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.     

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     

Effect of antioxidants on the oxidative stability of methyl soyate (biodiesel)

Biodiesel, an alternative diesel fuel derived from transesterification of vegetable oils or animal fats, is composed of saturated and unsaturated long-chain fatty acid alkyl esters. When exposed to air during storage, autoxidation of biodiesel can cause degradation of fuel quality by adversely affecting properties such as kinematic viscosity, acid value and peroxide value. One approach for increasing resistance of fatty derivatives against autoxidation is to treat them with oxidation inhibitors (antioxidants). This study examines the effectiveness of five such antioxidants, tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PrG) and α-Tocopherol in mixtures with soybean oil fatty acid methyl esters (SME). Antioxidant activity in terms of increasing oxidation onset temperature (OT) was determined by non-isothermal pressurized-differential scanning calorimetry (P-DSC). Analyses were conducted in static (zero gas flow) and dynamic (positive gas flow) mode under 2000 kPa (290 psig) pressure and 5 °C/min heating scan rate. Results showed that PrG, BHT and BHA were most effective and α-Tocopherol least effective in increasing OT. Increasing antioxidant loading (concentration) showed sharp increases in activity for loadings up to 1000 ppm followed by smaller increases in activity at higher loadings. Phase equilibrium studies were also conducted to test physical compatibility of antioxidants in SME-No. 2 diesel fuel (D2) blends. Overall, this study recommends BHA or TBHQ (loadings up to 3000 ppm) for safeguarding biodiesel from effects of autoxidation during storage. BHT is also suitable at relatively low loadings (210 ppm after blending). PrG showed some compatibility problems and may not be readily soluble in blends with larger SME ratios. Although α-Tocopherol showed very good compatibility in blends, it was significantly less effective than the synthetic antioxidants screened in this work.     

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.     

STABILITY AND SENSORY QUALITY OF SPRAY DRIED AVOCADO PASTE

ABSTRACT

Avocado (Persea americand) paste was spray dried at inlet air temperature of 180°C, 80°C outlet air temperature, air velocity of 27 m/s and a feed flow rate of 0.642 l/min. Lipids in the paste were emulsified using 10 % Monoacylglyceride (MAG). Treatments were applied according to the following antioxidants mixtures: 1) BHA (butylated hydroxyanisole) + BHT (butylated hydroxytoluene) (0.05 % each); 2) TBHQ (Tertiary butylated hydroxyquinone) + Citric Acid (0.05 + 0.1 %); 3) BHA + BHT + Citric Acid (0.05 + 0.05 + 0.1 %); 4) BHA + Propyl gallate (0.05 + 0.05 %); or 5) BHA + Propyl gallate + Citric acid (0.05 + 0.05 + 0.1 %). Samples were stored at 6, 12, 25, 28 and 40 °C. Peroxide values were determined periodically. Development of rancidity was detected by sensory evaluation of the samples. For samples kept at 6 and 12 °C, an antioxidant mixture containing BHA and propyl gallate at 0.05% gave the least protection to the stored avocado powder. The mixture containing TBHQ and citric acid yielded the lowest rancidity development.     

Canola extract as an alternative natural antioxidant for canola oil

The antioxidative activity of ethanolic extracts of canola meal at 100, 200, 500 and 1000 ppm on refined-bleached (RB) canola oil was examined and compared with commonly used synthetic antioxidants, such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), BHA/BHT/monoglyceride citrate (MGC) andtert-butyl-hydroquinone (TBHQ). Stability of RB oil was monitored under Schaal oven test conditions at 65°C over a 17-d period. Progression of oxidation was monitored by weight gain, peroxide, conjugated diene, 2-thiobarbituric acid and total oxidation values. Canola extracts at 500 and 1000 ppm were more active than BHA, BHT and BHA/BHT/MGC and less effective than TBHQ at a level of 200 ppm.     

The Behaviour of Phenolic Antioxidants,Synergists and their Mixtures in Two Vegetable Oils

Tertiary butylhydroquinone (TBHQ), hydroquinone (HQ), propyl gallate (PG), butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) had much higher antioxidant activity in crude safflower oil than in a commercial brand vegetable oil (Bint oil). The following active oxygen (AOM, hours at 97.8° C) and storage stability (days at 45° C) values for each antioxidant in safflower oil were; (27.9, 105.0), (21.2, 44.8), (15.3, 45.5), (9.8, 36.8) and (7.9, 33.5) respectively compared with (6.8, 31.5) for the control. Ascorbyl palmitate (AP), ascorbic acid (AA) and citric acid (CA) were found to improve the AOM stability of both oils. The same values in Bint oil were: (9.0, 34.3), (9.0, 28.3), (9.4, 41.0), (7.3, 28.5) and (6.2, 2.5) respectively compared with (5.3, 23.3) for the control. Ascorbyl palmitate (AP), ascorbic acid (AA) and citric acid (CA) were found to improve the AOM stability of both oils. AP was more effective and CA least effective in safflower oil, whereas the reverse was true in Bint oil. The five antioxidants were individually blended with the three synergists (0.01 % of each) and the 15 combinations added to each oil and compared with the antioxidant controls at 0.02 %. Safflower oil stability was greater with pure TBHQ, HQ and PG than with any of the synergist mixtures whereas the BHA, BHT-synergist mixtures were found equal or superior to that treated with BHA or BHT alone. Bint oil treated with CATBHQ or CA-HQ mixtures showed improved stability compared to oils treated with these antioxidants alone. However, the AOM method alone suggested CA-PG, CA-BHA and CA-BHT mixtures improved the stability compared to the oil-antioxidant controls. Chelation of metals by CA was assumed to be the primary cause of this synergism, whereas AP and AA behaved more like weak antioxidants.     

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.     

Effect of selected antioxidants on the stability of virgin olive oil

Virgin unrefined olive oil was protected from oxidation with the antioxidants butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and tertiary butylhydroquinone (TBHQ) and in one case propyl gallate (PG). All the antioxidants improved the stability of olive oil under accelerated conditions (oven test) and storage conditions at 50 C. In the oven test, where the type of oil used was the same as that used in long-term storage studies (room temperature and 50 C) the relative inhibition effect of the antioxidants was in the following order: TBHQ = BHA > BHT. The combinations of BHA and BHT with TBHQ displayed better stabilizing qualities. Antioxidants did not prevent peroxide formation in olive oil stored at room temperature in daylight; these samples oxidized to a high degree, probably due to the catalytic action of chlorophyll. Citric acid (CA) used alone did not affect the oxidative stability of the oil in the oven test and at room temperature in the dark, but exhibited a negative effect at 50 C. The reduction in peroxide content with teritary butylhydroquinone (TBHQ) in the dark at 50 C was greater than anticipated from the oven studies. Potency of the antioxidants under these conditions (50 C) was in the following order: TBHQ> BHT > BHA. The combinations of BHA 0.01% or BHT 0.01% with TBHQ 0.005% used in the dark at 50 C were less effective than TBHQ 0.01%.     

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.     

Synergistic Effects of Antioxidants on the Oxidative Stability of Soybean Oil- and Poultry Fat-Based Biodiesel

Biodiesel is an alternative fuel composed of saturated and unsaturated methyl ester fatty acids that is very prone to oxidation attack. Exposure to air, heat, light, and metallic contaminants can lead to autoxidation, and the degradation of fuel properties such as kinematic viscosity and total acid number. This study examines the effectiveness of blends of primary antioxidants from combinations of butylated hydroxyanisole (BHA), propyl gallate (PG), pyrogallol (PY) and tert-butyl hydroquinone (TBHQ) to increase oxidative stability. Results indicate that binary antioxidant formulations: TBHQ:BHA, TBHQ:PG and TBHQ:PY were most effective at 2:1, 1:1, 2:1 weight ratio, respectively in both distilled soybean oil- (DSBO) and distilled poultry fat- (DPF) based biodiesel. Antioxidant activity increased as the loadings were increased. The synergisms of the antioxidant pairs were different with different biodiesel types, suggesting a dependence on the fatty acid methyl ester (FAME) composition. The best synergistic effect was observed with the TBHQ:BHA blends while the best stabilization factors (SF) were achieved by using the TBHQ:PY blends. Quantification of antioxidant content in stored biodiesel with TBHQ:PY blend demonstrates that the main factor of synergy is the regeneration of PY by TBHQ.     

Stability of tapioca chips fried in RBD palm olein treated with antioxidants

The effectiveness of tertiarybutylhydroquinone (TBHQ), butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in stabilizing tapioca chips was assessed by determining the peroxide andp-anisidine values, absorbances at 232 nm and 268 nm and the 18:2/16:0 ratios of oil extracted from tapioca chips. The order of effectiveness of the antioxidants in stabilizing the chips was found to be TBHQ > BHT > BHA. The order of effectiveness of antioxidants, TBHQ > BHT > BHA, was maintained for chips from corresponding 1st, 4th and 7th fryings. The loss of antioxidants during storage could not be directly related to oxidation parameters.     

STABILITY AND SENSORY QUALITY OF SPRAY DRIED AVOCADO PASTE

Avocado (Persea americand) paste was spray dried at inlet air temperature of 180°C, 80°C outlet air temperature, air velocity of 27 m/s and a feed flow rate of 0.642 l/min. Lipids in the paste were emulsified using 10 % Monoacylglyceride (MAG). Treatments were applied according to the following antioxidants mixtures: 1) BHA (butylated hydroxyanisole) + BHT (butylated hydroxytoluene) (0.05 % each); 2) TBHQ (Tertiary butylated hydroxyquinone) + Citric Acid (0.05 + 0.1 %); 3) BHA + BHT + Citric Acid (0.05 + 0.05 + 0.1 %); 4) BHA + Propyl gallate (0.05 + 0.05 %); or 5) BHA + Propyl gallate + Citric acid (0.05 + 0.05 + 0.1 %). Samples were stored at 6, 12, 25, 28 and 40 °C. Peroxide values were determined periodically. Development of rancidity was detected by sensory evaluation of the samples. For samples kept at 6 and 12 °C, an antioxidant mixture containing BHA and propyl gallate at 0.05% gave the least protection to the stored avocado powder. The mixture containing TBHQ and citric acid yielded the lowest rancidity development.     

Efficacy of tertiary butylhydroquinone on the storage and heat stability of liquid canola shortening

The sensory (odor and flavor) and physicochemical characteristics of tertiary butylhydroquinone (TBHQ) treated and butylated hydroxyanisole/toluene (BHA/BHT) treated liquid canola shortenings, subjected to accelerated storage (Schaal oven test at 65°C) and deep fat heating (at 185°C), were determined. Data for the Schaal oven test indicate that TBHQ was effective in retarding oxidative rancidity in liquid canola shortenings. However, addition of the commonly used mixture of BHA/BHT to canola shortenings resulted in only a slight decrease in oxidation during schaal oven storage. The results obtained from deep fat heating of canola liquid shortening show that neither TBHQ nor BHA/BHT was effective in enhancing oxidative and thermal stability of this product.     

Effect of synthetic antioxidants on cholesterol stability during the thermal-induced oxidation of a polyunsaturated vegetable oil

As a molecule with an unsaturated bond, cholesterol is prone to oxidation. Cholesterol oxidation products (COP) are found in many common foods and have been shown to be atherogenic, cytotoxic, mutagenic, and possibly carcinogenic. Efforts to reduce the formation of oxidation products are considered important during the manufacture and processing of foods. The effect of synthetic antioxidants on cholesterol oxidation has not been extensively studied. We assayed the effect of five commonly used antioxidants—BHT, BHA, the n-propyl ester of 3,4,5-trihydroxy benzoic acid (PG), TBHQ, and 6-ethoxy-1,2-dihydro-2,4-trimethylquinoline (EQ)—on cholesterol stability when oxidation is induced in a Rancimat 679 instrument by bubbling air through the sample at 150°C. The sample consisted of 200 mg cholesterol dispersed in 100 g of a polyunsaturated vegetable oil (soybean oil). Formation of six COP was measured at the induction period, and at the 50 and 100 μS conductivity values. Under the experimental conditions, BHT and TBHQ were the most effective inhibitors of cholesterol oxidation. BHA and EQ were less effective, and PG was unable to prevent cholesterol oxidation. Synthetic antioxidants were more effective in preventing COP formation at the nucleus of the cholesterol structure than at the lateral chain.     

Food Additives Reducing Volatility of Antioxidants at Frying Temperature

At frying temperature, antioxidants are lost not only by reaction with radicals formed by oil oxidation but also by decomposition and evaporation before they are able to exert antioxidant activity. In this study, it was hypothesized that an additive that can bind or interact with an antioxidant could reduce volatility of the antioxidant at frying temperature. Three synthetic antioxidants, tert‐butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), which have relatively high volatility, were used as antioxidants in this study to examine the hypothesis. Thermogravimetric analysis (TGA) experiments showed that all 22 additives tested in this study effectively reduced volatility of the antioxidants. An NMR study showed that signals of BHT shifted by addition of an additive, evidencing the interaction between the two substances in the chloroform solution. To examine the effect of these interactions on antioxidant activity, heating tests were conducted with soybean oil (SBO) containing 200 ppm antioxidants at 180 °C. Oxidation was monitored with ¹H NMR for loss of olefinic protons and bisallylic protons in SBO and with gel permeation chromatography (GPC) for polymerized triacylglycerols (PTAG). Improved antioxidant activity of the antioxidants were observed when combined with several additives tested in this study, and HPLC analysis showed that the antioxidants were effectively reserved by the additives in SBO during the heating process. The concentrations of the antioxidants retained in SBO were relatively well correlated with the antioxidant activity.     

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.     

Analysis of antioxidants in oil

Oils containing from 0 to 200 ppm of the most common phenolic antioxidants, BHA, BHT and TBHQ, were analyzed by a new gas chromatographic method. This method requires neither extraction of antioxidants from oil nor derivatization of antioxidants. The correlation coefficients (r) between gas chromatographic peak heights or peak area and their concentrations in oils were 0.99 for BHA, BHT and TBHQ. This simple gas chromatographic method can accurately determine as little as 10 ppm of BHA, BHT and TBHQ in oils in 1 hr.     

Oxidative instability of CLA concentrate and its avoidance with antioxidants

This study evaluated the effectiveness of antioxidants, such as BHA, BHT, TBHQ, propyl gallate (PG), α-tocopherol (α-1), green tea extract (GTE), and rosemary extract (RE) on oxidative stability of CLA concentrate. Stability of CLA concentrate stored in air at 45°C up to 44 d was assessed by PV. During the storage period, the PV of the control CLA concentrate sample increased from 0.20 (fresh oil) to 1654 meq/kg (oxidized oil). On the other hand, the PV for CLA concentrates treated with 200 ppm of the single synthetic antioxidants, BHA, BHT, TBHQ, and PG, increased from 0.20 to 81, 107, 78, and 101 meq/kg, respectively. Also, the PV of CLA concentrate with the addition of 200 ppm single natural antioxidants α-T, GTE, and RE lowered the final PV to 122, 140, and 110 meq/kg, respectively. Under our experimental conditions, the protective effect of 200 ppm antioxidant was in the order of TBHQ>BHA>PG>BHT>RE>α-T> GTE. These results suggest that the appropriate use of antioxidants prolongs the oxidative stability of CLA concentrate.     

Stabilization of seal blubber and menhaden oils with green tea catechins

Catechins, namely (−)epicatechin (EC), (−)epigallocatechin (EGC), (−)epicatechin gallate (ECG) and (−)epigallocatechin gallate (EGCG), were isolated from commercial Chinese green leaves. The antioxidant activity of isolated catechins was compared with those of α-tocopherol, butylated hydroxyanisole (BHA), butylated hydroxytolene (BHT) andtert-butylhydroquinone (TBHQ), all at 200 ppm, in refined, bleached and deodorized seal blubber oil and menhaden oil. The study was carried out under Schaal oven test conditions at 65°C over a 144-h period, except for weight gain measurements, which were continued for up to 200 h. Progression of oxidation was monitored by measuring changes in weight gain and values of peroxide, conjugated diene, and 2-thiobarbituric acid-reactive substances. Oils treated with tea catechins showed excellent oxidative stability as compared with samples that contained commonly used antioxidants, such as α-tocopherol, BHA, BHT, and TBHQ. The potency of catechins in prevention of oxidation of marine oils was in the decreasing order of ECG> EGCG> EGC> EC; ECG was slightly more effective than TBHQ in systems studied.