Effect of trace contaminants on cold soak filterability of canola biodiesel

A cold soak filtration test (CSFT; ASTM D 7501-09b) was included in B100 specifications under ASTM D 6751-09, bringing new challenges to biodiesel producers and researchers investigating B100 quality. For a plant breeding program evaluating canola biodiesel quality traits, rapid assessment of biodiesel quality is important. Typically, a limited amount of seed from new canola lines is available; therefore, obtaining the required volume of biodiesel for evaluating cold soak filterability (300 mL) is not possible. In order to rapidly screen canola breeding lines for B100 quality, cold soak filterability must be assessed with reduced volumes of biodiesel. The primary objective of this study was to evaluate the impact of saturated monoglycerides, glycerin, and soap on cold soak filterability. Biodiesel filtration time rapidly escalated when the SMG concentration was above 0.28%. The influence of saturated monoglycerides (0.04-0.46% w/w) on biodiesel precipitate formation was also evaluated. A regression model was generated to predict the filterability of biodiesel against the concentrations of trace contaminants. The results will be instrumental to scaling down biodiesel CSFT for a canola breeding program.     

Variables Affecting the Production of Standard Biodiesel

Biodiesel is composed of fatty acid methyl esters, currently made from vegetable oils using basic catalysts. The oils must be reacted two or three times with methanol, in the presence of sodium methoxide to make products which meet the ASTM and European biodiesel standards. It is also believed that sodium hydroxide can never be used as the catalyst because it causes soap formation, which either lowers the yield or raises the acid number and makes product isolation difficult. Methods for producing standard biodiesel from low-acid-number soybean oil, in one chemical reaction using sodium hydroxide and a cosolvent, were recently reported. This study reports the effects of variables on the acid numbers and chemically bound glycerol contents of the products which led to the methods. These variables were the molar ratio of alcohol to oil, catalyst concentration, cosolvent volume, and reaction time. The alcohol-to-oil molar ratio must be at least 14, and the sodium hydroxide concentration should be at least 1.2 wt% (based on oil), to meet the necessary acid number and glycerol contents of the biodiesel. The volume of tetrahydrofuran cosolvent used must be 90–130% of that required to just create complete miscibility at the beginning of the reactions.     

Evaluation of partially hydrogenated methyl esters of soybean oil as biodiesel

Biodiesel, an alternative fuel derived from vegetable oils or animal fats, continues to undergo rapid worldwide growth. Specifications mandating biodiesel quality, most notably in Europe (EN 14214) and the USA (ASTM D6751), have emerged that limit feedstock choice in the production of biodiesel fuel. For instance, EN 14214 contains a specification for iodine value (IV; 120 g I₂/100 g maximum) that eliminates soybean oil as a potential feedstock, as it generally has an IV >120. Therefore, partially hydrogenated soybean oil methyl esters (PHSME; IV = 116) were evaluated as biodiesel by measuring a number of fuel properties, such as oxidative stability, low‐temperature performance, lubricity, kinematic viscosity, and specific gravity. Compared to soybean oil methyl esters (SME), PHSME were found to have superior oxidative stability, similar specific gravity, but inferior low‐temperature performance, kinematic viscosity, and lubricity. The kinematic viscosity and lubricity of PHSME, however, were within the prescribed US and European limits. There is no universal value for low‐temperature performance in biodiesel specifications, but PHSME have superior cold flow behavior when compared to other alternative feedstock fuels, such as palm oil, tallow and grease methyl esters. The production of PHSME from refined soybean oil would increase biodiesel production costs by US$ 0.04/L (US$ 0.15/gal) in comparison to SME. In summary, PHSME are within both the European and American standards for all properties measured in this study and deserve consideration as a potential biodiesel fuel.     

Ozonized vegetable oil as pour point depressant for neat biodiesel

The use of ozonized vegetable oils as pour point depressant for neat biodiesel was evaluated. Ozonized vegetable oils (1-1.5% by weight) were effective in reducing the pour point of biodiesel prepared from sunflower oil, soybean oil and rapeseed oil to −24, −12 and −30 °C, respectively. Cloud point however remained unaffected. In the case of palm oil biodiesel, significant reduction was observed in cloud point but not in pour point. Statistical analyses showed that neat biodiesel and biodiesel treated with ozonized vegetable oils showed no significant difference in other properties including density and viscosity. Although ozonized vegetable oils increase the flash point of biodiesel, the values are still within the limits set by the standards in the US and Europe. Lowest reduction in pour point was observed in cases where the biodiesel and the ozonized samples were prepared from the same vegetable oil. Hence, a correlation may exist between the nature of the biodiesel and ozonized oil. Microscopic analysis at low temperature revealed that ozonized vegetable oil impede agglomeration of biodiesel into network of solidified material giving crystals with sizes around 10 μm.     

Evaluation of Biodiesel Derived from <Emphasis Type="Italic">Camelina sativa</Emphasis> Oil

Biodiesel derived from camelina as well as other feedstocks including palm, mustard, coconut, sunflower, soybean and canola were prepared via the conventional base-catalyzed transesterification with methanol. Fatty acid profiles and the fuel properties of biodiesel from different vegetable oils were analyzed and tested in accordance with ASTM D6751. Camelina biodiesel contains 10–12%, 37–40%, and 48–50% saturated, monounsaturated and polyunsaturated components, respectively. Some fuel properties of camelina biodiesel are comparable to that of sunflower biodiesel including kinematic viscosity (40 °C), flash point, cloud point, cold filter plugging point, and oil stability index. However, camelina biodiesel exhibited the poorest oxidative stability, highest distillation temperature and has the highest potential to form coke during combustion, all of which are attributed to the high amounts of n-3-fatty acids in camelina oil. While neat camelina biodiesel may exhibit undesirable fuel properties, it is very comparable with soybean biodiesel at the B20 level.     

Optimization of biodiesel production from edible and non-edible vegetable oils

The non-edible vegetable oils such as Jatropha curcas and Pongamia glabra (karanja) and edible oils such as corn and canola were found to be good viable sources for producing biodiesel. Biodiesel production from different edible and non-edible vegetable oils was compared in order to optimize the biodiesel production process. The analysis of different oil properties, fuel properties and process parameter optimization of non-edible and edible vegetable oils were investigated in detail. A two-step and single-step transesterification process was used to produce biodiesel from high free fatty acid (FFA) non-edible oils and edible vegetable oils, respectively. This process gives yields of about 90-95% for J. curcas, 80-85% for P. glabra, 80-95% for canola, and 85-96% for corn using potassium hydroxide (KOH) as a catalyst. The fuel properties of biodiesel produced were compared with ASTM standards for biodiesel.     

Some physical properties and oxidative stability of biodiesel produced from oil seed crops

Biodiesel is a cleaner burning fuel than petrodiesel and a suitable replacement in diesel engine. It is produced from renewable sources such as vegetable oils or animal fats. Biodiesel fuel was prepared from castor (CSO), palm kernel (PKO) and groundnut (GNO) oils through alkali transesterification reaction. The biodiesel produced was characterized as alternative diesel fuel. Fuel properties such as specific gravity, viscosity, calorific (combustion) value, The CSO, PKO and GNO were measured to evaluate the storage/oxidative stability of the oils to compare them with commercial petrodiesel. The biodiesel produced had good fuel properties with respect to ASTM D 6751 and EN 14214 specification standards, except that the kinematic viscosity of castor oil biodiesel was too low. The viscosity of castor oil biodiesel at different temperatures was in the range of 4.12–7.21 mm²/s. However, promising results which conformed to the above specification standards were realized when castor oil biodiesel was blended with commercial petrodiesel. At 28 °C the specific gravity recorded for CSO, PKO and GNO biodiesel was higher than the values obtained for petrodiesel. Commercial petrodiesel had the highest oxidative stability than biodiesel produced from CSO, PKO and GNO oils.     

Development and Scale-up of Aqueous Surfactant-Assisted Extraction of Canola Oil for Use as Biodiesel Feedstock

Aqueous surfactant-assisted extraction (ASE) has been proposed as an alternative to n-hexane for extraction of vegetable oil; however, the use of inexpensive surfactants such as sodium dodecyl sulfate (SDS) and the effect of ASE on the quality of biodiesel from the oil are not well understood. Therefore, the effects on total oil extraction efficiency of surfactant concentration, extraction time, oilseed to liquid ratio and other parameters were evaluated using ASE with ground canola and SDS in aqueous solution. The highest total oil extraction efficiency was 80 %, and was achieved using 0.02 M SDS at 20 °C, solid–liquid ratio 1:10 (g:mL), 1,000 rpm stirring speed and 45 min contact time. Applying triple extraction with three stages reduced the amount of SDS solution needed by 50 %. The ASE method was scaled up to extract 300 g of ground canola using the best combination of extraction conditions as described above. The extracted oil from the scale-up of the ASE method passed the recommendation for biodiesel feedstock quality with respect to water content, acid value and phosphorous content. Water content, kinematic viscosity, acid value and oxidative stability index of ASE biodiesel were within the ASTM D6751 biodiesel standards.     

Comparative Study of the Physicochemical Properties of FAME from Seed Oils of Some Native Species of Brazilian Atlantic Forest

The rapid decline in fossil fuel reserves in the world, rising oil prices, and growing concerns about the increase in pollutant gas emissions from this type of energy, have led to the exploration of new energy sources for the production of alternative fuels. The use of vegetable oils as a low‐cost raw material for biodiesel production is an effective way to reduce biodiesel costs. This paper reports on the production and biodiesel properties of the seed oils of six native species belonging to different families of plants from the Atlantic Forest in northeast Brazil. The results are compared with those obtained from traditional crops such as soybean and olive. The relative oil content of the seeds ranged from 31.5 to 67.4 %, while the biodiesel yield from these oils ranged from 93.2 to 97.6 wt%. The fatty acid composition is mainly constituted of oleic acid in three species (Cissampelos andromorpha, Rauwolfia grandiflora, and Tabernaemontana flavicans), eicosenoic acid in two species (Serjania caracasana and Serjania salzmanniana) and palmitic acid in Protium heptaphyllum. The physicochemical parameters of oil (density, viscosity, % FFA, and % of linolenic acid) and biodiesel (density, viscosity, acid number, copper strip corrosion, flash point, sulfur content, sulfated ash, water, oxidative stability, free and total glycerin) were in agreement with ASTM 6751 and EN 14214 standards. The fatty acid composition, biodiesel yield, oil, and biodiesel properties of the six native species studied demonstrate the high potential for producing alternative fuel in conventional diesel engines.     

新型反应介质中脂肪酶催化多种油脂制备生物柴油

用叔丁醇作为反应介质,利用固定化脂肪酶催化油脂原料甲醇醇解反应制备生物柴油,消除了甲醇和甘油对酶的负面影响,酶的使用寿命显著延长. 用菜籽油作原料,叔丁醇和油脂的体积比为1:1,甲醇与油脂的摩尔比为4:1,3%的Lipozyme TLIM和1%的Novozym 435结合使用,35℃下130 r/min反应12 h,生物柴油得率可达95%. 该工艺在200 kg/d的规模下制得的生物柴油产品完全满足美国和德国生物柴油标准,脂肪酶重复使用200批次,酶活性基本没有下降. 且在叔丁醇介质体系中大豆油、桐籽油、棉籽油、乌桕油、泔水油、地沟油和酸化油都能被有效转化成生物柴油且脂肪酶保持很好的稳定性.     

Comparing Process Efficiency in Reducing Steryl Glucosides in Biodiesel

A significant obstacle to the commercial acceptance of biodiesel is the potential for filter plugging due to precipitates in the fuel. The majority of these precipitates can be attributed to either steryl glucosides (SGs) or monoacylglycerols in biodiesel. A GC–FID method to quantify minor components content in biodiesel is presented. The effectiveness of room temperature and cold soak filtration, adsorbent treatment, centrifuge, and vacuum distillation processes for SG removal was studied. The vacuum distillation process is the most effective method of removing the SG from biodiesel.     

The use of a modified TDSP for biodiesel production from soybean, linseed and waste cooking oil

In this study, the Transesterification Double Step Process (TDSP) for the production of biodiesel from vegetable oil was modified to yield a shorter reaction time and products with improved quality. TDSP consists in a two step transesterification procedure which starts with a basic catalysis, followed by an acidic catalysis. The process modifications included a reduction in the concentration of catalysts, a reduction in the reaction time of the first step and the direct mixing of methanol/acid solution, without cooling the system between the first and second step. A comparison between washed and unwashed biodiesel demonstrates that the final washing and drying procedure is necessary for satisfactory results. The products were analyzed by ¹H-NMR and nineteen different biodiesel analyses specific for international quality certification. The modified procedure resulted in a high conversion index (97% for waste cooking oil and soybean oil and 98% for linseed oil) and high yield (87 ± 5% for waste cooking oil, 92 ± 3% for soybean and 93 ± 3% for linseed oil). The biodiesel produced by the modified TDSP met ASTM, EN ISO and ABNT standards before the addition of stabilizer.     

Transesterification of vegetable oil to biodiesel fuel using alkaline catalyst

Biodiesel is gaining more and more importance as an attractive fuel due to the depleting fossil fuel resources. Chemically biodiesel is monoalkyl esters of long chain fatty acids derived from renewable feed stock like vegetable oils and animal fats. It is produced by transesterification in which, oil or fat is reacted with a monohydric alcohol in presence of a catalyst to give the corresponding monoalkyl esters. This article reports experimental data on the production of fatty acid methyl esters from vegetable oils, soybean and cottonseed oils using sodium hydroxide as alkaline catalyst. The variables affecting the yield and characteristics of the biodiesel produced from these vegetable oils were studied. The variables investigated were reaction time (1-3 h), catalyst concentration (0.5-1.5 w/wt%), and oil-to-methanol molar ratio (1:3-1:9). From the obtained results, the best yield percentage was obtained using a methanol/oil molar ratio of 6:1, sodium hydroxide as catalyst (1%) and 60 ± 1 °C temperature for 1 h. The yield of the fatty acid methyl ester (FAME) was determined according to HPLC. The composition of the FAME was determined according to gas chromatography. The biodiesel samples were physicochemically characterized. From the results it was clear that the produced biodiesel fuel was within the recommended standards of biodiesel fuel.     

Determination of Acylglycerols and Glycerol in Castor:Soybean Biodiesel Blend Produced by a Base/Acid-Catalyzed Process

This paper describes the production of the methyl biodiesel blend of hydroxylated vegetable (castor oil) and soybean oils by a base/acid‐catalyzed process and the first simultaneous determination by gas chromatography of the levels of total and free glycerol, mono‐, di‐ and triacylglycerols based on the standard method ASTM D 6584. Best results were observed for transesterification carried out in 6:1 (methanol:oil), sodium hydroxide 1 % w/w at 60 °C for 1.5 h. The analytical method not only produced curves with good linearity, but also had a coefficient of determination (r²) above 0.997 and accuracy between 70 and 141 % at relative standard deviations (RSD) lower than 10 %. The matrix effect (ME) was investigated and only diolein was found to have a significant matrix effect. The method was robust when applied to different chemical compositions of biodiesel. Results showed that the acid value and the contents of mono‐, di‐, and triacylglycerols, total and free glycerol were within the limits set by standardized methods and that biodiesel may be produced from soybean and castor oil blends.     

Exhaust Emissions from an Engine Fueled with Biodiesel from High-Oleic Soybeans

Biodiesel is a fuel comprising mono-alkyl esters of medium to long-chain fatty acids derived from vegetable oils or animal fats. Typically, engines operated on soybean-based biodiesel exhibit higher emissions of oxides of nitrogen (NOx) compared with petroleum diesel. The increase in NOx emissions might be an inherent characteristic of soybean oil’s polyunsaturation, because the level of saturation is known to affect the biodiesel’s cetane number, which can affect NOx. A feedstock that is mostly monounsaturated (i.e. oleate) helps to balance the tradeoff between cold flow and oxidative stability. Genetic modification has produced a soybean event, designated 335-13, with a fatty acid profile high in oleic acid (>85%) and with reduced palmitic acid (<4%). This high-oleic soybean oil was converted to biodiesel and run in a John Deere 4045T 4.5-L four-stroke, four-cylinder, turbocharged direct-injection diesel engine. The exhaust emissions were compared with those from conventional soybean oil biodiesel and commercial No. 2 diesel fuel. There was a significant reduction in NOx emissions (α = 0.05) using the high-oleic soybean biodiesel compared with regular soybean oil biodiesel. No significant differences were found between the regular and high-oleic biodiesel for unburned hydrocarbon and smoke emissions.     

Graphical method to select vegetable oils as potential feedstock for biodiesel production

Chemical compositions of 80 vegetable oils were collected from literature and the properties of the obtainable biodiesel (methyl esters) have been predicted by empirical relationships. The purpose has been to check the viability of predicting if a biodiesel could meet the EN 14214 standards knowing only the fatty acid profile (FAP) of the parent oil. Two parameters were used in this investigation: (i) average number of carbon atoms in the fatty acid chains, (ii) average number of double bonds (C?C) per molecule. Two new empirical relationships have been proposed to predict the viscosity and the cetane number of biodiesel from the two parameters. The range of values of the two parameters leading to biodiesel meeting the EN 14214 standard for viscosity, cetane number, iodine value, and cold filter plugging point have been graphically obtained by overlapping the corresponding level surfaces. Practical applications: This work provides biodiesel producers with indications of the quality of biodiesel without the need for analytical testing of the product (indeed, of the product itself). Only the fatty acid profile of the starting vegetable oil is required. The quality of biodiesel can be estimated by using a chart developed in this work, allowing to estimate, e.g. if the biodiesel meets the European standards. The work can be useful to rapidly screen oil seed crops in studies of genetic engineering that require high throughput.     

Effects of process variables for biodiesel production by transesterification

In this study, biodiesel production from various vegetable oils by transesterification was studied, to determine the optimum conditions. Experiments were carried out by using different kinds of catalysts (sodium hydroxide, potassium hydroxide, barium hydroxide, pyrolitic coke and wood ash) and feedstocks (corn oil, sunflower oil, soybean oil, olive pomace oil and cottonseed oil) at 65 °C and an agitation speed of 1000 rpm. The neutralization step with controlled pH was performed by treatment with phosphoric acid. An experimental design was used to evaluate the effects of the parameters such as types of vegetable oils, kinds of catalysts, reaction time, alcohol/oil volumetric ratio and amount of catalyst, on the methyl ester conversion. Using response surface methodology, a quadratic polynomial equation was obtained by multiple regression analysis. It was found that catalyst concentration was the most effective parameter. Sodium hydroxide and potassium hydroxide exhibited a superior catalytic behavior, whereas pyrolitic coke and wood ash had to be used in excess amount or for prolonged reaction times. Moreover, the properties such as viscosity, density, calorific value, acid value, and refractive index of the biodiesel were measured. The tri‐, di‐, monoacylglycerols and glycerol residuals in the methyl esters produced were also quantified by GC analysis.     

Synthesis of biodiesel fuel from safflower oil using various reaction parameters

Biodiesel fuel is gaining more and more importance because of the depletion and uncontrollable prices of fossil fuel resources. The use of vegetable oil and their derivatives as alternatives for diesel fuel is the best answer and as old as Diesel Engine. Chemically biodiesel fuel is the mono alkyl esters of fatty acids derived from renewable feed stocks like vegetable oils and animal fats. Safflower oil contains 75-80% of linoleic acid; the presence of this unsaturated fatty acid is useful in alleviating low temperature properties like pour point, cloud point and cold filter plugging point. In this paper we studied the effect of various parameters such as temperature, molar ratio (oil to alcohol), and concentration of catalyst on synthesis of biodiesel fuel from safflower oil. The better suitable conditions of 1:6 molar ratio (oil to alcohol), 60 degrees C temperature and catalyst concentration of 2% (by wt. of oil) were determined. The finally obtained biodiesel fuel was analyzed for fatty acid composition by GLC and some other properties such as flash point, specific gravity and acid value were also determined. From the results it was clear that the produced biodiesel fuel was with in the recommended standards of biodiesel fuel with 96.8% yield.     

The effect of flux and residence time in the production of biodiesel from various feedstocks using a membrane reactor

Biodiesel produced from lipid sources is a clean-burning, biodegradable, nontoxic fuel that is free of aromatic hydrocarbons. Current biodiesel production processes are tedious and involve two to three reaction steps each followed by separation and purification. Process integration of reaction and separation in a single step within a membrane reactor (MR) offers several advantages over conventional reactors.This investigation is aimed at studying the effect of membrane flux and residence time on the performance of a membrane reactor in treating a variety of raw and used feedstocks. A membrane reactor having three selectable reactor volumes was designed to decouple the effect of residence time in the reactor from membrane flux on the performance of the reactor. Low free fatty acid (FFA) oils (FFA < 1%), i.e. canola, corn, sunflower and un-refined soy oils, and high FFA waste cooking oil (FFA = 5%) were base transesterified and the quality of the biodiesel produced was determined in terms of free glycerine, mono-glyceride, di-glyceride and tri-glyceride content. All oils were base transesterified without pretreatment.Based on the composition of the final product, the MR could be operated at the upper limit of the flux tested (70 L/m²/h) and a residence time of 60 min. The ASTM D6751 and EN 14214 standards for glycerin and glycerides were reached in the washed biodiesel product for all feedstocks and run conditions. The operating pressure in the reactor was exceeded at 70 L/m²/h in treating waste oils and pre-treated corn oil. For these oils, reasonable operating pressures in the reactor were reached at a membrane flux of 30–40 L/m²/h. The quality of the washed biodiesel always met ASTM and EN standards. The FAME produced from WCO at intermediate fluxes and high residence times met the ASTM and EN standards without water washing.     

Non-Edible Plant Oils as New Sources for Biodiesel Production

Due to the concern on the availability of recoverable fossil fuel reserves and the environmental problems caused by the use those fossil fuels, considerable attention has been given to biodiesel production as an alternative to petrodiesel. However, as the biodiesel is produced from vegetable oils and animal fats, there are concerns that biodiesel feedstock may compete with food supply in the long-term. Hence, the recent focus is to find oil bearing plants that produce non-edible oils as the feedstock for biodiesel production. In this paper, two plant species, soapnut (Sapindus mukorossi) and jatropha (jatropha curcas, L.) are discussed as newer sources of oil for biodiesel production. Experimental analysis showed that both oils have great potential to be used as feedstock for biodiesel production. Fatty acid methyl ester (FAME) from cold pressed soapnut seed oil was envisaged as biodiesel source for the first time. Soapnut oil was found to have average of 9.1% free FA, 84.43% triglycerides, 4.88% sterol and 1.59% others. Jatropha oil contains approximately 14% free FA, approximately 5% higher than soapnut oil. Soapnut oil biodiesel contains approximately 85% unsaturated FA while jatropha oil biodiesel was found to have approximately 80% unsaturated FA. Oleic acid was found to be the dominant FA in both soapnut and jatropha biodiesel. Over 97% conversion to FAME was achieved for both soapnut and jatropha oil.