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).

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.

No description available.

A mathematical modeling framework for the methane steam reforming reaction operating in steady state has been developed. Performances are compared between the classic catalytic packed bed reactor and a Pd-based catalytic membrane reactor. Isothermal simulations on MATLAB © has first been conducted and show a higher performance of the membrane reactor over the packed bed reactor. Methane conversion of 1 can be reached for lower temperatures than used with industrial PBR, and better performances are shown for an increase in the operating pressure. Optimum conditions were defined for Temperature (500-600 Celsius), reaction side pressure (16-40 bars), membrane thickness (1-7 micrometers), steam/methane ratio (3-4), reactor length (5-10 meters) and permeate sweep ratio (20 or more). This model was validated by multiple recognized sources. Adiabatic simulations were conducted in order to develop a mathematical model base for non-isothermal simulations. The membrane reactor is again showing a higher conversion of methane compared to the packed bed reactor, however the heat loss due to the membrane and the hydrogen leaving through the tube is decreasing the performances of the MR over the PBR compared to the isothermal case. Results show also that most of the reaction occurs at the very beginning of the reactor.

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.

No description available.

The experimental analysis of an autothermal gasoline reformer for use in an auxiliary power unit was undertaken. The development of these auxiliary power units has the potential to create positive economical and environmental benefits. It will provide the necessary energy and heating while utilizing a fuel with a well established infrastructure. Autothermal reforming is a process in which both oxygen and steam are combined with a hydrocarbon fuel over a catalyst bed in order to produce a hydrogen rich gas stream. This process utilizes an exothermic partial oxidation reaction to promote the hydrogen efficient, endothermic steam reforming reaction. The main goals of this study were to design and test the operating conditions of a new autothermal reformer and to determine an operational envelope for the reactor. Furthermore, the data collected was used to validate a numerical model of the reactor that would assist in the development of future compact autothermal reformers. A compact autothermal reformer has been designed with the capability to produce detailed wall and centerline temperature profiles during operation. During the experimental phase of this project, a strong relationship between the main input variables (the oxygen to carbon and steam to carbon ratios) and the performance characteristics of the reactor was found. For the range of experimental conditions tested, the highest molar percent of hydrogen in the reformate for a gas hourly space velocity of 20,000h-1 was found at an oxygen to carbon ratio of 1.0 and a steam to carbon ratio of 2.0. Performance characteristics used for the reactor were the lower heating value, the percent hydrogen yield and fuel conversion, and were found to have maximum values of 46.0%, 47.6% and 67.7% respectively. Carbon deposition on the catalyst bed was found to be significant under certain operating conditions, but had a very small effect on the final conditions of the ATR. The computational fluid dynamics model was shown to have fairly accurate predictions for the temperature profiles as well as the reformate compositions when compared to the experimental data. A number of recommendations have been made to the experimental and numerical studies. It is likely that if employed in future testing, they would improve the overall performance of the compact autothermal reformer. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2008-04-23 17:14:46.198

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).