Doctor of Philosophy / Department of Biological & Agricultural Engineering / Donghai Wang / Cellulosic ethanol is a renewable source of energy. Lignocellulosic biomass is a complex material composed mainly of cellulose, hemicellulose, and lignin. Biomass pretreatment is a required step to make sugar polymers liable to hydrolysis. Mineral acids are commonly used for biomass pretreatment. Using acid catalysts that can be recovered and reused could make the process economically more attractive. The overall goal of this dissertation is the development of a recyclable nanocatalyst for the hydrolysis of biomass sugars. Cobalt iron oxide nanoparticles (CoFe[superscript]2O[subscript]4) were synthesized to provide a magnetic core that could be separated from reaction using a magnetic field and modified to carry acid functional groups. X-ray diffraction (XRD) confirmed the crystal structure was that of cobalt spinel ferrite. CoFe[superscript]2O[superscript]4 were covered with silica which served as linker for the acid functions. Silica-coated nanoparticles were functionalized with three different acid functions: perfluoropropyl-sulfonic acid, carboxylic acid, and propyl-sulfonic acid. Transmission electron microscope (TEM) images were analyzed to obtain particle size distributions of the nanoparticles. Total carbon, nitrogen, and sulfur were quantified using an elemental analyzer. Fourier transform infra-red spectra confirmed the presence of sulfonic and carboxylic acid functions and ion-exchange titrations accounted for the total amount of catalytic acid sites per nanoparticle mass. These nanoparticles were evaluated for their performance to hydrolyze the β-1,4 glycosidic bond of the cellobiose molecule. Propyl-sulfonic (PS) and perfluoropropyl-sulfonic (PFS) acid functionalized nanoparticles catalyzed the hydrolysis of cellobiose significantly better than the control. PS and PFS were also evaluated for their capacity to solubilize wheat straw hemicelluloses and performed better than the control. Although PFS nanoparticles were stronger acid catalysts, the acid functions leached out of the nanoparticle during the catalytic reactions. PS nanoparticles were further evaluated for the pretreatment of corn stover in order to increase digestibility of the biomass. The pretreatment was carried out at three different catalyst load and temperature levels. At 180°C, the total glucose yield was linearly correlated to the catalyst load. A maximum glucose yield of 90% and 58% of the hemicellulose sugars were obtained at this temperature.

Vibrational and thermal behavior of several important systems were studied. The first study was a measurement of the infrared vibrational spectra of glucose and two important glucose dimers (cellobiose and maltose) as a function of temperature. The purpose of his study was to measure shifts in vibrational band positions to gain insight into carbohydrate reactivity. The second study was on hydrothermally treated coffee waste biomass. Here, collaborators at University of Campinas (UNICAMP, Brazil) treated coffee waste biomass in a flow-through subcritical water hydrolysis reactor. The purpose of the M.S. study on coffee waste was to understand the chemical changes that occurred to the residual solids during hydrolysis treatment. Vibrational spectroscopy and thermal analysis techniques were used. The third and final study was to understand the chemical composition of the solid product resulting from co-solvent enhanced lignin fractionation (CELF) of several biomass feeds. Collaborators at University of California Riverside (UCR) recently developed the CELF process. The purpose of the M.S. study on the CELF solid product was to understand its composition to help guide the CELF reactor design and determine applications for the CELF solids. Taken together, the 3 studies are integrated into a cohesive whole that demonstrates the use of spectroscopic and thermal techniques for characterizing biomass and understanding its composition at the molecular level.

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Although much emphasis has been given to the analysis of continuous forest conversion in tropical regions, our understanding in detecting, mapping and interpreting the spatial pattern of woodland deforestation and degradation is still limited. This thesis focuses on two factors contributing to this limitation: uncertainties in retrieving woodland change from remote sensing imagery, and the complex processes that may cause woodland deforestation and degradation. Firstly, I investigate approaches to minimising uncertainty in ALOS PALSAR-derived biomass maps by modifying a widely used processing chain, with the aim of provide recommendations for producing radar-based biomass maps with reduced uncertainty. Secondly, to further improve the retrieval of woody biomass from ALOS PALSAR imagery, the semi-empirical Water Cloud Model (WCM) is introduced to account for backscattering from soil. In wooded areas with low canopy (such as the miombo woodland which dominates the study area) the effect from soil moisture on the received backscattered signal is critical. Thirdly, based on the biomass maps retrieved from the refined radar-remote-sensing-based methodology discussed above, the influence of driving variables of the woodland deforestation and degradation, and how they alter the spatial patterns of these two processes, are analysed. The threshold for defining woodland deforestation and degradation in terms of biomass loss intensity is generated through integration of radar-based biomass loss maps, an optical forest cover change map and fieldwork investigation. Multi-linear model simulations of the spatial variation of deforestation and degradation events were constructed at a district and 1 km resolution respectively to rank the relative importance of driving variables. Results suggest that biomass-backscatter relationships based on plots of approximately 1 ha, and processed with high resolution DEMs, are needed for low uncertainty biomass maps using ALOS PALSAR data. Although plots sizes of 0.1 - 0.5 ha lead to large uncertainties, aggregating 0.1 ha plots into larger calibration sites shows some promise even in hilly terrain, potentially opening up the use of common forest inventory data to calibrate remote-sensing-based biomass retrieval models. Such relationships appear to hold across the miombo woodland ecoregion, which implies that there is a consistent relationship at least in the miombo woodland. From this I infer that random error, different processing methods and fitting techniques, and data from small plots are the source of the differences in the savanna biomass-backscatter relationships seen in the literature. The interpreted WCM presented in this study for L-band backscatter at HV polarisation improves biomass retrieval for areas with a biomass value less than 15 tC/ha (or 0.025 m2/m2 in backscatter). Use of the WCM also results in better quality regional biomass mosaics. This is because the WCM helped to improve the correlation of biomass estimation for overlay areas by reducing bias between adjacent paths, especially the bias introduced by changes in soil moisture conditions between different acquisition dates for different paths. Result shows that active and combined soil moisture datasets (from the Climate Change Initiative Soil Moisture Dataset) can be used as effective soil moisture proxies in the WCM for biomass retrieval. This quantitative analysis on the driving variables of woodland deforestation and degradation suggests that large uncertainty exists in modelling the occurrence of deforestation and degradation, especially at a 1 km scale. The spatial patterns of woodland deforestation and degradation differ in terms of shape, size, intensity, and location. Agriculture-related driving variables account for most of the explained variance in deforestation, whereas for degradation, distance to settlements also plays an important role. Deforestation happens regardless of the original biomass levels, while degradation is likely to happen at high biomass areas. The sizes of degradation events are significantly smaller than those of deforestation events, with 90% of deforestation events sharing boundaries with degradation events. This thesis concludes by outlining the importance and difficulties in integrating 'distal' (underlying) drivers in modelling the spatial dynamics of deforestation and degradation. Further work on the causal connection between deforestation and degradation is also needed. The processing chain and biomass retrieval models presented in this study could be used to support monitoring and analysis of biomass change elsewhere in the tropics, and should be compatible with data derived from ALOS-2 and the future SAOCOM and BIOMASS satellite missions.

Biochar has often been described as a "win-win" technology for soil fertility, agronomic yields, carbon sequestration and poverty reduction. However, despite a growing body of physical research evidence to support these claims, there is much less socio-economic evidence for biochar's potential to achieve these "winwin" outcomes in real-world systems. Consequently, debates about biochar and its potential to contribute to sustainable development have often been polarised between extremes of opinion, with some claiming it is a key technology for mitigating climate change, and others warning of potentially dire effects for ecosystems and vulnerable populations. This inspired the objective for this PhD, which is to generate research that can inform and moderate the debate on biochar's win-win potential. Guided by the theory of ecological modernisation, this PhD aimed to generate a body of applied, policy-relevant research on the economic and environmental potential of biochar as a win-win use of biomass resources. It was important to adopt geographical and biomass boundaries for the research to provide a meaningful and focused contribution, therefore the research is focused on China and its agricultural straw residues. One of the central claims for biochar is that it can improve crop yields and, consequently, reduce poverty for smallholder farmers. This thesis investigated this from a socio-economic perspective using farm-scale linear programming models with primary data from interviews conducted across four contrasting Chinese agricultural systems. The results suggest that biochar is unlikely to provide even minor economic gains, let alone poverty-reducing change, to smallholder farmers in these systems. If biochar is not economic for farmers, there is a possibility that economies of scale made possible by business ventures could reduce the marginal costs per unit of biochar product and/or that governments/climate finance institutions may be interested in subsidising this technology where it has significant carbon mitigation impacts. Thus the next research question was whether biochar might be a profitable investment for businesses in China, and further whether businesses might also profit from carbon credits/subsidies where biochar's carbon sequestration potential is valued either by carbon markets or by climate conscious governments willing to provide appropriate incentives. Life-cycle and cost-benefit analyses demonstrated that, when compared to the main competing uses for straw feedstocks (briquetting for combustion in boilers, and gasification for electricity generation), pyrolysis of straw to produce biochar makes a financial loss under all subsidy scenarios considered, and is the least cost-effective technology for carbon sequestration. Overall it seems biochar made from China's straw feedstocks is not currently a win-win option for smallholder farmers, business investors or national/international climate mitigation strategies. In light of the relative dominance of bioenergy over biochar production as a financial and climate mitigating option for China's straw, the focus of the thesis shifts to explore win-win scenarios in this domain. Here the results are more promising. Combining a unique geographical dataset of China's coal fired powerstations and straw location with data on energy economics, the model suggests a small tweak to China's bioenergy subsidy system (an extension of the existing feed-in-tariff to include low energy replacement ratio cofiring) could contribute 42-62% of China's 2020 target to install 30GW of renewable energy generation capacity: a classic win-win scenario for the Chinese government's bioenergy targets, bioenergy investors and global climate change. Overall this thesis offers two main findings to the literature. Firstly it demonstrates that, within its current high application rate model, biochar will struggle to compete as a win-win strategy when viewed through financial and carbon sequestration lenses. However, secondly, it suggests that win-win strategies are available for China's straw resources under cofiring bioenergy applications. The thesis concludes with a critical discussion of these results in relation to the theory of ecological modernisation and the concept of win-wins.

Gasification is a process that converts organics or fossil fuel based material into syngas at high temperature under controlled amount of air. Gasification thus increases the practicality of using biomass as a renewable source of energy. The goal of this paper is to explore corn kernel gasification at the University of Iowa Oakdale pilot scale gasifier. The results of this paper consists of three parts; the temperature profile in the gasifier, gas analysis at 950F and 1050F, and bio char analysis. The temperature profile within the gasifier was obtained and studied; different temperature gasification zones were identified. Sample gases at 950F and 1050F were obtained and analyzed. It was seen that the syngas production (in volume) at 1050 F was 12.2% greater than that of 950F. A 37.4%, 27.1% and 38.3% increase in composition of H, CO and CH4 respectively was also observed. Ultimate analysis, proximate analysis, SEM and BET tests were carried on the corn bio char produced. From the ultimate and proximate analysis, it was observed that corn bio char was similar to activated carbon. Oakdale bio-char was compared with other processed powder bio char. It was observed that char produced from the Oakdale gasifier was more porous than powder bio-char, possibly making it a better soil amendment.

Computational modeling was completed on a simplified downdraft gasifier to be implemented at the University of Iowa Oakdale Power Plant. The model was created in Gambit and exported to FLUENT, a computational fluid dynamics software program, in order to process non-premixed combustion on biomass fuels and better understand the combustion and gasification zones. The fuels were modeled as coal particles with the empirical formula of the biomass found from off-site proximate and ultimate analyses. The coal model inherent to FLUENT contains the same chemicals (C, H, N, O, and S) as the biomass tested, so this model was determined to be accurate. The model was tested for varying packing densities, oxidizer inlet velocities and fuel type to describe the effects on the combustion zone. It was concluded that packing densities around 0.5 with oxidizer inlet velocities less than 5 m/s would be ideal for modeling wood. The temperature distribution was the most even in this environment and produced a large rich fuel combustion (RFC) zone where gasification and pyrolysis could occur. The different fuels were found to have similar temperature and mean mixture fraction patterns, although the maximum temperatures attained were very different (1080K for seed corn and 678K for wood), the wood showed a greater area of RFC for gasification and pyrolysis.

This thesis examines the effects of species, rainfall and soil type on tree biomass regressions, as well as the effects of stand dominance and structure on stand biomass regressions in north-east Australian woodlands. This was achieved by examining tree characteristics and biomass relationships for a series of woodland monitoring sites throughout the study area. This study utilised a modified data set from this permanent monitoring site network to provide structural attributes for trees and communities of varying composition in the grazed woodlands. These data were supplemented with environmental data and tree harvest data sets. Initially, the research reported in this thesis developed allometric and stand biomass regressions for Callitris glaucophylla communities. This research also demonstrated that changes in tree-form were not reflected in changes in the environment, nor did such changes reflect changes in tree biomass regressions for three eucalypt species. As a result, a common regression provides a robust estimate of total aboveground biomass of eucalypt trees in the study area. Thus expensive destructive harvesting can generally be avoided for minor eucalypt species. Finally, this study demonstrated a successful methodology that described the stand structure of all the grazed woodland sites based on tree heights. This methodology was developed to allow the expansion of a single stand regression to estimate stand biomass across the entire north-east Australian woodlands. The findings demonstrated in this study, combined with the long-term data from the permanent monitoring network sites, should enhance the estimation of carbon flux within eucalypt communities of north-east Australia’s grazed woodlands.

Oxides of nitrogen from coal-fired power stations are considered to be major pollutants, and there is increasing concern for regulating air quality and offsetting the emissions generated from the use of energy. Reburning is an in-furnace, combustion control technology for NOx reduction. Another environmental issue that needs to be addressed is the rapidly growing feedlot industry in the United States. The production of biomass from one or more animal species is in excess of what can safely be applied to farmland in accordance with nutrient management plans and stockpiled waste poses economic and environmental liabilities. In the present study, the feasibility of using biomass as a reburn fuel in existing coal-fired power plants is considered. It is expected to utilize biomass as a low-cost, substitute fuel and an agent to control emission. The successful development of this technology will create environment-friendly, low cost fuel source for the power industry, provide means for an alternate method of disposal of biomass, and generate a possible revenue source for feedlot operators. In the present study, the effect of coal, cattle manure or feedlot biomass, and blends of biomass with coal on the ability to reduce NOx were investigated in the Texas A&M University 29.31 kW (100,000 Btu/h) reburning facility. The facility used a mixture of propane and ammonia to generate the 600 ppm NOx in the primary zone. The reburn fuel was injected using air. The stoichiometry tested were 1.00 to 1.20 in the reburn zone. Two types of injectors, circular jet and fan spray injectors, which produce different types of mixing within the reburn zone, were studied to find their effect on NOx emissions reduction. The flat spray injector performed better in all cases. With the injection of biomass as reburn fuel with circular jet injector the maximum NOx reduction was 29.9 % and with flat spray injector was 62.2 %. The mixing time was estimated in model set up as 936 and 407 ms. The maximum NOx reduction observed with coal was 14.4 % and with biomass it was 62.2 % and the reduction with blends lay between that of coal and biomass.

Experimental and kinetic modeling studies were carried out on the conversion a wood-oil obtained from high pressure liquefaction of aspen poplar wood to liquid hydrocarbon fuels and useful chemicals in a fixed bed micro-reactor using HZSM-5 catalyst. Similar experiments were conducted using silicalite, H-mordenite, H-Y and amorphous silica-alumina catalysts. <p> Preliminary vacuum distillation studies showed that the wood-oil was made up of volatile and non-volatile fractions. A maximum yield of 62 wt% volatiles at 200 °C, 172 Pa was obtained. The volatile fraction consisted of over 80 compounds. These compounds were comprised of acids, alcohols, aldehydes, ketones, esters, ethers, furans, phenols and some hydrocarbons. The characteristics of the oil showed that it was unstable with time, i.e., its physical properties and chemical composition changed with time probably due to the reaction of free radicals or the oxidative coupling of some of the wood-oil components. However, when the oil was mixed with tetralin, the stability improved. <p> Upgrading studies were first conducted over inert berl saddles in the presence and absence of steam (i. e. non-catalytic treatment/blank runs). Yields of hydrocarbons were between 16 and 25 wt% of the wood-oil. High residue fractions of between 32 to 56 wt% were obtained after processing. Some portions of wood-oil formed a carbonaceous material (char or coke) when exposed to the experimental temperatures. The chars (coke) fraction increased with temperature from 4.7 to 12.5 wt% when processing with steam and 8.0 to 20.4 wt% when processing without steam. <p> Catalytic upgrading studies were first carried out using HZSM-5 catalyst in the presence and absence of steam. The results showed that approximately 40 to 65 wt% of the oil could be converted to a hydrocarbon-rich product (i.e. desired organic liquid product (distillate). This contained about 45 to 70 wt% hydrocarbons with selectivities ranging between 0.47 to 0.88. This fraction was highly aromatic in nature and consisted mainly of benzene, toluene, xylene (BTX compounds) and other alkylated benzenes within the gasoline boiling point range. The yield and selectivities were strong functions of the process time and temperature. A comparison between the two processes, i.e. upgrading in the presence and absence of steam, showed that about 30 to 45 % reduction in coke formation and 5 to 18 wt% increase in organic distillate could be achieved when processing in the presence of steam. These changes were probably due to changes in the rates of cracking, deoxygenation, aromatization and polymerization reactions resulting from the competitive adsorption processes between steam and wood-oil molecules in addition to changes in contact time of molecules. However, the selectivity for hyqrocarbons decreased in the presence of steam. <p> Yields of organic distillate fractions of between 72 to 93 wt% and hydrocarbon yields and selectivities of 44 to 51 wt% and 0.93 to 1.13, respectively, were obtained when wood-oil volatile fraction was upgraded over HZSM-5 after separation from the non-volatile fraction by vacuum distillation. <p> The spent HZSM-5 catalyst could be easily regenerated and reused with little change in its performance. <p> The yields and selectivities for hydrocarbons when upgrading with the other catalysts were between 9 and 22 wt%, and 0.12 and 0.29, respectively for silicalite, 16 and 28 wt%, and 0.22 and 0.28, respectively for H-mordenite, 15.5 and 21 wt%, and 0.17 and 0.21, respectively for H-Y and S.5 and 26.2, and 0.13 and 0.36, resrectively for silica-alumina. Compared to HZSM-5 (yield between 34 and 43 wt%, selectivity of 0.66 to O.SS) these yields and selectivities were much lower. These experiments also showed that the pore size, acidity and shape selectivity of the catalyst influenced the distribution of hydrocarbons in terms of the carbon number. The yield and selectivity of H-mordenite and H-Y (large pore zeolites) were mostly for kerosene range hydrocarbons (C_{<font size=2>9</font>} to C_{<font size=2>15</font>}) and for silicalite and HZSM-5 (medium pore zeolites) for gasoline range hydrocarbons. The hydrocarbon fraction from amorphous silica-alumina did not show any defined distribution. The performance followed the order: HZSM-5> H-mordenite> H-Y> Silicalite, Silica-alumina.<p> With the aid of model compound reactions involving acetic acid methyl ester, propanoic acid, 4-methylcyclohexanol, methylcyclopentanone, 2-methylcyclopentanone, methoxybenzene, ethoxybenzene, phenol, 2-methoxy-4-(2-propenyl) phenol, a synthetic and wood-oil volatile, two reaction pathways were proposed to explain the chemical steps through which the final products of upgrading were obtained. Also, reaction pathways were proposed for each chemical group. These experiments showed that the final products were formed probably through cracking, deoxygenation, olefin formation, oligomerization, hydrogen and hydride transfer, cyclization, isomerization, alkylation and polymerization reactions. <p> Rate models were derived based upon the two reaction pathways and the power law rate model. The rates of formation of products followed the general order: Organic distillate> Hydrocarbons> Residue> Coke> Gas >Aqueous Fraction. Estimates of the values of the kinetic parameters showed that the rate constants ranged between 10^{<font size=2>-6</font>} (aqueous fraction) and 1.81 (volatile fraction), activation energies between 6.7-76.0 x 10^{<font size=2> 3</font>} KJ/Kmol and reaction orders from 0.7 (gas formation) to 2.5 (residue formation). Two mathematical models were derived based on the integral reactor design equation and on the two reaction pathways. This was used to estimate the yield of products. The models predicted the experimental results fairly accurately. Model discrimination showed that the model based on coke and residue formation from both volatile and non­-volatile fractions of the wood-oil best predicted the experimental results.<p> Hydrocarbon selectivity relations which were based on coke, residue and combined coke and residue as undesired products were also derived. Application of these relations showed that lower temperatures and concentrations were most appropriate for higher hydrocarbon selectivity. However, this was at the expense of higher conversions.