Fractionation of squid visceral oil ethyl esters by short-path distillation

Squid visceral oil contains high levels of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Its ethyl esters were fractionated by short-path distillation in this study. The elimination temperatures of squid visceral oil ethyl esters (SVOEE) ranged from 50 to 140°C, increasing with the carbon number of ethyl esters. The elimination temperature of cholesterol was higher than those of SVOEE. The SVOEE of Illex argentinus (SVOEE-A) was more advantageous as the raw material (feed) than that of Ommastrephes bartrami (SVOEE-B) for the isolation of EPA and DHA, because SVOEE-A contained less 20∶1 and 22∶1. When SVOEE-A originally containing 9.0% EPA, 14.7% DHA, and 1,121 mg/100 g of cholesterol was distilled from 50 to 150°C with 20°C interval, the 130°C distillate could give 15.5% EPA and 34.7% DHA with 99 mg/100 g of cholesterol, and the yield was 21.8%. The 150°C distillate could give 43.1% DHA with 496 mg/100 g of cholesterol. Furthermore, the distillates collected from 110 to 150°C contained 24.4 to 50.2% of EPA plus DHA, and their total yield was 58.3%. The final residue after 150°C distillation contained 77% of the total cholesterol in the initial SVOEE-A, and the yield was 6.0%.     

Rapid quantitation of fish oil fatty acids and their ethyl esters by FT‐NIR models

Consumption of fish oil and dietary supplements containing eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) has steadily increased because of their reported health benefits. A rapid procedure based on Fourier Transform Near Infrared Spectroscopy (FT‐NIR) models was developed for analysis of fish oil and their ethyl ester derivatives to replace the time consuming GC method. Inclusion of fish oil or ethyl esters containing varied concentrations of OA, EPA, and DHA into the FT‐NIR classification models made possible their classification and quantification. Accurate GC analysis is essential in developing reliable quantitative models since FT‐NIR is matrix dependent. Development of FT‐NIR models based on 30 m PEG capillary GC column results, as recommended by the official GC method for analysis of marine oils, proved problematic, since these columns did not resolve many geometric isomers compared to 100 m highly polar cyanopropyl polysiloxane columns. Depending on the content of geometric isomers in fish oils and ethyl esters, the levels of long‐chain n‐3 PUFA would be overestimated if the model used were based on the results from a 30 m column. The FT‐NIR method was found to be applicable to all fish oil and ethyl ester samples, except when fatty acids were outside the range examined, or contaminants were present. The FT‐NIR method was applicable to analysis of in‐plant intermediates provided contaminants were absent, or identified so they could be incorporated into the model. The FT‐NIR method was suitable to evaluate the shelf life of n‐3 PUFA concentrates.     

A comparison of the effects of various purification treatments on the oxidative stability of squid visceral oil

Factors influencing the oxidative stability of refined squid visceral oil after various purification treatments were evaluated. Squid visceral oil was treated by refining, steam deodorizing, molecular distillation, Sep-Pak cartridge extraction, alumina adsorption, EDTA solution washing, and column chromatography, and the treated oils were compared for oxidative stability. Sep-Pak cartridge extraction and alumina adsorption were designed to eliminate phenolic compounds, α-tocopherol, phospholipids, and metal ions from the oil. The oxidative stability was measured using PV and increase in weight. The refined oil and the deodorized oil were the most stable, and the highly purified oil was the least stable. However, alumina-adsorbed oil that had been washed with EDTA was more resistant to oxidation than highly purified oil. When refined oil was passed through an activated carbon-Celite chromatography column, it could be separated into hexane, ether, and ethanol fractions. The ethanol eluate contained more α-tocopherol and phospholipids than the ether eluate. The addition of the ethanol eluate extracted from squid visceral oil to the highly purified oil resulted in excellent stability.     

脂肪酸乙酯合成工艺研究

研究了大豆油和乙醇进行酯交换反应合成脂肪酸乙酯的工艺。考察了催化剂类型、催化剂用量、n(醇)∶n(油)、反应温度以及反应时间对酯交换率的影响,结果表明最佳合成工艺条件为反应温度60℃,n(醇)∶n(油)=5∶1,w(NaOMe)=1.0%,反应时间4h,在此条件下,酯交换率可达到96.7%。     

Purification of polyunsaturated fatty acid esters from tuna oil with supercritical fluid chromatography

The technical and economic feasibility of producing docosahexaenoic acid (DHA)- and eicosapentaenoic acid (EPA)-ethyl ester concentrates from transesterified tuna oil using supercritical fluid chromatography (SFC) was studied. A systematic experimental procedure was used to find the optimal values for process parameters and the maximal production rate. DHA ester concentrates up to 95 wt% purity were obtained in one chromatographic step with SFC, using CO₂ as the mobile phase at 65°C and 145 bar and octadecyl silane-type reversed-phase silica as the stationary phase. DHA ester, 0.85 g/(kg stationary phase · h) and 0.23 g EPA ester/(kg stationary phase · h) can be simutaneously produced at the respective purities of 90 and 50 wt%. The process for producing 1,000 kg DHA concentrate and 410 kg EPA concentrate per year requires 160 kg stationary phase and 2.6 tons/h carbon dioxide eluant recycle. The SFC operating cost is U.S. $550/kg DHA and EPA ethyl ester concentrate.     

Properties of alkyl esters base on castor oil

Castor oil is a non‐traditional raw material for the preparation of methyl and ethyl esters of higher fatty acids as alternative fuels for diesel engines. Castor oil contains ricinoleic acid (12‐hydroxy octadecene acid) with a major share of about 90%. The article presents the parameters of castor oil‐based methyl esters (COME) and ethyl esters (COEE) defined by the standard EN 14 214. The densities of COME and COEE are higher than the limit defined by the standard EN 14 214. The viscosities are more than twice as high as the limit value. The cetane numbers are lower than defined by the standard EN 14 214. For the remaining parameters, COME and COEE meet, in principle, the standard EN 14 214. The presence of the free hydroxyl group has virtually no effect on the values of such parameters as carbon residue, filterability at low temperatures and oxidation stability, for which some influence was expected. The physicochemical parameters of the castor oil esters are discussed in comparison to the analogous esters of high‐oleic sunflower oil, which contain about 80% of oleic acid. Both the methyl and ethyl esters of high‐oleic sunflower oil meet the standard EN 14 214 in all prescribed parameters.     

Enrichment of high-purity nervonic acid ethyl ester from Acer truncatum Bunge seed oil by combination method of urea inclusion and molecular distillation

Acer truncatum Bunge is a type of maple that is unique to China. Its fruit setting rate and seed oil content are both high. The oil is mainly composed of C16–C24 fatty acids and contains 5%–7% nervonic acid (NA). NA and its derivatives can delay ageing and prevent and treat disorders such as senile dementia and Alzheimer's disease. The content of NA ethyl ester prepared by the seed oil of A. truncatum Bunge is 5.84%. We report a new process for the enrichment of NA ethyl ester by urea inclusion (UI) and molecular distillation (MD), with the aim of obtaining highly pure NA ethyl ester. First, based on the difference in fatty acid ethyl ester saturation and carbon chain length, unwanted compounds such as oleic acid ethyl ester, linoleic acid ethyl ester, and sterol were removed by one-stage UI, the content of NA ethyl ester was increased to 18.69%. The oil in the UI compound was used as a feed, and differences in the mean molecular free paths between the components were exploited to separate the C16–C20 fatty acid ethyl esters (FAEEs) by two-stage MD. The total content of C16–C20 FAEEs decreased to 3.69% and the purity of NA ethyl ester increased to 47.47%. A new purification process of UI-MD-UI was established and NA ethyl ester could be purified to 91.8%. The combination of MD and UI has an important reference value for the industrialization of producing high-purity NA ethyl ester.     

Supercritical carbon dioxide fractionation of fish oil fatty acid ethyl esters

Fractionation of fish oil fatty acid ethyl esters was investigated with the aim of obtaining a lipid fraction enriched in ω-3 fatty acids and with a suitable EPA/DHA ratio. The results obtained highlight the possibility of modifying the original fatty acid ethyl esters concentration by optimizing the extraction conditions in terms of pressure, temperature, and supercritical carbon dioxide flow rate. Supercritical fluid fractionation (SFF) appears to be a useful processing technique for changing the composition of lipids in order to obtain high value functional products. The use of proper fractionation temperatures and pressures along the column influenced the solvent-to-feed ratio to obtain fractions with suitable composition for market requirements.     

Viscosity and rheological behavior of carbon dioxide-expanded fish oil fatty acid ethyl esters: Measurement using a rotational viscometer and modeling

The viscosity of fish oil fatty acid ethyl esters (FAEE) in equilibrium with CO₂ was determined at 40, 55, and 70 °C and pressures ranging from 0.1 to about 12 MPa using a rotational rheometer equipped with a high pressure cell. Viscosity of CO₂-expanded (CX) FAEE decreased due to the dissolution of CO₂ with pressure, which was temperature dependent. The viscosity of CX FAEE was correlated using a new empirical model utilizing saturation pressure and temperature with temperature-dependent parameters, which allows interpolation of viscosity data for any pressure and temperature within the envelope of this study. As well, viscosity was modeled using available data for CO₂ solubility in FAEE at specific temperatures of this study utilizing simpler models with only one parameter, such as the Grunberg and Nissan model. The rheological data suggest shear thickening behavior of CX FAEE at elevated pressures. The limitations of the rotational rheometer for measuring CX liquids at viscosities below 1 mPa s are discussed. Understanding of viscosity and rheological behavior of CX FAEE is essential for equipment and process design involving such lipids.     

A rapid method for analysis of tert-butyl hydroquinone (TBHQ) in ethyl esters of fish oil

A rapid, quantitative gas Chromatographic method is described for quantitating the phenolic antioxidant,tert- butyl hydroquinone (TBHQ), in fish oil ethyl esters. The procedure entails silyl derivatization of TBHQ in an acetonitrile solution of ethyl esters followed by capillary gas chromatography (GC) analysis with an internal standard method of quantitation. Average recoveries of spiked samples were 98% at the legal limit of .02% (200 μg/g). The method can accurately determine as little as 20 μ/g of TBHQ in ethyl esters of fish oil. The technique has been applied to ethyl esters of vegetable oils with equal success.     

Fractionation of squalene from amaranth seed oil

Amaranth seed oil was fractionated in a bench-scale short-path distillation unit to obtain fractions rich in squalene. Fractionations were conducted with degummed amaranth oil, alkali-refined amaranth oil, and simulated amaranth oil. Squalene concentration was increased about sevenfold with a squalene recovery of 76.0% in the distillate when degummed amaranth oil was fractionated at 180°C and 3 mtorr vacuum. Free fatty acids codistilled with squalene, lowering the squalene content of the distillate, and resulted in a semisolid distillate at room temperature. Alkali-refining was subsequently used to reduce the free fatty acid content before fractionation. A simulated oil (7% squalene/93% soybean oil) and alkali-refined amaranth oil were fractionated at three temperatures (160, 170, and 180°C) and five vacuum settings (10, 100, 200, 400, and 600 mtorr). The highest squalene recoveries from simulated oil and alkali-refined amaranth oil were 73.4 and 67.8%, respectively, both at 180°C and 100 mtorr, which translates to 12.1-and 9.2-fold increases in squalene concentration, respectively. The squalene recovery of the alkali-refined amaranth oil at 180°C was not significantly different at 10 mtorr vs. 100 mtorr. The results of this study can be used as a component to assess the economic feasibility of fractionating amaranth seed for starch, oil, meal, and squalene.     

Continuous synthesis of castor oil ethyl esters under supercritical ethanol

The transesterification of castor oil under supercritical ethanol using a catalyst-free continuous process was investigated. The effect of water concentration on the reaction medium, reaction temperature, pressure, and substrates flow rate were studied. A maximum ester content of 74.2% was achieved when the reactor was operated at 573 K, 20 MPa, substrates flow rate of 0.8 ml min⁻¹, and 5 wt% water concentration in the alcohol. The ester content of the product increased with the operation temperature, but after certain temperature level the converse effect was observed. This adverse effect was attributed to oil degradation, which increased to 88.7% at 648 K (at the flow rate of 0.8 ml min⁻¹). A favorable effect on ester content was observed when the water concentration was increased, unlike the effect of water on the conventional alkali-catalyzed process.     

Application of raman spectroscopy to monitor and quantify ethyl esters in soybean oil transesterification

Biodiesel (FA esters) has become very attractive as an alternative diesel fuel owing to its environmental benefits. Transesterification is the most usual and important method to make biodiesel from vegetable oils. This article investigates the potential for using Raman spectroscopy to monitor and quantify the transesterification of soybean oil to yield ethyl esters. The differences observed in the Raman spectra of soybean oil after transesterification were a peak at 2932 cm⁻¹ ( ), the displacement of the v _C=O band from 1748 to 1739 cm⁻¹, and the bands at 861 (v _R-C=O and v _C-C) and 372 cm⁻¹ (δ _CO-O-C). Uni- and multivariate analysis methods were used to build several analytical curves and then applied in known samples, treated as unknowns, to test their ability to predict concentrations. The best results were achieved by Raman/PLS calibration models (where PLS=partial least squares regression) using an internal normalization standard (v _=C-H band). The correlation coefficient (R ²) values so obtained were 0.9985 for calibration and 0.9977 for validation. Univariate regression analysis between biodiesel concentration and the increasing intensity of band or v _C=O displacement showed R ² values of 0.9983 and 0.9742, respectively. Although spectroscopic methods are less sensitive than chromatographic ones, the data obtained by spectroscopy can be correlated with other techniques, allowing biodiesel yield and quality to be quickly assessed.     

Solubility of fish oil fatty acid ethyl esters in suband supercritical carbon dioxide

Mutual solubilities and K-values of fish oil fatty acid ethyl esters, prepared from sand launce oil, and sub- and supercritical carbon dioxide have been measured in an apparatus originally designed for phase equilibrium, density and gasoil ratio measurements of reservoir fluids. The measurements were performed at pressures from 2 to 22 MPa at temperatures of 283.2, 313.2 and 343.2°K. Experimental temperatures, pressures, solubilities, K-values and densities are reported. The K-values of ethyl myristate, palmitate, oleate, eicosapentaenoate and docosahexaenoate are compared with published experimental binary and/or multicomponent data. Because both vapor and liquid solubilities are reported, such data are applicable in the design of supercritical extraction plants.     

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.     

从废弃油脂生物柴油中分离不饱和脂肪酸甲酯

以废弃油脂制生物柴油为原料,以95%醇为溶剂,采用尿素包合法提取不饱和脂肪酸甲酯,为生物柴油联产具有高附加值化工产品打下基础.重点考察了尿素用量、溶剂用量、包合时间和包合温度对不饱和脂肪酸甲酯分离效果的影响.结果表明,尿素包合法从生物柴油中分离不饱和脂肪酸甲酯的适宜工艺条件为:尿素,生物柴油质量比为1.4～1.7,溶剂/生物柴油质量比为4.6～6.0,包合温度为10℃,包合时间为18 h.在适宜条件下,不饱和脂肪酸甲酯含量可达93.5%,收率可达55.8%.     

Concentrating PUFA from mackerel processing waste

Mackerel processing waste comprising skins, viscera, and muscle tissue was evaluated for concentrating PUFA by urea complexation. Fish oil was extracted using either chloroform/methanol (2∶1, vol/vol) or hexane/isopropanol (3∶2, vol/vol). The yield of oil, as well as iodine, peroxide, and acid values, was determined for fresh fish oil extracts, and oil samples were storel at −70°C in the presence of 100 ppm α-tocopherol. PUFA concentrates were prepared from saponified fish oil. The mean oil yields were 9.18±2.3, 9.2%±2.4, and 38.1±3% for viscera, muscle, and skin, respectively. The mean baseline iodine value was 134±5, which increased to 296±7 after urea complexation. It was possible to concentrate PUFA from mackerel processing waste. The type of tissue used did not affect the amount of PUFA concentrated. Mackerel skin was most desirable because of its high oil content.     

Stability of ethyl esters from soybean oil exposed to high temperatures in supercritical ethanol

It is well known that during the supercritical alcoholysis of vegetable oils the main transesterification reaction occurs simultaneously to several decomposition phenomena, In order to separately study the effect of such phenomena, pure ethyl esters from soybean oil (SBOEE) were mixed with ethanol at a molar ratio 40:3 (ethanol:SBOEE) and exposed for different periods to supercritical conditions in a continuous system, at 20 MPa and different temperatures from 250 to 375 °C. It was experimentally observed that the ester content of the processed samples were lower than that corresponding to the original SBOEE, indicating the occurrence of decomposition processes, which were more important as the temperature increased and the flow rate diminished. The content of polyunsaturated esters of the treated SBOEE was lower than that of the starting mixture, showing that the decomposition rate was highly dependent on the nature and instauration degree of the alkyl chain.