Due to security issues in energy supply and environmental concerns, renewable energy production from biomass becomes an increasingly important area of study. Thus, thermal conversion of biomass via pyrolysis and subsequent upgrading procedures were explored, in an attempt to convert an abundant agricultural residue, corn stover, into potential bio-fuels. Pyrolysis of corn stover was carried out at 400, 500 and 600oC and at moderate pressure. Maximum bio-char yield of 37.3 wt.% and liquid product yield of 31.4 wt.% were obtained at 400oC while the gas yield was maximum at 600oC (21.2 wt.%). Bio-char characteristics (energy content, proximate and ultimate analyses) indicated its potential as alternative solid fuel. The bio-oil mainly consisted of phenolic compounds, with significant proportions of aromatic and aliphatic compounds. The gas product has energy content ranging from 10.1 to 21.7 MJ m-3, attributed to significant quantities of methane, hydrogen and carbon dioxide. Mass and energy conversion efficiencies indicated that majority of the mass and energy contained in the feedstock was transferred to the bio-char. Fractional distillation of the bio-oil at atmospheric and reduced pressure yielded approximately 40-45 wt.% heavy distillate (180-250oC) with significantly reduced moisture and total acid number (TAN) and greater energy content. Aromatic compounds and oxygenated compounds were distributed in the light and middle fractions while phenolic compounds were concentrated in the heavy fraction. Finally, hydrotreatment of the bio-oil and the heavy distillate using noble metal catalysts such as ruthenium and palladium on carbon support at 100 bar pressure, 4 hours reaction time and 200o or 300oC showed that ruthenium performed better at the higher temperature (300oC) and was more effective than palladium, giving about 25-26% deoxygenation. The hydrotreated product from the heavy distillate with ruthenium as catalyst at 300oC had the lowest oxygen content and exhibited better product properties (lower moisture, TAN, and highest heating value), and can be a potential feedstock for co-processing with crude oils in existing refineries. Major reactions involved were conversion of phenolics to aromatics and hydrogenation of ketones to alcohols. Results showed that pyrolysis of corn stover and product upgrading produced potentially valuable sources of fuel and chemical feedstock.

In this work, Gold and Copper oxidation catalysts supported on a range of metal oxides were synthesised via 2 previously uninvestigated preparation methods. In the first chapter, Gold nanoparticle catalysts were deposited onto TiO2, CeO2 and ZrO2 nanoparticles via the non-aqueous Modified Photodeposition procedure. This method was found to produce smaller Gold particle sizes following intrinsic excitation of the support than the conventional aqueous phase method, with surface physisorbed water apparently acting as the sacrificial reductant. The as prepared catalysts were drastically more active than those prepared by the conventional method and under standardised tests were directly comparable to those prepared by the Deposition Precipitation Method. The second part of the work, explored the preparation of metal oxide supported Copper catalysts via the Flame Spray Pyrolysis process. CO Oxidation tests established the following order of activity for 4wt% Cu loaded on the various supports: Cu-CeO2 > Cu-TiO2 > Cu-ZrO2 > Cu-Al2O3 > Cu-SiO2. CO-TPD studies found that more active materials tended to adsorbed more CO and reacted higher proportions of this with lattice oxygen to form CO2 at lower temperatures. The addition of Cu to each metal oxide surface was found to induce lengthening of the average Metal-Oxygen bond length, with higher electron density on surface O. This phenomenum is proposed as being responsible for the widely reported ???synergistic effect??? reported for similar Cu catalysts. Cu-CeO2 (0-12wt%) catalysts were tested in the Preferential CO Oxidation (COPROX) reaction. Increasing Cu content, varied the Cu morphology from monomers, through to dimers and ultimately CuO crystallites. DFT simulations of the Cu dimer structure revealed higher levels of bonding ionicity in this morphology, relative to the monomeric structure. This coincided with higher levels of activity, reinforcing the earlier finding that highly ionic bonds are conducive to higher levels of activity. High levels of activity and selectivity were maintained until approximately 423 K. Surface redox properties of the 4wt% Cu-CeO2 catalyst were assessed using temperature-programmed reduction (CO, H2) and desorption (CO) experiments, as well as in situ and phase-resolved infrared spectroscopy to study the transition to nonselective conditions. For the first time, it was demonstrated that CO and H2 react at identical surface sites, with CO2 formation proceeding simultaneously via three distinct Cux+-CO carbonyl species. Under non-selective conditions, a gradual red-shift and loss of intensity in the carbonyl peak was observed, indicating reduction of Cu+ to Cu0 and the onset of an alternate non-selective redox-type oxidation mechanism. These results for Cu-CeO2 suggest that improved low temperature catalytic activity will only be achieved at the expense of reduced high temperature selectivity and vice versa. The final section of work explored the use of Cu-based catalysts for the low temperature oxidation of Acetaldehyde (ACA). Based on this work, it is concluded that the ACA oxidation activity of these materials is determined by two main factors: the basicity of the metal oxide support (and its subsequent ability to convert ACA to carboxylates) and the availability of surface oxygen during acetate decomposition. It is proposed that a high concentration of reducible sites (either by Cu addition or naturally occurring on CeO2) accelerates the activation and provision of oxygen and also potentially provides sites for the stabilization of methoxy intermediates resulting from the acetate decomposition.

Thesis (Ph.D.)--University of Tulsa, 1993. / Five colored photographs glued in book. Includes bibliographical references.

Diss. (sammanfattning) Stockholm : Karol. inst., 2003. / Härtill 5 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2005. / Härtill 5 uppsatser.

Diss. (sammanfattning) Uppsala : Uppsala universitet, 2006. / Härtill 4 uppsatser.

Thesis (Ph. D.)--University of Hong Kong, 2008. / Also available in print.

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In this work, inorganic membranes with highly dispersed metallic catalysts on macroporous titania-washcoated alumina supports were produced, characterized and tested in a catalytic membrane reactor. The reactor, operated as a contactor in the forced pore-flow-through mode, was used for the conversion of synthesis gas (H2 + CO) into mixed alcohols and hydrocarbons via the Fischer-Tropsch synthesis. Carbon monoxide conversions of 78% and 90% at near atmospheric pressure (300kPa) and 493K were recorded over cobalt and bimetallic Co-Mn membranes respectively. The membranes also allowed for the conversion of carbon dioxide, thus eliminating the need for a CO2 separation interphase between synthesis gas production and Fischer-Tropsch synthesis. Catalytic tests conducted with the membrane reactor with different operating conditions (of temperature, pressure and feed flow rate) on cobalt-based membranes gave very high selectivity to specific products, mostly higher alcohols (C2 – C8) and paraffins within the gasoline range, thereby making superfluous any further upgrading of products to fuel grade other than simple dehydration. Manganese-promoted cobalt membranes were found not only to give better Fischer-Tropsch activity, but also to promote isomerization of paraffins, which is good for boosting the octane number of the products, with the presence of higher alcohols improving the energy density. The membrane reactor concept also enhanced the ability of cobalt to catalyze synthesis gas conversions, giving an activation energy Ea of 59.5 kJ/mol.K compared with 86.9 – 170 kJ/mol.K recorded in other reactors. Efficient heat transfer was observed because of the open channel morphology of the porous membranes. A simplified mechanism for both alcohol and hydrocarbon production based on hydroxycarbene formation was proposed to explain both the stoichiometric reactions formulated and the observed product distribution pattern.

Hydrogen as a clean energy carrier has drawn great attention. Production of H2 from sustainable bio-oil is considered an alternative for conventional fossil fuel based energy system, since the overall process of bio-oil converting to H2 ideally is carbon-neutral and hence environmental friendly. This study focuses on developing an adequate catalyst for bio-oil steam reforming to produce H2. Ruthenium and/ or nickel based catalysts supported on alumina, ceria-alumina or ceria-silica were synthesized by sol-gel method or incipient wetness impregnation and characterized using BET Surface area analysis, Powder X-Ray diffraction (XRD), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). Steam reforming of selected model compounds, n-propanol, glycerol and acetic acid, was investigated in a fixed bed tubular flow reactor over the prepared catalysts at 450 or 500 °C. The effects of support nature, preparation method, catalyst composition and reaction temperature on the steam reforming activity and stability of catalysts were studied. Catalysts showing better performance in terms of reactant conversion and H2 yield were selected for investigating the steam reforming of an acetic acid/glycerol aqueous mixture, consisting of acetic acid and glycerol with a weight ratio of 3/7 similar to a bio-oil generated from fast pyrolysis of cellulose. The steam-to-carbon ratio (S/C) and the flow rate of feed were constant at 4 and 0.1 ml/min, respectively. The effluent gas was monitored by GC/TCD and the evolution of carbon conversion and product gas distribution as a function of time was studied. Among all catalysts investigated, the one with nominal composition A10C10N1Rnc showed the best performance in steam reforming at 500 °C as indicated by higher and more stable H2 yields achieved regardless the reactant used. In order to investigate the sorption-enhanced steam reforming, three CaO-based CO2 absorbents were synthesized: two derived from calcium acetate with or without MgO support, noted as CAM and CA, respectively, and the other MgO-supported one derived from calcium d-gluconate, denoted as CGM. Results from the 15-carbonation/regeneration-cycle test suggested that the MgO-containing absorbent CAM has the highest CaO molar conversion and stable CO2 absorption capacity. Though significantly higher CO2 absorption capacity was shown from absorbent CA in the first one cycle, CA absorbent soon lost most of the CO2 absorption capacity due to severe sintering. In addition, the CO2 absorption capacity of absorbent CGM might be underestimated due to insufficient carbonation time. The A10C10N1Rnc catalyst and the CAM absorbent were applied in the steam reforming of acetic acid/glycerol mixture at 500°C. However, no significant improvement can be observed in the presence of absorbent CAM