Thesis (M.S.)--University of Wisconsin--Madison. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 205-210).

Stringent legislation on control of vehicle exhaust emissions has led to consideration of alternative means of reducing emissions, with hydrogen fuel cell powered vehicles being accepted as one favoured possibility. However, the difficulties of storing and distributing hydrogen as a fuel are such that the conversion of more readily available fuels to hydrogen on board the vehicle may be required. The production of hydrogen by the partial oxidation of isooctane over Rh/Al2O3, Rh/CeO2-?l2O3 and Rh/CeO2-ZrO2 catalysts has been investigated. Oxidation was initiated at temperatures between 200 ?220 oC. The yield of hydrogen was 100%. CeO2-ZrO2 was found to be the best support. The production of hydrogen by the autothermal reforming of artificial gasoline has been studied. Part of gasoline is oxidised to produce heat and steam to promote the steam reforming of unburnt gasoline to produce hydrogen. The use of platinum impregnated on ceria supports (active for oxidation) and a commercial nickel based catalyst (Ni-com), for steam reforming of gasoline have been explored. Initiation of oxidation of artificial gasoline over unreduced platinum based catalysts occurred at temperature as low as 150 oC, depending on the oxygen:carbon ratio and the liquid hydrocarbon used. Detailed kinetic studies of the steam reforming of isooctane and artificial gasoline (a mix of cyclohexane, isooctane and octane) over pre-reduced Ni-com catalysts showed that the reaction was 0.17 order in isooctane and 0.54 order in steam, whilst the reaction was 0.08 order in artificial gasoline and 0.23 order in steam. Mechanisms have been proposed to account for the dual site surface reaction with dissociative adsorption of isooctane or artificial gasoline and steam. Combined oxidation and steam reforming systems (autothermal reforming) using Pt/CeO2 as a front catalyst bed and Ni-com as the rear bed at the feed conditions of oxygen:carbon (O:C) ratio of ca.1.2 and steam:carbon (S:C) ratio of ca.2, produces ca. 3.5 moles of hydrogen per mole of gasoline fed. The system reaction temperature could be controlled by adjusting the O:C and S:C ratios in feed.

Thesis (Ph. D.)--University of New South Wales, 2003. / Also available online.

Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2004. / Includes bibliographical references. Also available in electronic version.

Thesis (Ph. D.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains x, 174 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 155-166).

Thesis (Ph. D.)--West Virginia University, 2007. / Title from document title page. Document formatted into pages; contains xii, 162 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 139-150).

Recently there has been increasing interest in using glycerol as a substrate on steam reforming due to the increase of biodiesel production. With the increase of biodiesel production a glut of glycerol has resulted and this would be a more suitable substrate for value added production of hydrogen from reforming. Reforming biorenewable viscous fluids such as glycerol is difficult due to mass transfer limitations associated with vaporizing glycerol to gas phase before steam reforming. This study was to evaluate the feasibility of reforming electrically atomized liquid phase glycerol by means of a technique called electro-spray. It was hypothesized that reforming electrically charged glycerol nanodroplets on an oppositely charged conductive catalyst will increase the reforming performance as opposed to a neutral catalyst-substrate system. Hydrogen yield, selectivity was increased by 20%, 25% respectively when nanodroplets introduced. Exerting an electrical charge to the substrate-catalytic system significantly enhanced the reforming performance irrespective of the physical phase.

No description available.

The research presented in this dissertation involved characterization of the Cu/ZnO solid catalyst system as applied to methanol/steam reformation. Thermogravimetry was used to investigate in-lab synthesized samples and a commercial product G66B (Cu/ZnO 33/67 wt. %). The 33% Cu sample contained Cu ions in the ZnO matrix. This phase required the highest temperatures (400°C) for H₂ reduction. The 50% Cu sample reduced at a lower temperature (220°C) but its complete reduction required the same maximum temperature. The higher temperature process was similar to the 33% case, while the lower one was due to the reduction of a amorphous CuO phase. The 66% Cu sample reduced in a fairly narrow low temperature (270°C) range. Therefore, its CuO phase has a amorphous structure. G55B reduced at lower temperatures than the in-lab samples. This difference is possibly due to different synthetic procedures used in the production of G66B and the in-lab samples. The CuO phase of G66B appears to be amorphous and well dispersed. Raman spectroscopy was used to identify the crystal phases of these solids. The complexity of the initial precipitate was monitored versus the Cu/Zn ratio of the system. The nature of the phases present under reduction conditions was determined. This information has provided insight into the active phases involved in methanol reformation. The role of the solids lattice oxygen was determined. The reaction was carried out on labelled ¹⁸O-containing Cu/ZnO. Incorporation of ¹⁸O into both CO₂ and H₂O clearly indicates the involvement of these oxygens in the reaction. Observation of C¹⁸O¹⁸O indicates that the C-O bond in methanol does not remain intact. XPS was used to determine the effects of oxidation, reduction, and reaction on the Cu component of G66B. Upon oxidation all Cu exists as Cu⁺². The catalyst always contains Cu⁺¹ and Cuᵒ after H₂ reduction. After methanol/steam reformation with a 50/50 vol% mxiture, all Cu is reduced to Cuᵒ. Changes in the Cu/Zn ratio of the surface are interpreted in terms of changes in surface morphology.

In this work, a fundamental kinetic model for the catalytic reforming process has been developed. The complex network of elementary steps and molecular reactions occurring in catalytic reforming has been generated through a computer algorithm characterizing the various species by vectors and Boolean relation matrices. The algorithm is based on the fundamental chemistry occurring on both acid and metal sites of the catalyst. Rates are expressed for each of the elementary steps involved in the transformation of the intermediates. The Hougen-Watson approach is used to express the rates of the molecular reactions occurring on the metal sites of the catalyst. The single event approach is used to account for the effect of structure of reactant and activated complex on the rate coefficients of the elementary steps occurring on the acid sites. This approach recognizes that even if the number of elementary steps is very large they belong to a very limited number of types, and therefore it is possible to express the kinetics of elementary steps by a reduced number of parameters. In addition, the single event approach leads to rate coefficients that are independent of the feedstock, due to their fundamental chemical nature. The total number of parameters at isothermal conditions is 45. To estimate these parameters, an objective function based upon the sum of squares of the residuals was minimized through the Marquardt algorithm. Intraparticle mass transport limitations and deactivation of the catalyst by coke formation are considered in the model. Both the Wilke and the Stefan-Maxwell approaches were used to calculate the concentration gradients inside of the particle. The heterogeneous kinetic model was applied in the simulation of the process for typical industrial conditions for both axial and radial flow fixed bed reactors. The influence of the main process variables on the octane number and reformate volume was investigated and optimal conditions were obtained. Additional aspects studied with the kinetic model are the reduction of aromatics, mainly benzene. The results from the simulations agree with the typical performance found in the industrial process.