Conversão térmica e termocatalítica à baixa temperatura do óleo de girassol para obtenção de bio-óleo

The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

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.

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Superfícies de titânio modificadas termoquimicamente por plasma : avaliação da resposta biológica

This laboratory study involves the participation of a group with professionals from different areas that had contributed to the construction of a multidisciplinary knowledge, about biological response of titanium surfaces modified through thermochemical treatment by plasma. Thus, the crystalline phase was previously characterized in relation to the topography, roughness, molhability and nitrogen concentration in the samples surface. It s indispensable that materials implanted can influence in a good cellular response as well as promotes a bacteria action. Surfaces modified by plasma were exposed to different cultures such as: cellular (human osteoblastic) and bacteria (Staphylococcus epidermidis ATCC35984 and Pseudomonas aeruginosa ATCC 27853) in order to evaluate the biological response. It was evaluated the adhesion, proliferation, morphology and cellular preference of human ostheoblastic cells (HOST), as well as the formation of a biofilm and bacteria proliferation. It was still analyzed the bacteria selectivity ability in relation to the surfaces. The software Image Pro Plus was used to the counting of cells and bacteria adhered to the surface of disks. The results were submitted to the variance analysis (ANOVA), and then, by the Kruskal-Wallis test, using GraphPad Instat ® software, version 3.5 to Windows. The nitrided samples in spite of show a higher roughness and molhability showed a smaller bacteria growing and higher cellular proliferation, when compared to non treated samples, indicating that the treated material present a high efficiency to biomedical implants

Bioenergia e exclusão regional: a não política nacional agroenergética e os girassóis do RN

This doctoral thesis presents an analysis of the production of bicarbonates and related regional development in Brazil. It is widely believed that one of Brazil s vocations lies in the agro-energy sector. However, current national agro-energy policies, together with the experience of Petrobras (the national oil company) in rural settlements in the state of Rio Grande do Norte, show that Brazil has fallen short of effectively including the North and Northeast regions of the country, let alone small-scale rural producers (residing in rural settlements or not), in the development process and related benefits from the country s participation in the current world energy grid. The methodology entails secondary research related to the theme, such as books, official documents, websites and statistical databases from diverse sources, in addition to an analysis of statements from interviews of Petrobras representatives and other important scientific, institutional and labor union authorities, in relation to agro-energy issues and the socio-economic participation of family-based agriculture in this process. Principal findings show a correlation between agro-energy and regional development, creating the potential for numerous opportunities and challenges. Findings demonstrate the possibility of reversing/reducing historically rooted indices of hunger and poverty that continue to devastate the North and Northeast regions. At the same time, the thesis points to a potentially catastrophic increase in regional disparities, should the present historic moment not be seized upon so as to include these regions. Classic examples of non-policy at the federal level are presented as evidence of the absence of a regionally focused agroenergy policy in the current government, reinforced by the experiences of Petrobras in the Rio Grande do Norte rural settlements. Finally, the thesis concludes that there is an urgent need to create a government-sponsored enterprise (with a structure similar to Petrobras) with the purpose of implementing a truly broad and inclusive development process for the bicarbonates production sector, while remaining attentive to Brazil s opportune and critical role in the world s current agro-energy scenario.

O dumping ambiental no setor sucroalcooleiro à luz do princípio da livre concorrência

The goal of this study is to investigate about the existence or absence of environmental dumping in the production of fuel ethanol in Brazil, as well as identifying the reasons why the figure of ecological dumping is pernicious to the principles enumerated in constitutional economic order, in particular the principle of free competition. In the twenty-first century environmental issues gained momentum and importance in these terms, which was seen as a mere fallacy given the concern of governments of various countries, after all, environmental protection shows up as the only means of bringing about the maintenance of life at planet. Indeed, it is essential to halt the drastic effects of climate change, and think fast and efficient solutions. Undoubtedly, the contemporary requirements that resulted in the transition to a new economy brings with it the duty of enterprise search for sustainability, and this behavior can not be passive, otherwise it is imperative to work hard and incessant economic agents, even if initially costs are high, this step will ensure a production accountable, transparent and free from accusations of environmental degradation. It is also intended to study the importance of the sector not only as a source of economic growth, but mainly, its contribution to national development, without forgetting that this is devoted in the Constitution of 1988 as one of the objectives of the Federative Republic of Brazil. In fact, the criticism most common perceptions about the production of biofuels, said the interests of the countries producing them in large scale, will eventually generate a exhaustion of soil and a significant increase in food prices. However, the ethanol produced in Brazil is unique in that it is produced from cane sugar, a product is not intended for human or animal, not to mention that the recovery of land just to the rotation with the planting other cultures. It is expected that environmental certifications are useful to demonstrate the quality of ethanol for export and to refute unfounded criticism. Finally, this study will be analyzed further solutions for the plants to develop an economic activity without damaging the environment and in compliance with Brazilian law

O sistema de certificação do etanol brasileiro sob a ótica do princípio constitucional do desenvolvimento sustentável

The gradual inclusion of biofuels is a necessary change that countries must include in their energy mixes. Energy sources still widely used in the world, such as oil and coal, are endowed with a high pollution load to the environment, bringing damages to the water, to the air and to humans as well. In addition, although there are conflicting studies, they are also identified as major causes of the greenhouse effect and the global warming phenomenon. They are, moreover, finite sources of energy, given that its reserves will surely run out. However, even if the introduction of biofuels, such as ethanol, in the energy mix is crucial for the survival of the present and future populations, this insertion cannot settle so disorderly and, thus, one must ensure the quality of these resources and promote transparency in international trade. In this manner, a certification process for ethanol is essential to attest that this biofuel meets the sustainable requirements defined for its production. Hence, this study sought to address the importance of the adoption of certification in the ethanol industry, according to the principle of sustainable development, by analyzing the evolution of its concept, its combination with the fundamental objectives sculptured in the Constitution of 1988, its regulation under Brazilian laws and the need for a balance between economic activities and the mentioned principle. The work also encompassed the criteria used to establish certification standards and their participating actors, combined with a study of ongoing initiatives. Finally, the consequences of the adoption of a certification process for ethanol in Brazil were presented, both in terms of sustainable development and in international trade

A alteração do tipo penal de adulteração de combustíveis: reflexo da constitucionalização do direito penal no mercado de combustíveis

The neoconstitutionalism led to a process of ethical revaluation of the normative systems and the process of constitutionalization of the many fields of law. This study examines the consequences of this process in criminal law, so important a Law field for the protection of the most valuable assets by the society, including the fundamental guarantees, thus emphasizing the necessity of protection of the collective and individual rights, which are guided by the observance of the defendants individual rights in the course of criminal proceedings and the search for the best efficiency of penal protection, according to the corollaries of defense against the state (prohibition of the excess or Übermassverbot) and the provision of rights by the state (prohibition of insufficient protection or Untermassverbot). The offense of fuel adulteration is taken as an object of study, since it is a vital market to a nation dependent of people and good s movement for their living, driven by fossil and biofuels. Such a crime affects essential legal interests to the development of society, interests such as the environment, consumer relations and economic order, particularly the principle of free competition. This paper seeks to analyze the need of a greater efficiency of this particular criminal protection, once concluded the conduct harm and social fear as a consequence by it as growing, and therefore having its former crime type, engraved in Article 1 of Law No. 8.176/1991, rewritten in compliance with the criminal law s principle of legality. Thus, the reformation proposals and legislative creation involving this crime were observed, with emphasis on the bill No. 2498/2003, which keeps it as blank heterogeneous criminal norm, kind of penal normative whose constitutionality is raised, including the forethought of criminal responsibility in the perpetrating of the offense as culpable and subsequently increasing the applicable minimum penalty, as well as the inclusion of new activities in the typical nucleus

Diagnóstico para implantação do sistema de gestão ambiental em postos revendedores de combustíveis no município de Paranamirim RN: um estudo de caso

natural resources that still enjoy, in the certainty that if we do not, could culminate at the end of that remains. The environmental contamination by fuels in the retail service of oil and biofuels, has been a subject of growing research in Brazil, due to the large pollution potential of this activity. The aim of this study was to evaluate the importance of implementing the Environmental Management System (EMS) in fuel retail service stations in the city of Parnamirim-RN, but also describe the current situation the same as licensing and environmental characterization; identify existing barriers to implementation of EMS on the costs, technologies, knowledge, vision, present the potential benefits for the implementation of the EMS (social, economic and environmental), to identify the existence of plans for future action to implement the EMS , as a subsidy to promote the implementation of it. The methodology was developed through analysis of documents provided by the environmental agency responsible for licensing of retail service stations and fuel pala ANP. For data collection, we used the questionnaire was applied directly to managers or managers of sub-stations. Data were collected in 12 of 30 posts in the municipality. For purposes of data treatment was performed a descriptive analysis with respect to the opinion of twelve managers (respondents). The data acquired, according to the Likert scale were tabulated and analyzed using software SPSS 17.0 and Excel 2003, it was generated tables and graphs to observe the behavior of the data. The results showed that most respondents have a schooling level higher (58.3%) of the jobs surveyed 50% work on average 6 to 10 years and 41.6% are in operation for over 11 years , 75.0% do not have a license to operate and 12 stations, 58.3% were sued for not having a license to operate and are therefore in full commercial activity, 83% of jobs have some practice environmentally responsible, 75% agree in making planning future action to implement 8 the EMS in their ventures, 70% in full agreement that the high cost is a form of impediment to implementation of EMS; 66.67% agreed that resistance to change is an impediment to implementation of EMS; 90.91% agreed that the implementation of EMS is very complex, 80% of respondents agreed in a very significant environmental legislation is also a key factor preventing the implementation of EMS is noteworthy that 100% of respondents agreed that the knowledge about the use of the EMS will help to solve environmental problems in the fuel retail service stations, the implementation of the EMS will benefit with increased efficiency of resources applied to the findings by the agreement of 91.66% of respondents, where only 8, 33% disagreed, there was also a percentage of 100%, agreed that the company's image will be a great benefit, but also a contribution to solving environmental problems in the fuel retail service stations. Thus, the importance of the implementation of EMS in the fuel retail service stations in the city of Parnamirim-RN, with an urgent need to be deployed. And the bodies responsible for policy on state-run and supervise more tightly and action, this type of activity, in order to regulate the sustainable functioning of retail service stations of fuel, thus promoting a better quality of life for the population of the municipality of natal-RN

Análise Energética da cultura do crambe (Crambe abyssinica hochst) produzida em plantio direto

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo das propriedades físico-químicas de biocombustíveis microemulsionados

The development of new fuels is an important field of scientific and technological activities, since much of the energy consumed in the world is obtained from oil, coal and natural gas, and these sources are limited and not renewable. Recently it has assessed the employment of microemulsions as an alternative for obtaining fuel isotropic between phases originally not miscible. Among many advantages, emphasizes the application of substances that provide the reduction of levels of emissions compared to fossil fuels. Thus, this work was a study of various microemulsified systems, aiming to check the performance of the winsor regions front of the use of surfactants: RENEX 18 → 150, UNITOL L-60 → L-100 and AMIDA 60, together with structure of esters from soybean and castor bean oils. From the results it were chosen four systems to physico-chemical analyzes: System I RENEX 60, Soil bean oil, methylic ester (EMOS) and water; System II RENEX 60/AMIDA 60, EMOS and water; System III RENEX 70, mamona oil methylic ester (EMOM) and water and System IV RENEX 95, EMOM and water. The tests of physico-chemical characterization and study of temperature increase were done with nine points with different compositions in a way to include the interest area (microemulsion W/O). After this study, was conducted a modeling to predict the viscosity, the property is more varied as function of compositions systems changes. The best results were the systems II and IV with a temperature stability above 60°C. The system I had its physico-chemical characterization very similar to a fossil fuel. The system II was the best one due to its corrosivity be stable. In the modeling the four systems had shown good, with an error that varied between 5 and 18%, showing to be possible the viscosity prediction from the composition of the system. The effects the microemulsion and the engine´s performance with the microemulsion were also avaliated. The tests were performed in a cycle-diesel engine. The potency and consumption were analysed. Results show a slight increase the rendiment fuel compared with the conventional as well as a decrease in specific consumption

Influência do estresse nutricional programado na composição da microalga isochrysis galbana

Global warming due to Greenhouse Gases (GHG) emissions, especially CO2, has been identified as one of the major problems of the twenty-first century, considering the consequences that could represent to planet. Currently, biological processes have been mentioned as a possible solution, especially CO2 biofixation due to association microalgae growth. This strategy has been emphasized as in addition to CO2 mitigation, occurs the production of biomass rich in compounds of high added value. The Microalgae show high photosynthetic capacity and growth rate higher than the superior plants, doubling its biomass in one day. Its culture does not show seasons, they grow in salt water and do not require irrigation, herbicides or pesticides. The lipid content of these microorganisms, depending on the species, may range from 10 to 70% of its dry weight, reaching 90% under certain culture conditions. Studies indicate that the most effective method to promote increased production of lipids in microalgae is to induce stress by limiting nitrogen content in the culture medium. These evidences justify research continuing the production of biofuels from microalgae. In this paper, it was studied the strategy of increasing the production of lipids in microalgae I. galbana with programmed nutritional stress, due to nitrogen limitation. The physiological responses of microalgae, grown in f / 2 with different concentrations of nitrogen (N: P 15,0-control, N: 5,0 P and N: P 2,5) were monitored. During exponential phase, results showed invariability in the studied conditions. However the cultures subjected to stress in stationary phase, showed lower biomass yields. There was an increase of 32,5% in carbohydrate content and 87.68% in lipids content at N: P ratio of 5,0 and an average decrease of 65% in protein content at N: P ratios of 5, 0 and 2.5. There were no significant variations in ash content, independently of cultivation and growth phase. Despite the limitation of biomass production in cultures with N: P smaller ratios, the increase of lipid accumulation highest lipids yields were observed as compared to the control culture. Given the increased concentration of lipids associated to stress, this study suggests the use of microalgae Isochrysis galbana as an alternative raw material for biofuel production

Estudo da influência da temperatura na degradação termoquímica da biomassa de avelós (euphorbia tirucalli Linn)

The bio-oil obtained from the pyrolysis of biomass has appeared as inter-esting alternative to replace fossil fuels. The aim of this work is to evaluate the influence of temperature on the yield of products originating from the pyrolysis process of the powder obtained from the dried twigs of avelós (Euphorbia tirucalli), using a rotating cylinder reactor in laboratory scale. The biomass was treated and characterized by: CHNS, moisture, volatiles, fixed carbon and ashes, as well as evaluation of lignin, cellulose and hemicellulose, besides other instrumental techniques such as: FTIR, TG/DTG, DRX, FRX and MEV. The activation energy was evaluated in non-isothemichal mode with heating rates of 5 and 10 oC/min. The obtained results showed biomass as feedstock with potential for biofuel production, because presents a high organic matter content (78,3%) and fixed-carbon (7,11%). The activation energy required for the degradation of biomass ranged between 232,92 392,84 kJ/mol, in the temperature range studied and heating rate of 5 and 10°C/min. In the pyrolysis process, the influence of the reaction temperature was studied (350-520 ° C), keeping constant the other variables, such as, the flow rate of carrier gas, the centrifugal speed for the bio-oil condensationa, the biomass flow and the rotation of the reactor. The maximum yield of bio-oil was obtained in the temperature of 450°C. In this temperature, the results achieved where: content of bio-oil 8,12%; char 32,7%; non-condensed gas 35,4%; losts 23,8%; gross calorific value 3,43MJ/kg; pH 4,93 and viscosity 1,5cP. The chromatographic analysis of the bio-oil produced under these conditions shows mainly the presence of phenol (17,71%), methylciclopentenone (10,56%) and dimethylciclopentenone (7,76%)

Controvérsias do desenvolvimento dos assentamentos rurais em São Paulo: produção para os biocombustíveis e as alternativas de programas municipais

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hydrogen production utilizing glycerol from renewable feedstocks-The case of Brazil

Various reports concerning catalytic reaction of glycerol for hydrogen production is available. However, economic analyses of this activity are not found yet. The objective of this work is to evaluate the process of hydrogen production via steam reforming of glycerol obtained through transesterification process of bio-oils. The thermochemical process of steam reforming process was determined due to high efficiency, feasibility and lower cost of design, development, operation and maintenance. These bio-oils come from feedstocks largely encountered in Brazil such as soybean, palm, castor bean, peanut and cotton seed as also come from residues such as defective coffee, tallow beef, wastewater (scum) and others. Various findings were obtained such as potential of production of glycerol utilizing residues (considering available amounts in the Brazilian states) and some vegetable feedstocks (considering production of harvested feedstock per hectare). Subsequently, production of hydrogen via steam reforming of generated glycerol, and foreseen electricity production via fuel cells were also determined. An additional estimation was paid for production of H-BIO, an innovative fuel developed by PETROBRAS (Petroleo Brasileiro S.A.), where hydrogen and bio-fuel are utilized and generates propane as co-product. About this work, it was concluded that high amounts of hydrogen and electricity could be produced considering an enormous potential from each cited feedstock being an attractive alternative as distributed electricity source and as an additional source for some activities, inclusively those that produce their own feedstocks such as abattoirs (beef tallow), and wastewater treatment plants. (C) 2010 Elsevier Ltd. All rights reserved.