Determinação de teor de biodieseis de algodão e pinhão manso em misturas com diesel usando espectroscopia no infravermelho médio e quadrados mínimos parciais

Biodiesel is a renewable fuel derived from vegetable oils or animal fats, which can be a total or partial substitute for diesel. Since 2005, this fuel was introduced in the Brazilian energy matrix through Law 11.097 that determines the percentage of biodiesel added to diesel oil as well as monitoring the insertion of this fuel in market. The National Agency of Petroleum, Natural Gas and Biofuels (ANP) establish the obligation of adding 7% (v/v) of biodiesel to diesel commercialized in the country, making crucial the analytical control of this content. Therefore, in this study were developed and validated methodologies based on the use of Mid Infrared Spectroscopy (MIR) and Multivariate Calibration by Partial Least Squares (PLS) to quantify the methyl and ethyl biodiesels content of cotton and jatropha in binary blends with diesel at concentration range from 1.00 to 30.00% (v/v), since this is the range specified in standard ABNT NBR 15568. The biodiesels were produced from two routes, using ethanol or methanol, and evaluated according to the parameters: oxidative stability, water content, kinematic viscosity and density, presenting results according to ANP Resolution No. 45/2014. The built PLS models were validated on the basis of ASTM E1655-05 for Infrared Spectroscopy and Multivariate Calibration and ABNT NBR 15568, with satisfactory results due to RMSEP (Root Mean Square Error of Prediction) values below 0.08% (<0.1%), correlation coefficients (R) above 0.9997 and the absence of systematic error (bias). Therefore, the methodologies developed can be a promising alternative in the quality control of this fuel.

Numerical Analysis on a Dual-Loop Waste Heat Recovery System Coupled with an ORC for Vehicle Applications

The internal combustion (IC) engines exploits only about 30% of the chemical energy ejected through combustion, whereas the remaining part is rejected by means of cooling system and exhausted gas. Nowadays, a major global concern is finding sustainable solutions for better fuel economy which in turn results in a decrease of carbon dioxide (CO2) emissions. The Waste Heat Recovery (WHR) is one of the most promising techniques to increase the overall efficiency of a vehicle system, allowing the recovery of the heat rejected by the exhaust and cooling systems. In this context, Organic Rankine Cycles (ORCs) are widely recognized as a potential technology to exploit the heat rejected by engines to produce electricity. The aim of the present paper is to investigate a WHR system, designed to collect both coolant and exhausted gas heats, coupled with an ORC cycle for vehicle applications. In particular, a coolant heat exchanger (CLT) allows the heat exchange between the water coolant and the ORC working fluid, whereas the exhausted gas heat is recovered by using a secondary circuit with diathermic oil. By using an in-house numerical model, a wide range of working conditions and ORC design parameters are investigated. In particular, the analyses are focused on the regenerator location inside the ORC circuits. Five organic fluids, working in both subcritical and supercritical conditions, have been selected in order to detect the most suitable configuration in terms of energy and exergy efficiencies.

Emission Control in Diesel Engines by Alcohol Fumigation, 1990

Exhaust emissions from diesel engines are a substantial source of air pollution in this country. In recognition of this fact, the Environmental Protection Agency has issued strict new regulations due to take effect -in 1991 and 1994 that will drastically reduce the amount of some pollutants these engines will be allowed to emit. The technology is not currently available to produce diesel engines that can meet these regulations without large penalties in engine performance and efficiency. One technique that offers promise of being able to reduce emissions from both existing engines and new engines is alcohol fumigation.

Techno-Economic Assessment of LNG and Diesel Production and Global Trading Based on Hybrid PV-Wind Power Plants and PtG, GtL and PtL Technologies

With growing demand for liquefied natural gas (LNG) and liquid transportation fuels, and concerns about climate change and causes of greenhouse gas emissions, this master’s thesis introduces a new value chain design for LNG and transportation fuels and respective fundamental business cases based on hybrid PV-Wind power plants. The value chains are composed of renewable electricity (RE) converted by power-to-gas (PtG), gas-to-liquids (GtL) or power-to-liquids (PtL) facilities into SNG (which is finally liquefied into LNG) or synthetic liquid fuels, mainly diesel, respectively. The RE-LNG or RE-diesel are drop-in fuels to the current energy system and can be traded everywhere in the world. The calculations for the hybrid PV-Wind power plants, electrolysis, methanation (H2tSNG), hydrogen-to-liquids (H2tL), GtL and LNG value chain are performed based on both annual full load hours (FLh) and hourly analysis. Results show that the proposed RE-LNG produced in Patagonia, as the study case, is competitive with conventional LNG in Japan for crude oil prices within a minimum price range of about 87 - 145 USD/barrel (20 – 26 USD/MBtu of LNG production cost) and the proposed RE-diesel is competitive with conventional diesel in the European Union (EU) for crude oil prices within a minimum price range of about 79 - 135 USD/barrel (0.44 – 0.75 €/l of diesel production cost), depending on the chosen specific value chain and assumptions for cost of capital, available oxygen sales and CO2 emission costs. RE-LNG or RE-diesel could become competitive with conventional fuels from an economic perspective, while removing environmental concerns. The RE-PtX value chain needs to be located at the best complementing solar and wind sites in the world combined with a de-risking strategy. This could be an opportunity for many countries to satisfy their fuel demand locally. It is also a specific business case for countries with excellent solar and wind resources to export carbon-neutral hydrocarbons, when the decrease in production cost is considerably more than the shipping cost. This is a unique opportunity to export carbon-neutral hydrocarbons around the world where the environmental limitations on conventional hydrocarbons are getting tighter.

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Estudo térmico dos resíduos gerados da destilação atmosférica das misturas diesel/biodiesel de dendê

The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 °C.min-1, nitrogen atmosphere and heating to 600 ° C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance

Development of a 1-D Catalyzed Diesel Particulate Filter Model for Simulation of the Performance and the Oxidation of Particulate Matter and Nitrogen Oxides Using Passive Oxidation and Active Regeneration Engine Experimental Data

Back-pressure on a diesel engine equipped with an aftertreatment system is a function of the pressure drop across the individual components of the aftertreatment system, typically, a diesel oxidation catalyst (DOC), catalyzed particulate filter (CPF) and selective catalytic reduction (SCR) catalyst. Pressure drop across the CPF is a function of the mass flow rate and the temperature of the exhaust flowing through it as well as the mass of particulate matter (PM) retained in the substrate wall and the cake layer that forms on the substrate wall. Therefore, in order to control the back-pressure on the engine at low levels and to minimize the fuel consumption, it is important to control the PM mass retained in the CPF. Chemical reactions involving the oxidation of PM under passive oxidation and active regeneration conditions can be utilized with computer numerical models in the engine control unit (ECU) to control the pressure drop across the CPF. Hence, understanding and predicting the filtration and oxidation of PM in the CPF and the effect of these processes on the pressure drop across the CPF are necessary for developing control strategies for the aftertreatment system to reduce back-pressure on the engine and in turn fuel consumption particularly from active regeneration. Numerical modeling of CPF's has been proven to reduce development time and the cost of aftertreatment systems used in production as well as to facilitate understanding of the internal processes occurring during different operating conditions that the particulate filter is subjected to. A numerical model of the CPF was developed in this research work which was calibrated to data from passive oxidation and active regeneration experiments in order to determine the kinetic parameters for oxidation of PM and nitrogen oxides along with the model filtration parameters. The research results include the comparison between the model and the experimental data for pressure drop, PM mass retained, filtration efficiencies, CPF outlet gas temperatures and species (NO2) concentrations out of the CPF. Comparisons of PM oxidation reaction rates obtained from the model calibration to the data from the experiments for ULSD, 10 and 20% biodiesel-blended fuels are presented.

MODELING OF TRANSFER PATH FOR DETERMINATION OF COMBUSTION AND NOISE METRICS ON DIESEL ENGINES

Determination of combustion metrics for a diesel engine has the potential of providing feedback for closed-loop combustion phasing control to meet current and upcoming emission and fuel consumption regulations. This thesis focused on the estimation of combustion metrics including start of combustion (SOC), crank angle location of 50% cumulative heat release (CA50), peak pressure crank angle location (PPCL), and peak pressure amplitude (PPA), peak apparent heat release rate crank angle location (PACL), mean absolute pressure error (MAPE), and peak apparent heat release rate amplitude (PAA). In-cylinder pressure has been used in the laboratory as the primary mechanism for characterization of combustion rates and more recently in-cylinder pressure has been used in series production vehicles for feedback control. However, the intrusive measurement with the in-cylinder pressure sensor is expensive and requires special mounting process and engine structure modification. As an alternative method, this work investigated block mounted accelerometers to estimate combustion metrics in a 9L I6 diesel engine. So the transfer path between the accelerometer signal and the in-cylinder pressure signal needs to be modeled. Depending on the transfer path, the in-cylinder pressure signal and the combustion metrics can be accurately estimated - recovered from accelerometer signals. The method and applicability for determining the transfer path is critical in utilizing an accelerometer(s) for feedback. Single-input single-output (SISO) frequency response function (FRF) is the most common transfer path model; however, it is shown here to have low robustness for varying engine operating conditions. This thesis examines mechanisms to improve the robustness of FRF for combustion metrics estimation. First, an adaptation process based on the particle swarm optimization algorithm was developed and added to the single-input single-output model. Second, a multiple-input single-output (MISO) FRF model coupled with principal component analysis and an offset compensation process was investigated and applied. Improvement of the FRF robustness was achieved based on these two approaches. Furthermore a neural network as a nonlinear model of the transfer path between the accelerometer signal and the apparent heat release rate was also investigated. Transfer path between the acoustical emissions and the in-cylinder pressure signal was also investigated in this dissertation on a high pressure common rail (HPCR) 1.9L TDI diesel engine. The acoustical emissions are an important factor in the powertrain development process. In this part of the research a transfer path was developed between the two and then used to predict the engine noise level with the measured in-cylinder pressure as the input. Three methods for transfer path modeling were applied and the method based on the cepstral smoothing technique led to the most accurate results with averaged estimation errors of 2 dBA and a root mean square error of 1.5dBA. Finally, a linear model for engine noise level estimation was proposed with the in-cylinder pressure signal and the engine speed as components.

Effect of Pavement-Vehicle Interaction on Highway Fuel Consumption and Emission

Vehicle fuel consumption and emission are two important effectiveness measurements of sustainable transportation development. Pavement plays an essential role in goals of fuel economy improvement and greenhouse gas (GHG) emission reduction. The main objective of this dissertation study is to experimentally investigate the effect of pavement-vehicle interaction (PVI) on vehicle fuel consumption under highway driving conditions. The goal is to provide a better understanding on the role of pavement in the green transportation initiates. Four study phases are carried out. The first phase involves a preliminary field investigation to detect the fuel consumption differences between paired flexible-rigid pavement sections with repeat measurements. The second phase continues the field investigation by a more detailed and comprehensive experimental design and independently investigates the effect of pavement type on vehicle fuel consumption. The third study phase calibrates the HDM-IV fuel consumption model with data collected in the second field phase. The purpose is to understand how pavement deflection affects vehicle fuel consumption from a mechanistic approach. The last phase applies the calibrated HDM-IV model to Florida’s interstate network and estimates the total annual fuel consumption and CO2 emissions on different scenarios. The potential annual fuel savings and emission reductions are derived based on the estimation results. Statistical results from the two field studies both show fuel savings on rigid pavement compared to flexible pavement with the test conditions specified. The savings derived from the first phase are 2.50% for the passenger car at 112km/h, and 4.04% for 18-wheel tractor-trailer at 93km/h. The savings resulted from the second phase are 2.25% and 2.22% for passenger car at 93km/h and 112km/h, and 3.57% and 3.15% for the 6-wheel medium-duty truck at 89km/h and 105km/h. All savings are statistically significant at 95% Confidence Level (C.L.). From the calibrated HDM-IV model, one unit of pavement deflection (1mm) on flexible pavement can cause an excess fuel consumption by 0.234-0.311 L/100km for the passenger car and by 1.123-1.277 L/100km for the truck. The effect is more evident at lower highway speed than at higher highway speed. From the network level estimation, approximately 40 million gallons of fuel (combined gasoline and diesel) and 0.39 million tons of CO2 emission can be saved/reduced annually if all Florida’s interstate flexible pavement are converted to rigid pavement with the same roughness levels. Moreover, each 1-mile of flexible-rigid conversion can result in a reduction of 29 thousand gallons of fuel and 258 tons of CO2 emission yearly.

Development of Advanced Combustions using Cylinder Pressure Signal

Zero-carbon powertrains development has become one of the main challenges for automotive industries around the world. Following this guideline, several approaches such as powertrain electrification, advanced combustions, and hydrogen internal combustion engines have been aimed to achieve the goal. Low Temperature Combustions, characterized by a simultaneous reduction of fuel consumption and emissions, represent one of the most studied solutions moving towards a sustainable mobility. Previous research demonstrate that Gasoline partially premixed Compression Ignition combustion is one of the most promising LTC. Mainly characterized by the high-pressure direct-injection of gasoline and the spontaneous ignition of the premixed air-fuel mixture, GCI combustion has shown a good potential to achieve the high thermal efficiency and low pollutants in compression ignited engines required by future emission regulations. Despite its potential, GCI combustion might suffer from low combustion controllability and stability, because gasoline spontaneous ignition is significantly affected by slight variations of the local in-cylinder thermal conditions. Therefore, to properly control GCI combustion assuring the maximum performance, a deep knowledge of the combustion process, i.e., gasoline auto-ignition and the effect of the control parameters on the combustion and pollutants, is mandatory. This PhD dissertation focuses on the study of GCI combustion in a light-duty compression ignited engine. Starting from a standard 1.3L diesel engine, this work describes the activities made moving toward the full conversion of the engine. A preliminary study of the GCI combustion was conducted in a “Single-Cylinder” engine configuration highlighting combustion characteristics and dependencies on the control parameters. Then, the full engine conversion was performed, and a wide experimental campaign allowed to confirm the benefits of this advanced combustion methodologies in terms of pollutants and thermal efficiency. The analysis of the in-cylinder pressure signal allowed to study in depth the GCI combustion and develop control-oriented models aimed to improve the combustion stability.

Performance assessment of vehicular connectivity in hybrid electric vehicles for fuel and emissions reduction

Nowadays, the spreading of the air pollution crisis enhanced by greenhouse gases emission is leading to the worsening of global warming. Recently, several metropolitan cities introduced Zero-Emissions Zones where the use of the Internal Combustion Engine is forbidden to reduce localized pollutants emissions. This is particularly problematic for Plug-in Hybrid Electric Vehicles, which usually work in depleting mode. In order to address these issues, the present thesis presents a viable solution by exploiting vehicular connectivity to retrieve navigation data of the urban event along a selected route. The battery energy needed, in the form of a minimum State of Charge (SoC), is calculated by a Speed Profile Prediction algorithm and a Backward Vehicle Model. That value is then fed to both a Rule-Based Strategy, developed specifically for this application, and an Adaptive Equivalent Consumption Minimization Strategy (A-ECMS). The effectiveness of this approach has been tested with a Connected Hardware-in-the-Loop (C-HiL) on a driving cycle measured on-road, stimulating the predictions with multiple re-routings. However, even if hybrid electric vehicles have been recognized as a valid solution in response to increasingly tight regulations, the reduced engine load and the repeated engine starts and stops may reduce substantially the temperature of the exhaust after-treatment system (EATS), leading to relevant issues related to pollutant emission control. In this context, electrically heated catalysts (EHCs) represent a promising solution to ensure high pollutant conversion efficiency without affecting engine efficiency and performance. This work aims at studying the advantages provided by the introduction of a predictive EHC control function for a light-duty Diesel plug-in hybrid electric vehicle (PHEV) equipped with a Euro 7-oriented EATS. Based on the knowledge of future driving scenarios provided by vehicular connectivity, engine first start can be predicted and therefore an EATS pre-heating phase can be planned.

Obstacle Crossing With Dual Tasking Is A Danger For Individuals With Alzheimer's Disease And For Healthy Older People.

The aim of this study was to analyze the effects of dual tasking on obstacle crossing during walking by individuals with Alzheimer's disease (AD) and by healthy older people. Thirty four elderly individuals (16 healthy subjects and 18 individuals with AD) were recruited to participate in this study. Three AD individuals and one control participant were excluded due to exclusion criteria. The participants were instructed to walk barefoot at their own speed along an 8 m long pathway. Each participant performed five trials for each condition (unobstructed walking, unobstructed walking with dual tasking, and obstacle crossing during walking with dual tasking). The trials were completely randomized for each participant. The mid-pathway stride was measured in the unobstructed walking trials and the stride that occurred during the obstacle avoidance was measured in the trials that involved obstacle crossing. The behavior of the healthy elderly subjects and individuals with AD was similar for obstacle crossing during walking with dual tasking. Both groups used the posture first strategy to prioritize stability and showed decreased attention to executive tasking while walking. Additionally, AD had a strong influence on the modifications that are made by the elderly while walking under different walking conditions.

Characterization Of Anfo Explosive By High Accuracy Esi(±)-ftms With Forensic Identification On Real Samples By Easi(-)-ms.

Ammonium nitrate fuel oil (ANFO) is an explosive used in many civil applications. In Brazil, ANFO has unfortunately also been used in criminal attacks, mainly in automated teller machine (ATM) explosions. In this paper, we describe a detailed characterization of the ANFO composition and its two main constituents (diesel and a nitrate explosive) using high resolution and accuracy mass spectrometry performed on an FT-ICR-mass spectrometer with electrospray ionization (ESI(±)-FTMS) in both the positive and negative ion modes. Via ESI(-)-MS, an ion marker for ANFO was characterized. Using a direct and simple ambient desorption/ionization technique, i.e., easy ambient sonic-spray ionization mass spectrometry (EASI-MS), in a simpler, lower accuracy but robust single quadrupole mass spectrometer, the ANFO ion marker was directly detected from the surface of banknotes collected from ATM explosion theft.

Morphological analysis of glass, carbon and glass/carbon fiber posts and bonding to self or dual-cured resin luting agents

OBJECTIVE: The aim of this study was to evaluate the morphology of glass (GF), carbon (CF) and glass/carbon (G/CF) fiber posts and their bond strength to self or dual-cured resin luting agents. MATERIAL AND METHODS: Morphological analysis of each post type was conducted under scanning electron microscopy (SEM). Bond strength was evaluated by microtensile test after bisecting the posts and re-bonding the two halves with the luting agents. Data were subjected to two-way ANOVA and Tukey's test (α=0.05). Failure modes were evaluated under optical microscopy and SEM. RESULTS: GF presented wider fibers and higher amount of matrix than CF, and G/CF presented carbon fibers surrounded by glass fibers, and both involved by matrix. For CF and GF, the dual-cured material presented significantly higher (p<0.05) bond strength than the self-cured agent. For the dual agent, CF presented similar bond strength to GF (p>0.05), but higher than that of G/CF (p<0.05). For the self-cured agent, no significant differences (p>0.05) were detected, irrespective of the post type. For GF and G/CF, all failures were considered mixed, while a predominance of adhesive failures was detected for CF. CONCLUSION: The bonding between fiber posts and luting agents was affected by the type of fibers and polymerization mode of the cement. When no surface treatment of the post is performed, the bonding between glass fiber post and dual-cured agent seems to be more reliable.

Biomassa e energia

Biomass was the dominating source of energy for human activities until the middle 19th century, when coal, oil, gas and other energy sources became increasingly important but it still represents ca. 10% of the worldwide energy supply. The major part of biomass for energy is still "traditional biomass" used as wood and coal extracted from native forests and thus non-sustainable, used with low efficiency for cooking and home heating, causing pollution problems. This use is largely done in rural areas and it is usually not supported by trading activities. There is now a strong trend to the modernization of biomass use, especially making alcohol from sugar cane thus replacing gasoline, or biodiesel to replace Diesel oil, beyond the production of electricity and vegetable coal using wood from planted forests. As recently as in 2004, sustainable "modern biomass" represented 2% of worldwide energy consumption. This article discusses the perspectives of the "first" and "second" technology generations for liquid fuel production, as well as biomass gaseification to make electricity or syngas that is in turn used in the Fischer-Tropsch process.