Biochar has been heralded as a promising technology for climate change mitigation that can also benefit soils. Biochar is a carbonaceous solid produced by pyrolysis of biomass – the thermal decomposition of plant and plant-derived matter in the absence of oxygen. When added to soils, biochar has the potential to increase crop yields and suppress soil emissions of greenhouse gases, whilst sequestering carbon in a stable form. In addition to biochar, biomass pyrolysis produces liquids and gases that can serve as biofuels. Biochar production systems that generate excess heat or power are particularly environmentally and economically attractive. Rotary kilns are the favoured process reactor in many industries, given their potential to handle a wide range of feedstocks and provide good process control. This thesis investigates the potential to coproduce biochar and excess biofuels by slow pyrolysis in a pilot-scale rotary kiln. The work attempts to progress towards the ultimate aim of scaling up the rotary kiln and optimising its operating conditions to produce biochar of good quality along with an excess of useful biofuels. Experimental work, involving the development and application of new methodologies, was used to gain a better understanding of the process. The data gathered were then used to support preliminary numerical simulation efforts towards the development of a comprehensive process model. Five biomass feedstocks were considered: softwood pellets, miscanthus straw pellets, wheat straw pellets, oilseed rape straw pellets and raw rice husks. The granular flow of biomass feedstocks was observed in a short closed drum faced with acrylic and resting on rollers. All pelletized feedstocks displayed similar angles of repose, validating the use of softwood pellets as a model biomass for these feedstocks. Bed mixing, which can improve product uniformity, was slow under typical operating conditions, requiring 5 min to complete at 4 rpm for softwood pellets. Mixing quickened considerably at higher rotation rates. A digital image analysis method was developed to measure the distribution of solid residence times inside the rotary kiln. The mean residence time of softwood pellets ranged from 19 to 37 min under typical operating conditions, decreasing with increases in kiln rotation rate, but mostly unaffected by feeding rates. These findings show that kiln rotation rates must be selected to balance the residence time of solids inside the kiln with bed mixing levels. Thermogravimetry and differential scanning calorimetry were performed on samples of ground softwood pellets under five different heating profiles to study the kinetics and heat flows of the pyrolysis process. Both exothermic and endothermic regions were identified, with most reactions taking place between 250°C and 500°C. Results suggest that exothermic pyrolysis reactions can be promoted by altering the process heating rate, thereby improving net biofuel yield from the process. The thermogravimetric data collected was used to develop a distributed activation energy model (DAEM) of the kinetics of softwood pellet pyrolysis for integration into a comprehensive model of the process. The applicability of the kinetic model to large-scale processes was confirmed using a simplified process model developed to simulate biomass pyrolysis inside the pilot-scale rotary kiln. Although crude, the simplified process model produced sufficiently accurate estimates of char yield for preliminary design purposes. The simplified model also allowed important process parameters, such as kiln filling degree, solid residence time and heating rate, to be evaluated. A series of pyrolysis experiments was performed on the pilot-scale rotary kiln to evaluate the yields of biochar and biofuels and determine the temperature profile inside the kiln. This work required the design of a suspended thermocouple system that measures temperatures along the kiln, both in the gas phase and inside the solid bed. For most experiments at 550°C, a region of high temperature gas and solids was observed, possibly indicative of exothermic reactions. Biochar yield varied from 18% to 73% over the range of feedstocks and operating conditions tested. A vapour sampling methodology that relies on the use of a tracer gas was developed to determine the yield of pyrolysis liquids and gases. Due to analytical difficulties, it was not possible to obtain accurate mass closure with this method. However, the methodology revealed significant air ingress into the pilot-scale rotary kiln that is responsible for partially combusting biofuels produced by the process, thereby reducing their calorific value. Energy balances on the kiln confirmed that the calorific content of pyrolysis liquids and gases exceeds the energetic demand of the process, yielding between 0.3 and 11 MJ in excess biofuels per kg of biomass feedstock. An attempt was made to develop a multiphase model of the flow of vapours and solids inside the rotary kiln using computational fluid dynamics (CFD), but the continuous modelling approach was found inadequate to simulate the dense bed of biomass inside the kiln. The discrete element method (DEM) was sought as an alternative to model the granular flow of biomass inside the kiln. Extensive parameter calibration was required to reproduce the experimental behaviour of softwood pellets observed in the short closed drum. A model of the pilot-scale rotary kiln was constructed to simulate particle residence times. Further parameter calibration was required to replicate softwood pellet holdup inside the kiln. The calibrated model was able to reproduce the mean residence time of softwood pellets within 10% under different kiln operating conditions. However, simulated residence time distributions could not be established as a result of the long execution times required for this modelling work. Few data are currently available on large-scale continuous biomass pyrolysis processes; the experimental data gathered in this thesis help to fill this gap. Along with the numerical simulation work presented herein, they provide the foundation for the development of a comprehensive model of biomass pyrolysis in rotary kilns. Such a numerical model would prove invaluable in scaling up the process and maximizing its efficiency. Future work should consider the agronomic value and carbon sequestration potential of biochar produced under different operating conditions. In addition, the performance and efficiency of different conversion technologies for generating heat and power from biofuels need to be investigated.

Submitted by FÁBIO ROBERTO VIEIRA (fabiorobertovieira@bol.com.br) on 2018-04-18T19:02:13Z No. of bitstreams: 1 Fabio Roberto Vieira - Dissertação versão final.pdf: 2356751 bytes, checksum: 1c49b0709cb5e5a4d26bcf03bbbd3670 (MD5) / Approved for entry into archive by Pamella Benevides Gonçalves null (pamella@feg.unesp.br) on 2018-04-19T19:12:40Z (GMT) No. of bitstreams: 1 vieira_fr_me_guara.pdf: 2356751 bytes, checksum: 1c49b0709cb5e5a4d26bcf03bbbd3670 (MD5) / Made available in DSpace on 2018-04-19T19:12:40Z (GMT). No. of bitstreams: 1 vieira_fr_me_guara.pdf: 2356751 bytes, checksum: 1c49b0709cb5e5a4d26bcf03bbbd3670 (MD5) Previous issue date: 2018-02-20 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nessa dissertação é investigada o aproveitamento energético da casca de arroz pela aplicação do processo de pirólise lenta em um reator de leito fixo, o qual foi projetado e construído para realização de trabalho. É estudada a influência dos parâmetros do processo nas características do biochar obtido a partir da casca de arroz, com o objetivo avaliar a sua potencialidade na geração de energia. Para tal foi realizada caracterizações físico-química da casca de arroz in natura e do biochar obtido, aplicando-se diversas técnicas de análise, além da avaliação da eficiência energética. As análises foram estudadas a fim de determinar as condições experimentais que favorecem as características do biochar, tais como poder calorífico superior (PCS) e concentração de carbono fixo, e também o rendimento na produção do mesmo. Foi utilizado um planejamento experimental, conforme metodologia de Taguchi, utilizando-se uma matriz L9 e variando-se os parâmetros que influenciam na pirólise, sendo eles a taxa de aquecimento (β) 5, 10 e 20 ºC/min, temperatura (T) de 300, 400 e 500 ºC, tempo de residência (t) de 3600, 5400 e 7200 s e massa da biomassa in natura (m) de 125, 250 e 500 g. Os resultados indicaram que para os diferentes parâmetros estudados, o maior rendimento de biochar (37,71%) foi observado na condição experimental realizada no teste 7, sendo adotado β=20 ºC/min, T=300 ºC, t=5400 s, e m=500 g. O teste 6 apresentou o maior PCS, 49,05% maior que o da casca de arroz in natura, sendo adotado β=10 ºC/min, T=500 ºC, t=5400 s e m=125 g. Na condição de maior concentração de carbono fixo, o teste 3 apresentou melhor resultado (60,10 %), no qual foi adotado β=5 ºC/min, T=500 ºC, t=7200 s e m=500 g. A ANOVA foi aplicada para analisar a variância do processo, sendo que a temperatura foi o parâmetro de maior influência no processo. Também foram determinadas as condições de melhor ajuste para otimização do processo para maior rendimento na produção de biochar (β= 20 ºC/min, T=300 ºC, t=3600 s e m=500 g), para maior concentração de carbono fixo no biochar (β=5 ºC/min, T=500 ºC, t=7200 s e , m=250 g) e para obtenção de biochar com maior PCS (β=10 ºC/min, T=500 ºC, t=3600 s e m=125 g). A avaliação energética mostrou que, tecnicamente, há um ganho energético na aplicação da pirólise lenta da casca de arroz. / In this dissertation is investigated the utilization of the rice husk means slow pyrolysis process in a fixed bed reactor, which was designed and built to perform work. The influence of the process parameters on the characteristics of the biochar obtained from the rice husk is studied, with the objective of evaluating its potential in the energy. For this purpose, physicalchemical characterization of the in natura rice husk and the biochar obtained were performed, applying several analysis techniques, as well as the energy efficiency assessment. The analyzes were studied in order to determine the experimental conditions favoring the biochar characteristics, such as higher heat value (HHV) and fixed carbon concentration, as well as the yield in the production of the same. An experimental design was used, according to Taguchi's methodology, using a L9 matrix and varying the parameters that influence pyrolysis, being the heating rate (β) 5, 10 and 20 ºC / min, temperature (T) of 300, 400 and 500 ° C, residence time (t) of 3600, 5400 and 7200 if mass of the in natura biomass (m) of 125, 250 and 500 g. The results indicated that the highest biochar yield (37.71%) was observed in the experimental condition performed in test 7, using β = 20 ºC / min, T = 300 ºC, t = 5400 s, in = 500 g. Test 6 showed the highest HHV, 49.05% higher than in natura rice husk, being adopted β = 10 ºC / min, T = 500 ºC, t = 5400 s and m = 125 g. In the condition of higher fixed carbon concentration, test 3 presented the best result (60.10%), in which β = 5 ° C / min, T = 500 ° C, t = 7200 s and m = 500 g. ANOVA was applied to analyze the process variance, with temperature being the parameter of greatest influence in the process. It was also determined the conditions of better adjustment for process optimization for higher yield of biochar (β = 20 ºC / min, T = 300 ºC, t = 3600 m = 500 g) for higher fixed carbon concentration in biochar (β = 10 °C/min, T = 500 °C, t = 7200 s, m = 250 g) and to obtain biochar with higher HHV). The energy evaluation showed that, technically, there is an energetic gain in the application of the slow pyrolysis of the rice husk. / 134299/2017-5 / 301819/2015-7

The replacement of fossil resources through renewable alternatives is one way to mitigate global climate change. Biomass is the only renewable source of carbon available for replacing oil as a refining feedstock. Therefore, it needs to be utilized not just as a fuel but for both biochemical and thermochemical conversion through biorefining. Optimizing and combining various conversion processes using a system perspective to maximize the valorization, biomass usage, and environmental benefits is of importance. This thesis work has evaluated the integration opportunities for various thermochemical conversion processes within a biorefinery system. The aim for all evaluated concepts were syngas production through gasification or reforming. Two potential residue streams from an existing biorefinery were evaluated as gasification feedstocks, thereby combining biochemical and thermochemical conversion. Torrefaction as a biomass pretreatment for gasification end-use was evaluated based on improved feedstock characteristics, process benefits, and integration aspects. A system concept, “Bio2Fuels”, was suggested and evaluated for low-temperature slow pyrolysis as a way to achieve simultaneous biomass refinement and transport driven CO2 negativity. Syngas was identified as a very suitable intermediate product for residue streams from biochemical conversion. Resulting syngas composition and quality showed hydrolysis residue as suitable gasification feedstock, providing some adjustments in the feedstock preparation. Gasification combined with torrefaction pretreatment demonstrated reduced syngas tar content. The co-gasification of biogas and wood in a FBG was successfully demonstrated with increased syngas H2/CO ratio compared to wood gasification, however high temperatures (≥1000°C) were required for efficient CH4 conversion. The demonstrated improved feedstock characteristics for torrefied biomass may facilitate gasification of biomass residue feedstocks in a biorefinery. Also, integration of a torrefaction unit on-site at the biorefinery or off-site with other industries could make use of excess low-value heat for the drying step with improved overall thermal efficiency. The Bio2Fuels concept provides a new application for slow pyrolysis. The experimental evaluation demonstrated significant hydrogen and carbon separation, and no significant volatilization of ash-forming elements (S and Cl excluded)  in low-temperature (<400°C) pyrolysis. The initial reforming test showed high syngas CH4 content, indicating the need for catalytic reforming. The collective results from the present work indicate that the application of thermochemical conversion processes into a biorefinery system, making use of by-products from biochemical conversion and biomass residues as feedstocks, has significant potential for energy integration, increased product output, and climate change mitigation.

With a growing concern of climate change due to increased levels of CO2 in the atmosphere, carbon sequestration has been suggested as a possible solution for climate change mitigation. Biochar,a highly carbonaceous product produced through pyrolysis, is considered a viable option due to its content of stable carbon. This work covers the investigation of the possibility to produce biocharfrom four different feedstocks, namely peat, straw, horse manure and sewage sludge. The study includes a literature study and a five-week trial period at a 500 kW pilot plant, PYREG 500, in Högdalen. The thermal behaviour of the feedstocks, including garden waste, was investigated using thermogravimetric analysis (TGA). The TGA results were used to decide the optimal pyrolysis temperature for peat and straw at the pilot plant. The TGA results showed that the feedstocks behave differently when pyrolysed; the mass loss rate as well as the final mass loss varied. Physiochemical characterisation of the biochar was completed and the results were in agreement with previous studies. The produced biochar from straw and two types of peat had a C content above50 wt.% (76.6, 80.7, 79.2 wt.%) and low molar ratios of H/C (0.33, 0.36, 0.38) and O/C (0.032,0.023, 0.024). The pH increased as a consequence of pyrolysis and the biochars were alkaline (pH10.1, 8.5, 8.3). Polycyclic aromatic hydrocarbons (PAHs) were found in biochar from both strawand peat (8.26, 1.03, 5.83 mg/kg). In general, nutrients and heavy metals were concentrated in the biochar, except for Cd which decreased and Hg which could not be determined. The specific surface area of biochar from straw was considered small (21 m2/g) while biochar from peat had a higher specific surface area with a greater span (102-247 m2/g). The properties of the produced biochar were compared to the criteria included in the European Biochar Certificate and some of them were fulfilled, including the content of C, PAH and heavy metals. A flue gas analysis was completed when operating the pilot plant on straw pellets and it was showed that several emissions were released, including NO2, SOX, HCl and particulates, however, solely the emissions of NO2 exceed the regulations which will be applied in 2020. Regarding process design of a future pyrolysis plant, it is suggested that the means of material transport, particle separation, temperature control and quenching of biochar should be improved.

A casca da castanha de caju (CCC), um resíduo agrícola da produção de castanha, proveniente da região nordeste do Brasil foi caracterizada e submetida ao processo de pirólise lenta. As propriedades do bio-carrvão, do bio-óleo e dos gases produzidos foram investigados e potenciais aplicações foram propostas. A CCC foi caracterizada pela seguintes técnicas: análise elementar CHNS, umidade total, conteúdo de cinzas, matérias voláteis, poder calorífico superior e por análise termogravimétrica. A análise termogravimétrica sob fluxo de nitrogênio mostrou que a decomposição é dominada pela degradação da hemicelulose e celulose na faixa de 250 a 350oC e pela decomposição da lignina na faixa de 400 a 500oC. Na presença de ar, o perfil de degradação é semelhante, porém observa-se uma maior degradação da lignina. A pirólise lenta da casca da castanha de caju foi realizada em um reator tipo batelada aquecido por chama ar-GLP sob diferentes fluxos (mL min-1) de nitrogênio ou ar. O sólido obtido (bio-carvão), líquido (fase aquosa + bio-óleo) e a fase gás foram quantificados e caracterizados por diferentes técnicas. Os experimentos realizados sob fluxo de nitrogênio apresentaram um rendimento de cerca de 30, 40 e 30% em massa paras as fases sólido, líquida e gás, respectivamente. Sob fluxo de ar ocorreu uma diminuição no rendimento da fase líquida, principalmente na produção de bio-óleo, e um aumento da fase gás. Os bio-carvões produzidos apresentaram elevados teores de carbono, na faixa de 70-75% em massa, poder calorífico na faixa de 25 a 28 MJ kg-1, características de carbono amorfo, sem morfologias definidas e ausência de poros. Os espectros FTIR de bio-óleos produzidos sob fluxo de nitrogênio apresentaram um aumento da intensidade relativa das bandas cerca de 1700 cm-1 (ν C=O) e 1230 cm-1 (ν C-O) em comparação com os produzidos sob fluxo de ar, o que sugere a presença de grandes quantidades de compostos oxigenados de carbono, como aldeídos, cetonas e ácidos carboxílicos. As análises das fases gás mostraram a predominância de CO2 e CO a temperaturas inferiores a 400ºC e a formação preferencial de H2 acima desta temperatura. / Cashew nut shell (CNS), an agricultural waste of cashew nut production, from northeast region of Brazil was characterized and slow pyrolyzed. The properties of char, bio-oil and gases products were investigated and potential applications were proposed. CNS was characterized by the following analyses: CHNS, total moisture, ash content, volatile matter, high heating value and thermogravimetric analysis. The thermogravimetric analysis under nitrogen flow showed that the decomposition is dominated by the degradation of hemicellulose and cellulose in the range from 250 to 350oC and the decomposition of lignin in the range of 400 to 500oC. In the presence of air, the degradation profile is similar; however the decomposition of lignin increases. Slow pyrolysis of cashew nut shell was carried out in batch-type reactor heated by a combustion flame (air + GLP) under different nitrogen and air flow rates. The resulting solid (char), liquid (water + bio-oil) and gas phases were characterized and quantified. The experiments performed under nitrogen showed a yield of solid, liquid and gas phases of about 30, 40 and 30wt%, respectively. Under air the yield of liquid phase was reduced, primarily the bio-oil yield; production of the gas phase was, in turn, increased. The produced biochars had high carbon contents in the range of 70-80 wt%, high heating values in the range of 25-28 MJ Kg-1 and characteristics of amorphous carbons without defined morphology and the absence of pores. The FTIR spectra of bio-oils produced under nitrogen flow showed an increase of the relative intensity of the bands around 1700 cm-1 (ν C = O) and 1230 cm-1 (ν C-O) in comparison with those produced under air flow which suggests the presence of large amounts of oxygenated carbon compounds such as aldehydes, ketones and carboxylic acids. The analysis of gas phases showed the predominance of CO2 and CO at temperatures lower than 400oC and the preferential formation of H2 above this temperature.

A casca da castanha de caju (CCC), um resíduo agrícola da produção de castanha, proveniente da região nordeste do Brasil foi caracterizada e submetida ao processo de pirólise lenta. As propriedades do bio-carrvão, do bio-óleo e dos gases produzidos foram investigados e potenciais aplicações foram propostas. A CCC foi caracterizada pela seguintes técnicas: análise elementar CHNS, umidade total, conteúdo de cinzas, matérias voláteis, poder calorífico superior e por análise termogravimétrica. A análise termogravimétrica sob fluxo de nitrogênio mostrou que a decomposição é dominada pela degradação da hemicelulose e celulose na faixa de 250 a 350oC e pela decomposição da lignina na faixa de 400 a 500oC. Na presença de ar, o perfil de degradação é semelhante, porém observa-se uma maior degradação da lignina. A pirólise lenta da casca da castanha de caju foi realizada em um reator tipo batelada aquecido por chama ar-GLP sob diferentes fluxos (mL min-1) de nitrogênio ou ar. O sólido obtido (bio-carvão), líquido (fase aquosa + bio-óleo) e a fase gás foram quantificados e caracterizados por diferentes técnicas. Os experimentos realizados sob fluxo de nitrogênio apresentaram um rendimento de cerca de 30, 40 e 30% em massa paras as fases sólido, líquida e gás, respectivamente. Sob fluxo de ar ocorreu uma diminuição no rendimento da fase líquida, principalmente na produção de bio-óleo, e um aumento da fase gás. Os bio-carvões produzidos apresentaram elevados teores de carbono, na faixa de 70-75% em massa, poder calorífico na faixa de 25 a 28 MJ kg-1, características de carbono amorfo, sem morfologias definidas e ausência de poros. Os espectros FTIR de bio-óleos produzidos sob fluxo de nitrogênio apresentaram um aumento da intensidade relativa das bandas cerca de 1700 cm-1 (ν C=O) e 1230 cm-1 (ν C-O) em comparação com os produzidos sob fluxo de ar, o que sugere a presença de grandes quantidades de compostos oxigenados de carbono, como aldeídos, cetonas e ácidos carboxílicos. As análises das fases gás mostraram a predominância de CO2 e CO a temperaturas inferiores a 400ºC e a formação preferencial de H2 acima desta temperatura. / Cashew nut shell (CNS), an agricultural waste of cashew nut production, from northeast region of Brazil was characterized and slow pyrolyzed. The properties of char, bio-oil and gases products were investigated and potential applications were proposed. CNS was characterized by the following analyses: CHNS, total moisture, ash content, volatile matter, high heating value and thermogravimetric analysis. The thermogravimetric analysis under nitrogen flow showed that the decomposition is dominated by the degradation of hemicellulose and cellulose in the range from 250 to 350oC and the decomposition of lignin in the range of 400 to 500oC. In the presence of air, the degradation profile is similar; however the decomposition of lignin increases. Slow pyrolysis of cashew nut shell was carried out in batch-type reactor heated by a combustion flame (air + GLP) under different nitrogen and air flow rates. The resulting solid (char), liquid (water + bio-oil) and gas phases were characterized and quantified. The experiments performed under nitrogen showed a yield of solid, liquid and gas phases of about 30, 40 and 30wt%, respectively. Under air the yield of liquid phase was reduced, primarily the bio-oil yield; production of the gas phase was, in turn, increased. The produced biochars had high carbon contents in the range of 70-80 wt%, high heating values in the range of 25-28 MJ Kg-1 and characteristics of amorphous carbons without defined morphology and the absence of pores. The FTIR spectra of bio-oils produced under nitrogen flow showed an increase of the relative intensity of the bands around 1700 cm-1 (ν C = O) and 1230 cm-1 (ν C-O) in comparison with those produced under air flow which suggests the presence of large amounts of oxygenated carbon compounds such as aldehydes, ketones and carboxylic acids. The analysis of gas phases showed the predominance of CO2 and CO at temperatures lower than 400oC and the preferential formation of H2 above this temperature.

Recent developments in converting biomass to bio-chemicals and liquid fuels provide a promising sight to an emerging biofuels industry. Biomass can be converted to energy via thermochemical and biochemical pathways. Thermal degradation processes include liquefaction, gasification, and pyrolysis. Among these biomass technologies, pyrolysis (i.e. a thermochemical conversion process of any organic material in the absence of oxygen) has gained more attention because of its simplicity in design, construction and operation. This research study focuses on comparative assessment of two types of pyrolysis processes and catalytic upgrading of bio-oil for production of transportation fuel intermediates. Slow and fast pyrolysis processes were compared for their respective product yields and properties. Slow pyrolysis bio-oil displayed fossil fuel-like properties, although low yields limit the process making it uneconomically feasible. Fast pyrolysis, on the other hand, show high yields but produces relatively less quality bio-oil. Catalytic transformation of the high-boiling fraction (HBF) of the crude bio-oil from fast pyrolysis was therefore evaluated by performing liquid-phase reactions at moderate temperatures using Pt/HZSM-5 catalyst. High yields of upgraded bio-oils along with improved heating values and reduced oxygen contents were obtained at a reaction temperature of 200°C and ethanol/HBF ratio of 3:1. Better quality, however, was observed at 240 °C even though reaction temperature has no significant effect on coke deposition. The addition of ethanol in the feed has greatly attenuated coke deposition in the catalyst. Major reactions observed are esterification, catalytic cracking, and reforming. Overall mass and energy balances in the conversion of energy sorghum biomass to produce a liquid fuel intermediate obtained sixteen percent (16 wt.%) of the biomass ending up as liquid fuel intermediate, while containing 26% of its initial energy.

Wildland fire, which includes both planned (prescribed fire) and unplanned (wildfire) fires, is an important component of many ecosystems. Prescribed burning (controlled burning) is used as an effective tool in managing a variety of ecosystems in the United States to reduce accumulation of hazardous fuels, manage wildlife habitats, mimic natural fire occurrence, manage traditional native foods, and provide other ecological and societal benefits. During wildland fires, both live and dead (biomass) plants undergo a two-step thermal degradation process (pyrolysis and combustion) when exposed to high temperatures. Pyrolysis is the thermal decomposition of organic material, which does not require the presence of oxygen. Pyrolysis products may later react with oxygen at high temperatures, and form flames in the presence of an ignition source. In order to improve prescribed fire application, accomplish desired fire effects, and limit potential runaway fires, an improved understanding of the fundamental processes related to the pyrolysis and ignition of heterogeneous fuel beds of live and dead plants is needed.In this research, fast pyrolysis of 14 plant species native to the forests of the southern United States has been studied using a flat-flame burner (FFB) apparatus. The results of fast pyrolysis experiments were then compared to the results of slow pyrolysis experiments. The plant species were selected, which represent a range of common plants in the region where the prescribed burning has been performed. The fast pyrolysis experiments were performed on both live and dead (biomass) plants using three heating modes: (1) convection-only, where the FFB apparatus was operated at a high heating rate of 180 °C s-1 (convective heat flux of 100 kW m-2) and a maximum fuel surface temperature of 750 °C; (2) radiation-only, where the plants were pyrolyzed under a moderate heating rate of 4 °C s-1 (radiative heat flux of 50 kW m-2), and (3) a combination of radiation and convection, where the plants were exposed to both convective and radiative heat transfer mechanisms. During the experiments, pyrolysis products were collected and analyzed using a gas chromatograph equipped with a mass spectrometer (GC-MS) for the analysis of tars and a gas chromatograph equipped with a thermal conductivity detector (GC-TCD) for the analysis of light gases.The results showed that pyrolysis temperature, heating rate, and fuel type, have significant impacts on the yields and the compositions of pyrolysis products. These experiments were part of a large project to determine heat release rates and model reactions that occur during slow and fast pyrolysis of live and dead vegetation. Understanding the reactions that occur during pyrolysis then can be used to develop more accurate models, improve the prediction of the conditions of prescribed burning, and improve the prediction of fire propagation.

Prescribed (i.e., controlled) burning is a common practice used in many vegetation types in the world to accomplish a wide range of land management objectives including wildfire risk reduction, wildlife habitat improvement, forest regeneration, and land clearing. To properly apply controlled fire and reduce unwanted fire behavior, an improved understanding of fundamental processes related to combustion of live and dead vegetation is needed. Since the combustion process starts with pyrolysis, there is a need for more data and better models of pyrolysis of live and dead fuels. In this study, slow pyrolysis experiments were carried out in a pyrolyzer apparatus and a Thermogravimetric analyzer (TGA) under oxygen free environment in three groups of experiments. In the first group, the effects of temperature (400–800 °C), a slow heating rate (H.R.) (5–30 °C min−1), and carrier gas flow rate (50–350 ml min−1) on yields of tar and light gas obtained from pyrolysis of dead longleaf pine litter in the pyrolyzer apparatus were investigated to find the optimum condition which results in the maximum tar yield. In the second group of experiments, 14 plant species (live and dead) native to forests in the southern United States, were heated in the pyrolyzer apparatus at the optimum condition. A gas chromatograph equipped with a mass spectrometer (GC–MS) and a gas chromatograph equipped with a thermal conductivity detector (GC-TCD) were used to study the speciation of tar and light gases, respectively. In the third group of experiments, the slow pyrolysis experiments for all plant species (live and dead) were carried out in the TGA at 5 different heating rates ranged from 10 to 30 ℃ min-1 to study the kinetics of pyrolysis. The results showed that the highest tar yield was obtained at a temperature of 500 °C, heating rate of 30 °C min−1, and sweep gas flow rate of 100 ml min−1. In addition, the tar composition is dominated by oxygenated aromatic compounds consisting mainly of phenols. The light gas analysis showed that CO and CO2 were the dominant light gas species for all plant samples on a dry wt% basis, followed by CH4 and H2. The kinetics of pyrolysis was studied using one model-free method and three model-fitting methods. First, the model-free method of Kissinger-Akahira-Sunose (KAS) was used to calculate the rates of pyrolysis as a function of the extent of conversion. The results showed that different plant species had different rates at different conversions. Then, three model fitting methods were used to find the kinetic parameters to potentially provide a single rate for each plant species. The results showed that the simple one-step model did not fit the one-peak pyrolysis data as well as the distributed activation energy model (DAEM) model. The multiple-reaction DAEM model provided very good fits to the experimental data where multiple peaks were observed, even at different heating rates.

This study presents a techno-economic assessment of slow pyrolysis of pine sawdust continued by ex-situ catalytic upgrading. The overall process consists of six sections: feed drying, pyrolysis, vapor filtration, ex-situ catalytic upgrading, vapor quenching, and combustion of permanent gas. In the process simulation, biomass is objected to slow pyrolysis at 450ºC in an electrically-heated screw reactor and pyrolysis vapors is upgraded in fixed catalytic bed reactor at 425 ºC (using HZSM-5). The model is then used to investigate effects of feed moisture variation and type of heating source in pyrolysis unit, i.e. thermal vs. electrical heating, to oil energy efficiency. According to the simulation model, the endothermic pyrolysis step requires1.46 MJ/kg dry-feed. On the other hand, ex-situ upgrading is slightly exothermic and releases50kJ/kg dry-feed. Overall, the conversion of biomass to bio-oil demonstrates a mass efficiency of 19.65%wt and an energy efficiency of 29.10%. The energy efficiency raises to 32.81% if a direct thermal source is applied instead of electrical heating. The bio-oil energy efficiency increases by 1.38% if the moisture content of the biomass decreases by 10%wt. In average,bio-oil and char production in ex-situ catalytic upgrading generate profit 1.47 SEK/kg dry feed. The uncertainty of bio-oil price causes the highest profit variation.