Mixture Of Fatty Acid Methyl Esters Research Articles

Comments on a Method for Estimating Cloud Point and Cold Filter Plugging Point of Microalgal Oil Fatty Acid Methyl Esters

AbstractCloud points (CPs) of five vegetable oil fatty acid methyl esters (FAME) and three biodiesel mixtures estimated by a thermodynamic equation were compared to measured CPs. The results indicate that estimated CP of peanut oil FAME are similar to measured CP and for three biodiesel mixtures a minimum total saturated FAME (SFAME) concentration is required for measured CPs to be closer to estimated CPs. These comparisons provide the basis for comments on using this method for estimating CPs of 22 test data of microalgae FAME. Cold filter plugging points (CFPPs) calculated by equation CFPP = 1.0191 × CP − 2.9 with CPs verified from the thermodynamic equation was found to be identical to CFPPs reported in literature for 22 test data of microalgae FAME. Therefore these CPs were inserted in equation CFPP = CP −4.5 for another set of CFPPs. Plots of CFPPs versus percent SFAME of the 22 test data of microalgae FAME (>12 %) for these two equations indicates that CFPP is controlled by 85 % of SFAME. Calculated CFPPs of vegetable oil FAME and biodiesel mixtures using both equations for estimated and measured CPs is discussed. Low concentrations of long chain saturated FAME impacting the estimation of CPs of vegetable oil FAME is used as a rationale to discuss the role of unidentified other species (OS) in estimation of CPs of microalgae FAME.

Robotized method for the quantification of fatty acids by gas–liquid chromatography

Analysis of fatty acid profile in fats and oils is conventionally performed by gas–liquid chromatography (GLC) as their fatty acid methyl ester (FAME) derivatives. Accurate quantification can be achieved by adding internal standard(s) prior to the derivatization step and calibration of the system using certified FAME mixture. GLC instruments equipped with online sample preparation units became recently commercially available and in theory can be used to improve laboratory productivity and safety. However, studies showing that this type of approach can be used to obtain reliable results are scarce. In the present study, we developed a method suitable for quantitative analysis of fatty acids in fats and oils by robotic preparation and online GLC analysis of FAME using methanolic potassium hydroxide as transmethylation reagent. The method has been validated on different fats and oils including milk fat, palm kernel, rapeseed and long‐chain polyunsaturated fatty acids containing oil samples. Method performance has been compared to the corresponding manual procedure and results show good repeatability [CV(r)<5%] and good intermediate reproducibility [CV(iR)<5%] in accordance with FDA guidelines. The results obtained show that transmethylation and GLC analysis of fats and oils can be robotized while remaining accurate and providing fatty acid data expressed as g of fatty acid per 100 g of sample. Compared to conventional methods, the volume of reagent and solvent is three times lower per sample analyzed with the robotized version which contributes to the reduction of waste and chemical risk exposure.

Operation of a solid oxide fuel cell on a reformed FAME mixture

The operation of a solid oxide fuel cell (SOFC) using a reformed fatty acid methyl ester (FAME) mixture a biodiesel-like fuel, has been successfully demonstrated. This project had two main aspects: 1) determining the fuel reforming activity of a pyrochlore catalyst deposited onto a monolith; and 2) operating a SOFC on reformed fuel gas. Prior to integrated testing, parametric reforming studies of the FAME mixture were conducted using both Rh/γ-Al2O3 and Rh-substituted pyrochlore catalyst powders to determine the operating conditions to maximize syngas selectivity. Using the same pyrochlore catalyst as in the parametric studies, a monolith reformer converted 0.5 cm3 min−1 of the FAME mixture into mostly hydrogen and carbon monoxide (syngas). The syngas generated in the reformer was sent to an anode supported SOFC (H.C. Starck Ceramics GmbH & Co.) The SOFC operated on 98% H2/2% H2O for baseline testing before and after switching to the reformed FAME mixture for 100 h of operation. The results presented here demonstrate that FAME mixture can be successfully reformed to power a SOFC, making them a viable fuel for a SOFC-based auxiliary power unit that is both greenhouse gas neutral and renewable.

COMPARATIVE INVESTIGATIONS INTO ENERGETIC AND ECOLOGICAL PARAMETERS OF CAMELINA-BASED BIOFUEL USED IN THE 1Z DIESEL ENGINE

The paper presents the findings of comparative investigations into the operation of Audi 80 1.9l 4 cylinder diesel engine, TDI, type 1Z, 66 kW powered by new FAME (fatty acid methyl esters) mixtures of spring (SCME) and winter (WCME) camelina-based biofuel and mineral diesel. The article assesses the principles of operating electronic control over the diesel engine (ECS) and exhaust gas recirculation (EGR) and looks at a positive impact of the system on energetic (be, ηe) and ecological (CH, NOx, CO2, SM) parameters. The ECS of the average and maximal power of the engine improve in-cylinder air injection that has an impact on an increase in ηe by approximately 30% and reduces the emission of the harmful components from incomplete combustion. It is accepted that in case diesel fuel is replaced by FAME biofuels (RME – rapeseed methyl ester; SCME – spring camelina methyl ester; WCME – winter camelina methyl ester), ECS control parameters shall not be retrofitted or additionally optimized. The properties of camelina-based biofuel mixtures B30 (SCME) and B30 (WCME) and diesel fuel are similar to the properties of the standard mixtures of RME biofuel B30 (RME). If compared to diesel fuel, the use of camelina-based biofuel mixtures B30 (SCME) and B30 (WCME) enables lower emissions of harmful components from exhaust gases, which makes approximately 15% of CH and 20÷25% of SM.

EXHAUST EMISSIONS FROM THE ENGINE RUNNING ON MULTI-COMPONENT FUEL

Possible alternative raw materials for producing biodiesel fuel are as follows: Camelina sativa oil, fibre linseed oil and waste animal fat. The aim of this work was to analyse the emissions of the engine running on multi-component fuels containing fossil diesel fuel (D), linseed or Camelina sativa oil fatty acid methyl esters (LSME and CME respectively) and beef tallow (TME) fatty acid methyl esters. The concentration of fatty acid methyl esters (FAME) in the mixtures with fossil diesel fuel varied from 10% to 30%. The mass proportion of LSME (or CME) and TME in the mixtures was 1:4. The lowest NOxconcentration in exhaust gases was observed when the mixtures contained 10% of biofuel. For the mixtures containing CME and LSME, NOx concentrations reached 290 and 295 ppm respectively when the engine rotation speed was 1200 min−1 and 370 and 375 ppm respectively when rotation speed was 2000 min−1. CO concentration was the lowest when fuel contained 30% of the FAME mixture. HC concentration was slightly higher when the mixtures containing LSME were used relative to the mixtures containing CME. The amount of HC did not fluctuate considerably (195÷254 ppm) at rotation speeds between 1200 and 2000 min−1. Lower HC concentration was found in exhaust gas when the fuels containing 10% and 20% of biofuel were used. The lowest concentration of polycyclic aromatic hydrocarbons (PAHs) was found when the mixtures contained 30% of biofuel made of LSME or CME corresponding to 30 µg/m3 and 38 µg/m3 at a rotation speed of 1200 min−1 and 640 µg/m3 and 670 µg/m3 at a rotation speed of 2000 min−1 respectively. The greatest amount of smokiness at a high rotation speed of 2000 min−1 was observed when the mixture contained 30% of multi-component biodiesel fuel. It was found that the fuel containing a mixture of 30% of LSME biofuel and 20% of CME biofuel had a small advantage.

Identification of the double-bond position in fatty acid methyl esters by liquid chromatography/atmospheric pressure chemical ionisation mass spectrometry

Fatty acid methyl esters (FAMEs) were analysed by reversed-phase HPLC coupled with atmospheric pressure chemical ionisation (APCI) mass spectrometry. The chromatographic separations of the FAMEs were optimised using acetonitrile or binary acetonitrile gradients and C18 or C30 columns. The gas-phase reactions of acetonitrile and unsaturated FAMEs in the APCI source provided [M+C3H5N]+ adducts. When fragmented, these adducts yielded diagnostic ions, allowing the unambiguous localisation of double bonds. The formation and fragmentation of the acetonitrile-related adduct was utilised for the structural characterisation of the FAMEs separated by HPLC. The APCI-MS detection of FAMEs encompassed a full-spectrum scan (providing information on the number of carbons and double bonds) and a data-dependent MS/MS scan of the [M+C3H5N]+ ions (the position of the double bonds). The utility of this approach was demonstrated using a mixture of FAMEs from blackcurrant-seed oil. All the unsaturated fatty acids known to exist in the sample were correctly identified and several others were newly discovered. In terms of sensitivity, HPLC/APCI-MS appeared to be comparable to GC/EI-MS.

Effects of High-Melting Methyl Esters on Crystallization Properties of Fatty Acid Methyl Ester Mixtures

Effects of High-Melting Methyl Esters on Crystallization Properties of Fatty Acid Methyl Ester Mixtures

Relation Between Red Blood Cell Omega-3 Fatty Acid Index and Bleeding During Acute Myocardial Infarction

Omega-3 fatty acids have multiple cardiovascular benefits but may also inhibit platelet aggregation and increase bleeding risk. If this platelet inhibition is clinically meaningful, patients with the highest omega-3 indexes (red blood cell eicosapentaenoic acid plus docosahexaenoic acid), which reflect long-term omega-3 fatty acid intake, should be at the risk for bleeding. In this study, 1,523 patients from 24 United States centers who had their omega-3 indexes assessed at the time of acute myocardial infarction were studied. The rates of serious bleeding (Thrombolysis In Myocardial Infarction [TIMI] major or minor) and mild to moderate bleeding (TIMI minimal) were identified in patients with low (<4%), intermediate (4% to 8%), and high (>8%) omega-3 indices. There were no differences in bleeding across omega-3 index categories. After multivariate adjustment, there remained no association between the omega-3 index and either serious (per 2% increase, relative risk 1.03, 95% confidence interval 0.90 to 1.19) or mild to moderate bleeding (per 2% increase, relative risk 1.02, 95% confidence interval 0.85 to 1.23). In conclusion, no relation was found between the omega-3 index and bleeding in this large, multicenter cohort of patients with acute myocardial infarction, suggesting that concerns about bleeding should not preclude the use of omega-3 supplements or increased fish consumption when clinically indicated.

Experiment based model development for the enzymatic hydrolysis in a packed-bed reactor with biphasic reactant flow

A systematic experiment based development of a kinetic model for the immobilized lipase (Novozym 435) catalyzed hydrolysis of a short-chain fatty acid methyl ester mixture in a biphasic organic–aqueous system was conducted. It included kinetic experiments to find the influence of the operating conditions on the reaction rate, the examination of the catalyst wetting and of the liquid–liquid phase behavior, as well as the formulation of an integral mathematical model for the used packed-bed reactor assembly. From experiments it was found that the initial reaction rate was independent of the total water content and directly proportional to the catalyst to organic phase mass ratio. The produced fatty acids and methanol reduced the reaction rate reversibly. During the experiments no negative impact on the enzyme activity was observed for temperatures <65 °C. The organic phase retained in the particle pores and around the particle prevented the aqueous phase from penetrating it. The influence of the aqueous phase pH-value on the reaction rate was negligible. A good description of the liquid–liquid phase behavior was obtained from a UNIFAC (Dortmund) and literature data based UNIQUAC model. For the reaction rate and the chemical equilibrium activity based expressions were chosen. The very good consistency of the resulting kinetic model with the experimental data confirmed the ability of the chosen approach to elucidate the relationships between the singular effects simultaneously occurring in the reaction system.

Novel guanidinium-based ionic liquids as stationary phases for capillary gas chromatography

The present study describes guanidinium-based ionic liquids (GBILs) as stationary phases for capillary gas chromatography (CGC) and to the best of our knowledge, no related reports are available up to now. In this study, a hexaalkylguanidinium ionic liquid (DOTMG-NTf 2) was synthesized and coated statically onto capillary columns. Selectivity of the stationary phase was evaluated by separating Grob test mixture, test mixture, alcohols mixture, and fatty acid methyl esters mixture, and thermal stability was investigated as well. The present study demonstrates that GBILs as CGC stationary phases exhibit satisfactory selectivity and thermal stability and have a great potential as new candidates for CGC stationary phases.

SYNTHESIS ALKANOLAMIDE TETRAHIDROXY OCTADECANOATE COMPOUND FROM CANDLE NUT OIL

Candle nut oil could be transesterificated by methanol with concentrated H2SO4 as a catalyst to form fatty acid methyl esther. Methyl linoleate could be separated by Column Chromatography mechanism technic partition from fatty acid methyl ester (FAME) mixture, then it was treated by ethanolamine at base condition in benzene as solvent and sodium methylate as a catalyst at reflux condition for 6 hours to form an alkanolamide. Alkanolamide could be epoxydized by tert-buthyl hydroperoxyde and peroxygenase as a catalyst and it was refluxed for 6 hours at 40 °C and nitrogen gas condition to form the epoxy alkanolamide octadecanoate, and then it was hydrolyzed by HCl 0.1 M to form alkanolamide tetrahidroxy octadecanoate (Polyol). Alkanolamide tetrahidroxy octadecanoate could be separated by Column Chromatography using silica gel H 40 and the eluent was the mixture of chloroform, ethyl acetate, formic acid in a ratio 90:10:1 (v/v/v/). Determination of HLB value from alknolamide tetrahydroxy octadecanoate is 13.096. Therefore, this compound was particularly suitable for application as an o/w emulsifiers. All af the reaction steps were confirmed by using FT-IR, 1H-NMR, GC-MS, Gas Chromatography and TLC. Keywords: Esterification, Candle nut oil, Surfactant, Amidation, Polyol.

Polycyclic aromatic hydrocarbon removal from contaminated soils using fatty acid methyl esters

In this study, solubilization of PAHs from a manufactured gas plant (MGP) soil and two artificially spiked soils using fatty acid methyl esters (FAME) was investigated. PAH removals from both the MGP and the spiked soils by FAME, methanol, soybean oil, hydroxypropyl-β-cyclodextrin, Triton X-100, and Tween 80 were compared. The effect of FAME:MGP soil ratios on PAH removals was also investigated. Results showed that the FAME mixture synthesized by our lab was more efficient than the cyclodextrin and the two surfactants used for PAH removal from the spiked soils with individual PAH concentrations of 200 and 400 mg kg −1. However, the difference among three PAH removals by the FAME, soybean oil and methanol was not quite pronounced. The FAME synthesized and market biodiesel exhibited better performance for PAH removals (46% and 35% of total PAH) from the weathered contaminated MGP soil when compared with the other agents (0–31%). Individual PAH removals from the weathered MGP soil were much lower than those from the spiked soils. The percentages of total PAH removals from the MGP soil were 59%, 46%, and 51% for the FAME:MGP soil ratios of 1:2, 1:1, and 2:1, respectively. These results showed that the FAME could be a more attractive alternative to conventional surfactants in ex situ washing of PAH-contaminated soils.

Separation of cis/trans geometrical fatty acid isomers by silver-exchanged zeolite Y

The separation of cis and trans isomers is relevant for biological and nutritional applications, silver-exchanged zeolite Y was prepared and applied for the treatment of mixtures of cis and trans geometrical isomers of mono- and polyunsaturated fatty acid methyl esters (FAMEs). cis FAMEs were adsorbed into zeolite with a high degree of selectivity (cis/trans ratio in the range of 1.9–3.2). The effectiveness was due to the synergism of the π-complexation between the silver ion and the double bonds and the different FAME structures trapped into the zeolite cages. Some indication of the complex stabilities came from theoretical studies using unsaturated lipids. A prototype cartridge was also designed for application in the fractionation of cis/trans FAME mixtures.

Predicting Properties of Biodiesel Fuels using Mixture Topological Index

AbstractA new topological index for individual components based on the information of molar mass, bond length and bond energy was established to reflect the molecular structure of fatty acid methyl esters (FAME). Combined with the modified Grunberg–Nissan or Hind equation, the two series mixture topological index values of the biodiesels (mixture of FAME) were calculated, respectively. Some basic properties such as the density, viscosity, flash point (FP), high heating value (HHV) for biodiesel were correlated with these mixture topological indexes to find the relationship of structure and properties. The results show that the topological index can reflect the information of the molecular structure for FAME, such as the size of molecule, unsaturated bond, intensity of bond and branch degree. The modified Grunberg–Nissan equation has a higher precision of predicting for the properties of biodiesel studied than the Hind equation.

453 脂肪酸メチルエステル混合燃料が圧縮着火機関へ及ぼす影響(応用熱工学V)

453 脂肪酸メチルエステル混合燃料が圧縮着火機関へ及ぼす影響(応用熱工学V)

Crystallization Behavior of Fatty Acid Methyl Esters

AbstractBiodiesel 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 &lt; 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.

Predicting the surface tension of biodiesel fuels by a mixture topological index method, at 313 K

This paper described a method to predict the surface tension of a biodiesel fuel from the molecular structure of its fatty acid methyl ester (FAME) components. A topological index was proposed that used a combination of the distance matrix and adjacency matrix of the molecular structure. The topological index contains information on the molecular structure for the FAMEs, such as the carbon number and unsaturated bonds. The mean topological index values of five FAME mixtures (peanut, canola, coconut, and palm, soybean oil) were calculated by an integration using a modified Dalton-type mass-average equation. The relationship between the mean topological index and mean surface tension of FAME mixtures of biodiesel of known composition at 313 K was linear, and its regression equation allowed the surface tension of biodiesel fuels to be calculated. The relative error between the predicted surface tensions of the above biodiesel fuels and their measured values was within 2.19%. The surface tensions of five biodiesel fuels (corn, safflower, sunflower, and cottonseed, lard oil) were further predicted.

Norske Skog shelves biodiesel production plans

The production of fatty acid methyl esters (FAMEs) from waste activated bleaching earth (ABE) discarded by the crude oil refining industry using lipase from Candida cylindracea was investigated in a 50-L pilot plant. Diesel oil or kerosene was used as an organic solvent for the transesterification of triglycerides embedded in the waste ABE. When 1% (w/w) lipase was added to waste ABE, the FAME content reached 97% (w/w) after reaction for 12 h at 25 °C with an agitation rate of 30 rpm. The FAME production rate was strongly dependent upon the amount of enzyme added. Mixtures of FAME and diesel oil at ratios of 45:55 (BDF-45) and 35:65 (BDF-35) were assessed and compared with the European specifications for biodiesel as automotive diesel fuel, as defined by pr EN 14214. The biodiesel quality of BDF-45 met the EN 14214 standard. BDF-45 was used as generator fuel, and the exhaust emissions were compared with those of diesel oil. The CO and SO2 contents were reduced, but nitrogen oxide emission increased by 10%. This is the first report of a pilot plant study of lipase-catalyzed FAME production using waste ABE as a raw material. This result demonstrates a promising reutilization method for the production of FAME from industrial waste resources containing vegetable oils for use as a biodiesel fuel.

Lipase-catalyzed biodiesel production from waste activated bleaching earth as raw material in a pilot plant

The production of fatty acid methyl esters (FAMEs) from waste activated bleaching earth (ABE) discarded by the crude oil refining industry using lipase from Candida cylindracea was investigated in a 50-L pilot plant. Diesel oil or kerosene was used as an organic solvent for the transesterification of triglycerides embedded in the waste ABE. When 1% (w/w) lipase was added to waste ABE, the FAME content reached 97% (w/w) after reaction for 12 h at 25 °C with an agitation rate of 30 rpm. The FAME production rate was strongly dependent upon the amount of enzyme added. Mixtures of FAME and diesel oil at ratios of 45:55 (BDF-45) and 35:65 (BDF-35) were assessed and compared with the European specifications for biodiesel as automotive diesel fuel, as defined by pr EN 14214. The biodiesel quality of BDF-45 met the EN 14214 standard. BDF-45 was used as generator fuel, and the exhaust emissions were compared with those of diesel oil. The CO and SO 2 contents were reduced, but nitrogen oxide emission increased by 10%. This is the first report of a pilot plant study of lipase-catalyzed FAME production using waste ABE as a raw material. This result demonstrates a promising reutilization method for the production of FAME from industrial waste resources containing vegetable oils for use as a biodiesel fuel.

Quantitative Deuterium Isotopic Profiling at Natural Abundance Indicates Mechanistic Differences for Δ12-Epoxidase and Δ12-Desaturase in Vernonia galamensis

Quantitative (2)H NMR spectroscopy can determine the natural abundance ((2)H/(1)H) ratio at each site of a molecule. In natural products, variation in these values is related to the reaction mechanisms in the pertinent biosynthetic pathway. For the first time, this novel approach has been exploited to probe for mechanistic differences in the introduction of different functionalities into a long-chain fatty acid. Vernolic acid, a major component of the seed oil of Vernonia galamensis, contains both an epoxide and a desaturation. The site-specific isotopic distribution ((2)H/(1)H)(i) has been determined for both vernolic acid and linoleic acid isolated from the same V. galamensis oil. It is found that the ((2)H/(1)H) ratio of vernolic acid shows a pattern along the entire length of the chain, consistent with linoleic acid being its immediate precursor. Notably, the C13 relates to the C13 of linoleic acid but not to the C13 of oleic acid. Furthermore, the C12 and C13 positions in vernolic acid are less depleted, consistent with a change in hybridization state from sp(2) to sp(3). However, the C11 position shows a marked relative enrichment in the vernolic acid, implying that it plays a role in the epoxidase but not the desaturase mechanism. Thus, although it can be concluded that the catalytic mechanisms for the epoxidase and desaturase activities are similar, marked differences in the residual ((2)H/(1)H) patterns indicate that the reaction mechanisms are not identical.