Oxidative stability and storage behavior of fatty acid methyl esters derived from used palm oil

Fatty acid alkyl esters, especially FAME, are the most commonly used liquid biofuel. Because biofuels are expected to be important alternative renewable energy sources in the near future, more studies on their stability against oxidation need to be addressed. Biofuel derived from vegetable oils is well researched, currently with more attention focused on the reuse of waste oil sources than on pure vegetable oil for such production. A method to convert used palm oil, i.e., used frying oil, and residual oil of spent bleaching earths (SPE) to their respective methyl esters has been established by the Malaysian Palm Oil Board. These methyl esters can be used as diesel substitute. However, the methyl esters obtained from used frying oil have a low induction period (3.42 h). In Europe, any methyl esters must have an induction period of at least 6 h in Rancimat stability to be usable as biodiesel, as required by European Biodiesel Standard (EN 14214). To meet this requirement, the used frying oil methyl esters (UFOME) obtained can be treated with different types of antioxidants, either synthetic or natural, at different treatment levels, such as vitamin E, 3-ert-butyl-4-hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methyl-phenol (BHT), 2,5-di-tert-butyl hydroquinone (TBHQ), and n-propyl gallate (PG), to investigate their oxidative stability and storage behavior. The order of increasing antioxidant effectiveness with respect to the oxidative stability of UFOME is: vitamin E<BHT<TBHQ<BHA<PG. Because methyl esters derived from residual oil of SBE have an induction period of 14.6 h, their treatment with antioxidants is unnecessary.     

Hydrosilylation of long chain unsaturated fatty acid esters

The addition of a series of silicon hydrides: trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyl dichlorosilane, and methyl phenyl chlorosilane to esters of long chain unsaturated fatty acids, such as oleic, linoleic acids, and 10-undecenoic acid, was studied with respect to catalysts, temperature, and solvents. Higher yields were obtained on carrying out the hydrosilylation reactions in the presence of chloroplatinic acid or Pt on C catalysts in bulk without solvent, as compared with peroxide catalysts. The addition reaction with methyl 10-undecenoate, which has a terminal double bond, gave a higher yield than that with methyl oleate. NMR data of the products from methyl 10-undecenoate and methyl oleate, as well as their reduction products with lithium aluminum hydride, have shown that, with the former ester, the silyl moiety added exclusively to the terminal carbon atom, while, with the latter, no migration of the silyl moiety to the terminal carbon atom was observed.     

Field ionization mass spectrometry of long chain fatty methyl esters

Mass spectrometry is particularly useful for identifying lipid materials. One primary factor in the interpretation of mass spectra is the recording of the molecular ion peak giving the molecular weight of the compound. Regrettably many compounds, including hydroxy compounds, do not give significant molecular ion peaks; consequently their identification is difficult. A mass spectrometer equipped with a field ionization source produces a greatly different mass spectrum consisting almost entirely of the molecular ion peak. This new source was used to measure the mass spectra of methyl esters of saturated, unsaturated and hydroxy fatty acids. Saturated esters gave the molecular ion peak almost exclusively; unsaturated esters yielded molecular plus metastable ion peaks; whereas the hydroxy esters had molecular, M-18, meaastable and fragment ion peaks. Presented at the AOCS Meeting, Chicago, October 1967. No. Mktg. and Nutr. Res. Div., ARS, USDA.     

Solubilities of six cottonseed oil fatty acid methyl esters in methanol

Solubilities of six cottonseed oil fatty acid methyl esters in metha-nol have been determined. The esters were: methyl oleate, methyl linoleate, methyl malvalate, methyl dihydromalvalate, methyl sterculate and methyl dihydrosterculate. The solubility/temperature data are presented in graphical and tabular form.     

Recovery of short,medium, and long chain fatty acid methyl esters using wet halogenated hydrocarbons

Fatty acid methyl esters are prepared and analyzed by gas liquid chromatography using a simple procedure that does not involve evaporation steps or drying of the final extract. The esters of fatty acids down to caproate (C₆) are recovered quantitatively. The long chain fatty acid esters, including the polyunsaturated esters, are also recovered quantitatively and are at least as stable as esters isolated by conventional procedures. Preparation of the esters in methanolic reagents is followed by partition of the mixture between a small volume of ethylene chloride and a large volume of water. The lower halogenated hydrocarbon phase contains the methyl esters ready for analysis, and the aqueous phase contains the methanol, catalysts, and other water-soluble materials.     

Preparation of esters and anhydrides from long chain fatty acid chlorides

Conclusions The use of reduced pressure to remove the HCl formed in the reaction of acid chlorides with alcohols and acids appears to be generally applicable to reactants of low volatility. The lowest yield of recrystallized product obtained was 85.0%, and in most cases tested the yield was more than 90%. Any side reactions occurring are apparently minor as a single crystallization gave products of high purity. This paper was awarded an honorable mention in the 1957 Fatty Acid Producers' Award Competition administered by the American Oil Chemists' Society.     

Noncarotenoid hydrocarbons in palm oil and palm fatty acid distillate

Column chromatographic and gas chromatographic-mass spectroscopic (GCMS) analyses for minor and trace noncarotenoid hydrocarbons of crude palm oil and palm fatty acid distillate revealed the presence of a wide range of n-alkanes (C₁₂H₂₆ to C₃₆H₇₄) and n-alkenes in addition to the major component, squalene. Hydrocarbon components concentrated in palm fatty acid distillate where squalene was dominant, but degradation products such as alkenes (from fatty acids or glycerides), aromatic hydrocarbons (from carotenes) and diterpene hydrocarbons (from tocotrienols) were detected in significant quantities, superseding the naturally occurring n-alkanes. Mechanisms proposed suggest that degradation of the valuable vitamin E or tocotrienols needs to be minimized in physical refining.     

Separation of fatty acid methyl esters from tall oil by selective adsorption

Fatty acid methyl esters (FAME) and resin acids (RA) were separated from tall oil by selective adsorption. Commercial nonmodified molecular sieve 13X was used as adsorbent. The adsorption isotherms of fatty acids (FA), FAME, and RA on molecular sieve 13X at 25°C were determined using various solvents. The solvents were methanol, ethanol, isopropanol, acetone, benzene, hexane, isooctane, petroleum ether (40–60°C), and petroleum naphtha (80–180°C). With each solvent, FA and RA were adsorbed to a greater extent than FAME. Adsorption isotherms for RA and FAME in binary adsorption systems were also determined using petroleum ether, petroleum naphtha, benzene, and isopropanol. For each component in the binary adsorption, the equilibrium amounts are lower than the values for pure component adsorption. The adsorption of FAME decreased in the presence of RA markedly in petroleum ether and petroleum naphtha. This fact may be the indication of the phenomenon of selective adsorption. Separation was accomplished by adding a solution of esterified tall oil in solvents used in the binary adsorption systems, through a column packed with molecular sieve 13X. With petroleum naphtha, FAME and RA were recovered in yields of 93 and 94%, respectively, from esterified tall oil. Petroleum naphtha gave the best results. The effects of particle size of adsorbent and flow rate of solvent on the efficiency of the separation were also investigated in fixed-bed column studies. The particle size of adsorbent did not apparently alter the results. Changes in the particle size should not significantly change the number of available adsorption sites in a microporous molecular sieve.     

Stability studies on methyl and ethyl fatty acid esters of sunflowerseed oil

Fatty acid esters, high in linoleic acid, were prepared and stored for long-term engine tests. Storage tests with these esters were undertaken to obtain more information on optimal storage requirements and general stability characteristics. Samples were kept at three temperature levels (20 C, 30 C and fluctuating around 50 C) for a 90-day period and were removed at regular intervals for chemical and physical analysis. The influence of air, temperature, light, TBHQ and contact with mild steel was evaluated by comparing the free fatty acid, peroxide, anisidine, ultraviolet absorption, viscosity and induction periods. A statistical model was used to evaluate the data and to reduce the large number of data points to comparable curves. Storage of esters in contact with air, especially at a temperature above 30 C, resulted in significant increases in peroxide, ultraviolet absorption, free fatty acid, viscosity and anisidine values. Exclusion of air retarded oxidation at all temperature levels. A direct relationship between viscosity increases and oxidation parameters was evident. Exposure to light caused a small increase in the oxidation parameters of esters stored at the highest temperature level. Addition of TBHQ prevented oxidation of samples stored under moderate conditions. Under unfavorable storage conditions the anti-oxidant was no longer effective. Mild steel had very little effect on the oxidation parameters. Only the anisidine values of samples stored at the highest temperature level were slightly increased. Methyl esters performed slightly better than ethyl esters during the storage test. The following practical guidelines for storage of fatty acid ester fuels are: (i) airtight containers should be used; (ii) the storage temperature should be <30 C; (iii) mild steel (rust free) containers may be used, and (iv) TBHQ has a beneficial effect on oxidation stability.     

Combustion characteristics of fatty acid methyl esters derived from recycled cooking oil

The goal of this study is to find out the exhaust emissions differences produced by different kinds of fatty acid methyl esters (FAME) derived from used cooking oils and animal fats, as well as the importance of the purification step in exhaust emissions production. A total of 120 L of waste vegetable oil and 30 L of waste frying oil were collected and converted into three batches of FAME. There were two batches of FAME produced from waste vegetable oil (B01 and B02), and one batch of FAME produced by mixing 2% of waste frying oil with waste vegetable oil (B03). The FAMEs used in this study had higher density, kinematic viscosity, and flash point, but a lower gross heating value, when compared to the premium diesel. The B01 engine produced higher CO formation and the diesel-fuelled engine produced higher CO than the B02 and B03 did for engine speeds higher than 1400 rpm. Most of the FAME fuels produced higher CO₂ than the diesel fuel did. The FAME fuels emitted higher NO_x and PM, but lower SO₂, than the diesel fuel. C_nH_2n+2, diphenyl sulfone (C₁₂H₁₀O₂S), and diethyl phthalate (C₁₂H₁₄O₄) can be selected as the character index for the combustion of FAME.     

Very long chain PUFA in murine testicular triglycerides and cholesterol esters

Very long chain (VLC) PUFA of the n−6 and n−3 series are known to occur in mammalian testis. The aim of this work was to characterize further two testicular lipid classes with VLCPUFA, cholesterol esters (CE) and total triglycerides (TG) in rat and mouse testis. The VLCPUFA predominating in these lipids were a series of n−6 pentaenes and tetraenes with 24 to 32 carbons, including small amounts of odd-chain PUFA, 28∶5n−6 and 24∶5n−6 prevailing in CE and TG, respectively. Most of the VLCPUFA of TG were concentrated in a small fraction of TG, made up by 1-O-alkyl-2,3-DAG. This TG subclass was absent altogether from the TG of sexually immature testis. The TG and the CE with VLCPUFA only occurred in testis of adult fertile animals. The proportion of VLCPUFA in total TG and CE was higher in rodents than in other mammals. In the n−6 PUFA-rich adult mouse testis, the amounts of testicular triacylglycerols decreased significantly after consumption of fish oil for 2 wk. Whereas 18∶2n−6 was significantly reduced, the amounts of 22∶5n−6 and longer n−6 PUFA were less affected in all mamor testicular lipids including PC and PE, where they were unchanged. The 1-O-alkyl-2,3-DAG and their n−6 VLCPUFA were virtually unaffected by the diet. The VLCPUFA-containing molecular species of CE and TG may represent a form of storage of cholesterol and polyenoic FA required to sustain spermatogenesis. Via chain-shortening, VLCPUFA stored in the neutral lipids may serve as precursors of the major C₂₂ PUFA typical of cell membrane glycerophospholipids, protecting testicular cells against shifts in FA composition induced by dietary changes.     

Dilatometric investigations of fatty acid methyl esters

Summary The coefficients of expansion and melting dilations were measured for methyl palmitate, methyl stearate, methyl arachidate, methyl behenate, and methyl oleate. The dilatometric curve for the heating cycle of methyl palmitate and methyl stearate in the solid state was composed of a linear section to 49 degrees below the melting point, followed by a curvilinear section to the melting point. The heating and cooling cycle curves for methyl palmitate show the same volume change from −38°C. to 29°C., but the shape of the curves is different. The same relation holds for methyl stearate from −38°C. to 37.5°C. “After-contractions” were found in volume measurements within a few degrees of the melting point of both esters. Equilibrated points were found within 0.5 degrees of the final melting temperature of methyl stearate. A striking similarity exists between curves for variation of the dielectric constant with temperature for long chain linear molecules and the dilatometric data. Presented at the fall meeting, American Oil Chemists' Society, Mnneapolis, Minn., October 11, 1954. Issued as Paper No. 196 on the “Uses of Plant Products” and as N.R.C. No. 3671.     

Performance of sulfoxylated fatty acid methyl esters

Sulfoxidation of fatty acid methyl esters with SO₂, O₂, and ultraviolet light of appropriate wavelength has led to the synthesis of methyl esters sulfonates or sulfoxylates known as Φ-MES because of the possible random position of SO₃ group in the alkyl chain. This work describes experimental measurements of physical properties such as solubility and viscosity of sodium Φ-MES water solutions. Amphipathic properties such as surface tension, critical micelle concentration, wetting and foaming powers were measured as well and compared to linear alkylbenzene sodium sulfonate (LAS). Finally, stability to water hardness, dishwashing test, and detergency performance were evaluated. Expectedly, these products may be used as LAS partners either in heavy-duty powders or in hand dishwashing liquids. Experimental results on Φ-MES of varying carbon number indicate that C₁₆ is the optimal carbon chain length.     

Rapid gas-liquid chromatographic procedure for the analysis of methyl esters of long chain fatty acids

A gas-liquid chromatographic procedure permitting rapid analysis of the major fatty acids commonly found in vegetable oils was evaluated with standards of known composition and found to be both accurate and precise. A standard containing 20% by weight of each of the methyl esters of palmitic, stearic, oleic, linoleic, and linolenic acid was analyzed in 2.7 min with errors of 1.6, 0.7, 3.3, 0.8, and 3.1%, respectively. Six procedures, requiring from 2.7 to 25 min for the eluation of the effects of the operational parameters, carrier gas flow rate and column temperature, on the precision and accuracy of gasliquid chromatographic analysis of fatty acid methyl esters. The most rapid procedure, obtained with a column temperature of 235C and a helium flow rate of 110 ml/min was found to be comparable in accuracy and precision to the other procedures and gave quantitative results with National Heart Institute type fatty acid standards KA, KB, and KD, that agreed with stated composition with a relative error of less than 2% for major components (10% or more of total mixture) and less than 6% for minor components (less than 10% of total mixture). Approved as Journal Series Paper No. 535, Georgia Experiment Station. This research was supported in part by Corn Industries Research Foundation and by Corn Products Company.     

Soft polyurethane elastomers with adhesion properties based on palm olein and palm oil fatty acid methyl ester polyols

Soft polyurethane (PU) elastomers with >70% bio-based content and with properties characteristic of pressure sensitive adhesives were prepared from an equimolar ratio of a polyol derived from palm oil fatty acid methyl ester (PolyFAME-EG polyol) and palm olein polyols (Pioneer E-135 and Pioneer M-60) cured with 2,4′- and 4,4′- diphenylmethane diisocyanate isomeric mixture at isocyanate to hydroxyl equivalent weight ratio (Isocyanate Index) of 1.02 and 0.73. FTIR analyses of the resulting elastomers indicate high levels of free non-hydrogen bonded urethanes, indicating phase mixing of hard and soft segments, which explains the transparent nature of the elastomers. The physical properties of the elastomers were correlated with the cross-link density of the palm olein polyols and Isocyanate Index. Elastomers produced at an Isocyanate Index of 1.02 ranges in hardness from 21 to 67 Shore A which correlated with the average polyol functionality. However, at an Isocyanate Index of 0.72 the resulting elastomers were very soft with hardness ranging from 1 to 4 Shore A and with T-peel adhesion to polypropylene in the range from 2.27 to 1.98 N/25 mm. Based on these results, a polyurethane matrix with a high renewable content of palm oil polyols can be used as a platform for the development of transparent elastomers that can be used as soft energy-absorbing materials with potential use in pressure sensitive adhesives.     

Non-volatilea-branched chain fatty acid derivatives: IV. Addition of aryl esters to long chain olefins

The di-tertiary butyl peroxide initiated free radical addition of methyl phenylacetate, methylp-tolylacetate and methylp-methoxyphenylacetate to 1-decene gives two types of products. In addition to the expecteda-branched esters, dehydrodimer (bothmeso anddl) esters were also obtained. The highest yield ofa-branched ester was obtained from methyl phenylacetate. Higher yields of the dehydrodimer esters were obtained from the substituted phenyl esters. Attempts to add methylp-nitrophenylacetate to 1-decene were not successful and no evidence for the formation of a dehydrodimer product was observed.     

Oxidative stability of soybean oil fatty acid methyl esters by oil stability index (OSI)

Biodiesel, an alternative diesel fuel derived from transesterification of vegetable oils or animal fats, is composed of saturated and unsaturated long-chain FA alkyl esters. During long-term storage, oxidation caused by contact with air (autoxidation) presents a legitimate concern with respect to monitoring and maintaining fuel quality. Extensive oxidative degradation may compromise quality by adversely affecting kinematic viscosity, acid value, or PV. This work examines the oil stability index (OSI) as a parameter for monitoring the oxidative stability of soybean oil FAME (SME). SME samples from five separate sources and with varying storage and handling histories were analyzed for OSI at 60°C using an oxidative stability instrument. Results showed that OSI may be used to measure relative oxidative stability of SME samples as well as to differentiate between samples from different producers. Although addition of α-tocopherol or TBHQ increased OSI, responses to these antioxidants varied with respect to SME sample. Variations in response to added antioxidant were attributed to aging and other effects that may have caused oxidative degradation in samples prior to acquisition for this study. Results showed that OSI was more sensitive than iodine value in detecting the effects of oxidative degradation in its early stages when monitoring SME during storage.     

高级脂肪酸甲酯合成及其应用研究进展

本文综述了常见长碳链高级脂肪酸甲酯合成方法。简明阐述了高级脂肪酸甲酯具有可再生资源优势，正在引起人们关注，有望开发出一种新型能源—“生物柴油”，逐步替代肾俏的石油资源；以及高级脂肪酸甲酯具有良好生物降解性、不舍磷的理化特性，是一种优起的表面活性剂原料，正被广泛用于生产脂肪酸甲酯乙氧基化物、脂肪酸甲酯磺酸钠盐等环境友好的洗涤用品，具有广泛的开发前景。     

不同碳链长度脂肪酸甲酯的催化裂化产物分布规律

以辛酸甲酯、癸酸甲酯、月桂酸甲酯3种碳链长度不同的脂肪酸甲酯为原料,LVR-60为催化剂,在固定床上考察不同温度（350～500℃）下碳链长度对脂肪酸甲酯催化裂化产物分布的影响规律。结果表明,随着脂肪酸甲酯碳链长度的增长,脂肪酸甲酯转化率不断提高,脱氧产生的CO、CO₂逐渐增加,液体产物中烃类的含量逐渐增加而含氧衍生物逐渐减少。提高反应温度有利于提高脂肪酸甲酯转化率,得到较多的烃类,降低液相产物中含氧衍生物的含量。在低温下,脂肪酸甲酯裂化生成的醛、酯、羧酸、酮等含氧衍生物的含量较高,其裂化过程中CO₂是主要的脱氧产物;而高温下有机液体产物中几乎不含含氧衍生物,CO为主要脱氧产物。