Low temperature properties of winterized methyl babassu biodiesel

In this work, differential scanning calorimetry and X-ray diffraction techniques were employed to evaluate the influence of the winterization process on the low temperature properties of methyl babassu biodiesel. The results have shown that the crystallization onset temperature for the non-winterized biodiesel is around 266.4 K (?6.6 °C) which is reduced to 263.6 K (?9.4 °C) for the liquid fraction of winterized biodiesel. The 14 % reduction in the amount of saturated fatty acid methyl esters is probably responsible for the improvement of low temperature properties of winterized methyl babassu biodiesel.     

Thermo-oxidative decomposition of biodiesel samples obtained from mixtures of beef tallow,soybean oil,and babassu oil

Biodiesel can be obtained from various fatty acid sources. Each raw material has a different chemical composition that leads to different properties. Owing to these properties, the mixture of different proportions of raw materials can lead to biodiesels with best features in relation to physicochemical parameters such as viscosity, oxidative stability and flow properties, generating a fuel whose characteristics meet the requirements of the current legislation of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP). The objective of this study was to determine the physicochemical properties of biodiesel samples produced from mixtures of beef tallow, babassu oil, and soybean oil. The thermo-oxidative stability was evaluated using thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC). The results showed that all samples were in accordance to the ANP specifications. The biodiesel obtained from a mixture containing 50% of babassu oil had lower values of pour point, cold filter plugging point, and freezing point. This biodiesel also showed a higher thermo-oxidative stability in synthetic air and in oxygen atmospheres.     

Thermo-oxidative stability and cold flow properties of babassu biodiesel by PDSC and TMDSC techniques

The babassu (Orbignya Phalerata Mart.) biodiesel has lauric esters as main constituents, resulting in high oxidative stability and low cloud and freezing points. In order to reduce these side effects, the saturated ethyl esters content was reduced by means of winterization process. The TMDSC and PDSC techniques were used to verify the thermal and oxidative stabilities of the ethyl babassu biodiesel. During the heating stage, the winterized solid phase of ethyl esters presented an endothermic transition associated to the solidification process. This behavior was not observed for the liquid winterized FAEE, confirming the efficiency of the winterization process.     

Flow properties of biodiesel: correlation between TMDSC and dynamic viscosity

Sustainable and renewable energy has become more attractive due to its environmental benefits. Among these alternative sources, biodegradable and low emission biodiesels have been gaining attention as compared to diesel. However, their performance at low temperatures affects their commercial viability, because of engine performance problems, and when starting. Cold Filter Plugging Point, Pour Point, and Cloud Point are employed to predict the limits of operability for biodiesel. However, dynamic viscosity and TM-DSC methods are also useful to assess these properties and can be correlated. Viscosity curves were obtained, and TM-DSC revealed that the start temperature (transition liquid–solid) exhibits an increase in flow resistance for soybean, colza, sunflower, corn, and babassu oil biodiesels. The nucleation processes which occur during cooling are unique for each type of biodiesel due to the presence of different ester compositions and the values for viscosity and flow at low temperatures varied accordingly.     

Emission profile of rapeseed methyl ester and its blend in a diesel engine

Fatty acid methyl esters, also known as biodiesel, have been shown to have a great deal of potential as petro-diesel substitutes. Biodiesel comprise a renewable alternative energy source, the development of which would clearly reduce global dependence on petroleum and would also help to reduce air pollution. This paper analyzes the fuel properties of rapeseed biodiesel and its blend with petro-diesel, as well as the emission profiles of a diesel engine on these fuels. Fuels performance studies were conducted in order to acquire comparative data regarding specific fuel consumption and exhaust emissions, including levels of carbon monoxide (CO), carbon dioxide (CO₂), smoke density, and NO_x, in an effort to assess the performance of these biodiesel and blend. The fuel consumption amount of oil operations at high loads was similar or greater than that observed during petro-diesel operation. The use of biodiesel is associated with lower smoke density than would be seen with petro-diesel. However, biodiesel and its blend increased the emission of CO, CO₂, and nitrogen oxides, to a greater degree than was seen with petro-diesel. The above results indicate that rapeseed biodiesel can be partially substituted for petro-diesel under most operating conditions, regarding both performance parameters and exhaust, without any modifications having to be made to the engine.     

Thermal and rheological behavior of diesel and methanol biodiesel blends

The most feasible alternative among fuels derived from biomass seems to be the biodiesel, having the required characteristics for a total or partial substitution of diesel oil. Therefore, the aim of this work is to evaluate the thermal and rheological behavior of the blends of diesel with the methanol biodiesel obtained from soybean oil, using B5, B15 and B25 blends. All thermogravimetric curves exhibited one overlapping mass loss step in the 35–280°C temperature range at air atmosphere and one step between 37–265°C in nitrogen. The rheological study showed a Newtonian behavior (n=1) for all blends.     

Thermal behaviors of soy biodiesel

Biodiesel is a prospective and promising fuel for diesel engines. However, some aspects need improvement, to develop into an ideal fuel, such as flow properties at low temperatures and storage stability at high temperatures with exposure to the air. Thermal analysis is an efficient tool for measuring properties, such as crystallization temperature, and thermal and oxidative stabilities. In this study, the thermal behaviors of biodiesel at low and high temperatures were investigated by using thermogravimetric analyzer, differential scanning calorimetry, pressurized differential scanning calorimetry (PDSC), and sorption analyzer (SA). The soy biodiesel was obtained through a transesterification reaction with a homogeneous catalyst. The constituents of the soy biodiesel as determined by gas chromatography show that methyl esters content was 99?% and of these 84?% were unsaturated fatty acids. TG results illustrate that the total weight loss of the biodiesel was 99?% below 300?°C under nitrogen flow, indicating a high purity biodiesel. The onset decomposition temperature and the peak temperatrue of the soy biodiesel were 193 and 225?°C, respectively, implying the biodiesel has good thermal stability. PDSC results show that the oxidation onset temperature of the soy biodiesel was 152?°C, and the oxidative induction time was 24?min. DSC results demonstrate that the onset crystallization temperature of the soy biodiesel was 1.0?°C. The SA results point out that with increasing temperature and humidity, the soy biodiesel absorbed more water, and in which humidity was the dominant factor. The water absorption and desorption of the soy biodiesel is a non-reversible process. The preferable storage conditions for soy biodiesel occur when humidity is less than 30?% and the temperature is less than 30?°C. In summary, thermal analysis is a faster alternative for thermal behavior studies as compared with conventional standard methods.     

生物柴油的发展概况与应用前景

石化燃料是当前人类使用的主要能源,但其使用造成了严重的温室效应和环境污染．生物柴油具有安全、无污染、燃烧好、可再生等优点而被当作石化燃料的绿色替代品．本文阐述了生物柴油的本质及其相对于石化柴油在使用上的优良特性,综述了国内外生物柴油技术的研究、应用及产业发展概况,论述了生物柴油研究的重要意义．根据菜油的特点及油菜在我国的发展前景,认为油菜可能是我国发展生物柴油的理想原料．     

Effects of ytterbium ion on the growth,metabolism and membrane fluidity of <Emphasis Type="Italic">Tetrahymena thermophila</Emphasis>

This work evaluates the thermal and kinetic behaviour of corn biodiesel obtained by the methanol and ethanol routes. As to the TG curves, in air three thermal decomposition steps are for the methanol biodiesel and two steps are for the ethanol biodiesel. These steps are related to the evaporization and/or combustion of the methyl and ethyl esters, respectively. The corn oil presented four thermal decomposition steps in air, and only one step in nitrogen. These steps were attributed to the evaporization and/or decomposition of triglycerides. The TG and DTA profiles of the biodiesel approach the mineral diesel oil ones.     

Thermal investigation of oil and biodiesel from <Emphasis Type="Italic">Jatropha curcas</Emphasis> L.

Biodiesel is susceptible to autoxidation if exposed to air, light and temperature, during its storage. Physic nut (Jatropha curcas L.) seeds show potential application for biodiesel production since its oil yields high quality biodiesel. This work aims to evaluate the thermal behavior of the physic nut oil and biodiesel, from several Brazilian crops, by means of thermoanalytical techniques. Thermogravimetry (TG) and pressurized-differential scanning calorimetry (PDSC) were used in order to determine the applicability of physic nut biodiesel as fuel. Results suggest that physic nut biodiesel is a practical alternative as renewable and biodegradable fuel able to be used in diesel motors.     

Kinetic and thermodynamic parameters of volatilization of biodiesel from babassu, palm oil and mineral diesel by thermogravimetric analysis (TG)

The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol^?1), followed by babassu biodiesel (E = 76.37 kJ mol^?1), and palm biodiesel (E = 87.00 kJ mol^?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol^?1 K^?1, ΔH = +80.38 kJ mol^?1 and ΔG = +142.74 kJ mol^?1. For palm biodiesel ΔS = ?119.26 J mol^?1 K^?1, ΔH = + 90.53 kJ mol^?1 and ΔG = +141.21 kJ mol^?1, and for diesel ΔS = ?131.3 J mol^?1 K^?1, ΔH = +53.29 kJ mol^?1 and ΔG = +115.13 kJ mol^?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.     

Determination of methyl ester contents in biodiesel blends by FTIR-ATR and FTNIR spectroscopies

Partial last square regression (PLS) and artificial neural network (ANN) combined to FTIR-ATR and FTNIR spectroscopies have been used to design calibration models for the determination of methyl ester content (%, w/w) in biodiesel blends (methyl ester + diesel). Methyl esters were obtained by the methanolysis of soybean, babassu, dende, and soybean fried oils. Two sets of samples have been used: Group I, binary mixtures (diesel + one kind of methyl ester), corresponding to 96 biodiesel blends (0–100%, w/w), and Group II, quaternary mixtures (diesel + three types of methyl esters), corresponding to 60 biodiesel blends (0–100%, w/w). The PLS results have shown that the FTNIR model for Group I is more precise and accurate (±0.02 and ±0.06%, w/w). In the case of Group II the PLS models (FTIR-ATR and FTNIR) have shown the same accuracies, while the ANN/FTNIR models has presented better performance than the ANN/FTIR-ATR models. The best accuracy was achieved by the ANN/FTNIR model for diesel determination (0.14%, w/w) while the worthiest was that of dende ANN/FTIR-ATR model (0.6%, w/w). Precisions in Group II analysis ranged from 0.06 to 0.53% (w/w) and coefficients of variation were better than 3% indicating that these models are suitable for the determination of diesel–biodiesel blends composed of methyl esters derived from different vegetable oils.     

Thermal characterization of oil and biodiesel from oiticica (<Emphasis Type="Italic">Licania rigida</Emphasis> Benth)

Searching for other alternative sources, which are not part of the food chain, and which are able to supply the biofuel market is a promising option. In this context, it has been searched to investigate the oiticica oil, approaching its availability to the biodiesel synthesis, as well as its thermal stability. Few works retreat parameters such as: the optimization of the biodiesel synthesis, its physical–chemical properties, and thermal parameters etc. The characterization results revealed that the oil showed very high kinematic viscosity, and acidity value around 13 mg KOH/g, requiring a pre-treatment. To reduce the acid in the oil, it has been done the esterification of oil, which was studied in different molar ratios oiticica oil/ethanol (1:9) and 2.0% catalyst, in order to get the best reduction the index of acidity. The lowest level of acidity of the oil obtained after the esterification was 4.4 mg KOH/g. The reaction rate for the synthesis of biodiesel, compared to the initial mass of oiticica oil ester was 85%. This income can be overcome by pursuing an even smaller reduction of acid value of biodiesel oiticica. The acid value of biodiesel was 1.8 mg KOH/g. The results have revealed that the oiticica oil and biodiesel are stable at 224 and 179 °C, respectively.     

Production of biodiesel fuel by transesterification of rapeseed oil

Fatty acid methyl esters (FAMEs) show large potential applications as diesel substitutes, also known as biodiesel fuel. Biodiesel fuel as renewable energy is an alternative that can reduce energy dependence on petroleum as well as air pollution. Several processes for the production of biodiesel fuel have been developed. Transesterification processes under alkali catalysis with short-chain alcohols give high yields of methyl esters in short reaction times. We investigated transesterification of rapeseed oil to produce the FAMEs. Experimental reaction conditions were molar ratio of oil to alcohol, concentration of catalyst, type of catalyst, reaction time, and temperature. The conversion ratio of rapeseed oil was enhanced by the alcohol:oil mixing ratio and the reaction temperature.     

Thermal characterization of the poultry fat biodiesel

Chemical composition of oils and fats used in the biodiesel synthesis can influence in processing and storage conditions, due to the presence of unsaturated fatty acids. An important point is the study of the biodiesel thermal stability to evaluate its quality using thermal analysis methods. In this study the thermal stabilities of the poultry fat and of their ethyl (BEF) and methyl (BMF) biodiesels were determined with the use of thermogravimetry (TG/DTG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC), in different atmospheres. The TG/DTG curves of the poultry fat in synthetic air presented three decomposition steps while only one step was observed in nitrogen (N₂) atmosphere. The DSC results indicated four exothermic enthalpic transitions in synthetic air and an endothermic transitions in N₂ atmosphere attributed to the combustion process and to the volatilization and/or decomposition of the fatty acids, respectively. For both biodiesels the TG/DTG curves in air indicated two mass loss steps. In the DSC curves four exothermic transitions were observed in synthetic air besides an endothermic one in N₂ atmosphere.     

Entrainment of ambient air into a spectrochemical inductively coupled argon plasma

A spectrochemical inductively coupled argon plasma (ICP) is normally operated in the open air. Therefore, it is suggested in the literature that entrainment of air molecules into such an ICP may cause loss of electrons, especially so at the plasma's edge. The present study discusses the significance of this effect. The density and temperature of electrons and nitrogen molecules around the edge of the plasma were measured by Thomson and rotational Raman scattering. A region where both electrons and nitrogen were present in detectable amounts (10¹⁹ and 10²⁴ m⁻³, respectively) could not be observed. Above the torch inner wall the nitrogen concentration drops rapidly towards the plasma. Measurements suggest that the nitrogen concentration at 1 mm from the plasma is only a few percent, and in the active zones of the plasma (far) below 0.1%. This is not enough to affect the plasma significantly. Moreover, electron loss due to diffusion of nitrogen into the plasma is calculated to be much slower than the loss observed in earlier studies. Hence, air entrainment is unlikely to play a significant role in the ICP. A possible alternative is the formation and destruction of molecular rare gas ions.     

The use of microemulsion for determination of sodium and potassium in biodiesel by flame atomic absorption spectrometry

A new method for F AAS determination of sodium and potassium in biodiesel using water-in-oil microemulsion as sample preparation is proposed. The method was investigated for biodiesel produced from different sources, as soybean, castor and sunflower oil and animal fat and was also applied for vegetable oils. The optimized condition for microemulsion formation was 57.6% (w/w) of n-pentanol, 20% (w/w) of biodiesel or vegetable oil, 14.4% (w/w) of Triton X-100 and 8% (w/w) of water (aqueous standard of KCl or NaCl in/or diluted HNO₃). The optimized instrumental parameters were: aspiration rate of 2 mL min⁻¹ and the flame composition of 0.131 of C₂H₂/air ratio. For comparison purpose, the determination of sodium and potassium were also carried out according to European norms (EN 14108 and EN 14109, respectively). These norms are applied for determination of sodium and potassium in fatty acid methylic ester samples and consist in the sample dilution using organic solvent and determination by F AAS. The stability of microemulsified aqueous standards and samples was investigated and it was found to be stable for at least 3 days while the organic standard diluted with xylene showed a decrease around of 15% in the analytical signal in 1 h. The limits of detection were 0.1 μg g⁻¹ and 0.06 μg g⁻¹ and the obtained characteristic concentrations were 25 μg L⁻¹ and 28 μg L⁻¹ for sodium and potassium, respectively. The proposed method presented two times better limits of detection and better precision (0.4–1.0%) when compared with the dilution technique (1.5–4.5%). The accuracy of the method was evaluated through recovery tests and comparison with the results obtained by dilution technique. The recoveries ranged from 95% to 115% for biodiesel and 90% to 115% for vegetable oil samples. Comparison between the results obtained for biodiesel by both methods showed no significant differences at the 95% confidence level according to a Student's t-test. This study shows that the proposed method based on microemulsion as sample preparation can be applied as an efficient alternative for sodium and potassium determination in biodiesel samples.     

Non-conventional oils for biodiesel production: a study of thermal and oxidative stability

Vegetable oils with variable proportions of oleic, linoleic, and linolenic acids are more susceptible to oxidative processes. In this subject, this study evaluates the physical chemical properties and oxidative stability of non-conventional oils such as andiroba, babassu, sesame, oiticica, jatropha, and grape through accelerated oxidation techniques (pressurized differential scanning calorimetry, Rancimat and PetroOxy). It was verified that babassu and andiroba oil do not showed detectable induction period presenting high oxidative stability; moreover, it was observed that the enthalpic events occurred in 1.19, >10, 0.53, 0.49, 0.49, and 0.60 h for the andiroba oil, babassu oil, sesame seeds, jatropha, oiticica oils, and grapes, respectively, stimulating the conclusion of greater stability for the babassu oil.     

Determination of nutrients and potentially toxic elements in Jatropha curcas seeds, oil and biodiesel using inductively coupled plasma mass spectrometry

Biodiesel is a renewable and biodegradable fuel that can be used in diesel engines as a replacement for fossil diesel. A suitable alternative is to produce it from Jatropha curcas, which has high quality oil concentration. Nevertheless, the presence of particular chemical elements above certain limits can affect the product quality, leading to vehicle engine problems and acting as air pollution source. The objective of this work is to develop a method for the simultaneous determination of B, Na, Mg, P, S, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, and Pb in J. curcas seeds, oil and biodiesel using the inductively coupled plasma mass spectrometry (ICP-MS) technique. This material was evaluated because has been successfully employed in India for biodiesel production as well as in other places where there is an incentive to family farming, without affect the food chain. The oil was obtained from seeds via mechanical extraction and the biodiesel was achieved by oil transesterification. After optimization of the microwave digestion method for the different sample types, the samples were analyzed by ICP-MS. The certified reference material NIST SRM 1515 (apple leaves) and the recovery tests were carried out to ensure the accuracy of the proposed method, which made possible the quantification of several nutrients and potentially toxic elements in J. curcas seeds, oil and biodiesel, especially Na, K, Ca, Mg, P and S in biodiesel which are mandatory analyzed by Petroleum, Natural Gas and Biofuel National Agency (ANP). This work highlights the findings of the first study of potentially toxic and nutrient elements in the production chain steps seed–oil–biodiesel from J. curcas.     

Ethanol from babassu coconut starch

This study describes a pioneering industrial-scale experience by Tobasa in ethanol production from the amylaceous flour obtained by mechanical processing of the babassu mesocarp. Technical aspects related to enzymatic and fermentation processes, as well as overall economical aspects, are discussed. When produced in a small-size industrial plant (5000 L/d), babassu ethanol has a final cost of about $218/m³. The impact of raw materials, production, and processing (enzymes, steam, energy, and so on) on the final product cost is also presented. Babassu coconut ethanol can be produced at low cost, compared with traditional starchy raw materials or sugar cane. The net profitability of ethanol production is about 40% for babassu coconut and just 10% for sugar cane. If the estimated renewable babassu resources were entirely industrially used, 1 billion L/yr of ethanol could be produced, which would roughly correspond to 8% of the current Brazilian ethanol production.