The Effect of Natural and Synthetic Antioxidants on the Oxidative Stability of Biodiesel

A significant problem associated with the commercial acceptance of biodiesel is poor oxidative stability. This study investigates the effectiveness of various natural and synthetic antioxidants [α-tocopherol (α-T), butylated hydroxyanisole (BHA), butyl-4-methylphenol (BHT), tert-butylhydroquinone (TBHQ), 2, 5-di-tert-butyl-hydroquinone (DTBHQ), ionol BF200 (IB), propylgallate (PG), and pyrogallol (PY)] to improve the oxidative stability of soybean oil (SBO-), cottonseed oil (CSO-), poultry fat (PF-), and yellow grease (YG-) based biodiesel at the varying concentrations between 250 and 1,000 ppm. Results indicate that different types of biodiesel have different natural levels of oxidative stability, indicating that natural antioxidants play a significant role in determining oxidative stability. Moreover, PG, PY, TBHQ, BHA, BHT, DTBHQ, and IB can enhance the oxidative stability for these different types of biodiesel. Antioxidant activity increased with increasing concentration. The induction period of SBO-, CSO-, YG-, and distilled SBO-based biodiesel could be improved significantly with PY, PG and TBHQ, while PY, BHA, and BHT show the best results for PF-based biodiesel. This indicates that the effect of each antioxidant on biodiesel differs depending on different feedstock. Moreover, the effect of antioxidants on B20 and B100 was similar; suggesting that improving the oxidative stability of biodiesel can effectively increase that of biodiesel blends. The oxidative stability of untreated SBO-based biodiesel decreased with the increasing indoor and outdoor storage time, while the induction period values with adding TBHQ to SBO-based biodiesel remained constant for up to 9 months.     

The influence of antioxidants on the oxidation stability of biodiesel

Oxidation stability of bodiesel is an important issue because FA derivatives are more sensitive to oxidative degradation than mineral fuel. Therefore, in the most recent European Specifications for biodiesel, a minimum value of 6 h for the induction period at 110°C, measured with a Rancimat instrument, is specified. To guarantee this value at the filling station, the use of additional antioxidants will be necessary. In this paper we show the influence of different synthetic and natural antioxidants on the oxidation stability, using the specified test method. Biodiesel produced from rapeseed oil, sunflower oil, used frying oil, and beef tallow, both undistilled and distilled, was investigated. The four synthetic antioxidants pyrogallol (PY), propylgallate (PG), TBHQ, and BHA produced the greatest enhancement of the induction period. These four compounds and the widely used BHT were selected for further studies at concentrations from 100 to 1000 mg/kg. The induction periods of methyl esters from rapeseed, oil, used frying oil, and tallow could be improved significantly with PY, PG, and TBHQ, whereas BHT was not very effective. A good correlation was found between the improvement of the oxidation stability and the FA composition.     

The oxidative stability of biodiesel: Effects of FAME composition and antioxidant

A significant problem associated with the commercial acceptance of biodiesel is poor oxidative stability. This study investigated the effectiveness of individual and binary antioxidants to improve the oxidative stability of different types of biodiesel and distilled biodiesel. Results indicate that different types of biodiesel have different levels of oxidative stability, and that natural antioxidants and FAME composition play significant roles in determining oxidative stability. Synthetic antioxidants can enhance the oxidative stability of different types of biodiesel, and antioxidant activity increases as a function of its concentration. However, the effective activity level of antioxidant is dependent on biodiesel feedstock. Binary antioxidant formulations (TBHQ and PY) have a synergistic effect on oxidative stability of biodiesel. After long‐term storage at room temperature, the oxidative stability of untreated SBO‐based biodiesel significantly decreases as a function of time, while the addition of the antioxidant TBHQ can improve and maintain oxidative stability of biodiesel over an 18‐month period. However, the effectiveness of PY significantly decreases even after 2‐months.     

Evaluation and Predictive Model Development of Oxidative Stability of Biodiesel on Storage

Biodiesel comprises mono-alkyl esters of long-chain fatty acid methyl esters (FAME) derived from a renewable lipid feedstock. A major technical issue with the use of biodiesel is that it is more prone to oxidation during storage, when compared to petroleum fuel, due to the high content of polyunsaturated methyl esters that are easily oxidizable to compounds such as acids, aldehydes, and alcohols. Biodiesel (Jatropha and Pongamia) and antioxidants (Turmeric and butylated hydroxytoulene) were used for this study. We found that the acid value and viscosity for pongamia biodiesel increased significantly by 41.17% and 44.0% and that for jatropha biodiesel increased by 31.5% and 37.0%, respectively, after being stored for 3 months. The impact of antioxidants on the storage stability of biodiesel was examined according to the ASTM D4625 12-week procedure, and best results were found at a concentration level of 2500 ppm. The specific objective of this investigation is to develop models to determine the viscosity of biodiesel at any time “t” during long-term storage based on these experimental trials for upto 12 weeks. In addition, the models were used to predict the level of antioxidants that are to be added to biodiesel in order to minimize the effects of oxidative degradation during storage. The developed model recorded an adjusted R² of 0.86 and a modeling efficiency of 0.88.     

The Antioxidant Functions of Tocopherol and Tocotrienol Homologues in Oils,Fats, and Food Systems

This review paper is focused on the relative antioxidant activities of tocopherols and tocotrienols in oils and fats and certain food systems. α-Tocopherol generally showed better antioxidant activity than γ-tocopherol in fats and oils, but at higher concentrations γ-tocopherol was found to be a more active antioxidant. The results of studies on the optimum antioxidant concentrations of tocopherols in oils and fats indicated that the optimal level for α-tocopherol is usually lower than other tocopherols, meaning less α-tocopherol is needed for maximum antioxidant protection. There are comparatively very few studies related to the antioxidant activities of tocotrienols in oils and fats. It has been stated that generally γ-tocotrienol has higher antioxidant effect than α-tocotrienol, and tocotrienols may be better antioxidants than their corresponding tocopherols in certain oils and fats systems. Studies on the antioxidant activity of various tocopherols in food systems are varied and cannot be uniformly evaluated because experiments have generally focused on different foods and used various methods for the detection of antioxidant activities. Depending on the food system, in certain cases tocopherols were better antioxidants than synthetic antioxidants such as butylhydroxy toluene (BHT) or butylhydroxy anisole (BHA). However, in certain other food systems the synthetic antioxidants were more effective to increase the shelf life and the stability of foods than those containing tocopherols.     

The Effect of Antioxidants on Corn and Sunflower Biodiesel Properties under Extreme Oxidation Conditions

Biodiesel is an alternative to mineral fuels, with advantages such as biodegradability. However, this makes biodiesel unstable to oxidation. In this way, the use of natural or synthetic antioxidants is necessary. Although many studies have paid attention to the effect of these antioxidants on oxidation stability, not much literature about their effect of them on other properties (before and during storage) was found. The aim of this research study was to characterize biodiesel from corn and sunflower by adding two antioxidants, butylated hydroxyanisole (BHA) and tert-butylhydroquinone (TBHQ), in order to improve its oxidation stability. Moreover, the effect of oxidation on the parameters of biodiesel was studied by using extreme oxidation conditions to accelerate the oxidation process. Both antioxidants improved the oxidation stability of biodiesel, whereas some parameters were altered (viscosity and acid number), which could make this biofuel, if high concentrations of antioxidants are used, unsuitable for commercialization according to standards.     

Effect of fatty acids and tocopherols on the oxidative stability of vegetable oils

The oxidative stability of vegetable oils is determined by their fatty acid composition and antioxidants, mainly tocopherols but also other non‐saponifiable constituents. The effect of fatty acids on stability depends mainly on their degree of unsaturation and, to a lesser degree, on the position of the unsaturated functions within the triacylglycerol molecule. Vegetable oils contain tocopherols and tocotrienols, especially α‐ and γ‐tocopherols, as their main antioxidants. The antioxidant behavior of tocopherols represents a complex phenomenon as they are efficient antioxidants at low concentrations but they gradually lose efficacy as their concentrations in the vegetable oils increase. The “loss of efficacy” of tocopherols, sometimes referred to as a “pro‐oxidant effect”, is witnessed by an increase in the rate of oxidation during the induction period, despite elongation of this phase. The phenomenon is much obvious for α‐tocopherol, but is also evident for other tocopherols. In agreement with nature's wisdom, the tocopherol levels in vegetable oils seem to be close to the optimal levels needed for the stabilization of these oils. The presence of other antioxidants in the oils, e.g. carotenoids, phenolic compounds, and Maillard reaction products, may synergize with tocopherols and minimize this loss of efficacy.     

Analysis of oxidized biodiesel by 1H‐NMR and effect of contact area with air

Biodiesel is continuously gaining attention and significance as an alternative diesel fuel. An important issue facing biodiesel is fuel stability upon exposure to air due to its content of unsaturated fatty acids. Numerous factors influence the oxidative stability of biodiesel, and several methods for its assessment have been developed. In the present work, a defined amount of biodiesel (methyl soyate) was heated in open beakers, with the only difference being the size of the beaker, i.e. the surface area of the biodiesel exposed to air. Biodiesel oxidized in this fashion was analyzed by ¹H‐NMR, kinematic viscosity and acid value. Acid values and kinematic viscosity increased with time and surface area. A previously developed ¹H‐NMR procedure was used to evaluate the unsaturation and “residual” fatty acid composition. The amounts of saturated fatty acids determined by this method increased, with monounsaturated and diunsaturated species increasing and then decreasing with time. After “flash” (3 h, 165 °C) oxidation, NMR shows the greatest effect on saturates and compounds with two double bonds, the former increasing and the latter decreasing. The double bond originally located at δ15 in 18:3 is largely retained, showing that other double bond positions in 18:3 are initially affected by oxidation. The methyl ester signal decreases, coinciding with the increase in acid value. An increasingly strong absorption was observed in the UV‐VIS spectra. Increasing surface area accelerated oxidation and affected fatty acid composition.     

Effects of Temperature,Antioxidants, and High-Vacuum Distillation on the Oxidation of Biodiesel Derived from Waste Vegetable Oil

Biodiesel offers several environmental benefits and improvements to some fuel performance properties, but its poor oxidative stability has been a major concern. Currently, the accepted practice to improve biodiesel oxidative stability is the addition of antioxidants; numerous antioxidants have been studied but their effectiveness in inhibiting biodiesel oxidation is difficult to predict due to variation with resonance stability, solubility, reactivity, and volatility. To improve prediction efforts, this study explored the Rapid Small-Scale Oxidation Test (RSSOT) as a means to investigate how biodiesel oxidation is affected by antioxidant concentration and temperature, and compared its results with the oxidative stability index test. A weak correlation was identified due to antioxidant variation. A kinetic model expressed in temperature and induction period was developed for biodiesel before high-vacuum distillation (HVD), after HVD and also after HVD with three concentrations of propyl gallate (PG) and tert-butylhydroquinone (TBHQ) antioxidants. The approach was validated by comparing collected data on the oxidation of methyl oleate with kinetic parameters found in the literature. Antioxidant concentrations from 130–930 ppm were tested, and the results revealed that the apparent activation energy of biodiesel oxidation increases with increasing concentration of primary antioxidants and decreases during vacuum distillation. When treated with an increasing concentration (130–930 ppm) of PG and TBHQ, the apparent activation energies of a vacuum distilled biodiesel changed from 108.46 ± 4.45 to 112.72 ± 1.46 kJ·mol⁻¹ and from 77.14 ± 2.25 to 89.91 ± 2.29 kJ·mol⁻¹, respectively. These observed trends agree with both the accepted mechanism of primary oxidation of fuels and mode of action of primary antioxidants.     

A New Antioxidant Active Film Based on HDPE and Peppermint Essential Oil for Packaging Soybean Oil

In this research, the effect of antioxidant active package was studied on oxidative stability of soybean oil at 40 °C during 2‐month storage. A synthetic antioxidant [Butylatedhydroxytoluene (BHT), 200 ppm] and peppermint essential oil (200 and 400 ppm) were added to antioxidant free soybean oil. To prepare active packages, the oil was filled in antioxidant active high‐density polyethylene (HDPE) bottles containing synthetic antioxidant (3700 ppm) and the essential oil (3700 and 8400 ppm). Regarding peroxide and thiobarbituric acid values, the essential oil added to the oil delayed the oil oxidation more than BHT. In active packages, the synthetic and natural antioxidants migrated from the package to the oil (with 68 and 100 % migration rate, respectively) and retarded its oxidation over the storage time. However, no significant difference was observed between essential oil and BHT in antioxidant capacity for active packages. This study demonstrated that active packages containing antioxidants could be introduced as a good replacement for direct addition of synthetic antioxidants to the oil.     

A Screening Method to Evaluate Soybean Oil‐Based Biodiesel Oxidative Quality During Its Shelf Life

Biodiesel quality is negatively affected by oxidation, which occurs primarily during the storage and distribution steps. Therefore, the use of suitable analytical methods to assess the oxidation of this biofuel is a fundamental requirement. A direct ambient ionization mass spectrometric technique (EASI‐MS) was tested as a screening method to evaluate the oxidative quality of biodiesel during its shelf life. Using EASI‐MS, the relative abundance of the hydroperoxide ion of m/z 349 was monitored during the induction period (IP) in soybean and a blend of soybean/beef‐tallow (70/30) biodiesel samples. The peroxide value obtained by AOCS Cd 8b‐90 was used as a standard method to evaluate the EASI‐MS data by comparison. The results showed that the peroxide value and EASI‐MS data were highly correlated during the IP for both samples (r > 0.98). Relative abundances of the ion of m/z 349 below 72 % was also found to characterize biodiesel in an initial oxidation stage, whereas abundances exceeding 72 % indicated biodiesel samples nearing the end of their stability. EASI‐MS was therefore found to provide a simple and effective analytical protocol to evaluate the oxidative quality of biodiesel during the IP.     

Some aspects of biodiesel oxidative stability

Biodiesel, an “alternative” diesel fuel derived from vegetable oils, animals fats or used frying oils, largely consists of the mono-alkyl esters of the fatty acids comprising these feedstocks. One of the major technical issue facing biodiesel is its susceptibility to oxidation upon exposure to oxygen in ambient air. This susceptibility is due to its content of unsaturated fatty acid chains, especially those with bis-allylic methylene moieties. Oxidation of fatty acid chains is a complex process that proceeds by a variety of mechanisms. Besides the presence of air, various other factors influence the oxidation process of biodiesel including presence of light, elevated temperature, extraneous materials such as metals which may be even present in the container material, peroxides, and antioxidants, as well as the size of the surface area between biodiesel and air. Approaches to improving biodiesel oxidative stability include the deliberate addition of antioxidants or modification of the fatty ester profile. This article discusses some factors influencing biodiesel oxidative stability and their interaction. Resulting approaches to improving this property of biodiesel are related to these factors and the corresponding mechanisms.     

Study of the biodiesel B100 oxidative stability in mixture with antioxidants

Antioxidants are an alternative to prevent or retard biofuel degradation. This study assessed the oxidative stability of biodiesel B100, made from soybeans, in the presence of three synthetic antioxidants, butylhydroxyanisole (BHA), terbutylhydroquinone (TBHQ) and butylhydroxytoluene (BHT), pure or in mixture, from the simplex-centroid design. Results revealed that when the three oxidants were employed separately, as well as the ternary mixture, they presented induction period over 6 h, at 110 °C, being in accordance with specifications of the norm EN1412. Besides that, depending on the temperature, the BHA, TBHQ and BHT oxidants act in different ways, highlighting that BHA and TBHQ presented higher efficiency in the prevention of the oxidative process of the biofuel B100.     

Antioxidative potential of tocotrienols and tocopherols in coconut fat at different oxidation temperatures

The objective of this study was to compare the stabilizing effects of tocotrienols and their corresponding tocopherols at 60 °C and 160 °C. Stability was determined in coconut fat by observing the Oil Stability Index (OSI), the peroxide value (POV) and conjugated dienes (CD). α‐ and β‐tocotrienols as well as α‐tocopherol induced susceptibility of the systems against oxidative deterioration and reduced the life time of coconut fat. δ‐ and γ‐tocotrienols increased the fat's shelf‐life at ambient temperature (60 °C). At frying conditions the antioxidative potential increased in the following order: α<γ<δ (Tocopherols) α<β<gamma;<δ (Tocotrienols). Under these conditions γ‐ and δ‐tocotrienols were significantly more active than their corresponding tocopherols. Irrespective of the temperature employed, the protective effects of tocochromanols were dose dependent at 160 °C (mg/kg): 1000>500>100 (tocotrienols) and 5000 > 2000 > 1000 > 100 (tocopherols). Among the tested antioxidants δ‐tocopherol and δ‐tocotrienol were found to be most efficient against lipid oxidation both at 60 °C and at 160 °C. This study showed, that γ‐ and δ‐tocotrienols, similar to the much better investigated tocopherols, are good food antioxidants to enhance shelf‐life of coconut fat both at frying and at low temperature.     

Experimental Design Applied for Cost and Efficiency of Antioxidants in Biodiesel

Oxidation stability is a parameter of great importance for biodiesel quality control to both producers and subsequent consumers. To maintain the quality of biodiesel, currently the most effective and economical method is the addition of antioxidants that prevent or retard the biofuel oxidation reaction. In this study, efficiency and cost of synthetic antioxidants added to B100 biodiesel from soybean oil and pork fat were evaluated, using butylhydroxyanisole (BHA), butylhydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ), in pure form or in mixtures, according to a simplex-centroid mixture experimental design. Results demonstrate an increased induction period (IP) in all trials when compared to the control sample, and TBHQ was the only antioxidant alone that met all the specification standards, while BHT and BHA alone met only the American standard specifications. The antioxidant mixture that presented the highest synergistic effect was that of TBHQ and BHA. Multi-response optimization indicated an optimum formulation containing 75 % TBHQ and 25 % BHA with an IP of 7.27 h at 110 °C and the antioxidant mixture cost of 31.31 USD, to be added for a ton of biodiesel. This simplex-centroid mixture experimental design shows an ability to be applied in the biodiesel, oils and fats industry to evaluate the oxidation stability and the occurrence of synergism between different mixtures of synthetic or natural antioxidants and their costs.     

Oxidation stability of biodiesel derived from free fatty acids associated with kinetics of antioxidants

Biodiesel derived from free fatty acids (FFAs), which has the advantage of not competing with the edible-oil market, exhibited poor oxidation stability. The induction period (IP) of the FFA-based biodiesel determined by the Rancimat method at 110 °C was 0.20 h. This study investigates the effectiveness of one natural and ten synthetic antioxidants, including α-tocopherol (α-T); butylated hydroxyanisole (BHA); butylated hydroxytoluene (BHT); 2, 5-di-tert-butylhydroquinone (DTBHQ); Ethanox 4740; Ethanox 4760E; 2,2′-methylene-bis-(4-methyl-6-tert-butylphenol) (MBMTBP); N,N′-di-sec-butyl-p-phenylenediamine (PDA); propyl gallate (PG); pyrogallol (PY); and tert-butylhydroquinone (TBHQ), at concentrations between 100 and 1000 ppm to improve the oxidation stability of the FFA-based biodiesel. The order of antioxidant effectiveness with respect to the oxidation stability of the FFA-based biodiesel was PY > Ethanox 4760E > PG > Ethanox 4740 > PDA ~ BHA > BHT > MBMTBP ~ TBHQ > DTBHQ > α-T. The IP of the FFA-based biodiesel increased as the antioxidant concentration was increased and decreased at high test temperatures. Furthermore, the relationship between the IP values associated with the consumption of antioxidants in the FFA-based biodiesel was described by first-order reaction rate kinetics. However, the natural logarithm of IP (ln IP) at various concentrations of Ethanox 4760E showed a linear relation with the test temperature. The IP at ambient temperature was predicted based on the extrapolation method of the temperature dependence relation. After long-term storage at room temperature, the IP and acid value of the original FFA-based biodiesel significantly decreased and increased, respectively, with storage time, while the addition of antioxidants ensured the oxidation stability of the FFA-based biodiesel over 6 months of storage.     

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.     

The effect of antioxidants on butter in relation to storage temperature and duration

The effects of antioxidants on the oxidative stability of butter, under different storage time and temperature conditions, were evaluated. Natural (α‐tocopherol) and synthetic (BHA and BHT) antioxidants were added to the butter samples at two concentrations (50 and 100 ppm) immediately after the butter samples were produced from the pasteurised sweet cream, after which they were kept in the dark at 4 and ?20 °C for 6 months. Peroxide value (PV) and thiobarbituric acid (TBA) number and the residual antioxidants of the samples were examined at 30‐day intervals, starting on the second day until the end of the storage period. The measurements obtained by assaying PV and TBA number in butter samples showed that both the synthetic and natural antioxidants used were capable of protecting the butter samples against oxidation during storage at both temperatures. The butter samples with 50 ppm antioxidant could be stored for more than 180 days at 4 °C without spoilage. At ?20 °C, the addition of BHA, BHT and α‐tocopherol caused a reduction in the TBA number from 0.31 (control) to 0.21, 0.23 and 0.27 mg malonaldehyde/kg butter, respectively, and the PV decreased from 0.75 (control) to 0.46, 0.56 and 0.54 meq O₂/kg butter, respectively, after 6 months of storage. The highest residue values were determined in both the 100 and 50 ppm α‐tocopherol‐containing samples. These results indicate that α‐tocopherol exhibited a very strong antioxidant activity, which was almost equal to that of the synthetic antioxidants. Therefore, the use of α‐tocopherol is recommended as a natural antioxidant to suppress the development of rancidity in butter.     

Thermal stability of some commercial synthetic antioxidants

Synthetic antioxidants are widely applied substances in human food and in animal feed industries. These products, which are mainly derived from phenolic structures, were developed to avoid or retard the oxidative rancidity of fats and oils when added either to raw material or to end-products. Synthetic antioxidants such as butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tertiary butylhydroxyquinone (TBHQ), and ethoxyquin (EQ) are frequently applied during the cooking of the by-products (viscera, blood, and feathers) in the poultry feed industry. However, results in terms of oxidative prevention are unequal and usually modest. Because information about the thermal stability of synthetic antioxidants is scarce, we developed a laboratory model that simulates the cooking of poultry by-products to study the effectiveness of BHT, BHA, TBHQ, and EQ. The antioxidants were thermally treated at 100–200°C, over 1 or 2 h. The effectiveness of each antioxidant after the thermal treatment was assessed with the Rancimat test by measuring the modification of the induction period for the oxidation of sardine oil and comparing it to the oxidation kinetics of the oil without added antioxidants. Within our experimental conditions, all antioxidants assayed showed different degrees of thermal instability. BHT and TBHQ were effective as antioxidants at temperatures up to 175°C, exhibiting only 25 to 30% inactivation. However, BHA and EQ were inactivated by 70 and 60%, respectively, at 150°C. Heating time (1 and 2 h) at a given temperature did not significantly modify the behavior of the antioxidants assayed. EQ is the most frequently applied antioxidant to prevent oxidative rancidity in the cooking of poultry by-products. However, according to our results, EQ and BHA, which is another antioxidant frequently used by the poultry industry, are less suitable     

Protection of fish oil from oxidation by microencapsulation using freeze‐drying techniques

(N‐3)‐Polyunsaturated fatty acids (PUFAs) reduce the risk of coronary heart disease. Cold sea water plankton and plankton‐consuming fish are known sources of (n‐3)‐PUFAs. Enriching normal food components with fish oil is a tool for increasing the intake of (n‐3)‐PUFAs. Due to the high sensitivity of fish oil with respect to oxidation, it has to be protected from oxygen and light. The investigations presented demonstrate the microencapsulation of fish oil using freeze‐drying techniques. Emulsions containing 10% fish oil, 10% sodium caseinate, 10% carbohydrate and 70% water were frozen using different freezing techniques and subsequently freeze‐dried. Several parameters regarding formulation and process (addition of antioxidants to the fish oil, use of carbohydrates, homogenisation and freezing conditions, initial freeze‐drying temperature, grinding) were varied to evaluate their influence on the oxidative stability of dried microencapsulated fish oil. The shelf life of the produced samples was determined by measuring the development of volatile oxidation products vs. storage time. It could be shown that the addition of antioxidants to fish oil was necessary to produce dried microencapsulated fish oil with an adequate shelf life. The best shelf life was achieved for the dried product which was frozen with a slow freezing rate.