Ship exhausts contain high levels of sulphur oxides, nitrogen oxides, carbon dioxide and particles dueto the heavy fuel oil, HFO, used for combustion and the combustion characteristics of the engine.As a result of upcoming stricter regulations for shipping pollution, as well as growing attentionto greenhouse gas emissions, air pollution and uncertainty of future petroleum oil supply, a shifttowards a cleaner burning fuel is needed.This work explores potential alternative fuels, both conventional and unconventional, and abatementtechnologies, to be used by tankers in the worldwide spot market to comply with upcomingenvironmental regulations in the near and coming future. As a reference the product tanker M/TGotland Marieann is used and recommendations for which fuel that shall be used by the referenceship in 2015 and 2020 are presented.The environmental assessment and evaluation of the fuels are done from a life cycle perspective usingresults from Life Cycle Assessment, LCA, studies.This study illustrates that, of the various alternatives, methanol appears to be the best candidatefor long-term, widespread replacement of petroleum-based fuels within tanker shipping. It does notemit any sulphur oxides nor particles and the nitrogen oxides are shown to be lower than those ofmarine gas oil, MGO. The global warming potential of the natural gas produced methanol is notlower than that of MGO, but when gradually switching to bio-methanol the greenhouse gas emissionsare decreasing and with methanol the vision of a carbon free society can be reached.For 2015 a switch towards methanol is not seen as realistic. Further research and establishment ofregulations and distribution systems are needed, however there are indications that a shift will bepossible sometime between 2015 and 2020. For 2015 a shift towards MGO is suggested as it involveslow investment costs and there is no need for infrastructure changes. As MGO is more expensivethan methanol, a shift is preferable as soon as the market, technology and infrastructure are ready.

The aim for this study has been to evaluate the integration potential of turbo-machinery into the production processes of biofuels. The focus has been on bio-fuel produced via biomass gasification; mainly methanol and synthetic natural gas. The research has been divided into two parts; gas and steam turbine applications. Steam power generation has a given role within the fuel production process due to the large amounts of excess chemical reaction heat. However, large amounts of the steam produced are used within the production process and is thus not available for power production. Therefore, this study has been focused on lowering the steam demand in the production process, in order to increase the power production. One possibility that has been evaluated is humidification of the gasification agent in order to lower the demand for high quality steam in the gasifier and replace it with waste heat. The results show that the power penalty for the gasification process could be lowered by 18-25%, in the specific cases that have been studied. Another step in the process that requires a significant amount of steam is the CO2-removal. This step can be avoided by adding hydrogen in order to convert all carbon into biofuel. This is also a way to store hydrogen (e.g. from wind energy) together with green carbon. The results imply that a larger amount of sustainable fuels can be produced from the same quantity of biomass. The applications for gas turbines within the biofuel production process are less obvious. There are large differences between the bio-syngas and natural gas in energy content and combustion properties which are technical problems when using high efficient modern gas turbines. This study therefore proposes the integration of a natural gas fired gas turbine; a hybrid plant. The heat from the fuel production and the heat recovery from the gas turbine flue gas are used in a joint steam cycle. Simulations of the hybrid cycle in methanol production have shown good improvements. The total electrical efficiency is increased by 1.4-2.4 percentage points, depending on the fuel mix. The electrical efficiency for the natural gas used in the hybrid plant is 56-58%, which is in the same range as in large-scale combined cycle plants. A bio-methanol plant with a hybrid power cycle is consequently a competitive production route for both biomass and natural gas. / QC 20110128

Summary: Movement disorders are caused by impairment of the basal ganglia and extrapyramidal connections. The most common is Parkinson's disease (PD), characterised by hypokinesia together with resting tremor and / or rigidity, which may be influenced by dopaminergic therapy or invasive methods, including deep brain stimulation (DBS). Gait and balance disorders are part of the Parkinson's syndrome, progress during the disease course and limit daily activities, quality of life, may lead to falls and contribute to higher mortality of the patients in the late stages. Therapy is difficult. Gait disorders and parkinsonism may occur also in other diseases, including intoxications which may also lead to basal ganglia impairment. The theoretical part include the physiology of gait, gait disorders and examination. The section devoted to movement disorders focuses on Parkinson's disease and methanol intoxication. The practical part consists of 3 studies evaluating gait disorder in patients with advanced PD and possibilities of the treatment, the 4th study documents gait disorder in survivors after mass methanol poisoning with outbreak between 2012 and 2014 in the Czech Republic. The result confirm the effect of DBS in step length prolongation and gait speed increment in patients with PD. Compensation strategies using...

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a recently reported electrochemical method and were found to vary linearly with deposition time. The particles also exhibited electrocatalytic activity toward methanol oxidation. This immobilization strategy shows promise and may be translated to smaller nanoelectrodes in order to study electrocatalytic properties of single nanoparticles.

Since our society became industrialised, the levels of carbon dioxide in our atmosphere have been steadily rising, to the point where it in early 2020 at is 413 ppm. The high concentration is causing several troubling effects worldwide because of the increase in mean temperature that it creates, which causes longer draughts, more severe floods, and rising seawater levels to name a few. There are a few measures that can be taken to reduce carbon dioxide in the atmosphere, among which there are a number of methods that currently are being researched and/or used. The prospect of capturing carbon dioxide and using it as a carbon building block to make methanol is one solution that is particularly interesting, since it in theory could provide a fuel for combustion engines that is net neutral regarding carbon emission. Methanol can be synthesised from carbon dioxide using a heterogeneous catalyst consisting of copper, Cu, and zinc oxide, ZnO. This research is focused on one of the components of the catalyst, the metal oxide ZnO in the form of crystallites or nanoparticles (ZnO)n. Quantum chemistry is a branch of computational chemistry which is centered on solving the Schrödinger equation for molecular systems. Density functional theory, DFT, is an approach to quantum theory which in this study was used to calculate the geometry and energy of the particles. The supercomputer Tetralith in the National Supercomputer Centre, NSC, was used to carry out the calculations. The DFT calculations utilized the functional B3LYP and the basis set 6-31G (d,p). One of the largest particle sizes studied, (ZnO)20, with a structure that has a large, flat surface, was found to be the most energetically favourable. According to studies, the presence of an oxygen vacancy on the surface of ZnO reduces the amount of activation energy required for CO2 to bond to the particle, which increases the chance of forming CO and thus continuing the process of forming methanol. Two structures of (ZnO)20 were investigated in this regard, where oxygen atoms were removed at different locations, creating four versions of Zn20O19 in total. This proved yet again that the version with a large, flat surface yields the lesser amount of energy when an O atom is removed from the centre of its surface. The adsorption of CO2 to the ZnO clusters was studied by calculating the energy of adsorption, and this showed that it was the second version of (ZnO)20, without an O vacancy, that yielded the least amount of energy, thus being the most favourable species to engage in physisorption with CO2. Lastly, the activation energy was investigated, and a diagram of the reaction process of CO2 adsorbing to Zn20O19 forming (ZnO)20 and CO is presented in this paper, which shows that the required activation energy is 127 kJ/mol.

Notre société s’est considérablement développée grâce à l’utilisation des ressources fossiles. L’utilisation de ces ressources, dans le domaine de l’énergie ou de l’industrie chimique, provoque un dérèglement du cycle naturel du carbone par l’accumulation dans l’atmosphère d’un CO2 anthropogénique. Pour pallier ces difficultés, une des solutions envisagées consiste à abandonner progressivement les hydrocarbures fossiles au profit de ressources carbonées renouvelables telles que le CO₂ pour le stockage des énergies renouvelables et/ou comme sources de produits chimiques. Les premières briques obtenues grâce au CO2 sont des molécules comportant un seul atome de carbone, rassemblées dans la classe de composés C1. Elle comprend le méthane (CH4), le monoxyde de carbone (CO), le méthanol (CH3OH), l’acide formique (HCOOH). Ces réactions ne sont pas idéales, limitées par leur praticité, leur rendement ou par leur sélectivité. Dans ce contexte, le présent travail doctoral a exploré des chemins alternatifs permettant d’interconvertir ces composés pour offrir des voies de valorisation du CO2. En premier lieu, l’utilisation de HCOOH sera proposé comme vecteur de CO. Cette thématique est née de l’intérêt grandissant pour le secteur de la chimie organique d’obtenir des sources liquides ou solides de CO. Dans un second temps, il a été développé une nouvelle stratégie de dismutation pour accéder au CH3OH à partir de dérivés de HCOOH, les formiates de silicium. Ces réactifs permettent de s’affranchir de la limitation thermodynamique dont souffre la dismutation de HCOOH. Cette transformation a été assurée en maîtrisant le recyclage des coproduits silylés. Une nouvelle voie de production de CH4 a également été développée à partir du CH3OH, en utilisant HCOOH comme réducteur. Enfin, les connaissances acquises sur l’activiation et la réactivité du CO2 ont permis, par analogie, de transposer ces connaissances à l’étude d’autres molécules iso-électroniques, telles que les carbodiimides et leur transformation en isourées dans des conditions organocatalytiques. / Our society has grown considerably thanks to the use of fossil resources. The use of these resources, in the field of energy or the chemical industry, leads to a disruption of the natural carbon cycle caused by the accumulation of an anthropogenic CO2 in the atmosphere. To overcome this issue, one of the conceivable solutions is to gradually abandon fossil hydrocarbons in favor of renewable carbon resources such as CO₂ for the storage of renewable energies and / or as a source of chemical products. The first building blocks obtained from CO2 are one carbon atom containing molecules, known as C1 compounds. It includes methane (CH4), carbon monoxide (CO), methanol (CH3OH), formic acid (HCOOH). These reactions are limited by their practicality, their yield or by their selectivity. Therefore, they are not an ideal solution to the initial problem. In this context, this doctoral work has explored alternative ways of interconverting these compounds to offer CO2 recovery pathways. In the first place, the use of HCOOH was proposed as a CO vector. This topic is born of the growing interest for the organic chemistry sector to obtain liquid or solid sources of CO. In a second step, a new disproportionation strategy was developed to access CH3OH from HCOOH derivatives, the silicon formates. These reagents allow to avoid the thermodynamic limitation related to the disproportionation of HCOOH. The control of the silylated by-products recycling enabled the success of this transformation. A new CH4 production route was also developed from CH3OH using HCOOH as a reducing agent. Finally, the knowledge acquired on CO2 activation and reactivity enabled a transposition by analogy to other iso-electronic molecules, including carbodiimides in order to form the isoureas under organocatalytic conditions.

No description available.

Studies of aging processes were conducted on pyrolysis oils produced from pine and cottonwood biomass (clear wood, whole tree, bark and needles/leaves). Accelerated aging at 80 °C for up to 504 h was employed to investigate the short and long-term effects of feedstock, phase separation, char particulates, and solvent addition on pyrolysis oil properties. Feedstock containing forestry residue was found to increase water content of neat pyrolysis oil and the collection method (total vs. fractionated) affects all of the properties with the largest impact on viscosity and as produced molecular weight. Post-condensation liquid filtration did not prevent aging-related water content or molecular weight increases during aging but did retard aging reactions in pine clear wood and pine bark pyrolysis oils. Methanol addition retarded the aging reactions in pine needle fractionated pyrolysis oil; at 15 wt% phase separation was prevented and molecular weight increased 11 % after 504 h of aging.

Stable dinuclear complexes bis(heptane-2,4,6-trionato)dicopper(II) [Cu2(daa)2], bis(1,5-diphenyl-1,3,5-pentanetrionato)dicopper(II) [Cu2(dba)2], bis(1,5-diphenyl-1,3,5-pentanetrionato)dicobalt(II) [Co2(dba)2], and [6,11-dimethyl-7,10-diazahexadeca-5,11-diene-2,4,13,15-tetranato(4-)-N7N10O4O13;O2O4O13O15] copper(II)cobalt(II) [(CuCo(daaen)] were supported on Cab-O-Sil by the batch impregnation technique. The supported samples were characterized by UV-Vis, elemental analysis, X-ray powder diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and thermal gravimetric analysis (TGA). Elemental analysis and TGA data confirm that the Cu2(daa)2 complex loses one of its coordinated ligands upon adsorption onto silica in THF at greater than 4.43 wt% Cu loading. By contrast, at all Cu loadings the Cu2(dba)2 complex was adsorbed on the silica surface in CH2Cl2 without loss of ligand. XRD and DRIFTS results confirmed the formation of Cu2(dba)2 multilayer films on the Cab-O-Sil surface for samples containing greater than 2.64 wt% copper. The dinuclear cobalt complex and copper-cobalt complex also do not lose their coordination ligands upon adsorption on the surface. These two metal complexes are amorphous and did not produce XRD patterns. However, DRIFTS results confirm that the binuclear cobalt complex and the copper-cobalt complex begin forming multilayer films between 1.21and 2.53 wt% Cu. The Cu2(dba)2/silica precatalysts were subsequently converted to the catalysts by decomposing the organic ligands at 450 degrees Celsius followed by activation with 2% H2 at 250 degrees Celsius and were evaluated for methanol synthesis and methanol decomposition reactions. Kinetic studies demonstrated that the 3.70% Cu/silica[Cu2(dba)2] catalyst is more active for methanol decomposition than it is for methanol synthesis. The supported dinuclear cobalt and copper-cobalt precatalysts were converted to the catalyst by heating at 450 degrees Celsius followed by activation of the catalysts with 50% H2. Four different catalysts, 3.5% Co/silica[Co2(dba)2], 6.7% Co/silica[Co2(dba)2], 2.3% Co/silica[CuCo(daaen)], and 5.5% Co/silica[Co2(daa)2] were evaluated for the Fischer-Tropsch reaction at 350 degrees Celsius in a batch reactor. The supported binuclear cobalt catalyst produced C1-C7 alkanes and a significant amount of CO2. By contrast, the catalyst formed from heterobinuclear CuCo(daaen) showed the ability to convert syngas to aromatics with a narrow product distribution. In addition, the 6.7% Co/silica[Co2(dba)2] multilayer catalysts have above 98% conversion rates and 60% liquid hydrocarbon selectivity in a flow reactor.

No description available.