Quan Ming Wang. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (p. 119-133). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Doctor of Philosophy (PhD) / This work involves an experimental and kinetic modelling study of the silver catalysed reaction of methanol to formaldehyde. The motivation for this was the desire to investigate the potential for Process Intensification in formaldehyde production. Formaldehyde production from methanol over silver catalyst is a fast, exothermic process where dilution is used to control heat release, and these properties are both indicators of Process Intensification potential. The process is run adiabatically and produces hydrogen (which is currently burnt). Oxygen is consumed during the reaction but is also required to activate the catalyst and is fed in understoichiometric quantities. The central overall reactions in the silver catalysed process for formaldehyde production are oxydehydrogenation CH3OH + ½ O2 -> CH2O + H2O (DH = -159kJ/mol) and dehydrogenation CH3OH <-> CH2O + H2 (DH = 84kJ/mol). When sufficient oxygen is available, formaldehyde can be further oxidised to carbon dioxide CH2O + O2 -> CO2 + H2O (DH = -519kJ/mol). Formaldehyde can decompose to carbon monoxide and hydrogen CH2O <-> CO + H2 (DH = 12.5kJ/mol). Oxidation of methanol and hydrogen also occurs and other minor products of the reaction are methyl formate, methane and formic acid. These overall reactions do not adequately describe the silver catalysed reaction mechanism. In particular, the overall dehydrogenation reaction does not include oxygen as a reactant, but it will not occur over silver that does not have active atomic oxygen species adsorbed on the surface, and these atomic oxygen species are formed from gas phase oxygen. In the absence of a complete mechanism for silver catalysed formaldehyde production, the intensification of the process was investigated using a thermodynamic model (based on the overall oxydehydrogenation and dehydrogenation reactions, not reaction kinetics). It was found that by using heat exchange (rather than heat generated from the exothermic oxydehydrogenation path) and a lower oxygen concentration in the feed stream, hydrogen selectivity could be increased while maintaining the required methanol conversion. Before this iv opportunity could be further investigated, a complete reaction mechanism that would allow the requirement of oxygen for catalyst activation to be included was required. There is agreement in the literature that two active atomic oxygen species react with methanol on silver. These are weakly bound atomic oxygen (Oa) and strongly bound atomic oxygen (Og). The location of Oa is on the surface of the silver, while the location of Og has been described as being in the silver surface (where it substitutes for silver atoms). Both species react with methanol to form formaldehyde. When the concentration of Oa is high enough, Oa will also react with formaldehyde forming carbon dioxide (while Og will not). The literature presents differing views on the extent of involvement of each atomic oxygen species in industrial formaldehyde production. There is also disagreement on the pathways for water and hydrogen formation. An extensive experimental investigation of the partial oxidation of methanol to formaldehyde was carried out using a flow reactor. The effect of temperature (250- 650°C), reactant concentration (7000-40000ppm methanol) and the feed ratio of methanol to oxygen (2.5-5.5) were studied. The extreme case of methanol reaction with Og in the absence of gas phase oxygen was also investigated. To isolate the effect of secondary reactions, the oxidation of formaldehyde, carbon monoxide and hydrogen were investigated, both in the presence and absence of silver catalyst. When methanol was exposed to silver catalyst that had been activated by being covered in Og (with this being the only source of oxygen) the catalytic nature of Og was demonstrated by the high selectivity to formaldehyde and hydrogen that was achieved (with very little carbon dioxide or water production). When gas phase oxygen was fed to the reactor along with methanol, hydrogen selectivity over silver increased up to about 40% as the concentration of reactants was increased. This result is consistent with the general rule of thumb from industrial practice that hydrogen selectivity is about 50%. When formaldehyde and oxygen were exposed to silver in the flow reactor, the only reaction products were carbon v dioxide and water and the combination of high temperature and excess oxygen was required for complete conversion of formaldehyde. A pseudo-microkinetic model (based on a Langmuir-Hinshelwood mechanism) for the partial oxidation of methanol to formaldehyde (over silver) was taken from the literature and investigated. This model predicts formaldehyde production using only Oa (no other active atomic oxygen species are included) but lacks pathways for reactions between Oa and adsorbed hydrogen or hydroxyl (so the only possible fate of adsorbed H atoms is to desorb as H2). The Oa model was combined with literature models for hydrogen desorption and the reactions involving adsorbed hydroxyl (desorption, self reaction, decomposition and reaction with adsorbed hydrogen). Comparison of this Hybrid model with experimental data showed that reactions involving Oa will predict formaldehyde formation and oxidation, but not hydrogen formation (because the rate of hydrogen desorption is too slow compared with the rate of water formation). It is concluded that any detailed model must include the reaction between methanol and Og (producing hydrogen). Although the reaction between two adsorbed OgH species has been suggested as the pathway for hydrogen formation from Og, this is not certain and so all possible reactions involving Og and hydrogen need be investigated and the appropriate pathways added to the Hybrid model. Once a complete microkinetic mechanism for the partial oxidation of methanol to formaldehyde over silver is available it can be used to further investigate the process intensification of this process. In particular, the use of staged addition of oxygen (to keep the catalyst active) combined with heat exchange (to replace the heat normally supplied by the oxydehydrogenation path) with the aim of simultaneously maximizing methanol conversion and selectivity to formaldehyde and hydrogen.

Graduation date: 1952

A comparative thesis to study precious metals impact on a portfolio, during a long period of time, from the fourth quarter of 1986 to the third quarter of 2012. Five different portfolios are compared; three of the portfolios containing one of the following precious metals, gold, silver and platinum, the fourth portfolio contain all precious metals and shares, and the fifth portfolio containing only shares which is represented of OMXS30. This is done to determine the portfolio that generates the most return in relation to the least risk with the help of historical prices. Sharpe ratio is used to measure the profitability of precious metals by measuring the yield relative to the total risk. The study also measures precious metals correlation with shares. / En komparativ studie som undersöker ädelmetallers inverkan på portföljen under en längre tidsperiod, från den 1 oktober 1986 fram till den 28 september 2012. Fem olika portföljer jämförs, tre av portföljerna är kompletterade med en av följande ädelmetaller, silver, guld eller platina, den fjärde portföljen innehåller samtliga ädelmetaller och aktier, och en femte portfölj kommer att innehålla endast aktie vilket representeras av OMXS30. Detta görs för att fastställa den portfölj som genererar mest avkastning i förhållande till minst risk med hjälp av historisk data. Sharpekvoten användes för att mäta lönsamheten av ädelmetaller genom att mäta avkastningens storlek i förhållande till den totala risken. Studien mäter också ädelmetallers korrelation med aktier.

¡@Silver nanowires prepared by the the reduction of AgNO3 at low temperature with thermocatalystic biphase (anatase and brookite phases) TiO2 nanoparticles are described. Furthermore, the possible mechanism to grow silver nanowires without the help of the Ag seed and capping reagent is proposed. ¡@Firstly, the amorphous TiO2 nanoparticles prepared by sol-gel method were spin-coated on the silicon wafer to form amorphous TiO2 matrix. Then an aqueous AgNO3 (1 &#x00B5;L 0.7 M) solution was dropped on the amorphous TiO2 matrix. Following the heat treatment at 200 ¢XC for 8 h, the silver nanowires (length~10 &#x00B5;m, line width~100 nm) were grown on the silicon wafer. We found that amorphous phase of TiO2 was changed to the anatase and brookite phases during the thermal reduction of the aqueous solution of AgNO3. ¡@Silver nanowires were characterized as f.c.c. structure by XRD. The TiO2 particles play an important role in providing electrons and holes for redox reaction and nucleation. With the controlling of the heating temperature and the amount of AgNO3, the silver nanowires were selectively grown in one dimension with large energetic surface. A combination of HR-TEM imaging and selected area electron diffraction reveals that the growing direction for the Ag wires is <011>.

Thesis (B.S.)--University of Missouri, School of Mines and Metallurgy, 1894. / The entire thesis text is included in file. Holograph [Handwritten and illustrated in entirety by author]. C. D. Grove determined to be Claude Devlin Grove from "Directory of Male Students and Instructors From 1871 to 1901, of the School of Mines and Metallurgy of the University of Missouri". Title from title screen of thesis/dissertation PDF file (viewed February 9, 2010)

Thesis (B.S.)--University of Missouri, School of Mines and Metallurgy, 1911. / The entire thesis text is included in file. Typescript. Illustrated by authors. Title from title screen of thesis/dissertation PDF file (viewed February 10, 2010) Cannot find evidence of Mr. Taggart receiving a degree from MSM. Includes bibliographical references.

Inaug.-diss.--Göttingen. / Lebenslauf. "Verzeichnie d. benutzten literatur u.d. statistischen quellen": p. [117]-119.

Thesis--M.A., University of Hong Kong. / Typewritten.

Thesis (Ph. D.)--University of Hong Kong, 2002. / Includes bibliographical references (leaves 174-186).