This thesis was the report of the research done on the near-critical water gasification (NCWG) as an application for activated sludge treatment. The research started with the use of model compounds and binary mixtures of these compounds as feeds for the NCWG. High gasification yields were obtained using a commercial catalyst (Raney nickel), and it was found that interactions between model compounds in the binary mixtures resulted in lowering the gasification efficiencies. The research then shifted to the use of actual activated sludge samples and the search for novel catalysts for that application. Almost 70% of the sludge was gasified in the presence of the high amounts of Raney nickel. Hydrogen was the main product in the gas phase. However, Raney nickel lost half its activity after only 8 minutes of exposure to supercritical water. For some model compounds, novel catalysts formulated in our laboratories had better activities than the commercial ones. This was not the case for the NCWG of activated sludge.

This thesis was the report of the research done on the near-critical water gasification (NCWG) as an application for activated sludge treatment. The research started with the use of model compounds and binary mixtures of these compounds as feeds for the NCWG. High gasification yields were obtained using a commercial catalyst (Raney nickel), and it was found that interactions between model compounds in the binary mixtures resulted in lowering the gasification efficiencies. The research then shifted to the use of actual activated sludge samples and the search for novel catalysts for that application. Almost 70% of the sludge was gasified in the presence of the high amounts of Raney nickel. Hydrogen was the main product in the gas phase. However, Raney nickel lost half its activity after only 8 minutes of exposure to supercritical water. For some model compounds, novel catalysts formulated in our laboratories had better activities than the commercial ones. This was not the case for the NCWG of activated sludge.

The increasing yield of municipal solid waste (MSW) is one of the main by-products of modern society. Among various MSW treatment methods, plasma gasification in a fixed-bed melting reactor (PGM) is a new technology, which may provide an efficient and environmental friendly solution for problems related to MSW disposals. General objectives of this work are to develop mathematical models for the PGM process, and using these models to analyze the characteristics of this new technology. In this thesis, both experimental measurement and numerical analysis are carried out to evaluate the performance of both air gasification and air&steam gasification in a PGM reactor. Furthermore, parameter studies were launched to investigate the effect of three main operation parameters: equivalence ratio (ER), steam feedstock mass ratio(S/F) and plasma energy ratio (PER). Based on the above analysis, the optimal suggestions aiming at providing highest syngas calorific value, as well as system energy efficiency, are given. Six experimental tests were conducted in a demonstration reactor. These tests are classified into two groups: air gasification (case 1 and 2) and air&steam gasification (case 3 to 6). In all these cases, the plasma gasification and melting of MSW produced a   syngas with a lower heating value of 6.0-7.0 MJ/Nm3. By comparing the syngas yield and calorific value, the study found out that the steam and air mixture is a better gasification agent than pure air. It is also discovered that the operation parameters seriously influence the operation of the PGM process. A zero-dimensional kinetic free model was built up to investigate the influence of operation parameters. The model was developed using the popular process simulation software Aspen Plus. In this model, the whole plasma gasification and melting process was divided into four layers: drying, pyrolysis, char combustion&gasificaiton, and plasma melting. Mass and energy balances were considered in all layers. It was proved that the model is able to give good agreement of the syngas yield and composition. This model was used to study the influence of ER, S/F and PER on average gasification temperature, syngas composition and syngas yield. It is pointed out that a common problem for the PGM air gasification is the incomplete char conversion due to low ER value. Both increasing plasma power and feeding steam is helpful for solving this problem. The syngas quality can also be improved by reasonably feeding high temperature steam into the reactor.   In order to provide detailed information inside the reactor, a two-dimensional steady model was developed for the PGM process. The model used the Euler-Euler multiphase approach. The mass, momentum and energy balances of both gas and solid phases are considered in this model. The model described the complex chemical and physical processes such as drying, pyrolysis, homogeneous reactions, heterogeneous char reactions and melting of the inorganic components of MSW. The rates of chemical reactions are controlled by kinetic rates and physical transport theories. The model is capable of simulating the pressure fields, temperature fields, and velocity fields of both phase, as well as variations of gas and solid composition insider the reactor. This model was used to simulate both air gasification and air&steam gasification of MSW in the PGM reactor. For PGM air gasification, simulated results showed that when ER varies from 0.043 to 0.077, both the syngas yield and cold gas efficiency demonstrated a trend of increasing. This is explained mainly by the increase of char conversion rate with ER. However, the increase of ER was restricted by peak temperature inside the fixed-bed reactor. Therefore, it is not suggested to use only air as gasification in the PGM process. The influence of plasma power is not obvious when PER varies from 0.098 to 0.138.  The positive influences of steam addition on cold gas efficiency and syngas lower-heating-value are confirmed by the simulation results of PGM air&steam gasification. The main effect of steam addition is the rouse of water shift reaction, which largely accelerates the char conversion and final yields of hydrogen and carbon dioxide. The effect of steam injection is affected by steam feeding rate, air feeding rate and plasma power. Based on the above modeling work, Interactions between operation parameters were discussed. Possible operation extents of operation parameters are delimitated. The optimal points aiming at obtaining maximum syngas LHV and system CGE are suggested.

Of all coke properties the influence of the catalytic mineral matter on reactivity of metallurgical cokes is least understood. There is limited information about the form of minerals in the metallurgical cokes and no information about their relative concentration. A comprehensive study was undertaken for characterisation of mineral matter in coke (qualitative and quantitative), which enabled quantification of the effect of catalytic minerals on the reaction rate, and establishment of the effect of gasification on the mineral phases. Also, the relative importance of coke properties on the gasification reaction rate was determined. The reactivity experiments were performed at approximately 900??C using 100% CO2 under chemically controlled conditions. The mineralogical composition of the investigated cokes was found to vary greatly as did the levels of catalytic mineral phases. These were identified to be metallic iron, iron sulfides and iron oxides. The gasification reaction rate at the initial stages was strongly influenced by the content of catalytic mineral phases and also by the particle size of the catalytic mineral matter. The reaction rate increased as the contact surface between catalyst and carbon matrix increased. Catalytic mineral phases showed a strong influence on the reaction rate at early stages of reaction. But their influence diminished during gasification. At later stages of reaction the influence of micropore surface area became more important. The influence of the catalytic mineral phases diminished during gasification because the catalyst was inactivated to some degree and the contact surface between the catalyst and carbon matrix diminished due to the strong gasification of the carbon around the catalyst particles. The partial inactivation of the catalytic mineral phases occurred because metallic iron and pyrrhotite were oxidised by CO2 to iron oxide, and in turn iron oxide reacted with other mineral phases, which it is associated with, to form minerals that are not catalysts. It is noteworthy that a significant percentage of the mineral matter present in the investigated cokes was amorphous (44 - 75%). The iron, potassium and sodium present in the amorphous phase did not appear to catalyse gasification, but their potential contribution to gasification could not be completely excluded.

Bibliography: leaves 322-335. / xxxvii, 343 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Highlights the need for extensive testing of large particle coal devolatilization models with both volatile matter evolution and particle temperature data in order to ensure that the predictions generated by the model can be thoroughly trusted. By undertaking an in-depth investigation into the particle temperature measurements and associated model predictions, shows that accurate model predictions can be obtained for the evolution of volatile matter, and of individual volatile species. The model is also capable of predicting the behaviour of wet coal particles by assuming that drying is heat transfer controlled and that the enthalpy of drying observed by Chen is applicable. Ultimately, this model forms a sound basis for the on-going development of a model encompassing all of the reactions required to model the behaviour of a typical coal particle in a fluidished bed combustor or gasifier. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemical Engineering, 1999

Bibliography: leaves 322-335. / xxxvii, 343 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Highlights the need for extensive testing of large particle coal devolatilization models with both volatile matter evolution and particle temperature data in order to ensure that the predictions generated by the model can be thoroughly trusted. By undertaking an in-depth investigation into the particle temperature measurements and associated model predictions, shows that accurate model predictions can be obtained for the evolution of volatile matter, and of individual volatile species. The model is also capable of predicting the behaviour of wet coal particles by assuming that drying is heat transfer controlled and that the enthalpy of drying observed by Chen is applicable. Ultimately, this model forms a sound basis for the on-going development of a model encompassing all of the reactions required to model the behaviour of a typical coal particle in a fluidished bed combustor or gasifier. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemical Engineering, 1999

This work has examined the thermochemical conversion of sugar cane processing wastes (bagasse and cane harvesting trash) for use in the design of pressurised entrained flow gasification power cycles (~20 Barg, 600-900oC). The two key parameters of interest were the residual char yield from initial pyrolysis and the heterogeneous reactivity of the char with respect to carbon dioxide. Char yield and gasification rates were measured by a conventional wire mesh reactor and thermogravimetric (TGA) technique, an in-situ sample charring TGA technique and with an entrained flow reactor specifically designed for this work. The new experimental reactor concept is one of the major contributions of the work. Chars from the entrained flow experiments were characterised by optical microscope, SEM/EDS, TEM/EDS and XPS techniques, to help elucidate the processes occurring during pyrolysis and gasification. The key findings and conclusions of the work were as follows: 1. Initial (pyrolysis) char yields were consistent with the data reported in literature for similar materials. Char yields varied with reaction conditions, from 6 to 49 wt% daf for cane trash and 4 to 40 wt% daf for bagasse. Ash content also had a significant effect on char yield. The char yield for both cane trash and bagasse increased in proportion to the logarithm of system pressure. 2. A relatively simple empirical model for char yield under pressurised entrained flow conditions was formulated. This could predict char yields for both the experimental data in this work and those reported in literature for similar biomass materials. While temperature, pressure and ash content were all significant parameters in the model, the primary fitting parameter was a measure of the contribution of secondary char forming reactions and ongoing pyrolysis to char yield. The identification of this parameter is one of the contributions of this work. 3. The measured initial rate of char gasification by carbon dioxide was 0.06 to 1.2 mg per gram of initial char, over the temperature range 750 to 900oC. The rate of gasification was so low as to not contribute significantly to overall fuel conversion in the reaction residence times iv expected of a commercial gasifier. In essence almost all of the experimentally measured fuel conversion could be attributed to pyrolysis, which resulted in 85-95% fuel conversion. 4. Both the raw materials and the residual chars had low surface areas and negligible microporosity. The majority of the measured surface area may have been associated with the ash component rather than the carbonaceous component, which supported the finding of low reactivity. 5. The silica component of the chars exhibited crystalline silicate formation by migration of metal species over time periods of minutes. These silicates displayed signs of sintering, but otherwise remained physically intact; leaving a characteristic skeleton that corresponded to the original structure in the raw materials. 6. The gasification rate showed a time dependent decrease in the entrained flow experiments. This was attributed to coke formation on the char surface, followed by carbon trapping in the ash component at high levels of conversion. Both findings are significant contributions from this work, because they highlight key mechanisms that hinder fuel conversion in the proposed gasification concept. The broad coverage achieved in this work has provided an overall picture of how fuel conversion progresses during the pressurised entrained flow gasification of sugar cane wastes. It is recommended that many of the aspects highlighted in this work be examined further, to confirm the findings and to investigate the means to avoid the factors identified in this work as hindering fuel conversion.

Thesis (M.S.)--Brigham Young University. Dept. of Mechanical Engineering, 2006. / Includes bibliographical references (p. 137-140).

Thesis (M.S.)--Brigham Young University. Dept. of Mechanical Engineering, 2006. / Includes bibliographical references (p. 79-80).

Thesis (M.S.)--Humboldt State University, 2008. / Includes bibliographical references (leaves 114-118). Also available via Humboldt Digital Scholar.