Formulação de novos combustíveis base diesel: avaliação de desempenho e emissões

The industry, over the years, has been working to improve the efficiency of diesel engines. More recently, it was observed the need to reduce pollutant emissions to conform to the stringent environmental regulations. This has attached a great interest to develop researches in order to replace the petroleum-based fuels by several types of less polluting fuels, such as blends of diesel oil with vegetable oil esters and diesel fuel with vegetable oils and alcohol, emulsions, and also microemulsions. The main objective of this work was the development of microemulsion systems using nonionic surfactants that belong to the Nonylphenols ethoxylated group and Lauric ethoxylated alcohol group, ethanol/diesel blends, and diesel/biodiesel blends for use in diesel engines. First, in order to select the microemulsion systems, ternary phase diagrams of the used blends were obtained. The systems were composed by: nonionic surfactants, water as polar phase, and diesel fuel or diesel/biodiesel blends as apolar phase. The microemulsion systems and blends, which represent the studied fuels, were characterized by density, viscosity, cetane number and flash point. It was also evaluated the effect of temperature in the stability of microemulsion systems, the performance of the engine, and the emissions of carbon monoxide, nitrogen oxides, unburned hydrocarbons, and smoke for all studied blends. Tests of specific fuel consumption as a function of engine power were accomplished in a cycle diesel engine on a dynamometer bench and the emissions were evaluated using a GreenLine 8000 analyzer. The obtained results showed a slight increase in fuel consumption when microemulsion systems and diesel/biodiesel blends were burned, but it was observed a reduction in the emission of nitrogen oxides, unburned hydrocarbons, smoke index and f sulfur oxides

Obtenção de emulsões asfálticas modificadas utilizando resíduos industriais

The main objective of this research was the development and characterization of conventional and modified cationic asphalt emulsions. The asphalt emulsions were developed by using the Petroleum Asphalt Cement (CAP 50-70) from Fazenda Belém (Petrobras -Aracati-Ce). The first step in this research was the development of the oil phase (asphalt + solvent) and the aqueous phase (water + emulsifying agent + acid + additives), separately. During the experiments for the obtaining of the conventional asphalt emulsion, the concentration of each constituent was evaluated. For the obtaining of the oil phase, kerosene was used as solvent at 15 and 20 wt.%. For the development of the aqueous phase, the emulsifying agent was used at 0.3 and 3.0 wt.%, whereas the acid and the additive were set at 0.3 wt.%. The percentage of asphalt in the asphalt emulsion was varied in 50, 55, and 60 wt.% and the heating temperature was set at 120 °C. The aqueous phase in the asphalt emulsion was varied from 16.4 to 34.1 wt.% and the heating temperature was set at 60 °C. After the obtaining of the oil and the aqueous phases, they were added at a colloidal mill, remaining under constant stirring and heating during 15 minutes. Each asphalt emulsion was evaluated considering: sieve analysis, Saybolt Furol viscosity, pH determination, settlement and storage stability, residue by evaporation, and penetration of residue. After the characterization of conventional emulsions, it was chosen the one that presented all properties in accordance with Brazilian specifications (DNER-EM 369/97). This emulsion was used for the development of all modified asphalt emulsions. Three polymeric industrial residues were used as modifier agents: one from a clothing button industry (cutouts of clothing buttons) and two from a footwear industry (cutouts of sandals and tennis shoes soles), all industries located at Rio Grande do Norte State (Brazil).The polymeric residues were added into the asphalt emulsion (1 to 6 wt.%) and the same characterization rehearsals were accomplished. After characterization, it were developed the cold-mix asphalts. It was used the Marshall mix design. For cold-mix asphalt using the conventional emulsion, it was used 5, 6 and 7 wt.% asphalt emulsion. The conventional mixtures presented stability values according Brazilian specification (DNER-369/97). For mixtures containing asphalt modified emulsions, it was observed that the best results were obtained with emulsions modified by button residue

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Incorporação do resíduo oriundo do beneficiamento de caulim em concreto asfáltico

The municipal district of Equador-RN is located in an area of great amounts of ores, being your main economical activity the extraction and the kaolin improvement. The main originating from environmental problem that activity is the amount of generated residue, about 70% of the extracted kaolin. The residues are simply piled up in lands of the improvement companies, occupying like this a large area and causing impact in the existent flora. When dry, the residues transform powdered and for the action of the wind, they disperse, polluting the air. Being like this, the present work has as objective evaluates the incorporation of the great residue, originating from of the kaolin improvement, in partial substitution of all the employed aggregates in a conventional mixture of asphalt concrete, which was used in the paving of BR101/RN061 - passage between Ponta Negra and Ares. That evaluation was accomplished in three stages. The first refers to the evaluation of the physical, thermal and mineralogical characteristics of the residue with the intention of to classify it and to define your application as aggregate (small and great). The second refers to the physical characterization of the aggregates and of the asphalt material used in the conventional mixture. And the third, to the evaluation of the mixtures containing residue, which were elaborated starting from the conventional mixture with the gradual incorporation of the residue, from 5 to 40%, in substitution to the part of the conventional aggregates, in way to obtain similar particle size curves the one of the conventional mixture. That evaluation was accomplished through the comparison between the volumetric composition, the mechanical behavior and the susceptibility to the humidity of the mixtures containing residue with the one of the conventional mixture, and with the one of the DNIT specifications. The results show that the great residue originating from of the kaolin improvement has grains of the most varied size, being like this, it can substitute part of all the conventional aggregates and of the filler in an asphalt mixture. Besides, your mineralogical composition presented the same present minerals in the composition of conventional aggregates used in paving. The results evaluation of the volumetric composition of the mixtures containing residue indicates that it can use up to 30% of residue in substitution to the conventional aggregates. The evaluation of the mechanical behavior of those mixtures indicates that the residue increment in the studied mixtures caused an increase of the stability and a reduction of the resistance to the traction. The values obtained in the resistance to the traction meet below the minimum value specified by DNIT, but close to the value obtained in the conventional mixture. When taking in consideration the susceptibility of the same ones to the humidity, the results indicate that she can use up to 25% of residue

Análise da adição de resíduo oriundo do tratamento de esgotos em massa cerâmica utilizada para fabricação de telhas

Sludge of Wastewater Treatment Plants (WTPs) disposal is a problem for any municipality, for this reason the amount of sludge production is now a key issue in selecting treatment methods. It is necessary to investigate new applications for this waste type, due to the restrictions imposed by the environmental organs. The raw materials used in the Red Ceramic, are generally very heterogeneous, for this reason, such materials can tolerate the presence of different types of wastes. In Rio Grande do Norte, the roof tiles production corresponds to 60,61% from the total of ceramic units produced. Due to the importance of the ceramic industry of roof tiles for the state, allied to the environmental problem of the sludge disposal, this work had for objective to verify the possibility of the incorporation of sewage sludge in ceramic body used for production of roof tiles. In the research, sludge originating from drying beds of WTP of the Central Campus from UFRN and clays originating from a ceramic industry from Goianinha/RN were used. The raw materials were characterized by techniques of: analysis of particles distribution by diffraction to laser; real density; consistence limits; chemical analysis by X-ray fluorescence; mineralogical analysis by X-ray diffraction; organic matter; and solids content. Five batches of roof tiles were manufactured in the approximate dosages of 2%, 4%, 6%, 8% and 10%. To evaluate the properties of each final product, tests of water absorption, impermeability, bending strength, leachability and solubility were accomplished. The roof tiles manufactured with sludge presented characteristics similar to the roof tiles without sludge in relation to the environmental risk. The results showed that it is possible to use approximately up to 4% of sludge in ceramic bodies for production of roof tiles. However, it is observed that the high amount of organic matter (71%) present in the sludge is shown as factor that limits the sludge incorporation in ceramic bodies, worsening the quality of the roof tiles. It is necessary the use of mixtures of different raw materials under point of view of the granulometry and of the other chemical and mineralogical properties for the obtaining of a satisfactory mass to the production of ceramic roof tiles

Caracterização do comportamento geotécnico de mistura de resíduo de pneus e solo laterítico

A technological alternative for the correct disposal of tires is the use in the construction of embankment with soil and shredded tires. The use of waste tires in tropical soils requires prior knowledge of the properties and limitations of these materials. In this work, the results of an experimental program was devised to characterize the behavior of mixtures of waste tires and a lateritic soil. The residue used in this study is classified as tire buffings with an average size of 1.4 mm. The laboratory program included testing of particle size analysis, Atterberg limits, compaction, direct shear tests, permeability and confined compression tests with pure soil, pure tire and the mixtures. Proportions of 0% (pure soil), 10%, 20%, 40%, 50 % and 100% (pure tire) by weight were used. For the confining stress levels used in the study, the presence of tire residue provided a considerable increase in shear strength of the mixture. The maximum shear strength was obtained for a residue content of 40% by weight. Permeability tests on samples of waste under a confining stress of 100 kPa showed that the permeability increases significantly with increasing residue content until a residue content of 20%. The increase in permeability after that value showed to be negligible. Confined compression tests showed that the soil mixed with tire residue becomes more compressible than the pure soil. The secant constrained modulus (Msec) for the same vertical stress decreases with increasing percentage of residue.

Incorporação do lodo de tanque séptico como matéria-prima de uma mistura asfáltica

In Natal/RN, 68% of the population uses some kind of individual system for their domestic sewers treatment, being that the most used it is septic tank, followed by sumidouro. Every treatment system of sewers, usually used, generates a by-product denominated sludge. That residue presents some components, in its constitution, undesirable under the environmental and sanitary point of view. In such case, to assure that the system treatment has satisfactory results, it is necessary to do the adjusted disposition of the sludge sewage. Several countries are looking for technical alternatives for the use and disposition of residues. Under technical and environmental conditions appropriate, these materials can be used, decreasing the consumption of the natural resources and the treatment need, storage or elimination of the wastes, what decrease the risks created. Some of the alternatives of recycling of the sludge sewage are: the application in the agriculture, in the production of energy and as raw material in the civil construction. This study evaluated asphalt mixtures behavior that partially substituted conventional aggregates by septic tank sludge. The septic tank sludge gave origin to two raw materials called raw sludge and sludge ash. The raw sludge was put as a small aggregate and the sludge ash as filler. In the first experiment it was made a comparison between the mixture with conventional aggregates and the mixtures that replaced sand by raw sludge in the proportions from 5% to 40%. In the second experiment, it was made comparison between mixtures with 1%, 2% and 3% of sludge ash and cement. The stages developed along the study were: physical characterization of the conventional materials; physical, chemistry, thermal, mineralogical characterizations and analysis of environmental risk of the raw sludge; physical characterization and analysis of environmental risk of the sludge ash; analysis of the mixtures performance through its volumetric and mechanical characteristics; forecast of the mixtures susceptibility in the moisture presence. For the grain size composition used and with the percentage asphalt adopted, the mixtures with up to 7,5% of raw sludge in his composition attend to the National Department of Transports Infrastructure (DNIT) specifications. However, in agreement with the mixtures susceptibility in the moisture presence, the mixtures with addition of raw sludge don't present satisfactory acting. In such case, they could be used in arid and semi-arid areas. The raw sludge application in mixtures increased their voids volume and their stability. However, it damaged mixtures adhesiveness. Mixtures with sludge ash and with cement presented similar behavior. However, mixtures with sludge ash presented a better performance than mixtures with cement as for their stability and their tensile strength ratio. The mixture with 1% of sludge ash is better. The wastes studied don't represent environmental risk

Estudos de sinterização da mistura de pós cerâmicos diatomita-titânia

This work is part of an effort of consolidation of a daily search for powder technology at the Department of Physics of the Universidade Federal do Rio Grande do Norte. This work objective the study and development of new ceramic materials from raw materials abundant at the region. For this, were studied ceramic mixtures of powders from diatomite-titania to aiming at a new ceramic material from powder technology. The experimental work involved a characterization of ceramic powders from a diatomite-titania mixture. The powders obtained were pressed and then parameters like variation of mass, linear shrinkage, activation energy and the mechanism of sintering are studied in function of the time and temperature of sintering, beyond microstructural analysis. The obtained results allow us estimate the optimizing of sintering conditions of this material

Avaliação do comportamento termoanalítico e oxidativo do biodiesel de mamona

In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210°C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel

Preparação de resinas de poliuretana à base de óleo de mamona e dietanolamina

The aim of this work was the preparation of polyols from reactions between castor oil and dietanolamine to increase the hydroxyl content and the network degree in the products to application in electronic devices. The polyols and the mixtures obtained were characterized by nuclear magnetic ressonance. Castor oil (CO) is a natural triglyceride - based polyol possessing hydroxyl groups, which allow several reactions that produce many different products. Among them are the polyurethanes (PU), which have been considered an ideal product for the covering of electricelectronic circuits, due to their excellent electrical, shock-absorbing, solvents resistance and hydrolytic stability properties. About 90% of the fatty acids present in the castor oil are ricinoleic acid (12-hydroxyoleic acid), while the remaining 10% correspond to non-hydroxylated fatty acids, mainly linoleic and oleic acids. The chemical analysis of castor oil indicates a hydroxyl number of 2.7. In this work, a polyol was obtained by the reaction of the CO with diethanolamine (DEA), in order to elevate the hydroxyl value from 160 to 230 or to 280 mgKOH/g, and characterized by nuclear magnetic resonance (NMR) 1H and 13C (Mercury 200). The polyadition of the resulting polyol with isophorone diisocianate (IPDI) was carried out at 60°C, and the reaction kinetics was followed by rheological measurements in a Haake RS150 rheometer. The electrical properties were determined in a HP LCR Meter 4262A, at 1.0 Hz and 10.0 KHz. The chemical analysis showed that the polyols obtained presented hydroxyl number from 230 to 280 mgKOH/g. The polyadition reaction with IPDI produced polyurethane resins with the following properties: hardness in the range from 45 shore A to 65 shore D (ASTM D2240); a dielectric constant of 3.0, at 25°C (ASTM D150). Those results indicate that the obtained resins present compatible properties to the similar products of fossil origin, which are used nowadays for covering electric-electronic circuits. Therefore, the PUs from castor oil can be considered as alternative materials of renewable source, free from the highly harmful petroleum - derived solvents

Avaliação do comportamento de argila ativada na presença de água destilada, soluções salinas e inibidores de hidratação catiônicos

The clay swelling is today one of the major problems during the well drilling. Nearly 50% of clays that constitute shale expand easily in the presence of water molecules. During the drilling of a geological formation containing swelling clays, when is feasible the use of water base fluids, it is necessary to apply clay inhibitors. This avoids the incorporation of the cutting to the drilling fluid which is responsible for the wall swelling and crumbling. The aim of this work was to evaluate the synergistic behavior that occurs when swelling clay inhibitors are associated to NaCl and KCl salts. Three swelling clay inhibitors samples, INIB A, INIB B and INIB C, were analyzed. Each inhibitor was characterized by the amount of chlorides and active matter content. For the water-clay interaction evaluation in the presence of various fluids, it was used the Capillary Suction Timer (CST, Fann) and Linear Swell Meter (LSM 2000, Fann). For better interpretation of results, a Design of Experiments (DOE, Umetrics MODDE 7.0 TM) through Result Surface Methodology (RSM) was employed, taking into account the type, the swelling inhibitors concentration and the contact time with the clay. The results showed different efficiencies among the inhibitors employed, and the salt-inhibitors mixtures were more efficient than those products alone. However, for field operation, other parameters should be taking into account, as operational cost, environmental requests and time of application for each product

Análise química de produtos de incrustação em dutos de petróleo por espectometria de fluorescência de raios X

The quantitative chemical characterization of the inorganic fraction of scale products is very relevant in studying, monitoring and controlling corrosive processes of oil pipelines. The X-ray fluorescence spectrometry (XRF) is a very versatile analytical technique, which can be used in quantitative analysis in solid samples at low concentrations of the chemical element, in the order of few ppm. A methodology that involves sample preparation diluted in the proportion of 1:7 (one portion of the sample for seven of wax), pressed as pellets was used in the XRF calibration for chemical analysis of scale products from oil pipelines. The calibration involved the preparation of reference samples from mixtures of P.A. reagents, aiming to optimize the time consumed in the steps of sample preparation and analysis of Al, Ba, Ca, Fe, K, Mg, Mn, Na, P, S, Si, Sr and Ti, using the same pressed pellet for trace and major elements analysis

Avaliação da estabilidade térmica e oxidativa dos biodieseis de algodão, girassol, dendê e sebo bovino

The search for new sources of environmentally friendly energy is growing every day. Among these alternative energies, biodiesel is a biofuel that has had prominence in world production. In Brazil, law 11.097, determine that all diesel sold in the country must be made by mixing diesel/biodiesel. The latter called BX, , where X represents the percent volume of biodiesel in the diesel oil, as specified by the ANP. In order to guarantee the quality of biodiesel and its mixtures, the main properties which should be controlled are the thermal and oxidative stability. These properties depend mainly of the chemical composition on the raw materials used to prepare the biodiesel. This dissertation aims to study the overall thermal and oxidative stability of biodiesel derived from cotton seed oil, sunflower oil, palm oil and beef tallow, as well as analyze the properties of the blends made from mineral oil and biodiesel in proportion B10. The main physical-chemical properties of oils and animal fat, their respective B100 and blends were determined. The samples were characterized by infrared and gas chromatography (GC). The study of thermal and oxidative stability were performed by thermogravimetry (TG), pressure differential scanning calorimeter (PDSC) and Rancimat. The obtained biodiesel samples are within the specifications established by ANP Resolution number 7/2008. In addition, all the blends and mineral diesel analyzed presented in conformed withthe ANP Regularion specifications number 15/2006. The obtained results from TG curves data indicated that the cotton biodiesel is the more stable combustible. In the kinetic study, we obtained the following order of apparent activation energy for the samples: biodiesel from palm oil > sunflower biodiesel > tallow biodiesel > cotton biodiesel. In terms of the oxidative stability, the two methods studied showed that biodiesel from palm oil is more stable then the tallow. Within the B100 samples studied only the latter were tound to be within the standard required by ANP resolution N° 7. Testing was carried out according to the EN14112. This higher stability its chemical composition

Utilização de sílica gel organofuncionalizada para adsorção de íons metálicos em solução aquosa

In this work the organosilanes aminopropyltriethoxysilane, 3-mercaptopropyltryethoxisilane and n[-3-(trimetoxisilyl)propyl]ethylenetriamine, as well as tetraethylortosilicate (TEOS), were employed to produce, by sol-gel method, organofuncionalized silicon samples. The prepared samples were characterized by elementar analys by thermogravimetry and infrared spectroscopy. Those samples were employed to adsorb Cd2+, Pb2+, Ni2+ and Zn2+ from aqueous solutions (10, 20, 40, 60 and 80 mg L-1). In typical experiments, 50 mg of the organometrix was suspended in 20 mL of metal cation solutions at four different contact times: 30, 60, 90 and 120 minutes. The total amount of adsorbed cations were measured by atomic absorption spectrometry. To all investigated matrices, the following adsorption capacity was observed: Ni2+ > Zn2+ > Cd2+ > Pb2+. Such sequence is closely related with the cation radius, as well as the cation hardness

Utilização de microemulsão na remoção da cor de efluentes têxteis contendo corantes dispersos

Polyester fibers are the most used fibers in the world and disperse dyes are used for dyeing these fibers. After dyeing, the colorful dyebath is discharged into effluent streams, which needs a special treatment for color removal. Surfactants interaction with dyes has been evaluated in several studies, including the textile area, specifically in the separation of dyes from textile wastewater. In this work a cationic surfactant was used in a microemulsion system for the extraction of anionic dyes (disperses dyes) from textile wastewater. These microemulsion system was composed by dodecylamonium chloride (surfactant), kerosene oil (organic phase), isoamyl alcohol (cosurfactant) and the wastewater (aqueous phase). The wastewater that results after the dyeing process is acid (pH 5). It was observed that changing the pH value to above 12.8 the extraction could be made, resulting in an aqueous phase with low color level. The Scheffé net experimental design was used for the extraction process optimization, and the obtained results were evaluated using the program "Statistica 7.0". The optimal microemulsion system was composed by 59.8wt.% of wastewater, 30.1wt.% of kerosene, 3.37wt.% of surfactant and 6.73wt.% of cosurfactant, providing extraction upper than 96%. A mix of reactive dyebath (50%) and disperse dyebath (50%) was used as aqueous phase and it presented extraction upper than 98%. The water phase after extraction process can be reused in a new dyeing, being obtained satisfactory results, according to the limits established by textile industry for a good dyeing. Tests were accomplished seeking to study the influence of salt addition and temperature. An experimental design was used for this purpose, which showed that the extraction doesn't depend on those factors. In this way, the removal of color from textile wastewater by microemulsion is a viable technique (that does not depend of external factors such as salinity and temperature), being obtained good extraction results even with in wastewater mixtures