En el campo de la cinética de la pirólisis de biomasa se han desarrollado numerosos trabajos de investigación que no acaban de resolver aspectos básicos del proceso. El análisis de resultados termogravimétricos aún requiere el establecimiento de modelos y estrategias de evaluación más apropiadas para los diferentes tipos de biomasa. Esta tesis trata todos estos aspectos desde el punto de vista de la investigación fundamental. Se estudia el comportamiento térmico de biomasas representativas de los residuos de carpintería (madera de pino y haya) y de un cultivo energético (cardo borriquero) por medio de diferentes técnicas termoanalíticas, en el régimen de pirólisis lenta (slow pyrolysis), incluyendo varios pretratamientos de la biomasa para eliminar materia inorgánica y componente extractivo. La primera contribución de esta tesis corresponde a un estudio exhaustivo del efecto de los errores sistemáticos asociados a la experimentación en termogravimetría. El comportamiento térmico de un mismo material es observado en diferentes termobalanzas, bajo condiciones que se consideran equivalentes entre diferentes equipos, y los resultados son analizados estadísticamente. Consecutivamente, para la descripción de la pérdida global de masa, se estudian diferentes aproximaciones cinéticas basadas en reacciones parciales de primer y otros órdenes, por el modelo de pseudocomponentes. Se trata de determinar un conjunto común de parámetros cinéticos que describan satisfactoriamente experimentos provenientes de diversas termobalanzas y bajo diferentes regímenes de calentamiento: lineal y en escalera (aplicación sucesiva de rampas y periodos isotérmicos de calentamiento). Un conjunto común de energías de activación, resultado de la evaluación cinética de muestras pretratadas (lavadas con agua a 80 ºC), es aplicado en la descripción cinética de todos los tipos de experimentos llevados a cabo a lo largo de la tesis.Espectrometría de masas, acoplada simultáneamente a la termogravimetría, es la técnica empleada para el análisis de los productos volátiles. Se aplica una herramienta estadística para analizar la influencia de la composición de las muestras en la descomposición térmica global y en la distribución de productos. Por medio de datos de calibración se estima la producción individual de los principales productos volátiles de la pirólisis. Consecutivamente, se incluye una aproximación de la evolución de dichos productos en el modelo cinético global.El estudio de las reacciones secundarias de pirólisis ha sido también parte importante en esta tesis. A través de la calorimetría diferencial se estudia el calor de reacción de la descomposición primaria y secundaria. Adicionalmente, se analizan los resultados provenientes de un estudio de espectroscopía infrarroja acoplada a termogravimetría, con el objeto de investigar la descomposición secundaria mediante la observación de los perfiles de evolución de los productos volátiles. Finalmente, se prueba y optimiza el desempeño del modelo cinético global para describir la descomposición térmica de muestras bajo condiciones que claramente favorecen la descomposición secundaria.En conjunto, este trabajo de investigación representa un estudio termocinético exhaustivo y profundo de la pirólisis de biomasa. La descomposición térmica se aborda a través de la observación de la interconexión entre los diferentes fenómenos químicos que conforman el proceso. La propuesta de aproximación cinética, que se constituye a lo largo de la tesis, contribuye al entendimiento del proceso como un todo. Puede ser también considerada como un primer paso hacia la aplicación de los modelos cinéticos de pirólisis a otros estudios, requiriéndose la incorporación adicional de fenómenos de transporte y otras consideraciones para su posterior aplicación. / The abundant research literature on the field of biomass pyrolysis kinetics still leaves key issues unsolved. The exploitation of the information provided by thermogravimetry requires the establishing of appropriate models and evaluation strategies for the various biomass materials. The kinetic description of experiments measured at different conditions by exactly the same reaction kinetics is criticized due to some small, but inevitable systematic errors that depend on the experimental conditions. Practical models that predict the evolution of specific products of interest are still expected in the literature. Part of the chemical phenomena referred to the secondary interactions between the primary pyrolysis products has been traditionally avoided when modeling the pyrolytic process. The increased exploitation of herbaceous crops, in addition to the large quantity of woody residues that still remains largely unused, currently ask for a better description of the influence of the heterogeneities on biomass thermolysis.This thesis addresses all these issues in the context of fundamental research. The thermal behavior of biomass materials representative of carpentry residues (pine and beech), and an energy plantation (thistle) is studied by different thermoanalytical techniques, within the range of slow pyrolysis, including various pretreatments to eliminate inorganic matter and extractives. The first contribution aims at deeply observing the extent of systematic errors associated to the experimental part of the thermogravimetric studies. The thermal behavior of the same feedstock in different original equipments, under roughly equivalent experimental conditions, is statistically studied. Then, various approaches based on first and nth-order partial reactions in the summative model of pseudocomponents are employed in order to determine the best kinetic parameters that describe the experiments both at linear and stepwise heating programs and for experiments coming from different sources. A common set of activation energies, coming from the evaluation of water-washed samples, is applied for the kinetic description of all the types of experiments performed along this thesis.Mass spectrometry, simultaneously coupled to thermogravimetry, is used as the volatile product analysis technique. A chemometric tool is applied to help in elucidating the specific influence of the macromolecular composition of the samples on the thermal decomposition and on the product distribution. Making use of calibration data, we estimate the individual production of the major volatile species from slow pyrolysis. Then, an approximation of the vapor-phase product distribution is added to the kinetic mechanism.We are also interested in the study of the secondary biomass pyrolysis. Differential scanning calorimetry is the technique used to observe the information traced by the heat of pyrolysis on the primary and secondary decomposition. Additionally, we analyze results from a Fourier transform infrared spectroscopy device coupled with thermogravimetry, in order to assess the secondary phenomena by considering the evolution profiles of the volatile products, as well. Finally, we test the ability of the best kinetic approach, from the previous kinetic analysis, to describe the global mass loss under conditions that clearly favor secondary vapor-solid interactions.Overall, this research work represents a comprehensive and thorough thermokinetic study of biomass pyrolysis that approaches the thermal behavior by recognizing the connections between different chemical phenomena making up the pyrolytic process. The kinetic proposal, finally built up in this thesis, is a contribution for understanding the process as a whole. Additionally, it can be considered as a first step toward its extension to practical applications, where additional chemical and transport phenomena need to be incorporated.

An extensive study of intrinsic and extrinsic factors on biomass pyrolysis reactions is needed if valuable hydrocarbon gases are to be produced from pyrolysis of biomass. In the first phase of this study a spent coffee waste material was pyrolysed in a stainless steel batch reactor at 500 to 900°C with both N₂ and H₂ carrier gases. The use of H₂ gas did not affect the product distribution. Yields of pyrolysis gas products reached 61 and 74 wt% of the feed at 900°C for N₂ and H₂ carrier gases. Corresponding mass balance closures were obtained at 86 and 98 wt% of the feed. Catalytic effect of the stainless steel wall was confirmed. Maximum conversion of CO was found at pyrolysis zone temperature of 700°C. Pyrolysis experiments with spent coffee performed in a quartz (inert) batch reactor proved that the carrier gas had negligible influence on the primary pyrolysis product distribution. Pyrolysis with K₂CO₃ at 650, 700, and 800°C, showed catalysis of cracking reactions of pyrolysis tars and the water-gas shift reaction. Copyrolysis of biomass materials and coals were performed in the quartz reactor with the objective of producing a higher hydrocarbon content gas product. Copyrolysis of spent coffee and lignite coal at 800°C in a hydrogen atmosphere resulted in gas production of more than 45 wt% of the feed, compared with only 27 wt% for pure coal sample. Increases in production of CH₄ and C₂H₄ were 15.9 wt% and 21.3 Wt%. For copyrolysis with sub-bituminous coal, these synergistic increases were 36.5 wt% and 23.9 wt%. In the final phase of this research, a fluidized bed reactor was used to study hydropyrolysis of cellulose, spent coffee, aspen-poplar, bagasse and lignite coal in presence of sand (inert medium), ã-alumina catalyst, Engelhard US-260 (a silica alumina catalyst), 10 wt% nickel-ã-alumina, 10 wt% cobalt-ã-alumina and a 40 wt% nickel-refractory support catalyst. Over the temperature range of 500 to 600°C, the 10 wt% nickel catalyst was most effective in conversion of biomass. Overall it was found that the combination of cellulose with 10 wt% Ni catalyst at 550°C was the optimum catalyst-feed system for conversion of carbon content of biomass to methane. In this case the yield of CH₄ was 46.7 wt% of cellulose. Rate constants for (primary) pyrolysis, (secondary) tar-cracking and (tertiary) hydrogenation reactions at 550°C were determined. Rate constants for the above mentioned reactions were estimated to be k₁=2.88 s^-1 (pyrolysis model), k₁=2.88 and k₂=1.31 s^-1 (pyrolysis-cracking model), and k₁=2.88, k₂=13.1 and k₃=12.96 s^-1 (pyrolysis-cracking-hydrogenation model).

Glycerol is a waste by-product obtained during the production of biodiesel. Biodiesel is one of the alternative fuels used to meet our energy requirements and also carbon dioxide emission is much lesser when compared to regular diesel fuel. Biodiesel and glycerol are produced from the transesterification of vegetable oils and fats with alcohol in the presence of a catalyst. About 10 wt% of vegetable oil is converted into glycerol during the transesterification process. An increase in biodiesel production would decrease the world market price of glycerol. The objective of this work is to produce value added products such as hydrogen or syn gas and medium heating value gas from waste glycerol using pyrolysis and steam gasification processes. <p> Pyrolysis and steam gasification of glycerol reactions was carried out in an Inconel®, tubular, fixed bed down-flow reactor at atmospheric pressure. The effects of carrier gas flow rate (30mL/min-70mL/min), temperature (650oC-800oC) and different particle diameter of different packing material (quartz - 0.21-0.35mm to 3-4mm; silicon carbide 0.15 to 1mm; Ottawa sand 0.21-0.35mm to 1.0-1.15mm) on the product yield, product gas volume, composition and calorific value were studied for the pyrolysis reactions. An increase in carrier gas flow rate did not have a significant effect on syn gas production at 800oC with quartz chips diameter of 3-4mm. However, total gas yield increased from 65 to 72wt% and liquid yield decreased from 30.7 to 19.3wt% when carrier gas flow rate decreased from 70 to 30mL/min. An increase in reaction temperature, increased the gas product yield from 27.5 to 68wt% and hydrogen yield from 17 to 48.6mol%. Also, syn gas production increased from 70 to 93 mol%. A change in particle size of the packing material had a significant increase in the gas yield and hydrogen gas composition. Therefore, pyrolysis reaction at 800oC, 50mL/min of nitrogen and quartz particle diameter of 0.21-0.35mm were optimum reaction parameter values that maximise the gas product yield (71wt%), hydrogen yield (55.4mol%), syn gas yield (93mol%) and volume of product gas (1.32L/g of glycerol). The net energy recovered at this condition was 111.18 kJ/mol of glycerol fed. However, the maximum heating value of product gas (21.35 MJ/m3) was obtained at 650oC, 50mL/min of nitrogen and with a quartz packing with particle diameter of 3-4mm. <p>The steam gasification of glycerol was carried out at 800oC, with two different packing materials (0.21-0.35mm diameter of quartz and 0.15mm of silicon carbide) by changing the steam to glycerol weight ratio from 0:100 to 50:50. The addition of steam to glycerol increased the hydrogen yield from 55.4 to 64mol% and volume of the product gas from 1.32L/g for pyrolysis to 1.71L/g of glycerol. When a steam to glycerol weight ratio of 50:50 used for the gasification reaction, the glycerol was completely converted to gas and char. Optimum conditions to maximize the volume of the product gas (1.71L/g), gas yield of 94wt% and hydrogen yield of 58mol% were 800oC, 0.21-0.35mm diameter of quartz as a packing material and steam to glycerol weight ratio of 50:50. Syn gas yield and calorific value of the product gas at this condition was 92mol% and 13.5MJ/m3, respectively. The net energy recovered at this condition was 117.19 kJ/mol of glycerol fed. <p>The steam gasification of crude glycerol was carried out at 800oC, quartz size of 0.21-0.35mm as a packing material over the range of steam to crude glycerol weight ratio from 7.5:92.5 to 50:50. Gasification reaction with steam to glycerol weight ratio of 50:50 was the optimum condition to produce high yield of product gas (91.1wt%), volume of gas (1.57L/g of glycerol and methanol), hydrogen (59.1mol%) and syn gas (79.1mol%). However, the calorific value of the product gas did not change significantly by increasing the steam to glycerol weight ratio.

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3-(o-(Methylthio)phenyl)-1-phenylprop-2-en-1-one (48) ¡B1-(o-(methylthio)-phenyl)-3-phenylprop-2-en-1-one (49) and 1-(o-(methylthio)phenyl)-3-phenylprop-2-yn-1-one (50) had been studied by means of pyrolysis and photolysis. Under pyrolytic conditions, compound 48 gave phenanthrene (2) as the major product. Both compounds 49 and 50 gave thioflavone (53) as the major product. Under photolytic conditions, compounds 48-50 gave the expected products 2-benzoylbenzo[b]thiophene (51)¡B 2-benzylidenebenzo[b]thiophen-3-one (52) and thioflavone (53), respectively.

1-(o-(Dimethylamino)phenyl)-3-phenylprop-2-en-1-one (62), 3-(o-(dimethylamino)phenyl)-1-phenylpropenone (63) and 1-(o-(dimethyl- amino)phenyl)-3-phenylprop-2-yn-1-one (64) were synthesized and their pyrolytic and photolytic chemistry were studied. Flash vacuum pyrolysis (FVP) of 62 and 64 gave 11H-benzo[a]carbazole (72) and benzo[c]carba-zole (73), FVP of 63 gave phenanthrene (2) and 1-methylquinolin-2(1H)-one (84). Under photolytic conditions, 62 and 64 gave the expected photocyclic products 1-methyl-2-phenylquinolin-4-one (65), while 63 gave the expected photocyclic products (1-methyl-1H-indol-2-yl)phenyl-methanone (66).

1. Generation of nitrenes by means of photolysis of arylmethylazides and its derivatives have been studies. Pyrolysis of 2-azidomethylthiophene¡]44a¡^ gave 2-thiophenecarboxaldehyde¡]77a¡^and (2-thienylmethylidene)-2-thienylamine¡]45a¡^, and pyrolysis of 2-azidomethylbenzo[b]thiophene¡]44b¡^gave the corresponding products. Pyrolysis of 2-azido-1-(2-thienyl)ethanone¡]52a¡^gave 2-thiophenecarboxaldehyde¡]77a¡^, 2-acetylthiophene¡]80a¡^and 2-(thiophene-2-carbonyl)amino-1-(2-thienyl)ethanone¡]83a¡^, and pyrolysis of 2-azido-1-(2-benzo[b]thienyl)ethanone¡]52b¡^gave the corresponding products. 2. Pyrolysis of 3-cyclohexeno[b]furylmethyl benzoate¡]35¡^gave cyclohexeno-4-methylenecyclobuten-3-one¡]25¡^via highly reactive carbene intermediate. At high temperature, compound 25 can continue the reaction of elimination and ring opening to give benzene¡]43¡^, fulvene¡]46¡^, 2-ethylnylcyclohex-1-ene carbaldehyde¡]44¡^ and 4,5-dimethylenecyclopent-2-enone¡]45¡^.

¤@. Photolysis of 2-azido-1-(2- pyridyl)ethanone (68),2-azido-1-(3-pyridyl)ethanone) (69),2-azido-1-(1-methyl-2-pyrryl)ethanone (53) and 2-azido-1-(1-methyl-3-indo yl)ethanone gave Norrish products (71, 7 3-76), (84-86, 89), (92-94) and (93, 95-98). ¤G. Pyrolysis of 2-(azidomethyl)pyridine (9) and 4-(azidomethyl)pyr idine (10) gave the expected products 1,3,5-tri-2-pyridyl-2,4-diaza-1,4-pentadiene (13) and 1,3,5-tri-4-pyridyl-2,4-diaza-1,4-pentadiene (21). ¤T. Pyrolysis of 2-cyclohexeno[b]furylmethyl benzoate (31) gave 2-methylbenzo[b]- furan (40) and benzene products.

¤@¡BPyrolysis of 2-azido-1-(4-methoxyphenyl)ethanone (69) and 2-(2-azidoethyl)furan (85) gave nitrene intermediate to study. There is 2-(4-methoxybenzoyl)-4-(4- methoxyphenyl)imidazole (81) ¡B2-(4-methoxybenzoyl)-5-(4-methoxyphenyl) imidazole] (81¡¦)¡B2,3-di(4-methoxybenzoyl)-5-(4-methoxyphenyl) pyrazine] (82) and 3,5-di(2-furyl) pyridine (92) for pyrolysis products. ¤G¡BPyrolysis of3-methyl-2-cyclohexen[b] furylmethyl benzoate) (50) gave carbene intermediate to study. There is 2,3-dimethylene cyclohexen[b]furan (59) for pyrolysis products.