Fatty and Resinic Acids Extraction from Crude Tall Oil

Abstract

The separation of fatty and resinic acidic fractions from crude tall-oil soap solutions with n-heptane by the technique of dissociation extraction is discussed. The theory of the overall process is supported by a systematic study developed to cover the high selectivity demonstrated in the differential solubility and the aptness between fatty and diterpenic acids to both liquids phases. To study the main factors affecting those liquid-liquid extraction systems and the amphiphilic behavior of such molecules involved, sodium salts aqueous solutions of crude tall oil and synthetic mixtures as molecular acidic models were used.     

Microalgae as a Feedstock for Sustainable Fatty Acids: Factorial Design Study

Microalgal oil from Nannochloropsis gaditana cultivated in a laboratory-scale photobioreactor was submitted to enzymatic hydrolysis using Candida rugosa lipase. A 2² full factorial design was performed to evaluate the effects of the soy lecithin emulsifier concentration and the lipase loading on the formation of free fatty acids. As control, a similar set of reactions was carried out with macaw palm oil. The results showed similar hydrolysis yields for both feedstocks. The highest value was reached when the concentrations of soy lecithin and lipase were taken at their lowest and highest levels, respectively. The hydrolysate from microalgal oil showed that the majority of the fatty acids released by C. rugosa consisted of palmitic, oleic, and linoleic acids.     

Validation of Two Methods for Fatty Acids Analysis in Eggs

A comparative study between two methods (lipid extraction followed by saponification and methylation, and direct methylation) to determine the fatty acids in egg yolk was evaluated. Direct methylation of the samples resulted in lower fatty acid content and greater variation in the results than the lipid extraction followed by saponification and methylation. The low repeatability observed for the direct HCl methylation method was probably due to a less efficient extraction and conversion of the fatty acids into their methyl esters as compared to the same procedure starting with the lipid extract. As the lipid extraction followed by esterification method was shown to be more precise it was validated using powdered egg certified as reference material (RM 8415, NIST) and applied to samples of egg, egg enriched with polyunsaturated omega-3 fatty acids (n-3 PUFA), and commercial spray-dried whole egg powder.     

Continuous Extraction of Crude Tall Oil

Abstract

A new continuous extraction method for fatty and resinic acids separation from crude tall-oil sodium salts aqueous solutions by countercurrent contact with n-heptane was developed using a bench-scale multistage mixer-settler plant. The data obtained showed good recoveries and high purities, especially for resinic fraction stream, for which the consumption of chemical reagents is virtually obviated with consequent economic advantages.     

Simultaneous Determination of Free Fatty Acids and Esterified Fatty Acids in Rice Oil by Gas Chromatography

Free fatty acids (FFA) in crude rice oil were selectively and stoichiometrically derivatized to fatty acid N,N-dimethylamides (FADMA) by catalytic condensation at 45 °C, and then esterified fatty acids (eFA) were directly converted to fatty acid methyl esters (FAME) at 37 °C. The mixture of FADMA and FAME formed in a single test tube was injected into the capillary column of a gas chromatograph (GC). No mutual contamination occurred between FFA and eFA, and reliability of the method was confirmed by comparison between GC data obtained by this method and by a conventional isolation method. The advantages of the present method are that no FFA isolation procedures are required, the reactions proceed under mild temperature conditions, and FFA and eFA can be analyzed simultaneously by GC.     

Contents of Fatty Acids, Selected Lipids and Physicochemical Properties of Western Australian Sandalwood Seed Oil

The study was designed to characterise two extracts of Western Australian sandalwood (Santalum spicatum) seed oils for their physicochemical and lipid characteristics. Sandalwood plantation’s surplus seeds could be used for their oil content, to improve the commercial viability of this industry. The seed oils were obtained by solvent extraction and supercritical carbon dioxide extraction respectively. Important physicochemical parameters were compared with other oils commonly used in pharmaceutical and cosmetic products. Acid values were found to be higher (6.0–7.5 mg KOH/1 g oil) while peroxide values (6.7–9.0 mequiv/Kg) were lower than reported for other oils. Tocopherols were found to be lower than those usually reported for nut oils (α-tocopherol 1–3 mg/100 g; δ-tocopherol 2.2–5.7 mg/100 g), squalenes and phytosterols were found in considerable quantities. The fatty acid content consisted largely of ximenynic acid (35 %) and oleic acid (52 %). No oxidative derivatives of fatty acids were observed. Although there were statistically significant differences in some properties, the magnitude of these were insufficient to conclude there were any notable differences in the two oil extracts.     

Application of Fatty Acids for Chemotaxonomy of Reef-Building Corals

Sixteen scleractinian species of six coral families (Acroporidae, Pocilloporidae, Poritidae, Faviidae, Pectiniidae, and Fungiidae) from Vietnam were analyzed for fatty acid (FA) composition. Except for the Poritidae species, total lipids of the corals had the same set of FAs, about 50% of them being unsaturated acids. Some coral families had high levels of characteristic FAs: 20:3(n-6), 20:4(n-3), and 22:6(n-3) in Pocilloporidae; 18:1(n-9) and 22:6(n-3) in Poritidae; and 18:3(n-6) and 22:5(n-3) in Faviidae. For the first time in hexacorals, unsaturated C₂₄ FAs (24:1(n-9), 24:2(n-6), 24:2(5,9), 24:3(5,9,17), and 24:4(n-3)) were discovered in the Poritidae species. The highest level of 18:1(n-7), odd-chain and branched FAs (7.5% in total) was detected in Sandalolitha robusta. The data obtained on the contents of ten principal C₁₈–C₂₂ polyunsaturated FAs (PUFAs) for the 16 specimens were combined with data on the 19 reef-building coral specimens investigated previously and subjected to multidimensional scale analysis (MSA). The representative coral families (Acroporidae, Pocilloporidae, Poritidae, Faviidae, Dendrophylliidae, and Milleporidae) were separated by MSA according to the composition of their principal PUFAs. Therefore, PUFAs may serve as chemotaxonomic markers for reef-building corals at the family level. Family-specific compositions of coral zooxanthellae characterized by different PUFA profiles, which affect the PUFA content of whole coral colonies, were supposed to be the probable cause of the discovered chemotaxonomic distinctions between reef-building corals.     

高酸值原油环烷酸的结构组成

对苏丹Fula–North–3B原油及馏份油中环烷酸的酸值、结构、分子量分布等进行了分析测试和研究. 结果表明：苏丹Fula–North–3B原油中环烷酸的酸值(以KOH计)在10~14 mg/g之间，结构均以一、二、三环为主，在350℃以上，除一、二、三环外，还含有一定量的四、五环的环烷酸. 芳环含量很少, 烯烃双键含量也很少，环烷酸的构成主要是一元酸. 环烷酸的分子量分布情况与馏份的沸程趋势一致. 随着馏份变重，酸值增加、环烷酸的平均分子量增大、分布变宽、碳数范围增加.     

甲醇溶剂法分离蚕蛹油多不饱和脂肪酸

采用甲醇溶剂法分离蚕蛹油多不饱和脂肪酸。通过单因素实验探讨了温度、甲醇浓度、甲醇脂肪比、时间对多不饱和脂肪酸分离效果的影响,然后通过正交实验确定了多不饱和脂肪酸分离的较佳条件。结果表明,适宜的分离条件为：温度-10℃,甲醇浓度90%（w）,甲醇脂肪比2.5,结晶时间30min,在上述条件下多不饱和脂肪酸得率为62.3%,含量由71.0%提高到95.8%。     

鱼油不饱和脂肪酸的自由基氧化规律

从东海小杂鱼鱼油中鉴定出43种脂肪酸,主要16种脂肪酸占总脂肪酸95．01％。测定了鱼油加入自由基后在不同的时间及不同光照条件下的脂肪酸的氧化规律,并进行分析发现无论在光照还是避光条件下所有不饱和脂肪酸都随着时间的推移,含量都有下降的趋势,说明不断的被氧化,特别是EPA、DHA被氧化的更快。在光照条件下鱼油中的脂肪酸氧化比在避光条件下要快。在实验过程中,通过在鱼油加入自由基后再加入不同的抗氧化剂,利用TBA值的测定,筛选出对鱼油中的脂肪酸氧化有较好的抗氧化性的各种抗氧化剂的有效浓度。同时可以发现4-己雷琐辛的抗氧化性最强,由于此实验中用的TBHQ是食品级的,因此BHA的抗氧化性比TBHQ强。并且对鱼油在添加抗氧化剂前后脂肪酸的自由基氧化规律进行比较。     

Fatty Acids in Liver,Muscle and Gonad of three Tropical Rays including Non-Methylene-Interrupted Dienoic Fatty Acids

Scientific investigation of lipids in Elasmobranchs has been conducted mainly on shark species. Because rays seem to be neglected, this study was performed to examine the complete fatty acid (FA) composition with a particular interest for long-chain polyunsaturated FA (PUFA) content in different tissues of three ray species including parts usually discarded. The total FA and PUFA profiles of total lipids were determined in muscle, liver, and gonad of Rhinobatos cemiculus, Rhinoptera marginata, and Dasyatis marmorata, the most often caught ray species from the East Tropical Atlantic Ocean. Fifty FA were characterized as methyl esters and N-acyl pyrrolidides by gas chromatography/mass spectrometry, showing significant levels of 20:5n-3 (EPA) (up to 5.3%) and 22:5n-3 (DPA) (up to 7.3%), high levels of 20:4n-6 arachidonic (ARA) (4.8–8.6% of total FA) and 22:6n-3 (DHA) (up to 20.0%). The results show that muscle, liver and gonad of rays can provide high amounts of essential PUFA, specially DHA, for direct human nutrition or the food processing industry. High proportions of DHA were particularly found in all samples of R. cemiculus (11.6–20.0%), and in muscle and liver of D. marmorata (11.1–16.1%). Regarding the high amounts of (n-3) PUFA, this study shows that these rays deserve a better up-grading, including the normally discarded parts, and describes the occurrence of unusual NMID FA in all tissues studied. Five non-methylene-interrupted dienoic fatty acids (NMID FA) (0–3.4%) were reported, including previously known isomers, namely 20:2 Δ7,13, 20:2 Δ7,15, 22:2 Δ7,13, 22:2 Δ7,15, and new 22:2 Δ6,14. These acids are quite unusual in fish and unprecedented in rays. The 22:2 Δ6,14 acid occurred in gonads of male specimens of R. cemiculus at 2.9%.     

Up to 21 Different Sulfur-Heterocyclic Fatty Acids in Rapeseed and Mustard Oil

Three sulfur-heterocyclic fatty acids (SHFA) had been tentatively identified in rapeseed oil in the late 1980s. In this study we aimed to enrich and verify the presence of potential SHFA in one sample of native rapeseed oil, refined rapeseed oil and mustard seed oil. Fifty-gram samples of the three oils were individually saponified and converted into methyl esters. The resulting samples were hydrogenated and subjected three times to urea complexation. The resulting extracts of native rapeseed oil and mustard oil contained 21 different SHFA with 18, 20, 22 or 24 carbons. The refined rapeseed oil contained only nine C₁₈-SHFA. Structure investigation of the SHFA was performed by gas chromatography with mass spectrometry (GC/MS) using methyl esters and also 3-pyridylcarbinol esters. A direct screening of non-enriched samples by GC/MS in the selected ion monitoring mode and by GC with flame photometric detector (sulfur-selective) verified that the SHFA were native compounds of the oils and no artefacts of the sample preparation. Similar abundances of the four isomer groups of SHFA with monoenoic fatty acids of the same carbon number in these and five further rapeseed and mustard samples indicated that these could be the precursors of the SHFA.     

连续减压精馏分离椰子油脂肪酸的模拟研究

文章利用Aspen Plus化工模拟软件中的严格计算法RadFrac单元操作模块对椰子油脂肪酸进行了连续减压精馏分离模拟。考察了塔板数、回流比、进料位置对分离效果的影响。结果表明:采用两个精馏塔B1塔和B2塔串联操作,操作压强为2500 Pa(绝压),原料进料质量流率20 kg/h,B1塔理论板数为15,第8块塔板进料,回流比为2(体积比),塔顶可得到产物辛酸的质量流率为8.675 kg/h,质量分数可达98.58%及回收率可达99.83%。塔底物料经B2进一步分离,B2塔板数为15,第9块塔板进料,回流比为1,塔顶可得到产物癸酸的质量流率为10.86 kg/h,质量分数为99.79%及回收率为98.81%。模拟结果对实验研究及工业化生产具有指导意义。     

The Interaction of the Soybean Seed High Oleic Acid Oil Trait With Other Fatty Acid Modifications

Oil value is determined by the functional qualities imparted from the fatty acid profile. Soybean oil historically had excellent use in foods and industry; the need to increase the stability of the oil without negative health consequences has led to a decline in soybean oil use. One solution to make the oil stable is to have high oleic acid (>70%) and lower linolenic acid content in the oil. Other fatty acid profile changes are intended to target market needs: low‐saturated fatty acid and high stearic acid content in the oil. The objective of this study is to determine the interaction of the high oleic acid oil trait with other alleles controlling fatty acid profiles. Soybean lines containing high oleic acid allele combinations plus other fatty acid modifying alleles were produced, and the seed was produced in multiple field environments over 2 years. Stable high oleic acid with low linolenic acid (<3.0%) was achieved with a 4‐allele combination. The target of >20% stearic acid in the seed oil was not achieved. Reducing total saturated fatty acids below 7% in a high oleic acid background was possible with mutant alleles of both an acyl‐ACP thioesterase B and a β‐ketoacyl‐[acyl‐carrier‐protein] synthase III gene. The results identified allele combinations that met the target fatty acid profile thresholds and were most stable across environments.     

Clean Synthesis of Fatty Acids in an Intensive Lipase-Catalysed Bioreactor

The operation and performance of a laboratory-scale catalytic bioreactor used for the hydrolysis of mixed natural oils into free fatty acids in the presence of free lipase (triacylglycerol ester hydrolase, EC 3.1.1.3) is described. The novelty of the reactor system is the intensification of the reaction kinetics by electrostatic spraying of the lipase as a dispersion of very fine droplets into the oil phase. The effect of phase ratio and field strength on the kinetics were measured for a simple batch type spray reactor. Coalescence rates within the electrostatic spray reactor were shown to be significantly higher than conventional stirred systems. The kinetic data were compared with a control experiment in which the free lipase suspension and oil were contacted by mechanical mixing in the absence of any externally applied electrical field. © 1997 SCI.     

Enrichment of Omega-3 Fatty Acids of Refined Hoki Oil

Enrichment of the omega-3 (n-3) fatty acids of refined hoki oil (RHO) intact triglycerides (TG) and via free fatty acids (FFA), was carried out in the present study using established methods of dry fractionation (DF), low temperature solvent crystallization (LTSC) and urea complexation (UC) and positional distribution of fatty acids in the intact TG was determined by Nuclear Magnetic Resonance (NMR) analysis. Results showed that n-3 fatty acids were enriched in liquid fractions of all methods except DF, where the highest concentration was obtained via the UC method (83.00 %). The FFA form of the oil produced a higher concentration (40.81 %) of n-3 fatty acids via the LTSC method compared to the TG form (31.50 %). The percentages of the total saturated fatty acid (SFA) in the liquid fractions in all methods were lower, ranging from 1.60 % (UC) to 21.44 % (DF) compared to the RHO parent oil (24.05 %). The percentages of total monounsaturated fatty acids (MUFA) in the liquid fractions were similar to the solid fractions except for the UC method where total MUFA was six times higher in the solid fraction. In LTSC-FFA and UC methods, the enrichment factor for EPA was lower, ranging from 1.61 (LTSC-FFA) to 2.83 (UC), than DHA which ranged from 1.64 (LTSC-FFA) to 3.88 (UC). EPA was preferentially located at the sn-1,3 position and DHA was significantly located at the sn-2 position which is the favoured location for intestinal digestion.     

Fatty Acid Profile of Kenaf Seed Oil

The fatty acid profile of kenaf (Hibiscus cannabinus L.) seed oil has been the subject of several previous reports in the literature. These reports vary considerably regarding the presence and amounts of specific fatty acids, notably (12,13-epoxy-9(Z)-octadecenoic (epoxyoleic) acid, but also cyclic (cyclopropene and cyclopropane) fatty acids. To clarify this matter, two kenaf seed oils (from the Cubano and Dowling varieties of kenaf) were investigated regarding their fatty acid profiles. Both contain epoxyoleic acid, the Cubano sample around 2 % and the Dowling sample 5-6 % depending on processing. The cyclic fatty acids malvalic and dihydrosterculic were identified in amounts around 1 %. Trace amounts of sterculic acid were observed as were minor amounts of C17:1 fatty acids. The results are discussed in the context of the fatty acid profiles of other hibiscus seed oils.     

GC-FID/MS Analysis of Fatty Acids in Indian Cultivars of Moringa oleifera: Potential Sources of PUFA

In the present investigation, the fatty acid profile was analysed in vegetative and reproductive parts of eight commercially cultivated Indian cultivars of Moringa oleifera and verified by gas chromatography mass spectra. In leaves, α-linolenic acid (C_18:3, cis-9,12,15) was found in the highest quantity (49–59 %) followed by palmitic acid (C_16:0) (16–18 %), and linoleic acid (C_18:2, cis-9,12) (6–13 %). The total content of saturated fatty acids and unsaturated fatty acids showed a ratio of 0.33 (cv. DHANRAJ) to 0.39 (cv. PKM-2) in leaves, 0.53 in flowers and 0.56 in tender pods. Similarly, polyunsaturated fatty acids and total monounsaturated fatty acids were found in a ratio of 5.68 (cv. DHANRAJ) to 9.71 (cv. CO-1) in leaves, 1.11 in flowers and 2.79 in tender pods. The total lipid content was recorded in the range of 1.92 % (flowers) to 4.82 % (leaves, cv. CO-1). When considering health benefits, M. oleifera leaves contain low amounts of saturated fatty acids, a high mono- and polyunsaturated fatty acid content, which can enhance the health benefits of Moringa-based products.