Dissertation (Ph.D.)--Worcester Polytechnic Institute. / Keywords: microkinetics, reaction routes, mechanism analysis, water-gas-shift. Includes bibliographical references (p.295-305).

Thesis (M.S.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xiii, 172 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 123-125).

In recent years economic, environmental, and strategic concerns over the use of petroleum resources have led to increased interest in renewable resources. Biomass gasification produces a synthesis gas composed of primarily carbon monoxide, hydrogen, and carbon dioxide, which can be fermented into a variety of fuels and chemicals. This study evaluated the performance of a two-stage approach to batch synthesis gas fermentations. The first stage employs a rich medium optimized for cell growth, while the second stage is designed to maximize production of acetic acid from synthesis gas. This two-stage approach is hypothesized to be more metabolically efficient than previous single-stage designs. This study presents the evaluation of known acetic acid producing organisms described in the literature, and efforts to isolate a novel microbial catalyst for synthesis gas fermentations. Finally, new techniques were developed and implemented in order to develop a more effective system for batch synthesis gas fermentations.

Partial oxidation of CH4, CO2 reforming of CH4, and oxidative CO2 reforming of CH4 to produce synthesis gas at 700°C over supported Ni catalysts have been studied. A Ni/Mg-Al catalyst was prepared by the solid phase crystallization (spc-) method starting from a hydrotalcite-type (HT) anionic precursor. From XRD analysis, only Ni0.5Mg2.5Al catalyst consists of the layered hydrotalcite-type structure; not Ni0.5Ca2.5Al and Ni/Al2O3 catalysts. By TPR test, the Ni0.5Mg2.5Al-HT catalyst requires a high reduction temperature than the Ni0.5Ca2.5Al catalyst. It implies that the Ni0.5Mg2.5Al-HT which has a layered structure shows the stronger interaction strength between the molecules. It might increase the resistance of coke formation on the surface of the catalyst. For the reaction tests, the Ni0.5Ca2.5Al showed the highest initial activity for synthesis gas production for all reactions; but, its activity was decreased quickly due to coke formation except during the partial oxidation of CH4. The Ni0.5Mg2.5Al-HT showed a relatively higher reactivity compared to the equilibrium level than Ni/Al2O3 catalyst; and it shows very stable reactivity than other catalysts. By TPO test, the Ni0.5Mg2.5Al-HT has the lower amount of coke formed during the reaction than the Ni0.5Ca2.5Al catalyst. It confirms that the Ni0.5Mg2.5Al-HT catalyst has stronger resistance to coke formation; and it leads to provide stable reactivity in any reforming conditions at high temperature. Therefore, the Ni0.5Mg2.5Al-HT catalyst was the most promising catalyst in terms of activity and stability for partial oxidation, CO2 reforming, and oxidative CO2 reforming of CH4. The Ni0.5Mg2.5Al-HT catalyst was used to investigate the CO2 reforming of CH4 kinetics. With increasing CH4 partial pressures at constant CO2 partial pressure, the rates of CH4 consumption were increased. However, with increasing CO2 partial pressure at constant CH4 partial pressure, CH4 consumption rates was increased at lower CO2 partial pressure, but turned to independent at higher CO2 partial pressure. When the partial pressure of H2 was increased, the CO formation rate was decreased; it confirmed that the reverse water-gas shift (RWGS) reaction was occurring during the CO2 reforming of CH4 reaction. In addition, the reaction kinetic expression was proposed when the CH4 dissociation step was considered as a rate-limiting step.

Partial oxidation of CH4, CO2 reforming of CH4, and oxidative CO2 reforming of CH4 to produce synthesis gas at 700°C over supported Ni catalysts have been studied. A Ni/Mg-Al catalyst was prepared by the solid phase crystallization (spc-) method starting from a hydrotalcite-type (HT) anionic precursor. From XRD analysis, only Ni0.5Mg2.5Al catalyst consists of the layered hydrotalcite-type structure; not Ni0.5Ca2.5Al and Ni/Al2O3 catalysts. By TPR test, the Ni0.5Mg2.5Al-HT catalyst requires a high reduction temperature than the Ni0.5Ca2.5Al catalyst. It implies that the Ni0.5Mg2.5Al-HT which has a layered structure shows the stronger interaction strength between the molecules. It might increase the resistance of coke formation on the surface of the catalyst. For the reaction tests, the Ni0.5Ca2.5Al showed the highest initial activity for synthesis gas production for all reactions; but, its activity was decreased quickly due to coke formation except during the partial oxidation of CH4. The Ni0.5Mg2.5Al-HT showed a relatively higher reactivity compared to the equilibrium level than Ni/Al2O3 catalyst; and it shows very stable reactivity than other catalysts. By TPO test, the Ni0.5Mg2.5Al-HT has the lower amount of coke formed during the reaction than the Ni0.5Ca2.5Al catalyst. It confirms that the Ni0.5Mg2.5Al-HT catalyst has stronger resistance to coke formation; and it leads to provide stable reactivity in any reforming conditions at high temperature. Therefore, the Ni0.5Mg2.5Al-HT catalyst was the most promising catalyst in terms of activity and stability for partial oxidation, CO2 reforming, and oxidative CO2 reforming of CH4. The Ni0.5Mg2.5Al-HT catalyst was used to investigate the CO2 reforming of CH4 kinetics. With increasing CH4 partial pressures at constant CO2 partial pressure, the rates of CH4 consumption were increased. However, with increasing CO2 partial pressure at constant CH4 partial pressure, CH4 consumption rates was increased at lower CO2 partial pressure, but turned to independent at higher CO2 partial pressure. When the partial pressure of H2 was increased, the CO formation rate was decreased; it confirmed that the reverse water-gas shift (RWGS) reaction was occurring during the CO2 reforming of CH4 reaction. In addition, the reaction kinetic expression was proposed when the CH4 dissociation step was considered as a rate-limiting step.

In 2004 the Department of Chemical and Process Engineering (CAPE) at University of Canterbury began a programme to investigate using biomass gasification integrated combined cycle (BIGCC) technology to convert waste products and residues to useful energy for the wood processing sector. This research was conducted as a part of Objective Two of the programme to develop gasification and gas cleaning technology. This project involved commissioning and characterising the operation of the Fast Internal Circulating Fluidised Bed (FICFB) gasifier and comparing its operation with a more conventional up-draught process owned and operated by Page Macrae in Mount Manganui. The wood derived gas composition of each gasifier was measured using gas chromatography and these compositions were used to calculate lower heating values (LHV). The CAPE FICFB gasifier has proven to produce successfully a gas with a lower heating value of 10400-12500 kJ/Nm³. The Page Macrae gasification process produces a low quality gas with a lower heating value of 4100-5100 kJ/Nm³. This is much lower than the CAPE gasifier since the oxidant used in the up-draught gasification process is air and the product gas is diluted by nitrogen. The Page Macrae gasification system combusts wood derived gas to produce steam for a laminar veneer lumber (LVL) processing plant so gas quality and heating value are less important than in electrical production applications. Reducing the nitrogen content of the CAPE product gas will increase the heating value of the gas. Improvements to the boiler system will reduce the amount of air required for gasification and hence reduce the nitrogen content. Further improvements to gas quality can be gained from a change in the fuel feed point from on top of the gasification column's bubbling fluidised bed to the side of the bubbling fluidised bed. The CAPE gasifier is much more complicated and requires specialised operators but produces a gas suitable for gas engine and gas turbine technology. Overall the CAPE gasification system is more suited to BIGCC applications than the Page Macrae process.

Hydrogen is universally known as the most efficient renewable energy source capable of meeting global energy demands. Chlamydomonas reinhardtii has the ability to produce biohydrogen during the metabolic engineering of the photosynthetic pathways. The aim of this study was to 1) use leachate as a feedstock to enhance microalgal biomass and subsequent hydrogen production, 2) use Pulse Amplitude Modulated (PAM) Fluorometry to elucidate the role of photosystem one during hydrogen production, 3) use Nicotinamide Adenine Dinucleotide Phosphate (NADPH) fluorescence as an indicator of hydrogen production and 4) design a modular pilot scale biohydrogen bioprocessing system implementing experimental findings into a conceptual model. This resulted in a cost effective source of renewable hydrogen produced from waste. The use of 16% landfill leachate was found to increase biomass production by 26% as compared to using Tris- Acetate Phosphate (TAP) media alone. Hydrogen induction resulted in an increased gas synthesis of 37% as well as an increased production period of 8 days compared to the normal 5 days. Landfill leachate further reduced the costs as it acted as a free nutrient source with the added ecological advantage of leachate treatment. Hydrogen production was induced by sulphur depletion and physiological parameters were measured using PAM Fluorometry. Photosystem I was found to be dominant during hydrogen production while photosystem II was down-regulated due to the sulphur depletion and damaged D1 proteins. NADPH fluorescence was significantly correlated to hydrogen yields allowing for NADPH to be utilised as a molecular indicator for hydrogen synthesis. The overall functionality of this bioprocessing system relies on the optimum physiological functioning of cells. The above findings were implemented into a pilot scale design, maximising the physiological performance during hydrogen production. This study has contributed knowledge regarding the production of hydrogen gas from leachate, the physiological changes of photosystem I during hydrogen production and the use of NADPH fluorescence as an indicator. The fundamental theories of bioprocessing incorporate a firm understanding of cellular and biochemical processes. The use of molecular indicators determined from physiological studies can be used at pilot scale to improve overall efficiency of hydrogen production. / Ph.D. University of KwaZulu-Natal, Durban 2014.

Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Realff, Matthew; Committee Member: DeMartini, Nikolai; Committee Member: Muzzy, John; Committee Member: Sievers, Carsten.

Orientador: Carlos Alberto Luengo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-22T18:52:15Z (GMT). No. of bitstreams: 1 Filizola_AlexandreRodrigues_M.pdf: 3632264 bytes, checksum: 03e1e31881e49ad653e27f6ff8d6fc88 (MD5) Previous issue date: 2013 / Resumo: O objetivo deste trabalho é o desenvolvimento e a caracterização de nanocatalisadores ativos na catálise heterogênea da obtenção de gás de síntese a partir de bio-óleos. Com este fim pretende-se utilizar nanotubos de carbono NTC como suportes tridimensionais para os metais catalíticos. A amostra obtida pelo método de arco elétrico automatizado foi caracterizada utilizando-se as técnicas de espectroscopia Raman, medidas de área superficial (BET) e distribuição de tamanho de poro (BJH), difração de Raios-X, medidas de magnetização SQUID e microscopia de transmissão eletrônica TEM. Espera-se que estes nanocatalisadores diminuam a temperatura do processo de gaseificação dos bio-óleos / Abstract: The aim of this thesis is the development and characterization of nanocatalysts for the heterogeneous conversion of bio-oils into synthesis gas. To this end we intend to use carbon nanotubes (NTC) as unconventional supports for the catalytic transition metals. The sample obtained by a computer controlled electric arc method was characterized using the techniques of Raman spectroscopy, surface area measurement (BET) and pore size distribution (BJH), X-ray diffraction, SQUID magnetization measurements and transmission electron microscopy TEM. It is expected that these nanocatalysts would reduce the temperature of the gasification process of the bio-oil samples / Mestrado / Física / Mestre em Física

A fermentação anaeróbia da matéria orgânica produz uma mistura de gases chamada biogás. Este biogás contém CH4 e CO2 como componentes majoritários. Estes dois compostos são gases de efeito estufa e sua utilização é muito importante do ponto de vista ambiental e econômico. O presente trabalho teve por objetivo produzir gás de síntese (H2/CO), uma matéria prima de alto valor industrial, a partir da reforma oxidativa do biogás com adição de oxigênio (1,5CH4+1,0CO2+0,25O2) sobre catalisadores de NiO-MgO-ZrO2 e NiO-Y2O3-ZrO2. Os catalisadores foram preparados usando o método de polimerização numa única etapa e foi estudada a variação do teor de MgO e de Y2O3 contido nas amostras. Estes materiais foram caracterizados por DRX, RTP, Adsorção-dessorção de N2, XPS, XAS-XANES, MEV e EDX e foram avaliados na reação de reforma oxidativa de um biogás modelo (composição molar:1,5 CH4/1CO2) em presença de oxigênio, a 750&deg;C e 1atm, visando à obtenção de gás de síntese. Os teores de MgO utilizados no sistema NiO/MgO/ZrO2 foram de 0%, 4%, 20%, 40% e 100% em relação ao ZrO2 (os mesmos teores foram utilizados para Y2O3 no sistema NiO/Y2O3/ZrO2) e o teor mássico de Ni foi 20%. As análises de DRX, TPR, XPS confirmaram a formação das soluções sólidas NiO-MgO e MgO-ZrO2 nos catalisadores NiO-MgO-ZrO2, e das soluções sólidas NiO-Y2O3 e Y2O3-ZrO2 nos catalisadores NiO-Y2O3-ZrO2. Estas soluções sólidas juntas, nos correspondentes catalisadores, melhoraram o desempenho catalítico, levando a altos valores de conversão e baixas taxas de deposição de coque. O teor de MgO ótimo foi de 20%mol no sistema NiO/MgO/ZrO2, e de 20% e 40% mol de Y2O3 no sistema NiO/Y2O3/ZrO2. Nos catalisadores NiO-MgO-ZrO2, a solução sólida NiO-MgO favoreceu principalmente a reação de reforma seca do metano (CH4+CO2), enquanto que nos catalisadores NiO-Y2O3-ZrO2 a solução sólida Y2O3-ZrO2 favoreceu principalmente à oxidação parcial do metano (CH4+1/2O2). Os catalisadores Ni20MZ e Ni20YZ apresentaram resultados promissores para a reforma oxidativa de biogás em presença de oxigênio sendo estes catalisadores melhores do que uma amostra comercial de Ni/Al2O3 (20%Ni) testada nas mesmas condições de reação. A razão H2/CO nos produtos das reações sobre os melhores catalisadores foi muito próxima de 1,0; o que permite seu uso direto em diversas reações, como reação de Fischer-Tropsch, síntese direta de dimetil-éter (processo STD) e síntese de formaldeído. / The anaerobic fermentation of the organic material produces a mixture of gases called biogas. This biogas contains CH4 and CO2 as major components. These two compounds are greenhouse gases and their use are very important from the environmental and economic point of view. The present study aimed to produce synthesis gas (H2/CO), a high-value raw material for the chemical industry, from the oxidative reforming of biogas using oxygen (1.5CH4 +1.0CO2+0.25O2) over NiO-MgO-ZrO2 and NiO-Y2O3-ZrO2 catalysts. These catalysts were prepared by the one-step polymerization method. The variation content of MgO and Y2O3 in each catalyst was studied. These materials were characterized by XRD, TPR, adsorption-desorption of N2, XPS, XAS, SEM and EDX; they were evaluated in the oxidative reforming reaction of a model biogas (molar composition: 1.5 CH4/1CO2) in the presence of oxygen at 750 &deg;C and 1atm, aiming to produce synthesis gas.<br /> The content of MgO in the NiO/MgO/ZrO2 system was varied ranging from 0-100% (0%, 4%, 20%, 40% and 100%mol in relation to ZrO2) , the same contents were used for the Y2O3 in the NiO/Y2O3/ZrO2 system. All catalysts had 20% wt of Ni. The XRD, TPR and XPS confirmed the formation of NiO-MgO and the MgO-ZrO2 solid solutions in the NiO-MgO-ZrO2 catalysts; and NiO-Y2O3 and Y2O3-ZrO2 solid solutions in the NiO-Y2O3-ZrO2 catalysts. These solid solutions together, in the corresponding catalysts, inproved the catalytic performance, leading to high conversion rates and low carbon deposition rates. The optimum MgO content was 20mol% for the NiO/MgO/ZrO2 system and 20% and 40mol% of Y2O3 for the NiO/Y2O3/ZrO2 system. In the NiO-MgO-ZrO2 catalysts, the NiO-MgO solid solution promoted primarily the dry reforming reaction of methane (CH4 + CO2), while in the NiO-Y2O3-ZrO2 catalysts, the Y2O3-ZrO2 solid solution primarily favored the partial oxidation of methane (CH4 + 1/2O2). The Ni20MZ and Ni20YZ catalysts showed promising results for the oxidative reforming of biogas in the presence of oxygen; these catalysts being better than a commercial catalysts (Ni/Al2O3; 20%wt Ni) tested under the same reaction conditions. The H2/CO ratio in the reaction products over the best catalysts was very close to 1.0, which allows its direct use in various processes such as Fischer-Tropsch process, Syngas-to-dimethyl-ether process (STD) and in the synthesis of formaldehyde.