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.     

Study of ethylic Babassu biodiesel properties at low temperatures

Nowadays the growing fuel deficit requires the development of alternative fuel sources. Biodiesel is a good substitute to the conventional diesel because it is quite similar to the fossil fuel in its main characteristics. However, there are some obstacles, as the properties of cold-flow, to the development of a more useful alternative fuel. In this work we use the X-ray diffraction and differential calorimetry scanning to study low temperature properties of ethylic Babassu biodiesel. Our results show that the nucleation of crystals starts below ?8 °C and the crystallization temperature does not change significantly when the sample was submitted to a winterization process. The higher concentrations of ethyl esters from saturated fat acid are probably responsible for this characteristic. The X-ray diffraction, combined with DSC measurements, was efficiently employed in the characterization of cold-flow biodiesel properties, showing to be very helpful techniques.     

Biodiesel from soybean oil,castor oil and their blends

Even not being described in the EN 14112 standard, PDSC has been used for the determination of the biodiesel oxidative stability, by OIT and OT measurements. In this study, biodiesel blends were obtained by mixing soybean (BES) and castor (BEM) ethyl esters and its induction periods were measured by Rancimat and PDSC. The blends (BSM _X ) showed intermediate values of OSI, OT, and OIT, compared with BES and BEM. Although, the molar fraction of the components varied linearly in BSM _X , OSI, OT, and OIT values increased exponentially in relation to the castor biodiesel amount in the blends. Introduction of castor oil biodiesel increased the blend stability, so the BSM₃₀ blend reached the OSI limit of 6 h. OSI, OIT, and OT showed a high-linear correlation, pointing out that PDSC can be used in the analysis of this kind of biodiesel, with a smaller sample and analysis time, as compared to Rancimat. The use of biodiesel blends was a good alternative in the correction of the oxidative stability of the final product without the need of antioxidant addition.     

Influence of the storage on the thermo-oxidative stability of methyl and ethyl esters by PDSC

Biodiesel oxidation is a complex process widely influenced by the chemical composition of the biofuel and storage conditions. Several oxidation products can be formed from these processes, depending on type and amount of the unsaturated fatty acid esters. In this work, fatty acid methyl and ethyl esters were obtained by base-catalyzed transesterification of soybean oil and physicochemically characterized according to standards from ASTM, EN, and ABNT. The thermal and oxidative stabilities of biodiesel samples were investigated during the storage process by pressure differential scanning calorimetry (PDSC) and by viscosity measurements. Absolute viscosities of biodiesels after accelerated aging were also determined. The viscosity increased as the aging temperature and time were raised. The results showed that oxidation induction can occur during storage, decreasing the biodiesel stability. PDSC analysis showed that during storage under climate simulation the values of high-pressure oxidative induction times (HPOIT) were reduced for both FAEE and FAME.     

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.     

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.     

Thermogravimetric and calorimetric evaluation of babassu biodiesel obtained by the methanol route

The growing petroleum deficit requires the development of alternative fuel sources. Biodiesel is a good alternative, as it is a biodegradable and renewable product, which obeys the carbon cycle. In this work, the biodiesel from babassu was synthesized using the methanol route, and characterized by physico-chemical analyses in order to make able the investigated biodiesel to fulfill with its properties the requirements of Brazilian National Agency for Petroleum, Natural Gas and Biofuel (ANP). Besides gas chromatography, IR spectroscopy experiments and thermoanalytical measurements in air and in nitrogen were done to determine the main thermal decomposition processes and calorimetric events. The evaporation temperature of babassu biodiesel was similar in both atmospheres, started around 52 in air and around 60°C in nitrogen.     

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.     

Antioxidative properties of hydrogenated cardanol for cotton biodiesel by PDSC and UV/VIS

Biodiesel is a non-toxic biodegradable fuel that consists of alkyl esters produced from renewable sources, vegetal oils and animal fats, and low molecular mass alcohols, and it is a potential substitute for petroleum-derived diesel. Depending on the raw materials used, the amount of unsaturated fatty acids can vary in the biodiesel composition. Those substances are widely susceptible to oxidation processes, yielding polymeric compounds, which are harmful to the engines. Based on such difficulty, this work aims to evaluate the antioxidant activity of cashew nut shell liquid (cardanol), as additive for cotton biodiesel. The oxidative stability was investigated by the pressure differential scanning calorimetry (PDSC) and UV/Vis spectrophotometer techniques. The evaluated samples were: as-synthesized biodiesel — Bio T₀, additivated and heated biodiesel — Bio A (800 ppm L⁻¹ of hydrogenated cardanol, 150°C for 1 h), and a heated biodiesel — Bio B (150°C, 1 h). The oxidative induction time (OIT) analyses were carried out employing the constant volume operation mode (203 psi oxygen) at isothermal temperatures of 80, 85, 90, 100°C. The high pressure OIT (HPOIT) were: 7.6, 15.7, 22.7, 64.6, 124.0 min for Bio T₀; 41.5, 77.0, 98.6, 106.6, 171.9 min for Bio A and 1.7, 8.2, 14.8, 28.3, 56.3 min for Bio B. The activation energy (E) values for oxidative processes were 150.0±1.6 (Bio T₀), 583.8±1.5 (Bio A) and 140.6±0.1 kJ mol⁻¹(Bio B). For all samples, the intensities of the band around 230 nm were proportional to the inverse of E, indicating small formation of hyper conjugated compounds. As observed, cardanol has improved approximately four times the cotton biodiesel oxidative stability, even after the heating process.     

Sunflower biodiesel

The higher is the degree of unsaturation in ester chain of a biodiesel, the smaller is its oxidation stability. Sunflower biodiesel obtained by the ethyl route possesses a high amount of unsaturated fatty acids, mainly oleic acid (C18:1) and linoleic acid (C18:2), thus being more prone to the oxidation process. In Brazil, with the purpose of meeting the specifications of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP), antioxidant additives, from synthetic and natural origins, have been added to the biofuel. Antioxidants are an alternative to prevent the oxidative deterioration of the fatty acid derivatives, as they are substances able to reduce the oxidation rate. In this study, the oxidative stability of sunflower biodiesel, obtained by the ethyl route and additivated with different concentrations of the antioxidants butylated hydroxytoluene (BHT) and t-butylhydroquinone (TBHQ), was evaluated by means of Pressure differential scanning calorimetry (P-DSC) and the Accelerated oxidative stability test (Rancimat, Method EN 14112). The results obtained by the two techniques showed the same oxidation tendency. Thus, P-DSC can be used as an alternative to determine the oxidative stability of biodiesel. The antioxidant TBHQ, added to biodiesel at the concentrations of 2000 and 2500 mg kg⁻¹, raised the oxidation induction time to a value higher than 6 h, the limit established by the Resolution ANP number 7/2008, thus being the best alternative among the studied antioxidants.     

Comparative study of oxidative stability of sunflower and cotton biodiesel through P-DSC

Biodiesel can contain unsaturated fatty acids, which are susceptible to oxidation, being able to change into polymerized compounds. Oxidative stability is very important in the quality control of oils and biodiesel. In this study, biodiesel samples were produced through the methyl route, using a homogeneous catalyst. The determination of methyl esters was performed by gas chromatography in order to confirm the conversion of the carboxylic acids present in the raw material for the methyl esters. Also proved the presence of methyl linoleate and methyl oleate to the major constituent of biodiesel. The thermal and oxidative stability of sunflower and cotton oils and their biodiesel, using TG and P-DSC techniques were investigated. The use of P-DSC to measure the oxidative induction time was very important. These measurements were used to evaluate the cotton and sunflower oils, and their respective biodiesel. It was found that the thermal-oxidative stability of vegetable oils and their biodiesel were similar, due to the fact that both presented chemical composition and percentages of fatty acids similar.     

Analysis of thermal,oxidative and cold flow properties of methyl and ethyl esters prepared from soybean and mustard oils

Oilseed crop with high oil content and promising ecological adaptability are potential sources for competitive biodiesel production. This study investigates the scope of utilizing biodiesel development through the methyl and ethyl ester from soybean and mustard oil as an alternative fuel. Methyl and ethyl esters of oils having different fatty acids compositions such as soybean (SOME and SOEE) and mustard oil (MUME and MUEE) were prepared by transesterification with methanol and ethanol in the presence of an alkali-KOH catalyst. The gas chromatographic (GC) analysis of oil samples revealed that primary fatty acid composition in soybean oil was linoleic acid (C_18:2, 51.93%), followed by oleic acid (C_18:1, 22.82%), palmitic acid (C_16:0, 11.56%), linolenic acid (C_18:3, 5.95%) and stearic acid (C_18:0, 4.32%). Whereas, the main components in mustard oil were erucic acid (C_22:1, 32.81%), oleic acid (C_18:1, 24.98%), eicosenoic acid (C_20:1, 10.44%), linolenic acid (C_18:3, 8.61%) and palmitic acid (C_16:0, 2.80%). The physicochemical properties (acid value, iodine value, calorific value, flash point, pour point etc.) of methyl and ethyl ester samples were estimated and found to be within the acceptable range of ASTM D6751 standards specifications. The prepared esters and oil samples were examined for cold flow properties by differential scanning calorimetry (DSC). Results revealed better cold flow properties for MUME (−2.55 °C) and MUEE (−3.10 °C) than SOME (3.21 °C) and SOEE (1.83 °C) due to more unsaturated fatty acid content in MU. Thermal and oxidative stability of samples was determined by thermogravimetric analysis (TG) and differential thermal analysis (DTA). The thermal and oxidative stability ranking of the samples was in the order of oil > methyl esters > ethyl esters.

     

Analysis of thermal and oxidative stability of biodiesel from Jatropha curcas L. and beef tallow

The oxidation of oils and biodiesels occurs due to several factors: the quantity of double bonds and the presence of allylic and bis-allylic hydrogens. Esters (biodiesel) that have large amounts of unsaturated fatty acids are more susceptible to oxidation than saturated. The aim of this work was to analyze the thermal and oxidative stability of ethyl biodiesel from Jatropha curcas L. and beef tallow by thermogravimetric, pressure differential scanning calorimetry, and PetroOxy methods. The samples of biodiesel from beef tallow present higher oxidation stability compared to biodiesel from J. curcas. In relation to calorimetric curves of biodiesel from J. curcas and beef tallow stored by 60 days without and with antioxidant, there was verified displacement of peak temperature of the transition to higher temperatures, respectively. Just a sample of biodiesel from beef tallow stored for 60 days with 3,000 ppm of antioxidant t-butyl-hydroxyquinone was within the standard established by Brazilian National Agency of Petroleum, Natural Gas, and Biofuels (ANP). The biodiesel from beef tallow was more stable in terms of thermal and oxidative stability than biodiesel from J. curcas. The thermal and oxidative stability of biodiesel depends on its chemical structure; this corroborates the fact that the oils with a predominance of saturated fatty acids are more stable than the unsaturated.     

A tandem Finkelstein-rearrangement-elimination reaction: a straightforward synthetic route to allyl esters

Allyl esters can be obtained by a Finkelstein-rearrangement-elimination reaction of 2-chloro-1-(chloromethyl)ethyl esters induced by NaI. Sodium iodide can be used below equivalence using a reductive agent as sodium thiosulfate. High yields are obtained with most of the diverse esters studied. The method described avoids the use of allyl alcohol as a reagent. 2-Chloro-1-(chloromethyl)ethyl esters are prepared from glycerol, the main by-product of biodiesel industry. The effectiveness of iodine as reagent to hydrolyze allyl esters is also confirmed.     

Production of biodiesel by immobilized Candida sp. lipase at high water content

A new process for enzymatic synthesis of biodiesel at high water content (10–20%) with 96% conversion by lipase from Candida sp. 99–125 was studied. The lipase, a no-position-specific lipase, was immobilized by a cheap cotton membrane and the membrane-immobilized lipase could be used at least six times with high conversion. The immobilized lipase could be used for different oil conversion and preferred unsaturated fatty acids such as oleic acid to staturated fatty acids such as palmitic acid. The changes in concentration of fatty acids, diglycerides, and methyl esters in the reaction were studied and a mechanism of synthesis of biodiesel was suggested: the triglycerides are first enzymatically hydrolyzed into fatty acids, and then these fatty acids are further converted into methyl esters.     

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.     

Thermochemistry of methyl and ethyl esters from vegetable oils

This paper deals with the gas‐phase thermodynamic properties of methyl ester and ethyl ester of vegetable oils (fatty acid methyl esters and fatty acid ethyl esters respectively) present in biodiesel. The standard enthalpies of formation at 298.15 K, heat capacities, and entropies in the temperature range 300–5000 K are determined by means of quantum chemistry calculations along with a protocol developed for these compounds. The resultant data, currently not available in the literature for most of them, are critical to the modeling of combustion chemistry of the subject compounds. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 481–491, 2007     

Determination of the vapor pressure of ethyl esters by Differential Scanning Calorimetry

Differential Scanning Calorimetry (d.s.c.) was used to determine the vapor pressure of the following ethyl esters: ethyl laurate, ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate and ethyl linoleate in the range from 1.33 to 9.33 kPa. These esters are the major constituents of the biodiesel obtained from the transesterification of some vegetable oils with ethanol. Samples of 2 to 5 mg were used in the analysis, with a heating rate of 25 °C · min^?1 and a pinhole with a diameter of 0.25 mm. The results showed that Differential Scanning Calorimetry was a suitable technique for measuring the vapor pressure of organic compounds like fatty esters. The constants of the Antoine equation were determined from the experimental data and the validity of this equation in representing the vapor pressure and vaporization enthalpy of the compounds under study was examined.     

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.     

Characterization and kinetic study of sunflower oil and biodiesel

In this study, the physico-chemistry characterization and kinetic study of the thermal decomposition of sunflower oil and its biodiesel were carried out. Sunflower biodiesel was synthesized by the methanol route and basic homogeneous catalysis. The physicochemical characterization of the sunflower oil and biodiesel were performed according to standards set out in the ANP resolution, and both are in accordance to the specifications. The chromatographic analysis was obtained by GC-FID. The yield of conversion of 97.4 wt% of sunflower oil in methyl esters confirms the efficiency of the conversion of the fatty acids into esters. The thermal analysis was performed on a thermobalance, using heating rates of 5, 10, and 20 °C min⁻¹. In these three rates, we observed a single well-defined step of mass loss that describes the volatilization and decomposition of the sunflower oil and the biodiesel. The kinetic study was performed using equations of approximation and integration methods such as Coats–Redfern, Van Krevelen, and Horowitz–Metzger. The kinetic parameters reaction order (n) and apparent activation energy (E _a), obtained by applying these method were correlated.