This work had the objective of determining both the kinetic parameters for the pyrolysis of oil shale and kerogen as well as using analytical techniques coupled with pyrolysis to shed light on the structure of a specific Green River oil shale. Because of the problems with linearized methods and disagreement among literature values and methods, a new method was developed tofit kinetic parameters to non linearized data. The method was demonstrated to determine the "correct" answer for mathematically generated data within a few percent error and was shown to have a lower sum squared error than the linearized methods. The curve-fitting methodology was then applied to pyrolysis kinetic data for kerogen and oil shale. Crushed samples were pyrolyzed at heating rates from 1 to 10 K/min and at pressures of 1 and 40 bar. The transient pyrolysis data were fit with a first-order model and a progressive Distributed Activation Energy Model (DAEM). An F-test was used to determine confidence regions and compare the kinetic parameters among the samples. The activation energies determined ranged from 173 to 226 kJ/mol, with most values around 200-220 kJ/mol. The kinetic coefficients determined for oil shale and the demineralized samples were statistically the same. Only small differences in kinetic coefficients were seen in the size-graded samples. The first-order and DAEM were shown to be statistically different, but a visual inspection of a graph of the model predictions and the data revealed that both models performed well. The largest effect on the kinetic parameters was between samples collected from different geographic allocations. The pyrolysis products (and the parent kerogen sample) were analyzed by several chemical techniques to determine chemical structure information about the parent sample. TheGC/MS data for the tars collected showed a distribution of alkenes/alkanes with 11 to 12 carbonsin length being the most frequent. XPS analysis demonstrated that any chemical model must have pyridinic and pyrrolic nitrogens as well as carbonyls and carboxyl groups. Therefore a chemical structure model of kerogen should have heteroatoms of nitrogen in the aromatic region(i.e., the portions of the kerogen that are stable at moderate temperatures).

Maturity of high-temperature polymer-reinforced composites defer to conventionally expensive and intensive methods in both material and manufacturing aspects. Even traditional carbon-carbon, aerogel, and ceramic approaches are highly limited by difficult manufacturing techniques and are subject to sensitive handling throughout their processing and lifetime. Despite their utility in extreme environments, the high costs of existing high-temperature composites find limited practical applicability under high-performance applications. The development of continuous fiber-reinforced pyrolysis-derived carbon-matrix composites aim to circumvent the issues surrounding the manufacturing and handling of conventional high-temperature composites. Polymer matrix composites (PMCs) have a number of attractive properties including light weight, high stiffness-to-weight and strength-to-weight ratios, ease of installation on the field, potential lower system-level cost, high overall durability and less susceptibility to environmental deterioration than conventional materials. However, since PMCs contain the polymer matrix, their applications are limited to lower temperatures. In this study, a pyrolysis approach was used to convert the matrix material of phenolic resin into carbon-matrix to improve the mechanical and thermal properties of the composites. Composite material consisting of basalt fiber and phenolic resin was pyrolyzed to produce basalt-carbon composites through a novel method in which the pyrolysis promoted in-situ carbon nanotube growth to form “fuzzy fibers”. The carbon phenolic composites were pyrolyzed to produce carbon-carbon composites. Several types of composites are examined and compared, including conventional phenolic and carbon-matrix composites. Through Raman spectroscopy and scanning electron microscopy, the composition of materials are verified before testing. Investigation into the improvements from in-situ carbon growth was conducted with an open-flame oxyacetylene test (ASTM-E285), to establish high-temperature thermal behavior, in addition to mechanical testing by three-point bending (ASTM-D790), to evaluate the mechanical and thermal properties of the pyrolyzed composites.

The fire debris analyst is often faced with the complex problem of identifying ignitable liquid residues in the presence of products produced from pyrolysis and incomplete combustion of common building and furnishing materials. The purpose of this research is to investigate a modified destructive distillation methodology provided by the Florida Bureau of Forensic Fire and Explosive Analysis to produce interfering product chromatographic patterns similar to those observed in fire debris case work. The volatile products generated during heating of substrate materials are extracted from the fire debris by passive headspace adsorption and subsequently analyzed by GC-MS. Low density polyethylene (LDPE) is utilized to optimize the modified destructive distillation method to produce the interfering products commonly seen in fire debris. The substrates examined in this research include flooring and construction materials along with a variety of materials commonly analyzed by fire debris analysts. These substrates are also burned in the presence of a variety of ignitable liquids. Comparisons of ignitable liquids, pyrolysis products, and products from pyrolysis in the presence of an ignitable liquid are performed by comparing the summed ion spectra from the GC-MS data. Pearson correlation was used to determine if substrates could be discriminated from one another. A pyrolysis products database and GC-MS database software based on comparison of summed ion spectra are shown to be useful tools for the evaluation of fire debris.

Due to its low cost and large availability lignocellulosic biomass is being studied worldwide as a feedstock for renewable liquid biofuels. Currently there are several routes being studied to convert solid biomass to a liquid fuel, which involve multiple steps at long residence times thus greatly increasing the cost of biomass processing. Catalytic fast pyrolysis (CFP) is a new promising technology to convert directly solid biomass to gasoline-range aromatics that fit into the current infrastructure. CFP involves the rapid heating of biomass (~500˚C sec-1) in an inert atmosphere to intermediate temperatures (400 to 600 ˚C) in the presence of zeolite catalysts. During CFP, biomass is converted in a single step to produce gasoline-range aromatics which are compatible with the gasoline of the current market. CFP has many advantages over other conversion processes including short residence times (2-10 s) and inexpensive catalysts. The major impediment to the further development of CFP is the lack of fundamental understanding of the underlying chemistry of the process. The first goal of this thesis is to study the underlying chemistry of the CFP process using model compounds in a small pyroprobe micro reactor. For this part of the study the homogeneous thermal decomposition routes of glucose were identified along with the key intermediates. Through isotopic labeling studies the heterogeneous C-C bond forming reactions were determined. Lastly, the relative rates of the homogeneous and heterogeneous reactions were estimated. Since CFP in the small pyroprobe reactor is not scalable the second part of the study focused on designing and building a bench scale fluidized bed reactor to demonstrate CFP on a larger scale. This fluidized bed reactor was used to optimize the CFP of pine wood with ZSM-5 catalyst. The effect of reaction conditions such as temperature and biomass space velocity on the aromatic yield and selectivity was determined. The long term stability of the catalyst was also studied.

There is a growing need to develop the processes to produce renewable fuels and chemicals due to the economical, political, and environmental concerns associated with the fossil fuels. One of the most promising methods for a small scale conversion of biomass into liquid fuels is fast pyrolysis. The liquid product obtained from the fast pyrolysis of biomass is called pyrolysis oil or bio-oil. It is a complex mixture of more than 300 compounds resulting from the depolymerization of biomass building blocks, cellulose; hemi-cellulose; and lignin. Bio-oils have low heating value, high moisture content, are acidic, contain solid char particles, are incompatible with existing petroleum based fuels, are thermally unstable, and degrade with time. They cannot be used directly in a diesel or a gasoline internal combustion engine. One of the challenges with the bio-oil is that it is unstable and can phase separate when stored for long. Its viscosity and molecular weight increases with time. It is important to identify the factors responsible for the bio-oil instability and to stabilize the bio-oil. The stability analysis of the bio-oil showed that the high molecular weight lignin oligomers in the bio-oil are mainly responsible for the instability of bio-oil. The viscosity increase in the bio-oil was due to two reasons: increase in the average molecular weight and increase in the concentration of high molecular weight oligomers. Char can be removed from the bio-oil by microfiltration using ceramic membranes with pore sizes less than 1 µm. Removal of char does not affect the bio-oil stability but is desired as char can cause difficulty in further processing of the bio-oil. Nanofiltration and low temperature hydrogenation were found to be the promising techniques to stabilize the bio-oil. Bio-oil must be catalytically converted into fuels and chemicals if it is to be used as a feedstock to make renewable fuels and chemicals. The water soluble fraction of bio-oil (WSBO) was found to contain C2 to C6 oxygenated hydrocarbons with various functionalities. In this study we showed that both hydrogen and alkanes can be produced with high yields from WSBO using aqueous phase processing. Hydrogen was produced by aqueous phase reforming over Pt/Al2O3 catalyst. Alkanes were produced by hydrodeoxygenation over Pt/SiO2-Al2O3. Both of these processes were preceded by a low temperature hydrogenation step over Ru/C catalyst. This step was critical to achieve high yields of hydrogen and alkanes. WSBO was also converted to gasoline-range alcohols and C2 to C6 diols with up to 46% carbon yield by a two-stage hydrogenation process over Ru/C catalyst (125 °C) followed by over Pt/C (250 °C) catalyst. Temperature and pressure can be used to tune the product selectivity. The hydroprocessing of bio-oil was followed by zeolite upgrading to produce C6 to C8 aromatic hydrocarbons and C2 to C4 olefins. Up to 70% carbon yield to aromatics and olefins was achieved from the hydrogenated aqueous fraction of bio-oil. The hydroprocessing steps prior to the zeolite upgrading increases the thermal stability of bio-oil as well as the intrinsic hydrogen content. Increasing the thermal stability of bio-oil results in reduced coke yields in zeolite upgrading, whereas, increasing the intrinsic hydrogen content results in more oxygen being removed from bio-oil as H2O than CO and CO2. This results in higher carbon yields to aromatic hydrocarbon and olefins. Integrating hydroprocessing with zeolite upgrading produces a narrow product spectrum and reduces the hydrogen requirement of the process as compared to processes solely based on hydrotreating. Increasing the yield of petrochemical products from biomass therefore requires hydrogen, thus cost of hydrogen dictates the maximum economic potential of the process.

Diminishing petroleum resources combined with concerns about global warming and dependence on fossil fuels are leading our society to search for renewable sources of energy. In this respect, lignocellulosic biomass has a tremendous potential as a renewable energy source, once we develop the economical processes converting biomass into useful fuels and chemicals. Catalytic fast pyrolysis (CFP) is a promising technology for production of gasoline range aromatics, including benzene, toluene, and xylenes (BTX), directly from raw solid biomass. In this single step process, solid biomass is fed into a catalytic reactor in which the biomass first thermally decomposes to form pyrolysis vapors. These pyrolysis vapors then enter the zeolite catalysts and are converted into the desired aromatics and olefins along with CO, CO2, H2O, and coke. The major challenge with the CFP process is controlling the complicated homogeneous and heterogeneous reaction chemistry. The focus of this thesis is to study the reaction chemistry, catalyst design, and process development for CFP to advance the CFP technology. To gain a fundamental understanding of the underlying chemistry of the process, we studied the reaction chemistry for CFP of glucose (i.e. biomass model compound). Glucose is thermally decomposed in a few seconds and produce dehydrated products, including anhydrosugars and furans. The dehydrated products then enter into the zeolite catalyst pore where they are converted into aromatics, CO, CO2, H2O and coke. The zeolite catalyzed step is far slower than the initial decomposition step (>2 min). Isotopic labeling studies revealed that the aromatics are formed from random hydrocarbon fragments composed of the dehydrated products. The major competing reaction to aromatic production is the formation of coke. The main coking reaction is the polymerization of the furan intermediates on the catalyst surface. CFP is a shape selective reaction where the product selectivity is related to the zeolite pore size and structure. The shape selectivity of the zeolite catalysts in the CFP of glucose was systematically studied with different zeolites. The aromatic yield is a function of the pore size and internal pore space of the zeolite catalyst. Medium pore zeolites with pore sizes in the range of 5.2 to 5.9 Å and moderate pore intersection size, such as ZSM-5 and ZSM-11 produced the highest aromatic yield and least amount of coke. The kinetic diameter estimation of the aromatic products and the reactants revealed that the majority of these molecules can fit inside the zeolite pores of the medium pore zeolites. The ZSM-5 catalyst, the best catalyst for aromatic production, was modified further to improve its catalytic performance. These modifications include: (1) adjusting the concentration of acid sites inside the zeolites catalyst; (2) incorporation of mesoporosity into the ZSM-5 framework to enhance its diffusion characteristics, and (3) addition of Ga to the ZSM-5. Mesoporous ZSM-5 showed high selectivity for heavier alkylated monoaromatics. Ga promoted ZSM-5 increased the aromatic yield over 40%. A process development unit was designed and built for continuous operation of the CFP process in a pilot scale. The effects of process variables such as temperature, biomass weight hourly space velocity, catalyst to biomass ratio, catalyst static bed height, and fluidization gas velocity were studied to optimize the reactor performance. It was demonstrated that CFP could produce liter quantities of aromatic products directly from solid biomass.

The physicochemical properties of pyrolysis oil have been shown to be dependent on feedstock composition. Accelerated aging tests were performed to understand the effects of feedstock, condensate fraction collected, and filtration on the stability of pyrolysis oil. In this study, pyrolysis oil properties critical for downstream upgrading were measured and compared for different feedstock weight ratios of pine clearwood and pine bark. Post-condensation filtration of pyrolysis oil was evaluated using both lab-scale and pilot plant-scale centrifugal filtration with several operational parameters evaluated. The pilot-plant centrifuge can be used as a three-phase separator [light liquid-heavy liquid-solids] or a two-phase clarifier [liquid-solid]. Since pyrolysis oil is an oil-water micro-emulsion, separation of the heavy and light liquid phases is difficult; therefore, emulsion destabilization studies were performed in concert with centrifugation. Physicochemical properties were monitored to determine the impact of the production and processing parameters on the oil properties critical to biofuel applications.

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