Long-term storage stability of biodiesel produced from Karanja oil

Biodiesel is an alternative diesel fuel made from vegetable oil or animal fat. It is more susceptible to oxidation or autoxidation during long-term storage than conventional petrodiesel. Karanja oil methyl ester (KOME) was prepared and stored for a period of 180 days under different storage conditions. The physicochemical parameters, peroxide value (PV) and viscosity (v) of samples were measured at regular interval of time under different storage conditions. The stability of Karanja oil methyl ester (KOME) was studied under different storage conditions. The stability of KOME was improved by adding different antioxidants Tert-Butylated Hydroxy toluene (BHT), Tert-Butylated Hydroxyanisole (BHA), Pyrogallol (PY), Propyl galate (PrG) and Tert-Butyl Hydroxyl Quinone (TBHQ). The effectiveness of three antioxidants BHT, BHA and PrG on Karanja oil methyl ester was examined at varying loading level during the storage period.     

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.     

Relationships derived from physical properties of vegetable oil and biodiesel fuels

The aim of this study was to estimate mathematical relationships between higher heating value (HHV) and viscosity, density or flash point measurements of various biodiesel fuels. The HHV is an important property defining the energy content and thereby efficiency of fuels, such as vegetable oils and biodiesels. The biodiesels were characterized for their physical and main fuel properties including viscosity, density, flash point and higher heating value. The viscosities of biodiesels (2.8–5.1 mm²/s or cSt at 311 K) were much less than those of pure oils (23–53 mm²/s at 311 K), and their HHVs of approximately 41 MJ/kg were 10% less than those of petrodiesel fules (～46 MJ/kg). Compared to No. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The density and flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. The HHVs of vegetable oils and their biodiesels were measured and correlated using linear least square regression analysis. There is high regression between viscosity and higher heating value for vegetable oil and biodiesel samples. An increase in density from 848 to 885 g/L for biodiesels increases the viscosity from 2.8 to 5.1 cSt and the increases are highly regular. There is high regression between density and viscosity values vegetable oil methyl esters. The relationships between viscosity and flash point for vegetable oil methyl esters are considerably regular.     

黄连木油脂基生物柴油的合成及其性能分析

以黄连木油脂为原料,对预酯化和酯交换两步法制备生物柴油的工艺进行了研究.通过正交实验,得出预酯化最佳工艺条件为:醇油摩尔比8∶1、催化剂加入量为0.8%、反应时间为3 h;酯交换最优工艺为:催化剂用量为0.6%、醇油摩尔比6∶1、反应时间为2 h、反应温度为50℃;此条件下制备的生物柴油得率达到92.3%;通过二聚化反应,所得生物柴油的主要性能指标均达到了国家标准GB/T 20828-2007.     

Flavor and oxidative stability of northern-grown sunflower seed oil

Flavor and oxidative stabilities of a northern-grown sunflower seed oil were investigated. Taste panel and oxidative evaluations were made on alkali-refined, deodorized, unbleached samples treated with commercial antioxidant mixtures, phenolic antioxidants, metal scavengers and added trace metals. Similar evaluations were conducted on a sample of the same oil after bleaching. Commercial antioxidant mixtures containing both phenolic antioxidants and a metal scavenger improve the flavor and oxidative stabilities of refined unbleached oil. Although phenolic antioxidants alone improve oxidative stability as measured by the active oxygen method test, flavor stability did not improve significantly for antioxidant-treated refined, unbleached samples after accelerated storage. Conversely, alkali-refined and bleached sunflower oil responded to treatment with certain phenolic antioxidants. Although iron and copper are deleterious to oil stability at concentrations of 0.1 ppm, such metal-inactivating agents as citric acid are effective in improving flavor stability. N. Market. Nutr. Res. Div., ARS, USDA.     

Some physical properties ofSimmondsia oil

Refractive index, density, viscosity, dielectric constant, specific conductivity, and surface tension ofSimmondsia oil have been measured at different temperatures.     

Effects of seed damage on the oxidative stability of poppy seed oil

This study was conducted to assess the reduction of life time and quality of poppy seeds considering a mechanical damage, which may occur during harvesting. Vienna, Vienna, Austria Poppy seeds were crushed to receive 90%, 80%, 70%, 60% and 50% intact seeds, the undamaged 100% intact seeds served as controls. The samples were stored at 40 °C for 175 d and oxidation experiments performed periodically by assessing conjugated dienes, p‐anisidine reactive products, the iodine value, the acid value and γ‐tocopherol content. With increasing degree of mechanical damage the shelf life declined, the oxidation products were formed more rapidly and the main antioxidant in poppy seeds γ‐tocopherol was consumed. Considering the reduction of life time by including all quality parameters the shelf life of the 10% damaged seeds was reduced by 50.5%. This reduction was reached up to 82% for the 50% damaged seeds compared to the control. A high correlation was found between the increase in oxidation products and the degradation of γ‐tocopherol. This study show that increased damage during harvesting (10‐50%) is responsible for a faster loss of product quality especially in seeds containing high amounts of polyunsaturated fatty acids like poppy seeds.     

Fuel properties of biodiesel produced from the crude fish oil from the soapstock of marine fish

The soapstock of a mixture of marine fish was used as the raw material to produce the biodiesel in this study. The soapstock was collected from discarded fish products. Crude fish oil was squeezed from the soapstock of the fish and refined by a series of processes. The refined fish oil was transesterified to produce biodiesel. The fuel properties of the biodiesel were analyzed. The experimental results showed that oleic acid (C18:1) and palmitic acid (C16:0) were the two major components of the marine fish-oil biodiesel. The biodiesel from the mixed marine fish oil contained a significantly greater amount of polyunsaturated fatty acids than did the biodiesel from waste cooking oil. In addition, the marine fish-oil biodiesel contained as high as 37.07 wt.% saturated fatty acids and 37.3 wt.% long chain fatty acids in the range between C20 and C22. Moreover, the marine fish-oil biodiesel appeared to have a larger acid number, a greater increase in the rate of peroxidization with the increase in the time that it was stored, greater kinematic viscosity, higher heating value, higher cetane index, more carbon residue, and a lower peroxide value, flash point, and distillation temperature than those of waste cooking-oil biodiesel.     

Physical‐chemical characteristics and oxidative stability of oil obtained from lyophilized raspberry seed

Fresh raspberry (Rubus idaeus), cultivar Willamette, was freeze‐dried (lyophilization). A byproduct of lyophilization is “fine dust” of raspberry consisting of finely ground raspberry fruit body and seed. The seeds were separated. The seed oil was isolated and its physical and chemical characteristics were determined. Parameters that characterize the seed and quality of the oil were examined, including fatty acid composition, oxidative stability under different storage conditions, and radical‐scavenging activity. The fatty acid composition was determined by GC/FID and the contents of the dominant fatty acids were found as: oleic 16.92%, linoleic 54.95%, and α‐linolenic acid 23.97%. The oxidative stability of the oil was poor. The induction period by Rancimat test at 100 °C was 5.2 h. The radical‐scavenging activity is similar to that of resveratrol [1,3‐benzenediol 5‐(1^E‐2‐4‐hydroxy‐phenyl‐ethyl)]. Although this product is used in the candy industry, it would be far more useful if raspberry oil of satisfactory quality could be extracted. This paper demonstrates that sifted lyophilized seeds can be used for the extraction of oils. This process allows for maximal usage of the byproducts, reduces losses and it increases the development of new products.     

Fuel properties of biodiesel produced from Camellia oleifera Abel oil through supercritical-methanol transesterification

The fuel properties of the biodiesel produced from Camellia oleifera Abel oil through supercritical-methanol transesterification with no catalyst was investigated in this study. An emulsion of raw C. oleifera Abel oil dispersed in methanol was prepared prior to being poured into a supercritical-methanol reaction system to undergo the transesterification reaction. The fuel properties of the resulting biodiesel were analyzed and compared with those of a commercial biodiesel and with ASTM No. 2D diesel fuel. The experimental results show oleic acid (C18:1) and palmitic acid (16:0) to be the two major components of the C. oleifera Abel oil biodiesel. It also contains significantly higher mono-unsaturated fatty acids and long carbon-chain fatty acids ranging from C20 to C22 than those found in the commercial biodiesel. However, relative to the commercial biodiesel, the C. oleifera Abel oil biodiesel has significantly fewer poly-unsaturated fatty acids with more than three double bonds, which implies that it also has a much higher degree of oxidative stability. In addition, the biodiesel produced from C. oleifera Abel oil was also found to have more favorable fuel properties than the commercial biodiesel produced from waste cooking oil, including a higher heat of combustion and flash point and lower levels of kinematic viscosity, water content, and carbon residue. Moreover, the former appears to have much lower peroxide and acid values, and thus a much higher degree of oxidative stability than the latter.     

Impact of antioxidant additives on the oxidation stability of biodiesel produced from Croton Megalocarpus oil

The increase in crude petroleum prices, limited resources of fossil fuels and environmental concerns have led to the search of alternative fuels, which promise a harmonious correlation with sustainable development, energy conservation, efficiency and environmental preservation. Biodiesel is well positioned to replace petroleum-based diesel. Biodiesel is a non-toxic, biodegradable and renewable biofuel. But the outstanding technical problem with biodiesel is that, it is more susceptible to oxidation owing to its exposure to oxygen present in the air and high temperature. This happens mainly due to the presence of varying numbers of double bonds in the free fatty acid molecules. This study evaluates oxidation stability of biodiesel produced from Croton megalocarpus oil. Thermal and Oxidation stability of Croton Oil Methyl Ester (COME) were determined by Rancimat and Thermogravimetry Analysis methods respectively. It was found that oxidation stability of COME did not meet the specifications of EN 14214 (6 h). This study also investigated the effectiveness of three antioxidants: 1,2,3 tri-hydroxy benzene (Pyrogallol, PY), 3,4,5-tri hydroxy benzoic acid (Propyl Gallate, PG) and 2-tert butyl-4-methoxy phenol (Butylated Hydroxyanisole, BHA) on oxidation stability of COME. The result showed that the effectiveness of these antioxidants was in the order of PY > PG > BHA.     

Physical-chemical properties of waste cooking oil biodiesel and castor oil biodiesel blends

This work presents the physical-chemical properties of fuel blends of waste cooking oil biodiesel or castor oil biodiesel with diesel oil. The properties evaluated were fuel density, kinematic viscosity, cetane index, distillation temperatures, and sulfur content, measured according to standard test methods. The results were analyzed based on present specifications for biodiesel fuel in Brazil, Europe, and USA. Fuel density and viscosity were increased with increasing biodiesel concentration, while fuel sulfur content was reduced. Cetane index is decreased with high biodiesel content in diesel oil. The biodiesel blends distillation temperatures T₁₀ and T₅₀ are higher than those of diesel oil, while the distillation temperature T₉₀ is lower. A brief discussion on the possible effects of fuel property variation with biodiesel concentration on engine performance and exhaust emissions is presented. The maximum biodiesel concentration in diesel oil that meets the required characteristics for internal combustion engine application is evaluated, based on the results obtained.     

Some chemical and physical properties of tailings water from oil sands extraction plants

We have carried out quantitative analyses of dissolved sodium, potassium, calcium, magnesium, chloride, carbonate, bicarbonate, ‘alkalinity’, sulphate, aluminum, iron, and silicon in tailings water from the GCOS tailings pond and from the Syncrude pilot plant. Surface tensions of these waters have been measured over a range of pH values, and effects of added Mg²⁺ and Ca²⁺ ions on surface tension have been investigated. Some similar measurements have been made on ‘synthetic pond water’. Infrared and proton n.m.r. measurements have been made on the organic material extracted from GCOS pondwater. This information on tailings water is relevant to the large accumulation of tailings that has become known as the ‘pondwater problem’ in connection with extraction of bitumen from mined Alberta oil sands.     

Some physical properties of castor oil esters and hydrogenated castor oil esters

Esters of castor oil and hydrogenated castor oil were prepared with C₆, C₁₂, C₁₆, C₁₈ fatty acids, using tetra‐n‐butyl titanate as a catalyst and n‐butyl benzene as a water entrainer. Physical properties such as melting point, refractive index, viscosity, and specific gravity of these esters were measured. Slip melting points of the esters were very low in both cases. These esters did not crystallize even at low temperature. The highest slip melting point obtained was 21 °C with stearoyl hydrogenated castor oil ester and lowest slip melting point obtained was —6 °C with hexanoyl castor oil ester.     

Evaluation of the oxidative stability of corn biodiesel

The main factors responsible for the oxidative processes of biodiesel are oxygen, metal traces, high temperature and the amount of unsaturated fatty acids. The biodiesel quality is harmed by the oxidation products, which are corrosive to engine chambers and may lead to clogging of the injection pumps and filters, besides increasing the biodiesel viscosity. Thus, this work aimed at investigating the oxidative stability of corn biodiesel, obtained by base-catalyzed transesterification reaction, using the ethanol route. As-synthesized, stored and heated biodiesel samples were characterized by peroxide value, iodine value and dynamic viscosity. UV/Vis absorption was used to evaluate the oxidative degradation of biodiesel, by means of the 232 and 272 nm absorption peaks, ascribed to double bonds and carbonyl groups, respectively. The TG and PDSC thermal analysis techniques were also employed to analyze the oxidative stability. The oxidative decomposition was confirmed by the increase of the dynamic viscosities. PDSC curves showed that the oxidation onset temperature was reduced as the sample was exposed to degradation factors during heating and storage. Such results were in agreement with the peroxide and iodine values, as well as with dynamic viscosity values.     

Long storage stability of biodiesel made from rapeseed and used frying oil

The degree of physical and chemical deterioration of biodiesel produced from rapeseed and used frying oil was studied under different storage conditions. These produced drastic effects when the fuel was exposed to daylight and air. However, there were no significant differences between undistilled biodiesel made from fresh rapeseed oil and used frying oil. The viscosity and neutralization numbers rose during storage owing to the formation of dimers and polymers and to hydrolytic cleavage of methyl esters into fatty acids. However, even for samples studied under different storage conditions for over 150 d the specified limits for viscosity and neutralization numbers had not been reached. In European biodiesel specifications there will be a mandatory limit for oxidative stability, because it may be a crucial parameter for injection pump performance. The value for the induction period of the distilled product was very low. The induction period values for the undistilled samples decreased very rapidly during storage, especially with exposure to light and air.     

Influence of lipase-catalyzed interesterification on the oxidative stability of melon seed oil triacylglycerols

Melon seeds are rich in oil. However, the stability of melon seed oil (MSO) is low because of its high content of the essential fatty acid, linoleic acid (18:2n-6). MSO was physically blended or enzymatically interesterified with higholeic sunflower oil (HOSO). The fatty acid composition of MSO was remarkably changed after interesterification. Palmitic (16:0), stearic (18:0), and oleic (18:1n-9) acid contents increased at the sn-2 position of triacylglycerols, whereas 18:2n-6 decreased due to interesterification. The oxidative stability of the physical and Pseudomonas sp. (PS30) lipase-interesterified blends was assessed with the Oxidative Stability Instrument, peroxide value, and conjugated diene methods. The stability of MSO increased with increased proportions of HOSO, which was the source of 18:1n-9 in the blends. The ratio of 18:1n-9/18:2n-6 improved from 0.18 in MSO to 1.47 in the enzymatically interesterified blend. Calculated oxidizability and the results of oxidation tests of the blends confirmed the improvement in MSO stability by both physical blending and enzymatic interesterification.     

Effects of processing on the oxidative stability of soybean oil produced in Mexico

The stability parameters of 22 samples of soybean oil produced in Mexico were determined. Samples were analyzed for moisture, color, free fatty acids, peroxide value, p-anisidine value, fatty acid profile, metals, flavor, and Rancimat test for oxidative stability. Results obtained were compared with the stability parameters of soybean oil sproduced in the United States and Costa Rica. The fatty acid profile in all samples analyzed corresponded to the expected profile for a 100% soybean oil. Sixty-four percent of the oils had oxidative stabilities similar to those reported for soybean oils from the United States and Costa Rica. This suggests that in spite of the good quality, the soybean oil production process in Mexico needs further improvement. Especially important is maintaining appropriate control during the degumming and bleaching steps. Special consideration should be given to preserving the natural antioxidants present in the oil.     

Microwave roasting effects on the physico-chemical composition and oxidative stability of sunflower seed oil

The purpose of the present study was to explore the influences of microwave heating on the composition of sunflower seeds and to extend our knowledge concerning the changes in oxidative stability, distribution of FA, and contents of tocopherols of sunflower seed oil. Microwaved sunflower seeds (Helianthus annuus L.) of two varieties, KL-39 and FH-330, were extracted using n-hexane. Roasting decreased the oil content of the seeds significantly (P<0.05). The oilseed residue analysis revealed no changes in the contents of fiber, ash, and protein that were attributable to the roasting. Analysis of the extracted oils demonstrated a significant increase in FFA, p-anisidine, saponification, conjugated diene, conjugated triene, density, and color values for roasting periods of 10 and 15 min. The iodine values of the oils were remarkably decreased. A significant (P<0.05) decrease in the amounts of tocopherol constituents of the microwaved sunflower oils also was found. However, after 15 min of roasting, the amount of α-tocopherol homologs was still over 76 and 81% of the original levels for the KL-39 and FH-330 varieties, respectively. In the same time period, the level of σ-tocopherol fell to zero. Regarding the FA composition of the extracted oils, microwave heating increased oleic acid 16–42% and decreased linoleic acid 17–19%, but palmitic and stearic acid contents were not affected significantly (P<0.05).