Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages

Compósito de poliuretano de mamona e vermiculita para isolação térmica

They are in this study the experimental results of the analysis of thermal performance of composite material made from a plant matrix of polyurethane derived from castor oil of kernel of mamona (COF) and loading of clay-mineral called vermiculite expanded. Bodies of evidence in the proportions in weight of 10%, 15% and 20% were made to determine the thermal properties: conductivity (k), diffusivity (ά) and heat capacity (C), for purposes of comparison, the measurements were also performed the properties of polyurethane of castor without charge and also the oil polyurethane (PU), both already used in thermal insulation. Plates of 0.25 meters of material analyzed were manufactured for use as insulation material in a chamber performance thermal coverage. Thermocouples were distributed on the surface of the cover, and inside the material inside the test chamber and this in turn was subjected to artificial heating, consisting of a bank of incandescent lamps of 3000 w. The results obtained with the composite materials were compared with data from similar tests conducted with the camera alone with: (a) of oil PU, (b) of COF (c) glass wool, (d ) of rock wool. The heat resistance tests were performed with these composites, obtaining temperature limits for use in the range of 100 º C to 130 º C. Based on the analysis of the results of performance and thermal properties, it was possible to conclude that the COF composites with load of expanded vermiculite present behavior very close to those exhibited by commercial insulation material

Desenvolvimento de um compósito de espuma rígida de poliuretana de mamona e fibras de sisal para isolação térmica

The search for sustainable technologies that can contribute to reduce energy consumption is a great challenge in the field of insulation materials. In this context, composites manufactured from vegetal sources are an alternative technology. The principal objectives of this work are the development and characterization of a composite composed by the rigid polyurethane foam derived from castor oil (commercially available as RESPAN D40) and sisal fibers. The manufacture of the composite was done with expansion controlled inside a closed mold. The sisal fibers where used in the form of needlepunched nonwoven with a mean density of 1150 g/m2 and 1350 g/m2. The composite characterization was performed through the following tests: thermal conductivity, thermal behavior, thermo gravimetric analysis (TG/DTG), mechanical strength in compression and flexural, apparent density, water absorption in percentile, and the samples morphology was analyzed in a MEV. The density and humidity percentage of the sisal fiber were also determined. The thermal conductivity of the composites was higher than the pure polyurethane foam, the addition of nonwoven sisal fibers will become in a higher level of compact foam, reducing empty spaces (cells) of polyurethane, inducing an increase in k value. The apparent density of the composites was higher than pure polyurethane foam. In the results of water absorption tests, was seen a higher absorption percent of the composites, what is related to the presence of sisal fibers which are hygroscopic. From TG/DTG results, with the addition of sisal fibers reduced the strength to thermal degradation of the composites, a higher loss of mass was observed in the temperature band between 200 and 340 °C, related to urethane bonds decomposition and cellulose degradation and its derivatives. About mechanical behavior in compression and flexural, composites presented a better mechanical behavior than the rigid polyurethane foam. An increase in the amount of sisal fibers induces a higher rigidity of the composites. At the thermal behavior tests, the composites were more mechanically and thermally resistant than some materials commonly used for thermal insulation, they present the same or better results. The density of nonwoven sisal fiber had influence over the insulation grade; this means that, an increaser in sisal fiber density helped to retain the heat

Estudo das propriedades termofísicas com variação da expansibilidade de compósito desenvolvido com matriz PUR-NOP e carga funcional de argilomineral

In this study were conducted experimental procedures for determination of variation of the expandability of rigid polyurethane foam (PUR) from a natural oil polyol (NOP), specifically the Castor oil plant, Ricinus communis, pure and additions of the vermiculite in phase dispersed in different percentage within a range from 0% to 20%, mass replacement. From the information acquired, were defined the parameters for production of bodies of test, plates obtained through controlled expansion, with the final volume fixed. Initially, the plates were subjected to thermal performance tests and evaluated the temperature profiles, to later be extracted samples duly prepared in accordance with the conditions required for each test. Was proceeded then the measurement of the coefficient of thermal conductivity, volumetric capacity heat and thermal diffusivity. The findings values were compared with the results obtained in the tests of thermal performance, contributing to validation of the same. Ultimately, it was investigated the influence that changes in physical-chemical structure of the material had exerted on the variation of thermophysical quantities through gas pycnometry, scanning electron microscopy (SEM) combined with energy dispersive X-ray fluorescence spectroscopy (EDXRF), infrared spectroscopy using Fourier transform (FTIR), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). Based on the results obtained was possible to demonstrate that all load percentage analyzed promoted an increase in the potential expansion (PE) of the resin. In production of the plates, the composites with density near at the free expansion presented high contraction during the cure, being the of higher density adopted as definitive standard. In the thermal performance tests, the heating and cooling curves of the different composites had presented symmetry and values very close for lines of the temperature. The results obtained for the thermophysical properties of composites, showed little difference in respect of pure foam. The percentage of open pores and irregularities in the morphology of the composites were proportionate to the increment of vermiculite. In the interaction between the matrix and dispersed phase, there were no chemical transformations in the region of interface and new compounds were not generated. The composites of PUR-NOP and vermiculite presented thermal insulating properties near the foam pure and percentage significantly less plastic in its composition, to the formulation with 10% of load

Estudo do aproveitamento de resíduo de gesso como carga para compósito com matriz de resina expansiva de mamona

In the execution of civil engineering works, either by wasting during the coating of wall or demolition of gypsum walls, the generation of the gypsum waste involves serious environmental concerns. These concerns are increased by the high demand of this raw material in the sector and by the difficulties of proper disposal byproduct generated. In the search for alternatives to minimize this problem, many research works are being conducted, giving emphasis in using gypsum waste as fillers in composites materials in order to improve the acoustic, thermal and mechanical performances. Through empirical testing, it was observed that the crystallization water contained in the residue (CaSO4.2H2O) could act like primary agent in the expanding of the polyurethane foam. Considering that polyurethane produced from vegetable oils are biodegradable synthetic polymers and that are admittedly to represent an alternative to petrochemical synthetic polyurethane, this research consist an analysis of the thermal behavior of a composite whose matrix obtained from a resin derived from the expansive castor oil seed, with loads of 4%, 8%, 12% and 16% of gypsum waste replacing to the polyol prepolymer blend. Contributors to this analysis: a characterization of the raw material through analysis of spectroscopy by Fourier transform infrared (FTIR), chemical analysis by X-Ray Fluorescence (XRF) and mineralogical analysis by X Ray Diffraction (XRD), complemented by thermo gravimetric analysis (TGA). In order to evaluate the thermo physical properties and thermal behavior of the composites manufactured in die closed with expansion contained, were also carried tests to determine the percentage of open pore volume using a gas pycnometer, scanning electronic microscopy (SEM), in addition to testing of flammability and the resistance to contact with hot surfaces. Through the analysis of the results, it appears that it is possible to produce a new material, which few changes in their thermo physical properties and thermal performance, promotes significant changes and attractive to the environment

Desenvolvimento de compósito de pu de mamona com carga de resíduo de couro para isolação térmica

The standardization of the bovine skin thickness in the leather industry generates a residue known as wet-blue . At the end of twentieth century, the brazilian industry discarded about 131 thousand tons of this residue in nature, provoking a great environmental liability. In this paper is presented the analyses of the termophysical properties, thermal and volumetric expansion performance of a composite of vegetable resin of castor oil plant (Ricinus communis) with load of industrial residue of leather "wet-blue", for application as thermal isolation material of warm surfaces. There were considered four percentile levels of residue load in the proportions in mass of 0%, 5%, 10% and 15%, added to the expansible resin of castor oil plant in two configurations: sawed leather and crushed leather in a smaller particle (powder) by grinding in a mill of balls. Twenty-one proof bodies were produced for termophysical properties analysis (three for each configuration) and four proof bodies for rehearsals of thermal acting. Analyses of thermal acting were done in test cameras. The results of the rehearsals were compared to those obtained considering the castor oil plant foam without residue addition. A small reduction of the thermal conductivity of the composite was observed in the proportion of 10% of leather residue in both configurations. Regarding thermal conductivity, calorific capacity and diffusivity, it was verified that the proposed composite showed very close values to the commercial insulating materials (glass wool, rock wool, EPS). It was still demonstrated the technical viability of the use of composite as insulating thermal for systems of low potency. The composite presented larger volumetric expansion with 15% of sawed residue of leather.

Composito de poliuretano de mamona e residuo industrial para isolacao termica e absorcao sonora

This work proposes the development of an innovative material made from a vegetable polyurethane matrix and load of industrial waste, from retread tires, for thermal insulation and environmental comfort. Experimental procedures are presented, as well as the results of the thermal and acoustic performance of this composite material, made from an expansive foam derived from the castor seed oil and fiber of scrap tires. The residue was treated superficially with sodium hydroxide, to eliminate contaminants, and characterized macroscopically and microscopically. Samples were produced with addition of residues at levels of 5%, 10%, 15% and 20% by weight, for determination of thermal properties: conductivity, heat capacity and thermal diffusivity, sound absortion index and density. The results were compared to commercially available thermal insulation and sound absorbing products. According to the analysis of results, it was concluded that the developed composite presents characteristics that qualify it as a thermal insulation with superior performance, compared to commercial available insulation, and sound absorption capacity greater than the castor oil polyurethane s, without addition of the residue

Utilização de um secador solar para desintoxicação da torta de mamona

It´s been motivating motivated by the current rulers as an energy solution the use of the biodiesel as source of energy, that doesn't damage the environment and promotes the development of the areas where the base plant are grown. The process of production of the biodiesel, starting from the castor oil plant and its derivers, generates a known product as castor oil plant pie that has been used as fertilizer. Once disintoxicated, it can serve as animal ration, because it contains high content of proteins, presenting larger joined value. The disintoxication process, can be obtained through the process of drying the pie with the construction and use of models of dryers capable to elevate the temperature of the castor oil plant pie to approximately 60ºC.In this temperature the product tends to eliminate the ricina, with the aid of an aqueous solution of hydroxide of calcium, or still reach higher temperatures to make the disintoxication without a chemical treatment. It was made a bibliographical research about known processes of disintoxication of the castor oil plant pie from the autoclave use to the drying direct exposure to the sun. Starting from the state of the art and identification of the object, it was chosen solar dryers to eliminate the ricina. It was applied two types of solar dryers: the one of solar direct exposure, and the one with concentrador. The castor oil plant pie was separated in samples, with measurement of its initial mass, codified and placed in the dryers. The results were presented in graphs and tables forms, with the values of temperatures noticed. It was noticed the variations of temperature and the relationships analyzed related with the ricina content eliminated from the pie. The analysis of the ricina content was accomplished by Embrapa - Campina Grande, by eletroforese method. The analysis of the result of considering the content of ricina of the samples. It was observed that, we obtained lower rate of ricina in samples that had larger drying time and average value temperature above 60ºC. Comparing with the ones submitted to higher temperatures and in a shorter period of time. It was possible to evaluate the efficiency of the dryers in the desintoxication process of the samples, as well as the type of more appropriate dryer for the drying pie process. Finally, it was concluded that the solar dryer with concentrador presents higher values temperatures than the direct exposure one. So, it´s being more opportune applied in the castor oil plant pie drying process. However, more than one hour for drying time is needed

Preparação de poliuretana à base de óleo de mamona

Polyurethanes are very versatile macromolecular materials that can be used in the form of powders, adhesives and elastomers. As a consequence, they constitute important subject for research as well as outstanding materials used in several manufacturing processes. In addition to the search for new polyurethanes, the kinetics control during its preparation is a very important topic, mainly if the polyurethane is obtained via bulk polymerization. The work in thesis was directed towards this subject, particularly the synthesis of polyurethanes based castor oil and isophorone diisocianate. As a first step castor oil characterized using the following analytical methods: iodine index, saponification index, refraction index, humidity content and infrared absorption spectroscopy (FTIR). As a second step, test specimens of these polyurethanes were obtained via bulk polymerization and were submitted to swelling experiments with different solvents. From these experiments, the Hildebrand parameter was determined for this material. Finally, bulk polymerization was carried out in a differential scanning calorimetry (DSC) equipment, using different heating rates, at two conditions: without catalyst and with dibutyltin dilaurate (DBTDL) as catalyst. The DSC curves were adjusted to a kinetic model, using the isoconversional method, indicating the autocatalytic effect characteristic of this class of polymerization reaction

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

Síntese enzimática de biosurfactante e sua aplicabilidade na indústria do petróleo

Enzymes have been widely used in biosynthesis/transformation of organic compounds in substitution the classic synthetic methods. This work is the first writing in literature of enzymatic synthesis for attainment the biossurfactants, the use glucose sucrose, ricinoleic acid e castor oil as substratum, and as biocatalyst, used immobilized lipase Thermomyces lanuginose, Rhizomucor miehei and the Candida antarctica lipase B; alkaline protease and neutral protease from Bacillus subtillis and yeast Saccharomyces cerevisiaeI. The analysis of HPLC (high performance liquid chromatography) showed that highest conversions were reached of used the alkaline protease from Bacillus subtillis. Laboratory tests, to evaluate the applicability, indicated that the produced biosurfactantes had good stability in presence of salts (NaCl) and temperature (55 e 25°C), they are effective in the reduction of the superficial tension and contac angle, but they have little foaming capacity, when compared with traditional detergents. These results suggest that the prepared surfactants have potential application as wetting agent and perforation fluid stabilizer

Remoção, por flotação, de óleo em águas produzidas na indústria de petróleo: eficiência e modelagem do processo

The separation oil-water by the use of flotation process is characterized by the involvement between the liquid and gas phases. For the comprehension of this process, it s necessary to analyze the physical and chemical properties command float flotation, defining the nature and forces over the particles. The interface chemistry has an important role on the flotation technology once, by dispersion of a gas phase into a liquid mixture the particles desired get stuck into air bubbles, being conduced to a superficial layer where can be physically separated. Through the study of interface interaction involved in the system used for this work, was possible to apply the results in an mathematical model able to determine the probability of flotation using a different view related to petroleum emulsions such as oil-water. The terms of probability of flotation correlate the collision and addition between particles of oil and air bubbles, that as more collisions, better is the probability of flotation. The additional probability was analyzed by the isotherm of absorption from Freundlich, represents itself the add probability between air bubbles and oil particles. The mathematical scheme for float flotation involved the injected air flow, the size of bubbles and quantity for second, the volume of float cell, viscosity of environment and concentration of demulsifier. The results shown that the float agent developed by castor oil, pos pH variation, salt quantity, temperature, concentration and water-oil quantity, presented efficient extraction of oil from water, up to 95%, using concentrations around 11 ppm of demulsifier. The best results were compared to other commercial products, codified by ―W‖ and ―Z‖, being observed an equivalent demulsifier power between Agflot and commercial product ―W‖ and superior to commercial product ―Z‖

Estudo da influência do biodiesel de mamona como aditivo antioxidante para o biodiesel de girassol e soja

Biodiesel is a fuel made up by mono-alkyl-esters of long chain fatty acids, derived from vegetable oils or animal fat. This fuel can be used in compression ignition engines for automotive propulsion or energy generation, as a partial or total substitute of fossil diesel fuel. Biodiesel can be processed from different mechanisms. Transesterification is the most common process for obtaining biodiesel, in which an ester compound reacts with an alcohol to form a new ester and a new alcohol. These reactions are normally catalyzed by the addition of an acid or a base. Initially sunflower, castor and soybean oil physicochemical properties are determined according to standard test methods, to evaluate if they had favorable conditions for use as raw material in the transesterification reaction. Sunflower, castor and soybean biodiesel were obtained by the methylic transesterification route in the presence of KOH and presented a yield above 93% m/m. The sunflower/castor and soybean/castor blends were studied with the aim of evaluating the thermal and oxidative stability of the biofuels. The biodiesel and blends were characterized by acid value, iodine value, density, flash point, sulfur content, and content of methanol and esters by gas chromatography (GC). Also studies of thermal and oxidative stability by Thermogravimetry (TG), Differential Scanning Calorimetry High Pressure (P-DSC) and dynamic method exothermic and Rancimat were carried out. Biodiesel sunflower and soybean are presented according to the specifications established by the Resolution ANP no 7/2008. Biodiesel from castor oil, as expected, showed a high density and kinematic viscosity. For the blends studied, the concentration of castor biodiesel to increased the density, kinematic viscosity and flash point. The addition of castor biodiesel as antioxidant in sunflower and soybean biodiesels is promising, for a significant improvement in resistance to autoxidation and therefore on its oxidative stability. The blends showed that compliance with the requirements of the ANP have been included in the range of 20-40%. This form may be used as a partial substitute of fossil diesel