gas as energy source failed. In contrast, the successful project was undertaken by military R&D, i.e. in a different system of innovation than the projects that failed. Analysis of these cases points to the importance of a systemic approach to innovations—and to policy making. One challenge for policy makers is to decide how they should promote this development which is crucial for the vision of a future “Hydrogen Economy”, i.e. what kind of policy incentives should be introduced to spur efficiency in technological development and diffusion. Theoretically, many options are available; however, understanding the innovation dynamics in this sector is fundamental for making choices. In this article, focus will be set on policy aspects using an innovation systemic approach to analyze development of fuel cells and related hydrogen technology in Norway.     

Intermediates in the Methanol-to-hydrocarbons (MTH) Reaction: A Gas Phase Study of the Unimolecular Reactivity of Multiply Methylated Benzenium Cations

In order to reach a deeper insight into the reaction mechanism of the zeolite catalyzed methanol to hydrocarbons reaction (MTH), the proposed reaction intermediates, i.e., a series of multiply methyl-substituted benzenium ions has been generated in the gas phase by chemical ionization. The fragmentations of the corresponding long-lived (metastable) ions have been investigated. While expulsion of H₂ dominates for the lower homologues, elimination of methane dominates for the higher homologues, accompanied by increasing amounts CH₃^·. Loss of larger fragments relevant to the MTH-reaction, in particular ethene, propene and even butene, is also observed in minor amounts. This latter finding is consistent with a proposed reaction cycle in the MTH reaction known as the paring mechanism, and the feasibility of this mechanism has thus been demonstrated. The metastable gas-phase ions studied here are considerably more energetic than those residing in a zeolite catalyst, but they were found to decompose with markedly higher selectivity towards alkenes as compared to those activated by collision-induced dissociation (CID).     

Performance-based modelling of long-term deterioration to support rehabilitation and investment decisions in drinking water distribution systems

Managing the urban drinking water system in the long term in order to maintain system performance can be challenging due to the difficulty of modelling future deterioration of the networks. This paper establishes a methodology for cohort survival models where historical (empirical) data on decommissioning ages of pipes are used to calibrate survival functions of pipe cohorts according to service level targets. The benefit of the approach is that remaining useful life of pipes, future renewal rates and investment needs can be governed by a required level of service in the network. A case study shows how the methodology can be applied to a cohort of drinking water pipes to create a ‘calibration curve’, which is a survival function calibrated with empirical data.     

Oligocrystalline Shape Memory Alloys

Copper‐based shape memory alloys (SMAs) exhibit excellent shape memory properties in single crystalline form. However, when they are polycrystalline, their shape memory properties are severely compromised by brittle fracture arising from transformation strain incompatibility at grain boundaries and triple junctions. Oligocrystalline shape memory alloys (oSMAs) are microstructurally designed SMA structures in which the total surface area exceeds the total grain boundary area, and triple junctions can even be completely absent. Here it is shown how an oligocrystalline structure provides a means of achieving single crystal‐like SMA properties without being limited by constraints of single crystal processing. Additionally, the formation of oSMAs typically involves the reduction of the size scale of specimens, and sample size effects begin to emerge. Recent findings on a size effect on the martensitic transformation in oSMAs are compared and a new regime of heat transfer associated with the transformation heat evolution in these alloys is discussed. New results on unassisted two‐way shape memory and the effect of loading rate in oSMAs are also reported.     

Temporal change analysis of public attitude,knowledge and acceptance of hydrogen vehicles in Greater Stavanger, 2006–2009

This study examines the trends of public opinions concerning the introduction of hydrogen vehicles in Greater Stavanger as well as public attitudes towards the natural environment over the course of the three-year period. This study is based on two surveys of the hydrogen highway project (HyNor) which were collected in the Greater Stavanger region, the west coast of Norway, between 2006 and 2009 (n=2000). The results of the study highlight that – despite an increased awareness of hydrogen vehicles – the proportions of those with pro-environment attitudes who support hydrogen vehicles’ introduction decreased between 2006 and 2009. The results reveal that knowledge about sustainable environment can affect hydrogen energy's acceptance whereas the level of pro-environment attitudes can increase not only public acceptance of hydrogen vehicles, but also people's willingness to pay for hydrogen fuels. These results were consistently found throughout the observed periods, based on the Greater Stavanger's case. A set of recommendations was discussed to improve public acceptance of hydrogen vehicles, and the next avenue of research regarding analysis of public acceptance and awareness about hydrogen vehicles was proposed.