Preparation of fatty acid methyl esters from hazelnut,high-oleic peanut and walnut oils and evaluation as biodiesel

Refined hazelnut, walnut and high-oleic peanut oils were converted into fatty acid methyl esters using catalytic sodium methoxide and evaluated as potential biodiesel fuels. These feedstocks were of interest due to their lipid production potentials (780–1780 L ha^?1 yr^?1) and suitability for marginal lands. Methyl oleate was the principal constituent identified in hazelnut (HME; 76.9%) and peanut (PME; 78.2%) oil methyl esters. Walnut oil methyl esters (WME) were comprised primarily of methyl esters of linoleic (60.7%), oleic (15.1%) and linolenic (12.8%) acids. PME exhibited excellent oxidative stability (IP 21.1 h; EN 14112) but poor cold flow properties (CP 17.8 °C) due to its comparatively high content of very-long chain fatty esters. WME provided low derived cetane number and oxidative stability (IP 2.9 h) data as a result of its high percentage of polyunsaturated fatty esters. HME yielded a satisfactory balance between all fuel properties when compared to the biodiesel standards ASTM D6751 and EN 14214 due to its high content of monounsaturated fatty esters. Also explored were the properties of blends of HME, PME and WME in ultra-low sulfur (<15 ppm) diesel (ULSD) fuel and comparison to petrodiesel standards ASTM D975, D7467 and EN 590. With increasing content of biodiesel, the oxidative stability, cold flow properties and calorific value of ULSD was negatively affected, whereas lubricity was markedly improved. Kinematic viscosity, specific gravity and surface tension were impacted to lesser extents by addition of biodiesel to ULSD. In summary, HME, PME and WME are suitable based on their fuel properties as biodiesel fuels and blend components in ULSD.     

The effect of temperature and pressure on the physicochemical properties of petroleum diesel oil and biodiesel fuel

Three commercial fuels were studied: biodiesel (based mainly of the fatty acids methyl esters of rapeseed oil), diesel oil Ekodiesel Ultra (standard petroleum diesel oil with sulphur content less than 10 mg/kg), and ON BIO 10 (blend of 20 vol.% of biodiesel with 80 vol.% of standard petroleum diesel oil with sulphur content less than 10 mg/kg). The speeds of sound were measured within the temperatures from 293 to 318 K and at pressures from 0.1 to 101 MPa. The densities and heat capacities were measured under atmospheric pressure in the temperature range from 273 to 363 K and 283 to 359 K, respectively. Using the experimental results, the physicochemical properties such as: density, isentropic bulk modulus, heat capacity, and isobaric thermal expansion were calculated in the same temperature and pressure range as the speed of sound was measured. The results obtained show that although the bulk modulus of ON BIO 10 is higher than that of diesel oil Ekodiesel Ultra over the whole pressure range, the difference is rather small and can be compensated by temperature. Isobaric thermal expansivity of biodiesel decreases with pressure slightly less than that of the diesel oil Ekodiesel Ultra. It is approximately independent of temperature and composition of the fuel at pressures 40 ± 5 MPa.     

Vapor pressure measurements on saturated biodiesel fuel esters by the concatenated gas saturation method

The purpose of this work was to determine vapor pressures for saturated biodiesel esters at the low-temperature end of their liquid range. A “concatenated” gas saturation apparatus capable of simultaneous measurements on 18 samples was used for measurements on methyl palmitate, ethyl palmitate, methyl stearate, ethyl stearate, and eicosane (C₂₀H₄₂) over the temperature range 323.15 K-343.15 K. Eicosane, a linear alkane with a well known vapor pressure curve (in the same range as the biodiesel esters), was included as a control compound. Importantly, the measured vapor pressures for eicosane are in excellent agreement with reference values, which is good evidence of the low uncertainty of the measurements on the biodiesel esters. Over this temperature range, the measured vapor pressure ranges were 0.145 Pa-1.11 Pa for methyl palmitate, 0.0687 Pa-0.616 Pa for ethyl palmitate, 0.0159 Pa-0.183 Pa for methyl stearate, and 0.00704 Pa-0.0912 Pa for ethyl stearate. The combined standard uncertainty in the vapor pressure measurements ranged from 8% to 15%.     

Predicting the temperature dependent viscosity of biodiesel fuels

The purpose of this work was to develop a method for predicting temperature dependent viscosities of biodiesel based on fatty acid ester composition. The Grunberg-Nissan equation combined with a group contribution method was used as the mixing rule to calculate viscosities of mixtures of fatty acid esters. Prediction errors at 25 °C were less than 2.5% for 22 mixtures of fatty acid ethyl esters. Compared with experimentally measured viscosities at 20-100 °C, predicted viscosities of soybean oil and yellow grease methyl esters were within 3%. For coconut, palm and canola oil methyl esters, maximum errors were underestimations at approximately 7%.     

Crystallization Behavior of Fatty Acid Methyl Esters

Biodiesel from most agricultural feedstocks has flow properties that are prone to startup and operability problems during cold weather. Biodiesel from soybean oil is generally a mixture of long-chain fatty acid alkyl esters composed of 0.15–0.20 mass fraction saturated esters (melting point [MP] ≫ 0 °C) mixed with unsaturated esters (MP < 0 °C). This work investigates the crystallization properties of two saturated fatty acid methyl esters (FAME) commonly found in biodiesel from soybean oil. Differential scanning calorimetry (DSC) heating and cooling scans of methyl palmitate (MeC16), methyl stearate (MeC18) and methyl oleate (MeC18:1) in pure form were analyzed. Crystallization behavior in ternary FAME mixtures was inferred by the application of thermodynamic models based on ideal solution and freezing-point depression theories. Activity coefficients for MeC16 and MeC18 in MeC18:1 solvent were determined by analyzing DSC cooling curves for binary FAME mixtures. Eutectic points were predicted by both models. Crystallization onset temperatures inferred from freezing point depression theory were more accurate than those for ideal solutions with respect to a direct DSC cooling curve analysis of corresponding ternary mixtures. This work shows that the crystallization onset temperature (cloud point) of biodiesel may be predicted by freezing-point depression theory if the activity coefficients of the component FAME are known. The use of trade, firm, or corporation names in this publication is for the information and convenience of the reader. Such use does not constitute an official endorsement or approval by USDA or ARS of any product or service to the exclusion of others that may be suitable.     

Prediction of biodiesel properties and its characterization using fatty acid profiles

Biodiesel, the mono-alkyl esters of vegetable oils or animal fats, is an eco-friendly alternative to petrodiesel. The molecular structures of biodiesels, fatty acid methyl esters were applied to predict the characteristics of biodiesel fuels. Based on the structural similarity of biodiesel and petroleum fractions, molecular weight of biodiesel was correlated with other characteristics including boiling point, viscosity and specific-gravity in the form of three equations. For 24 different kinds of biodiesel, the minimum average relative deviation (ARD) of these correlations was calculated to be 0.68%. Moreover, two correlations were developed to predict viscosity and flash point of biodiesel as a function of weighted-average number of carbon atoms (N _C ) and weighted-average number of double bonds (N _DB ) with ARD 3.72% and 4.24% respectively. Also, a high degree of correlation was shown by the logarithmic function with ARD 0.30% between specific gravity and viscosity of biodiesel. Proposed predictive models were verified by experimental data.     

Predicting the surface tension of biodiesel fuels from their fatty acid composition

The emergence of biodiesel fuels as diesel fuel substitutes has led to several studies on their properties. Surface tension, which plays a role in atomization, has lacked attention compared to other properties. This paper presents a method to predict the surface tension of biodiesel fuels based on the fatty acid composition. Several binary, ternary, and quaternary mixtures of fatty acid ethyl ester gas chromatographic (GC) standards were prepared, and we found that a mass-average equation predicted the surface tension of these mixtures within ±3.5% of their measured values. Six complex mixtures of fatty acid methyl ester GC standards that simulated typical oils used as biodiesel fuels were also prepared. For these complex mixtures the predicted surface tensions of the mixtures, calculated from a mass-average equation, were 2–6% higher than the measured values. A mass-average equation was developed in which we used a weighted surface tension for the individual components, and we found that this method predicted the surface tension of the simulated oils within ±4.5% of their measured values. Five natural vegetable oils were used to produce biodiesel fuels by the transesterification process. The predicted surface tensions of these fuels were all within ±3.5% of their measured values. The surface tensions of 15 biodiesel types were then predicted, based on their fatty acid composition as published in the literature. These results show that the differences in surface tension between biodiesel types are not the main cause of the reported differences in engine tests.     

A Comprehensive Evaluation of the Melting Points of Fatty Acids and Esters Determined by Differential Scanning Calorimetry

The melting point is one of the most important physical properties of a chemical compound and it plays a significant role in determining possible applications. For fatty acid esters the melting point is essential for a variety of food and non-food applications, the latter including biodiesel and its cold-flow properties. In this work, the melting points of fatty acids and esters (methyl, ethyl, propyl, butyl) in the C₈–C₂₄ range were determined by differential scanning calorimetry (DSC), many of which for the first time. Data for triacylglycerols as well as ricinoleic acid and its methyl and ethyl esters were also acquired. For some compounds whose melting points have been previously reported, data discrepancies exist and a comprehensive determination by DSC has not been available. Variations in the present data up to several °C compared to data in prior literature were observed. The melting points of some methyl-branched iso- and anteiso-acids and esters were also determined. Previously unreported systematic effects of compound structure on melting point are presented, including those for ω-9 monounsaturated fatty acids and esters as well as for methyl-branched iso and anteiso fatty acids and esters. The melting point of a pure fatty acid or ester as determined by DSC can vary up to approximately 1 °C. Other thermal data, including heat flow and melting onset temperatures are briefly discussed. Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Viscosity measurement of biodiesel at high pressure with a falling sinker viscometer

In this work, we report the measurement of the viscosity of biodiesels derived from waste cooking oil and vegetable oil under high pressure. Using a falling sinker-type viscometer, dynamic viscosity measurements were made at pressures up to 140 MPa which are typically to be found in common-rail automotive diesel engines. Reproducible and reliable viscosity data were obtained from sinker fall times and calibration data. The biodiesel viscosities were compared to that of petrochemical diesel fuels also under high pressure. Both fuel types were found to increase exponentially with pressure with the biodiesels being slightly the more viscous. Above 140 MPa, a marked increase in sinker fall time was observed. This was due to a pressure-freezing effect which is known to also occur with longer chain molecules found in petrochemical diesel, oils, fatty acids and biodiesel.     

Diffusion coefficients of C18 unsaturated fatty acid methyl esters in supercritical carbon dioxide containing 10% mole fraction ethanol as modifier

To determine the molecular diffusion coefficients of C18 unsaturated fatty acid methyl esters in supercritical carbon dioxide (scCO₂) containing 10 mol% ethanol as a modifier, four methyl esters of C18 fatty acids, i.e., methyl oleate, methyl ricinoleate, methyl linoleate and methyl linolenate were selected as the typical solutes. The diffusion coefficients were measured at temperatures from 313.15 to 333.15 K and pressures from 15 to 27 MPa using the Taylor–Aris chromatographic peak broadening (CPB) technique. The influences of temperature, pressure, density and viscosity of the solvent mixture on the diffusion coefficients were examined. The results show that methyl oleate always diffuses faster than methyl ricinoleate at the same operating condition. Moreover, the D₁₂ values in ethanol-modified scCO₂ decrease with the increase of the number of C-C double bonds in C18-methyl ester, which is consistent with the trend reported in pure scCO₂. The diffusivity data are compared with the estimation of eleven predictive models. The modified Wilke–Chang equation is the best purely predictive model and the free volume model of Dymond with two adjustable parameter gives the least errors with average absolute deviations lower than 2.5%.     

Predicting cetane number,kinematic viscosity,density and higher heating value of biodiesel from its fatty acid methyl ester composition

Biodiesel is a renewable bio-fuel derived from natural fats or vegetable oils, and it is considered as a promising alternative to substitute diesel fuels. Cetane number, viscosity, density, and higher heating value are important properties to affect the utilization of biodiesel fuels, because they are involved in the definition of fuel quality and are required as input data for predictive engine combustion models. This work presents the characterization of two biodiesel samples made from beef tallow and soybean oil through their fatty acid methyl esters (FAMEs) profile. Empirical equations were developed to estimate four physical properties of methyl esters; and an average absolute deviation (AAD) of 5.95%, 2.57%, 0.11% and 0.21% for the cetane number, kinematic viscosity, density, and higher heating value were founded. Cetane number, viscosity, and higher heating value increases because of the increase of molecular weight and these physical properties decrease as the number of double bonds increases. Unlike that of above properties, density decreases as molecular weight increases and density increases as the degree of unsaturation increases. Two general mixing rules and five biodiesel samples were used to study the influence of FAMEs over the physical properties of biodiesel. The prediction of the cetane number, kinematic viscosity, density and higher heating value of biodiesel is very close to the experimental values.     

Preparation of rapeseed oil esters of lower aliphatic alcohols

Rapeseed oil esters with lower aliphatic alcohols (C₁−C₄) were prepared in simple batch mode using an alkali (KOH) or acid (H₂SO₄) catalyst. The transesterification reaction conditions were optimized in order to obtain high yields of esters of the quality defined by standards for biodiesel fuels and for a short reaction time. Under these conditions it was possible to prepare only the methyl and ethyl esters catalyzed by KOH. Propyl and butyl esters were obtained only under acid catalysis conditions. The reaction catalyzed by H₂SO₄ was successfully accelerated using slightly higher catalyst concentrations at the boiling points of the alcohols used. The branched-chain alcohols reacted more slowly than their linear homologs, while t-butanol did not react at all. It was also possible to transesterify rapeseed oil using a mixture of alcohols characteristic of the end products of some fermentation processes (e.g., the acetone-butanol fermentation). A simple calculation was made which showed that, because of the higher price of longer-chain alcohols and because of the more intensive energy input during production the esters of these alcohols, they are economically unfavorable as biodiesel fuels when compared with the methyl ester.     

Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40 °C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40 °C down to −10 °C in increments of 5 °C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0 °C and 40 °C (divide viscosity value at 0 °C by viscosity value at 40 °C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated.     

Determination of environmentally relevant physical-chemical properties of some fatty acid esters

Fat models frequently use input parameters that are defined at environmental conditions. In a recently developed gas-liquid chromatography method (GC-VAP), vapor pressures, heats of vaporization, and heat capacity differences (gas-liquid) of fatty acid esters are determined over a large temperature range that includes environmental temperatures. This method also allows an accurate determination of the normal boiling point temperature of a substance. Literature values of vapor pressure, boiling point temperature, and heat of vaporization at 298.15 K for the chosen esters are all in excellent agreement with those determined with the developed method. Correlations between carbon number and heat of vaporization are high.     

Palm fatty acid biodiesel: process optimization and study of reaction kinetics

The relatively high cost of refined oils render the resulting fuels unable to compete with petroleum derived fuel. In this study, biodiesel is prepared from palm fatty acid (PFA) which is a by-product of palm oil refinery. The process conditions were optimized for production of palm fatty acid methyl esters. A maximum conversion of 94.4% was obtained using two step trans-esterification with 1:10 molar ratio of oil to methanol at 65°C. Sulfuric acid and Sodium hydroxide were used as acid and base catalyst respectively. The composition of fatty acid methyl esters (FAME) obtained was similar to that of palm oil. The biodiesel produced met the established specifications of biodiesel of American Society for Testing and Materials (ASTM). The kinetics of the trans-esterification reaction was also studied and the data reveals that the reaction is of first order in fatty acid and methanol (MeOH) and over all the reaction is of second order.     

Fuel properties and nitrogen oxide emission levels of biodiesel produced from animal fats

FAME of lard, beef tallow, and chicken fat were prepared by base-catalyzed transesterification for use as biodiesel fuels. Selected fuel properties of the neat fat-derived methyl esters (B100) were determined and found to meet ASTM specifications. The cold-flow properties, lubricity, and oxidative stability of the B100 fat-derived fuels also were measured. In general, the cold-flow properties of the fat-based fuels were less desirable than those of soy-based biodiesel, but the lubricity and oxidative stability of the fat-based biodiesels were comparable to or better than soy-based biodiesel. Nitrogen oxide (NO_x) emission tests also were conducted with the animal fat-derived esters and compared with soybean oil biodiesel as 20 vol% blends (B20) in petroleum diesel. The data indicated that the three animal fat-based B20 fuels had lower NO_x emission levels (3.2–6.2%) than did the soy-based B20 fuel.     

Biodiesel production from tall oil with synthesized Mn and Ni based additives: Effects of the additives on fuel consumption and emissions

In this study, biodiesel fuel and fuel additives were produced from crude tall oil that is a by-product in the pulp manufacturing by craft or sulphate pulping process. Fatty acids and resinic acids were obtained from crude tall oil by distillation method. Tall oil methyl ester (biodiesel) was produced from fatty acids. Resinic acids were reacted with NiO and MnO₂ stoichiometrically for production of metallic fuel additives. Each metallic fuel additive was added at the rate of 8 μmol/l and 12 μmol/l to make mixtures of 60% tall oil methyl ester/40% diesel fuel (TE60) for preparing test fuels. Metallic fuel additives improved properties of biodiesel fuels, such as pour point and viscosity values. Biodiesel fuels were tested in an unmodified direct injection diesel engine at full load condition. Specific fuel consumption of biodiesel fuels increased by 6.00%, however, in comparison with TE60, it showed trend of decreasing with adding of additives. Exhaust emission profile of biodiesel fuels improved. CO emissions and smoke opacity decreased up to 64.28% and 30.91% respectively. Low NO_x emission was also observed in general for the biodiesel fuels.     

A Comprehensive Evaluation of the Density of Neat Fatty Acids and Esters

Density is one of the most important physical properties of a chemical compound, affecting numerous applications. An application in the case of fatty acid esters (biodiesel) is that density is specified in some biodiesel standards. In the present work, the density of fatty acid methyl, ethyl, propyl, and butyl esters as well as triacylglycerols in the C₈–C₂₄ range was determined in the range of 15–40 °C with a densitometer utilizing the oscillating U-tube technique. Literature data on density are compiled and compared, showing that data for these compounds are incomplete with discrepancies existing in some cases. Besides known effects such as density decreasing with increasing chain length and increasing saturation, it is shown that trans fatty compounds exhibit lower density than cis fatty compounds. Density data for several saturated odd-numbered, C₁₈, as well as C₂₀ and C₂₂ polyunsaturated fatty esters are reported for the first time. The density contribution of compounds with high melting points is predicted. An equation is given for the calculation of the density of mixtures.     

Methyl Esters (Biodiesel) from and Fatty Acid Profile of Gliricidia sepium Seed Oil

Increasing the supply of biodiesel by defining and developing additional feedstocks is important to overcome the still limited amounts available of this alternative fuel. In this connection, the methyl esters of the seed oil of Gliricidia sepium were synthesized and the significant fuel‐related properties were determined. The fatty acid profile was also determined with saturated fatty acids comprising slightly more than 35 %, 16.5 % palmitic, 14.5 % stearic, as well as lesser amounts of even longer‐chain fatty acids. Linoleic acid is the most prominent acid at about 49 %. Corresponding to the high content of saturated fatty acid methyl esters, cold flow is the most problematic property as shown by a high cloud point of slightly >20 °C. Otherwise, the properties of G. sepium methyl esters are acceptable for biodiesel use when comparing them to specifications in biodiesel standards but the problematic cold flow properties would need to be observed. The ¹H‐ and ¹³C‐NMR spectra of G. sepium methyl esters are reported.