Rozprawy doktorskie na temat „Petroleum and Biomass”

This thesis examined the conversions of biomass and biomass components to petrochemicals and total aliphatic gasoline like products. There are three major projects of the thesis. Since biomass is very complicated, to understand the thermal decomposition pathways of biomass, the pyrolytic behaviors of various biomass components including lignin and cellulose under different reaction were investigated in the first phase. Due to complexity and limited volatility, the thermal decomposition products from biomass bring insurmountable obstacles to the traditional analysis methods such as GC-MS, UV and FT-IR. Therefore, precise characterization of the whole portion of thermal decomposition products has significant impacts on providing insight into the pyrolysis pathways and evaluating the upgrading processes. Various NMR methods to characterize different functional groups presented in liquid and solid pyrolysis products by 1H, 13C, 31P, 2D-HSQC and solid state 13C-NMR were introduced in the second phase. Nevertheless, the major drawback towards commercialization of pyrolysis oils are their challenging properties including poor volatility, high oxygen content, molecular weight, acidity and viscosity, corrosiveness and cold flow problems. In situ upgrading the properties of pyrolysis oils during thermal conversion process by employing zeolites has been discussed in the third phase. The further hydrogenation of pyrolysis oils to total aliphatic gasoline like products by heterogeneous catalysis in “green medium” – water has also been examined in the third project.

Gasification is a process used to convert any carbonaceous species through heterogeneous reaction to obtain the desired gaseous products of H2 and CO which are used to make chemicals, liquid transportation fuels, and power. Both pyrolysis and heterogeneous gasification occur in commercial entrained-flow gasifiers at pressures from 4 to 65 atm with local gas temperatures as high as 2000 °C. Many gasification studies have been performed at moderate temperatures, heating rates, and pressures. In this work, both pyrolysis and char gasification experiments were performed on coal, petroleum coke, and biomass at conditions pertinent to commercial entrained-flow gasifiers. Rapid biomass pyrolysis experiments were performed at atmospheric pressure in an entrained-flow reactor for sawdust, switchgrass, corn stover, and straw mostly using a peak gas temperature of 1163 K at particle residence times ranging from 34 to 113 ms. Biomass pyrolysis was modeled using the Chemical Percolation Devolatilization model assuming that biomass pyrolysis occurs as a weighted average of its individual components (cellulose, hemicellulose, and lignin). Thermal cracking of biomass tar into light gas was included using a first-order model with kinetic parameters regressed in the current study. Char gasification rates were measured for biomass, petroleum coke, and coal in a pressurized entrained-flow reactor at high heating-rate conditions at total pressures between 10 and 15 atm. Peak centerline gas temperatures were between 1611 and 1879 K. The range of particle residence times used in the gasification experiments was 42 to 275 ms. The CO2 gasification rates of biomass and petroleum coke chars were measured at conditions where the reaction environment consisted of approximately 40 and 90 mol% CO2. Steam gasification rates of coal char were measured at conditions where the maximum H2O concentration was 8.6 mol%. Measured data was used to regress apparent kinetic parameters for a first-order model that describes char conversion. The measured char gasification rates were far from the film-diffusion limit, and are pertinent for pulverized particles where no internal particle temperature gradients are important. The modeling and measured data of char gasification rates in this research will aid in the design and efficient operation of commercial entrained-flow gasifiers, as well as provide validation for both existing and future models at a wide range of temperatures and pressures at high heating-rate conditions.

Clean and efficient electricity can be generated using an Integrated Gasification Combined Cycle (IGCC). Although IGCC is typically used with coal, it can also be used to gasify other carbonaceous species like biomass and petroleum coke. It is important to understand the pyrolysis and gasification of these species in order to design commercial gasifiers and also to determine optimal conditions for operation. High heating-rate (100,000 K/s) pyrolysis experiments were performed with biomass (sawdust) in BYU's atmospheric flat-flame burner reactor at conditions ranging from 1163 to 1433 K with particle residence times ranging from 23 to 102 ms. Volatile yields and mass release of the sawdust were measured. The measured pyrolysis yields of sawdust are believed to be similar to those that would occur in an industrial entrained-flow gasifier since biomass pyrolysis yields depend heavily on heating rate and temperature. Sawdust pyrolysis was modeled using the Chemical Percolation Devolatilization model assuming that biomass pyrolysis occurs as a weighted average of its individual components (cellulose, hemicellulose, and lignin). Thermal cracking of tar into light gas was included using a first-order kinetic model. The pyrolysis and CO2 gasification of petroleum coke was studied in a pressurized flat-flame burner up to 15 atm for conditions where the peak temperature ranged from 1402 to 2139 K. The measured CO2 gasification kinetics are believed to be representative of those from an entrained-flow gasifier since they were measured in similar conditions of elevated pressure and high heating rates (100,000 K/s). This is in contrast to the gasification experiments commonly seen in the literature that have been carried out at atmospheric pressure and slow particle heating rates. The apparent first-order Arrhenius kinetic parameters for the CO2 gasification of petroleum coke were determined. From the experiments in this work, the ASTM volatiles value of petroleum coke appeared to be a good approximation of the mass release experienced during pyrolysis in all experiments performed from 1 to 15 atm. The reactivity of pet coke by CO2 gasification exhibited strong pressure dependence.

Despite the huge national energy resources, many Nigerians do not have access to high quality, modern energy services. For those with access, energy supply lacks reliability, especially in the case of liquefied petroleum gas (LPG). Hence this research considers the possibility of enhancing the household use of LPG. It analyzes the factors affecting the current demand and supply. Salient features of the LPG supply and distribution system were also discussed. On the basis of the existing situation, barriers of increasing LPG use, in particular, the problems regarding affordability, priCing, government poliCies, safety, transportation and distribution were analyzed and identified statistically using the chi-square statistical method as a tool. Finally, on the basis of the challenges identified, suggestions and recommendations were made regarding the policies through which the problems could be overcome. Furthermore, a model was developed and tested for an effective marketing strategy of LPG in Warri Nigeria. ii
Thesis (M.Ing. (Development and Management Engineering))--North-West University, Potchefstroom Campus, 2009.

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2016.
The high cost of fossil fuels and the fact that the world has arguably reached its peak oil production, has driven the need to seek alternative fuel sources. The main objective of the current study is to determine the performance of a laboratory-mounted diesel engine when fuelled with varying laboratory prepared biofuel and biodiesel and whether the advancement of the injection timing parameters will improve the engine power output and improve the smoke effect of these different fuel blends. The laboratory prepared biofuels used in this project range from 100% bio-fuel (BF100) to 50%, 30% and 10% biodiesel blends (BF50, BF30 and BF10, respectively). It should be noted that these blends are not commercially available, since they were blended in the laboratory specifically for these tests. The overall results of the study show that there is a distinct opportunity for using certain bio-fuel blends in specific applications as the power outputs are no more than one quarter less than that of base diesel. Concomitantly, the smoke opacity in all of the blends is lower than that of base diesel, which is a significant benefit in terms of their overall air emissions.

Thesis (Ph. D.)--Georgia State University, 2006.
Title from title screen. George E. Pierce,committee chair; Eric S. Gilbert, Sidney A. Crow, committee members. Electronic text (135 p. : ill. (some col.)) : digital, PDF file. Description based on contents viewed Aug. 20, 2007. Includes bibliographical references (p. 120-124).

Orientador: Arsenio Oswaldo Seva Filho
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica
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Resumo: Neste trabalho, procurou-se desenvolver uma análise que pemútisse avaliar as possibilidades locais da implantação de geração de eletricidade descentralizada com fontes energéticas renováveis no estado de Rondônia, para contribuir na diminuição e na substituição do Diesel e em uma proposta de planejamento diferenciado. Entende-se que o consumo do Diesel é um fator estruturante da colonização e da eletrificação na região Amazônica e em Rondônia. Historicamente, a eletrificação em Rondônia é Diesel-dependente. Mesmo com o início da operação da UGH Samuel, em 1989, e com operacionalização de PCH' s, a geração continuou utilizando esse combustível como uma fonte importante de energia tanto no atendimento isolado quanto no sistema estadual de transmissão. O sistema estadual de transmissão é hidrotémúco, com uma UHE, motores Diesel e quatro turbinas a gás também operando com Diesel. A UHE está operacionalmente comprometida por problemas de assoreamento do lago e do regime hidrológico da região Amazônica. Os atendimentos isolados são témúcos com motores Diesel e hidrelétricos com mais sete PCH' s. O Planejamento para atendimento da demanda futura no sistema interligado é dependente do gás natural, que num curto espaço de tempo não será disponibilizado. Para o atendimento isolado existem três propostas, i- interligação de algumas localidades ao linhão, ii- formação de interligações locais e iii- continuação de atendimento Diesel- elétrico, principalmente para as cidades mais distantes do linhão e com cargas pequenas. Durante a pesquisa ficou claro que havia limitações e uma necessidade de conscientização da sociedade, quanto ao tratamento devastador dispensado atualmente aos recursos naturais da região, e quanto ao processo de desenvolvimento que pode ser empreendido a partir do aproveitamento sustentado desses recursos. As oportunidades para a geração descentralizada foram analisadas para as localidades de Rondônia consideradas pólos madeireiros, de acordo com os critérios: disponibilidade de resíduos da indústria madeireira e da produção agrícola, disponibilidade de potencial hídrico, disponibilidade de recursos humanos para operação e para a manutenção, possibilidade de interligação ao sistema UHE- linhão, existência de esquemas institucionais e de financiamento para os empreendimentos, ocorrência de complicações no suprimento de Diesel e existência de demandas industriais de energia
Abstract: In this work it was developed an analysis of the local possibilities to set up decentralized power generation by using renewable energy resources in Rondônia in order to contribute towards the reduction of the Diesel use and its substitution and in a proposal of differentiate resources planning. Diesel consumption is a structural factor in the colonization and electrification of the Amazon region and in Rondônia. Historically, the electrification is Diesel dependent in Rondônia. Even with UHE Samuel's starting up in 1989 and the operation ofsome small hydroelectric power stations, Diesel is still the main source of electric generation both in isolated and in the state system of transmission. The state system of transmission is hydrothermal based, consisting of one hydroelectric power station, Diesel engines, and four gas turbines that are also operating with Diesel. The hydroelectric power station is operationally endangered because of the lake silting up and the rainfalllevels in the Amazon region. The isolated systems are based on Diesel engine generators and on seven small hydroelectric power stations. The planning for attending the future requirements of energy in the interconnected system is dependent upon the natural gas that is not available for the short termo For attending the isolated systems there are three proposals, i- connecting some locations to the main regional line, iiorganizing local interconnections, iii- keeping the Diesel-electric system provision, specially to the most distant cities and smallloads. During the research of course there were limitations and a necessity to raise the public awareness of the devastating treatment given to the natural resources in the region and the development process that can be followed to achieve the sustainable exploitation of these resources. Decentralized generation opportunities were analyzed in Rondônia's wood exploitation centers, according to the following criteria: residue availability trom the wood industry and the agriculture production, hydropower potential availability, human resources availability for operating and maintaining the systems, possibility to connect these centers to the main power line, existence of institutional sponsorship and funding to these enterprises, Diesel supply failures and existence of energy demand by local industry
Doutorado
Doutor em Planejamento de Sistemas Energéticos

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Tecnológico. Programa de Pós-Graduação em Engenharia Química
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Quando correntes oleosas entram em contato com o meio ambiente prejudicam e influenciam tanto a fauna e a flora, quanto à população no entorno dos lugares contaminados. A procura por tratamentos eficientes, de baixo custo, que demandem pouca energia e provenientes de fontes renováveis fazem com que os bioadsorventes ocupem um lugar de destaque na redução dos contaminantes oleosos. Neste trabalho, utilizou-se o bagaço da cana-de-açúcar como bioadsorvente alternativo no tratamento de águas contaminadas com óleos. O efluente sintético foi simulado através de uma dispersão de água destilada e decahidronaftaleno, com concentração inicial de 8900 mg·L-1. O óleo residual, após os experimentos de adsorção, foi quantificado por cromatografia gasosa. A biomassa foi caracterizada pelas análises de umidade, FTIR, MEV, CHNS e análise superficial. Os experimentos foram desenvolvidos em processo batelada, com agitação de 120 rpm, sendo avaliado o tempo de equilíbrio do processo adsortivo, bem como a influência dos parâmetros pH, temperatura e tamanho das partículas do bioadsorvente. O processo de adsorção resultou na remoção de 80% de óleo em apenas 5 min de contato entre a dispersão e a biomassa. Os parâmetros que influenciaram significativamente a remoção do hidrocarboneto pelo bagaço-de-cana foram a temperatura e o tamanho de partícula do material. Para as condições testadas, o maior desempenho foi obtido a 25oC. O melhor ajuste para a Isoterma de Adsorção foi obtido com o modelo de Langmuir-Freundlich, fornecendo uma capacidade máxima de adsorção de 6,65 g de hidrocarboneto/g de biomassa. Os ensaios mostraram grande potencial do bagaço da cana-de-açúcar ser utilizado como bioadsorvente na redução do teor de óleos e graxas em efluentes aquosos, apresentando-se como uma alternativa sustentável a dois grandes problemas ambientais: o resíduo sólido gerado pelo processo de cultivo e industrialização da cana-de-açúcar e a contaminação de fontes aquosas pela indústria do petróleo e petroquímica.
When oily streams come in contact with the environment, they affect and influence the fauna and flora, as the population surrounding the contaminated places. The search for effective treatments that are low cost, require little energy and are from renewable resources, turn the biosorbents a prominent material in the oily contamination reduction. In this work, we have studied the bagasse from sugarcane as an alternative bioadsorbent in the treatment to oils and greases contaminated waters. The synthetic effluent was simulated by a distilled water and decahydronaphthalene dispersion, with initial concentration of 8900 mg o L -1. The residual oil, after adsorption experiments, was determined by gas chromatography. The biomass was characterized by moisture analysis, FTIR, SEM, CHNS and surface analysis. The experiments were carried out in batch process with agitation of 120 rpm, evaluating the equilibrium time of adsorptive process, as well as the influence of some parameters such as pH, temperature and the particle bioadsorbent size. The adsorption process resulted in removal of 80% of oil in only 5 minutes of contact between the dispersion and biomass. The parameters that significantly influenced the removal of hydrocarbon by bagasse were the temperature and particle size of the bioadsorbent. For the conditions tested, the best performance was obtained at 25oC. The best fit for the adsorption isotherm was obtained with Langmuir-Freundlich model, providing a maximum adsorption capacity of 6.65 g hydrocarbon/g biomass. The experiments showed the great potential of the sugarcane bagasse to be used as bioadsorvente in reducing the oil and grease levels in aqueous effluents, presenting itself as a sustainable alternative to two environmental problems: the solid waste deriving from the cultivation and industrialization of sugarcane and the aqueous sources contamination coming from oil and petrochemical industry.

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The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.
A demanda por fontes alternativas de energia impulsiona o desenvolvimento tecnol?gico de tal forma que muitos combust?veis e processos de convers?o energ?tica, antes julgada como inadequados ou mesmo invi?veis, s?o agora concorrentes de combust?veis e processos ditos tradicionais. Assim, a biomassa exerce um papel relevante, sendo considerada uma das fontes de energia renov?vel mais importante de nosso planeta. A biomassa contribui com 29,2 % de todas as fontes renov?veis de energia. A participa??o de energia de biomassa do Brasil na OIE ? de 13,6 %, sendo bem superior a m?dia mundial de participa??o. V?rios tipos de processos de pir?lise v?m sendo estudados nos ?ltimos anos, destacando-se o processo de pir?lise r?pida de biomassa para obten??o de Bio-?leo. Os processos cont?nuos de pir?lise r?pida, mais investigados e aprimorados s?o os de leito fluidizado e leito ablativo, entretanto vem sendo estudados e desenvolvidos outros tipos, visando obter um bio-?leo de melhor qualidade, com maior produtividade, menor consumo de energia, maior estabilidade e confiabilidade de processo e menor custo de produ??o. A estabilidade do produto Bio-?leo ? fundamental para a concep??o de dispositivos consumidores, tais como queimadores, motores de pist?o e turbinas. O presente estudo foi motivado para a produ??o de Bio-?leo, atrav?s da convers?o da biomassa vegetal ou do aproveitamento de seus res?duos industriais e agr?colas, sendo apresentada uma proposta alternativa de processo de pir?lise termoqu?mica, aproveitando a vantagem din?mica das part?culas no leito rotativo o que favorece a raz?o de contato g?s-s?lido e a transfer?ncia de calor e massa. O pirolisador foi projetado para operar em processo cont?nuo, contendo um alimentador de dois est?gios, um sistema desagregador da biomassa integrado com um separador de finos de carv?o e um sistema de condensa??o de vapores pirol?ticos. O Prot?tipo foi submetido a ensaios com serragem de madeira, utilizando um planejamento experimental completo em dois n?veis para investigar a sensibilidade dos fatores: temperatura do processo, fluxo de g?s de arraste e velocidade de centrifuga??o em rela??o ao rendimento m?ssico de Bio-?leo. O melhor resultado foi obtido na condi??o de 570 oC, 25 Hz e 200 cm3/min, sendo a temperatura o par?metro de maior signific?ncia. O balan?o Tese de Doutorado PPGCEP/UFRN L?cio ?ngelo de Oliveira Fontes vi de massa elementar das fases apresentou da ordem de 20 % liquidos pirol?ticos e 37 % de carv?o. Foram determinadas as propriedades dos produtos l?quidos e s?lidos da pir?lise como densidade, viscosidade, pH, PCI, sendo a composi??o caracterizada atrav?s an?lise qu?mica, revelando as propriedades e composi??o de um Bio-?leo.

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Cementing operation is one of the most important stages in the oil well drilling processes and has main function to form hydraulic seal between the various permeable zones traversed by the well. However, several problems may occur with the cement sheath, either during primary cementing or during the well production period. Cements low resistance can cause fissures in the cement sheath and compromise the mechanical integrity of the annular, resulting in contamination of groundwater and producing zones. Several researches show that biomass ash, in particular, those generated by the sugarcane industry have pozzolanic activity and can be added in the composition of the cementing slurries in diverse applications, providing improvements in mechanical properties, revenue and cement durability. Due to the importance of a low cost additive that increases the mechanical properties in a well cementing operations, this study aimed to potentiate the use of sugarcane bagasse ash as pozzolanic material, evaluate the mechanisms of action of this one on cement pastes properties and apply this material in systems slurries aimed to cementing a well with 800 m depth and geothermal gradient of 1.7 ?F/100 ft, as much primary cementing operations as squeeze. To do this, the ash beneficiation methods were realized through the processes of grinding, sifting and reburning (calcination) and then characterization by X-ray fluorescence, XRD, TG / DTG, specific surface area, particle size distribution by laser diffraction and mass specific. Moreover, the ash pozzolanic activity added to the cement at concentrations of 0%, 20% and 40% BWOC was evaluated by pozzolanic activity index with lime and with Portland cement. The evaluation of the pozzolanic activity by XRD, TG / DTG and compressive strength confirmed the ash reactivity and indicated that the addition of 20% in the composition of cement slurries produces improvement 34% in the mechanical properties of the slurry cured. Cement slurries properties evaluated by rheological measurements, fluid loss, free fluid, slurry sedimentation, thickening time and sonic strength (UCA) were satisfactory and showed the viability of using the sugarcane ash in cement slurries composition for well cementing
A opera??o de cimenta??o ? uma das etapas mais importantes no processo de perfura??o de po?os de petr?leo e tem a fun??o primordial de promover a veda??o hidr?ulica entre as diversas zonas perme?veis atravessadas pelo po?o. No entanto, v?rios problemas podem ocorrer com a bainha de cimento, seja durante a cimenta??o prim?ria ou no decorrer do per?odo produtivo do po?o. Cimentos de baixa resist?ncia podem causar trincas na bainha de cimento e comprometer a integridade mec?nica do anular, resultando em contamina??o de len??is fre?ticos e zonas produtoras. V?rias pesquisas comprovam que cinzas de biomassa, em particular, as geradas pela ind?stria sucroalcooleira apresentam atividade pozol?nica e podem ser adicionadas na composi??o das pastas cimentantes em diversas aplica??es, proporcionando benef?cios nas propriedades mec?nicas, no rendimento e na durabilidade do cimento. Dada a import?ncia de um aditivo de baixo custo e que aumenta as propriedades mec?nicas em uma opera??o de cimenta??o de po?os, este trabalho objetivou potencializar o uso da cinza de biomassa da cana-de-a??car (CBCC) como material pozol?nico, avaliar os mecanismos de atua??o desta nas propriedades de pastas de cimento e aplicar este material em sistemas de pastas destinadas ? cimenta??o de um po?o com 800 m de profundidade e gradiente geot?rmico de 1,7 ?F/100 p?s, tanto para as opera??es de cimenta??o prim?ria quanto corretiva (squeeze). Para isso, foram realizados m?todos de beneficiamento da cinza atrav?s dos processos de moagem, peneiramento e requeima (calcina??o) e, em seguida, a caracteriza??o por fluoresc?ncia de raios-X, DRX, TG/DTG, superf?cie espec?fica, granulometria a laser e massa espec?fica. Al?m disso, a atividade pozol?nica da cinza, adicionada ao cimento nas concentra??es de 0% (pasta padr?o), 20% e 40% BWOC, foi avaliada pelo ?ndice da atividade pozol?nica com a cal e com o cimento Portland. A avalia??o da atividade pozol?nica atrav?s das an?lises de DRX, TG/DTG e resist?ncia ? compress?o comprovaram a reatividade do material e indicaram que a adi??o de 20% de cinza na composi??o das pastas produz melhorias em at? 34% das propriedades mec?nicas da pasta endurecida. As propriedades das pastas avaliadas atrav?s dos ensaios de propriedades reol?gicas, perda de filtrado, ?gua livre, estabilidade, tempo de espessamento e resist?ncia ? compress?o (UCA) mostraram-se satisfat?rias e indicaram a viabilidade da utiliza??o da cinza na composi??o das pastas de cimento para po?os de petr?leo

ABSTRACT Mixed Petroleum Hydrocarbons and Biomass Derived Compounds Used in the Thermal Catalytic Steam Cracking (TCSC) Process for the Production of Light Olefins HaiTao Yan Light olefins and diolefins such as ethylene, propylene, butenes and 1,3-butadiene are considered as the backbone of the petrochemical industry as they are precursors of numerous plastic materials, synthetic fibers, and rubbers. The most prevalent technologies for producing these precursors are steam cracking and fluid catalytic cracking using petroleum-based feedstock like light naphtha and gas oil. However, petroleum based feeds have several problems in terms of limited reserves, environmental pollution and economic and geopolitical problems. Therefore, it is imperative to find an alternative source, which may be able to overcome the limitation of petroleum oil. In the current work, hydrocarbons-alcohol mixed feeds have been used in the Thermal-Catalytic/Steam-Cracking (TCSC) process for the production of propylene and ethylene. Alcohols like methanol and ethanol can be obtained from biomass, a potential sustainable and renewable source, through gasification and/or fermentation, and they can also be produced from natural gas and coal which are longer lasting fossil fuels than petroleum. The results from on-stream cracking of mixed feedstocks indicated difference in behaviors of ethanol and methanol. While ethanol undergoes predominantly dehydration into ethylene, methanol predominantly intervenes directly on reactions involving hydrocarbons (reactants and their intermediates). Moreover, the addition of methanol to hydrocarbons feedstock significantly increased the product yield of C2-C4 olefins, particularly that of ethylene and propylene. However, there was a maximum limit of efficiency for the methanol content in the mixed feed. Over 25wt% of methanol, the beneficial effect was not as important as expected. In addition, the increasing presence of methanol in the feed significantly accelerated the kinetics of the catalytic cracking. The gradual and significant decrease of the apparent activation energy with increasing methanol concentration in the mixed feed was attributed to the effect of intensive interactions between the hydrocarbons and methanol. These results demonstrated the possibility of partial replacement of petroleum based feedstocks by methanol for the production of propylene and ethylene. In the last part of this work, co-processing biomass derived glycerol with hydrocarbon feedstock over TCSC process was studied. It was found that glycerol as an additive to hydrocarbon feed, can be beneficial till a content of 30 wt%. However, the main concern is the rapid catalyst decay caused by formation of coke. Therefore, there is a need for a more advanced hybrid catalyst having higher hydrogen spillover activity.

The huge energy demand of our society is causing fossil fuel resources to diminish rapidly. Therefore, it is critical to search for alternative energy resources. Biomass is currently both abundant and inexpensive. Biofuels (fuels produced from biomass) have the potential to replace fossil fuels if a cost effective process can be develop to convert biomass into fuels. Catalytic fast pyrolysis is a technology that can convert biomass into gasoline ranged aromatics in a single step. By heating biomass quickly to an intermediate temperature, biomass will thermally decompose into small molecules which can fit into zeolite catalyst pores. Inside the catalyst pores, these small molecules undergo a series of reactions where aromatics are formed along with olefins, CO, CO2, CH4 and water. Gallium promoted ZSM-5 catalyst has been shown to promote small alkanes aromatization, thus it has the potential to increase aromatic yield in catalytic fast pyrolysis process. The focus of the thesis is to study the behavior of catalyst fast pyrolysis of biomass over Gallium promoted catalyst, and explore various ways to utilize the gas phase olefins to increase the aromatic yield. [CG1] The effect of reaction parameters (temperature, weight hourly space velocity, and fluidized gas velocity) on catalytic fast pyrolysis of biomass with Ga/ZSM-5 were studied in a fluidized bed reactor using pine saw dust as the biomass feed. The product distribution and hydrocarbon selectivity are shown to be a strong function of temperature and weight hourly space velocity. Compared to ZSM-5 catalyst at the same reaction conditions, Ga/ZMS-5 has been shown to increase the aromatic yield by 40%. Olefins can be recycled back to the CFP fluidized bed reactor to further increase the aromatic yield. The olefin co-feeding with pine saw dust experiments indicates that co-feeding with propylene can increase the aromatic yield, however, co-feeding with ethylene will cause a decrease in aromatic yield. In both co-feeding experiments, an increase in the amount of coke formed was also observed. Besides a simple olefin recycle, another possible way to utilize these olefins, while avoiding the high cost to separate them from other gas phase products (CO, CO2 and CH4),is adding a secondary alkylation unit after the fluidized bed reactor. The alkylation unit could provide a way to produce additional ethylbenzene after the main CFP process. Three zeolite catalysts (ZSM-5, Y-zeolite and Beta zeolite) were tested in the alkylation unit, and ZSM-5 catalyst shows the highest activity and selectivity in the alkylation of benzene and ethylene.

碩士
大葉大學
國際企業管理學系碩士班
101
Increasingly in recent years as soaring international crude oil prices, international issues related to energy demand day by the attention, coupled with global warming issues persistent fever, seek alternative sources of energy has become the trend of the future. Advanced countries for the use of biomass energy increased significantly, joint lead corn, sugar cane and other crops increased demand, coupled with rising international maritime transport prices fueled by the interlocking caused international grain prices. Due to various grain prices, making the relevant food stocks were affected. Therefore, this paper attempts to find out the chain of interlocking parts that can be predicted, for enterprises and related industries equity investors, as a reference for decision-making.

Thesis (M.Com. (Development Theory and Policy))--University of the Witwatersrand, Faculty of Commerce, Law and Management, School of Economic and Business Sciences, 2016.
Energy security, particularly liquid fuels, is a vital economic goal for both developed and developing nations.As a region, SADC has large coal, oil and gas reserves,and land for potential crop production for biofuels, yet access to liquid fuels is still a major constraint to economic and social development. Some coal is utilised in the region for petrochemical industries, power generation, and for heating. Crude oil reserves are largely exported due to the lack of refineries and pipelines in the region. Whilst biofuels production is in its infancy. This paper explores the challenges and opportunitiesthe SADC region faces in developing refining capacity and in investing in new CTL/GTL facilities as well as liquid fuels from renewable energy resources. A primary focus will be on Malawi and her neighbouring states, as a case study.
MT2017