2009 Quality survey of retail biodiesel blends in Michigan

A fuel quality survey of biodiesel blends collected in June 2009 from 26 Michigan retail stations was performed, 8 months after the publication of ASTM D7467. Measured blend levels were not consistent in stations where pump labels indicate specific biodiesel blend levels. Fatty acid methyl ester (FAME) analyses revealed that majority of the samples are soybean oil-based (SBO) biodiesel. Full compliance with the ASTM D7467 requirements for kinematic viscosity and flash point (FP) were observed with the biodiesel blends; all but one for cetane number (CN). Barely half of the samples were able satisfy the total acid number (TAN) specification with select samples reflecting as high as 1.6 mg KOH/g. The most pressing is that only 45% were able to meet the 6 h induction period (IP) requirement; out of those that did not qualify 42% are even low blends hinting the degraded quality of the biodiesel component. Inconsistencies on the expected correlations of the tested properties were evident, suggesting that additives may be present in many samples. When compared with results from a similar survey in 2007, the properties of the 2009 samples are even poorer, indicating poor observance of fuel standards by the producers.     

Flow properties of biodiesel fuel blends at low temperatures

The dynamic viscosities of biodiesel derived from ethyl esters of fish oil, no. 2 diesel fuel, and their blends were measured from 298 K down to their respective pour points. Blends of B80 (80 vol.% biodiesel–20 vol.% no. 2 diesel), B60, B40 and B20 were investigated. All the viscosity measurements were made with a Bohlin VOR Rheometer. Cloud point and pour point measurements were made according to ASTM standards. Arrhenius equations were used to predict the viscosities of the pure Biodiesel (B100), no. 2 diesel fuel (B0) and the biodiesel blends (B80, B60, B40, and B20) as a function of temperature. The predicted viscosities agreed well with measured values. An empirical equation for calculating the dynamic viscosity of these blends as a function of both temperature and blend has been developed. Furthermore, based on the kinematic viscosity and density measurements of B100 up to 573 K by Tate et al. [Tate RE, Watts KC, Allen CAW, Wilkie KI. The viscosities of three biodiesel fuels at temperatures up to 300 °C. Fuel 2006;85:1010–5; Tate RE, Watts KC, Allen CAW, Wilkie KI. The densties of three biodiesel fuels at temperatures up to 300 °C. Fuel 2006;85:1004–9] an empirical equation for predicting the dynamic viscosity of pure biodiesel for temperatures from 277 K to 573 K is given. Empirical equations for predicting the cloud and pour point for a given blend give values in good agreement with experiments. The dynamic viscosity of biodiesel and its blends increases as temperature decreases and show Newtonian behaviour down to the pour point. Dynamic viscosity, cloud point and pour point decreases with an increase in concentration of no. 2 diesel in the blend.     

Prediction of the density and viscosity in biodiesel blends at various temperatures

Biodiesel defined as mono-alkyl esters of vegetable oils and animal fats, has had a considerable development and great acceptance as an alternative fuel for diesel engines. Density and viscosity are two important physical properties to affect the utilization of biodiesel as fuel. In this work, mixtures of biodiesel and ultra low sulfur diesel (ULSD) were used to study the variation of density (ρ) and kinematic viscosity (η) as a function of percent volume (V) and temperature (T), experimental measurements were carried out for six biodiesel blends at nine temperatures in the range of 293.15-373.15 K. Both, density and viscosity increases because of the increase in the concentration of biodiesel in the blend, and both of them decrease as temperature increases. One empirical correlation was proposed to estimate the density: ρ = α·V + β·T + δ; and three empirical correlations were developed to predict the kinematic viscosity: η = exp[ln(γ) + ?·V + ω/T + λ·V/T²], η = exp[ln(γ) + ω/T + λ·V/T²] and η = exp[ln(γ) + ω/T + λ·V/T]. The corresponding parameters were optimized by the Levenberg-Marquardt method. The estimated values of density and viscosity are in good agreement with the experimental data because absolute average prediction errors of 0.02% and 2.10% were obtained in the Biodiesel(1) + ULSD(2) system studied in this work.     

Real-time and robust estimation of biodiesel blends

Biodiesel as a renewable alternative fuel produces lower exhaust emissions with the exception of nitrogen oxides (NO_x) when compared to the conventional diesel fuel. Reducing nitrogen oxides produced from engines running on biodiesel requires proper engine controller adaptations that are linked to the specifics of the fuel blend. Therefore, online estimation of fuel blend is a critical step in allowing diesel engines to maintain performance while simultaneously meeting emission requirements when operating on biodiesel blends. Presented in this paper are three different model-based biodiesel blend estimation strategies using: (i) crankshaft torsionals, (ii) NO_x emissions measurement from the exhaust stream, and (iii) oxygen content measurement of the exhaust stream using a wide-band UEGO sensor. Each approach is investigated in terms of the accuracy and robustness to sensor errors. A sensitivity analysis is conducted for each method to quantify robustness of the proposed fuel blend estimation methods.     

An optimum biodiesel combination: Jatropha and soapnut oil biodiesel blends

Jatropha (Jatropha curcas) and soapnut (Sapindus mukorossi) oils are considered potential non-edible oil feedstocks for biodiesel production and present complementary fuel properties. Apparently, the poor oxidation stability of jatropha oil biodiesel and the high cold filter plugging point of soapnut oil biodiesel can be successfully improved to satisfy all biodiesel specifications at an optimum blending ratio. The optimum biodiesel combination was further blended with diesel at various volumetric percentages to evaluate the variations of fuel properties. The biodiesel–diesel blends up to B40 would show the satisfactory fuel properties.     

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.     

Flame temperature analysis of biodiesel blends and components

Meeting sustainable energy demand with minimum environmental impact is a major area of concern in the energy sector. Alternative fuels such as biodiesel, ethanol etc. have been quite promising for fulfilling both these aspects. While biodiesel reduces emissions of CO, life cycle CO₂, SO_x, volatile organic compounds (VOC) and particulate matter (PM) significantly, the propensity for the production of NO_x is an important problem that requires extensive research. NO_x emission from a direct-injection diesel engine is mainly due to formation of thermal NO that is described by Zeldovich mechanism. Thus, studying temperature profile during biodiesel combustion can provide useful insights to the formation and destruction of NO_x. The main objective of this work is to investigate the effect of component methyl esters of biodiesel on open air flame temperature distribution and the effect of blending biodiesel with diesel and oxygenates (ethanol and methyl acetate) on open air flames. This objective was achieved by obtaining thermocouple measurements and thermal infrared imaging of local flame temperatures of wick-generated open air flames. A relationship between blend proportions and relative flame temperatures were obtained. In general, it was found that blending oxygenates such as ethanol and methyl acetate into petroleum diesel tended to increase the flame temperature in comparison with straight diesel fuel. The analyses of relative flame temperatures of different components of biodiesel were performed to evaluate the effect of unsaturation level and the hydrocarbon chain length on the flame temperature. It was found that the saturated methyl esters resulted in greater flame temperatures in comparison to unsaturated methyl esters. It was also revealed that shorter chained fatty acid methyl esters lead to higher flame temperatures as compared to its longer chained counterparts.     

Oxidation stability of blends of Jatropha biodiesel with diesel

Biodiesel, an ecofriendly and renewable fuel substitute for diesel has been receiving the attention of researchers around the world. Due to heavy import of edible oil, the production of biodiesel from edible oil resources in India is not advisable. Therefore it is necessary to explore non-edible seed oils, like Jatropha curcas (J. curcas) and Pongamia for biodiesel production. The oxidation stability of biodiesel from J. curcas oil (JCO) is very poor and therefore an idea is given to increase the oxidation stability of biodiesel by blending it with petro-diesel. J. curcas biodiesel (JCB), when blended with petro diesel leads to a composition having efficient and improved oxidation stability. The results have shown that blending of JCB with diesel with less than 20% (v/v) would not need any antioxidants but at the same time, need large storage space. Similarly, if the amount of diesel is decreased in the blend, it will require the addition of antioxidant but in lesser amount compared to pure JCB. For the purpose five antioxidants were used namely butylated hydroxytoluene (BHT), tert-butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), propyl gallate (PG), and pyrogallol (PY). A B₃₀ blend (30% JCB in the blend of JCB and petro-diesel) has been tested for the same purpose. PY is found to be the best antioxidant among all five antioxidants used. The optimum amount of antioxidant (PY) for pure biodiesel tested for the present experiment is around 100 ppm while it is around 50 ppm for B₃₀ blend to maintain the international specification of oxidation stability.     

Modifying soybean oil for enhanced performance in biodiesel blends

Soybean (Glycine max Merr.) oil is primarily composed of five fatty acids; palmitic acid (∼13%), stearic acid (∼4%), oleic acid (∼18%), linoleic acid (∼55%) and linolenic acid (∼10%). The average U.S. production of soybean oil from 1993 to 1995 was 6.8 billion kg and in 2002 soybeans were harvested from more than 30 million ha across the U.S., which accounts for 40% of the total world soybean output. This production capacity accounts for more than 50% of the total available biobased oil for industrial applications. A useful industrial application of soybean oil is in biodiesel blends. On a liquid basis, the total soybean oil production capacity would be equivalent to 1.9 billion gal of diesel, about 6.9% of the diesel fuel consumed in the United States for transportation in 1996. A number of positive attributes are realized with the use of soybean oil-derived biodiesel, including enhanced biodegradation, increased flashpoint, reduced toxicity, lower emissions and increased lubricity. However, the two parameters that have limited usefulness of a soybean oil-derived biodiesel as a fuel are oxidative instability and cold flow in northern climates. The latter is not an issue in warmer environments, and thus soybean oil modifications designed to maximize engine performance should be targeted with marketplace locale considerations in mind. Implementing the tools of biotechnology to modify the fatty acid profile of soybean for locale performance enhancement may increase the attractiveness of biodiesel derived from this commodity crop.     

Evaluation of the oxidation stability of diesel/biodiesel blends

Biodiesel is an alternative fuel derived from vegetable oils, animal fats and used frying oils. Due to its chemical structure, it is more susceptible to oxidation or autoxidation during long-term storage compared to petroleum diesel fuel. One of the major technical issues regarding the biodiesel blends with diesel fuel is the oxidation stability of the final blend, which is, nowadays, of particularly high concern due to the introduction of ultra low sulphur diesel, in most parts of the EU. This study examined the factors influencing the stability of several biodiesel blends with low and ultra low sulphur automotive diesel fuels. The aim of this paper was to evaluate the impact of biodiesel source material and biodiesel concentration in diesel fuel, on the stability of the final blend. Moreover, the effects of certain characteristics of the base diesels, such as sulphur content and the presence of cracked stocks, on the oxidation stability are discussed.     

An empirical approach for predicting kinematic viscosities of biodiesel blends

Kinematic viscosity (η) is an important property of diesel fuels, including biodiesels, which are marketed mostly as the blends in many countries around the world. In this study, the free energy of viscous flow (ΔG_vis) for a non-associated liquid mixture is assumed to be the summed of ΔG_vis of individual components. Hence, the Eyring’s equation, η = Ae(−ΔG_vis/RT), is transformed to ln η_blend = a + bn₁ + c/T + dn₁/T (where, a, b, c and d, T and n₁ are thermodynamically related constants, absolute temperature and mole fraction of biodiesel, respectively). The transformed equation is used to predict kinematic viscosity of biodiesel blends (η_blend) of different degree of blending at any temperatures from pour point to 100 °C. The predicted kinematic viscosities are in good agreement with those reported in literatures at all temperatures. The highest deviation is ±5.4% and the average absolute deviation (AAD) is less than 2.86%. The transformed equation can also be used to predict kinematic viscosities of pure fatty acid methyl esters in diesel fuel. Methyl ricinoleate is an exception. The AAD is 4.50% and the deviation is as high as 12.80%. The high deviation suggests that molecular interactions between methyl ricinoleate and diesel fuel is high and cannot be ignored.     

Combustion characteristics of waste-oil produced biodiesel/diesel fuel blends

In this study, wasted cooking oil from restaurants was used to produce neat (pure) biodiesel through transesterification, and this converted biodiesel was then used to prepare biodiesel/diesel blends. The goal of this study was to compare the trace formation from the exhaust tail gas of a diesel engine when operated using the different fuel type: neat biodiesel, biodiesel/diesel blends, and normal diesel fuels. B20 produced the lowest CO concentration for all engine speeds. B50 produced higher CO₂ than other fuels for all engine speeds, except at 2000 rpm where B20 gave the highest. The biodiesel and biodiesel/diesel blend fuels produced higher NO_x for various engine speeds as expected. SO₂ formation not only showed an increasing trend with increased engine speed but also showed an increasing trend as the percentage of diesel increased in the fuels. Among the collected data, the PM concentrations from B100 engines were higher than from other fuelled engines for the tested engine speed and most biodiesel-contained fuels produced higher PM than the pure diesel fuel did. Overall, we may conclude that B20 and B50 are the optimum fuel blends. The species of trace formation in the biodiesel-contained fuelled engine exhaust were mainly C_nH_2n+2, DEP, and DPS. For the B100, B80, B50, and D fuelled engines, C₁₅H₃₂ was the dominant species for all engine speeds, while squalene (C₃₀H₅₀) was the dominant for B20. DEP was only observed in the B100, B80, and B50 fuelled engines in this study. The D fuelled engine showed a higher DPS production for engine speeds higher than 1200 rpm.     

Sedimentation in biodiesel and Ultra Low Sulfur Diesel Fuel blends

A biodiesel storage stability study was conducted on Ultra Low Sulfur Diesel Fuel (ULSDF) and three biodiesel fuels (B100), including a Tallow-based Methyl Ester (TME), a Canola-based Methyl Ester (CME), and, a Yellow Grease Methyl Ester (YGME), and fuel blends (B5 and B20). The stability study was conducted over ten months (Aug 07-Jun 08) and consisted of storing fuel samples in quarter filled plastic and steel 20 L cans, in an unheated shed. Fuel cans were vented twice a week to ensure exposure of the fuel to air. Changes in Acid Number, kinematic viscosity and free water and sediments levels were monitored over the storage period. Temperature and relative humidity ranged from −25 °C to 35 °C and 25% to 100%, respectively. Acid Number and the viscosity did not increase beyond the uncertainty of the method used. Reference samples kept at 40 °C were used for comparison. Free water and sediment levels were barely above the detection limit of 0.003 mL/100 mL of fuel for CME and YGME and their blends. TME and its B20 blend displayed free water and sediment levels up to 0.05 mL/100 mL of fuel in February, after six months of storage. These values decreased considerably after the warm Summer months back to below 0.01 mL/100 mL. All free water and sediment levels were measured after fuel samples came to equilibrium with room temperature. The TME B5 free water and sediment levels remained low throughout the storage period. Proton Nuclear Magnetic Resonance (NMR) spectroscopy performed on particulates from the sediments revealed a similar composition but a slightly lower concentration for protons in alkenyl groups. The presence of these sediments was attributed to more saturated molecules coming out of solution in colder weather and very slowly going back to solution at room temperature.     

Influence of soybean biodiesel content on basic properties of biodiesel-diesel blends

The world tendency in last years is to restrict the use of fossil fuels and replace them partially or totally by renewable fuels. Accordingly, biodiesel is being studied as one of the main alternatives and the production and consumption of this pure biofuel and its binary blends with fossil diesel have been markedly grown. Thus, the present work evaluated the influence of biodiesel concentration on such blends when mixed to diesel in 5, 15, 25 and 50 volume percentages. For each blend, both methanol and ethanol biodiesels were investigated. The biodiesel samples were physicochemically characterized. Their rheological behavior was analyzed. It was observed that the biodiesel enrichment leads to an acceptable increase in the viscosity and to a decrease in the volatilization of the binary blends. The viscosity was also shown to be temperature-dependent, as well as the fatty acids chain length and unsaturation.     

The specific gravity of biodiesel and its blends with diesel fuel

The specific gravities of biodiesel and 75, 50, and 20% blends with No. 1 and No. 2 diesel fuels were measured as a function of temperature from the onset of crystallization to 100°C. The results indicate that biodiesel and its blends demonstrate temperature-dependent behavior that is qualitively similar to the diesel fuels. The temperature dependence of the specific gravity for biodiesel and its blends was compared with the ASTM D 1250-80 procedure for the temperature correction of hydrocarbon fuels, and the procedure was found to provide accurate corrections. A blending equation was developed that allows the specific gravity of blends to be calculated from the specific gravities of the biodiesel and diesel fuels.     

Effect of commercially available antioxidants over biodiesel/diesel blends stability

The main obstacle in biodiesel/conventional diesel blends acceptance worldwide seems to be its poor oxidative stability. Low resistance towards oxygenation is due to the fatty constituent in the blend. Even low concentrations of biodiesel (5%, 10% and 20%) can contribute to sticky, viscous and polymeric deposits formation after several months of storage. Two correlations were derived concerning insolubles formed in both stabilized and not stabilized blends, stressed under conditions of ASTM D2274.For treated with antioxidant additive:

Total insol.=0.6561+80.1213∗ΔTAN-114.27∗ΔPC-2.6073∗ΔIV     

The kinematic viscosity of biodiesel and its blends with diesel fuel

As the use of biodiesel becomes more wide-spread, engine manufacturers have expressed concern about biodiesel’s higher viscosity. In particular, they are concerned that biodiesel may exhibit different viscosity-temperature characteristics that could result in higher fuel injection pressures at low engine operating temperatures. This study presents data for the kinematic viscosity of biodiesel and its blends with No. 1 and No. 2 diesel fuels at 75, 50, and 20% biodiesel, from close to their melting point to 100°C. The results indicate that while their viscosity is higher, biodiesel and its blends demonstrate temperature-dependent behavior similar to that of No. 1 and No. 2 diesel fuels. Equations of the same general form are shown to correlate viscosity data for both biodiesel and diesel fuel, and for their blends. A blending equation is presented that allows the kinematic viscosity to be calculated as a function of the biodiesel fraction.     

Fuel properties and precipitate formation at low temperature in soy-, cottonseed-, and poultry fat-based biodiesel blends

The formation of precipitates in biodiesel blends may have serious implications for diesel engine fuel delivery systems. Precipitates were observed in Soybean oil (SBO-), cottonseed oil (CSO-), and poultry fat (PF-) based biodiesel blends after storage at 4 °C. CSO- and PF-based biodiesel had a lower mass of precipitates observed than the SBO-based. Moreover, different rates of precipitate formation were observed for the B20 versus the B100. These suggested that the formation of precipitate during cold temperature storage was dependent on the feedstock and blend concentration. The solvency effects of biodiesel blends were more pronounced at low temperature than at room temperature leading to a higher amount of precipitates formed. Fourier transform infrared (FTIR) spectra, and gas chromatography-flame ionization detector (GC-FID) chromatograms indicated that steryl glucosides are the major cause of precipitate formation in SBO-based biodiesel; while for PF-based biodiesel, the precipitates are due to mono-glycerides. However, the precipitates from CSO-based biodiesel are due to both steryl glucosides and mono-glycerides.     

Jatropha–Palm biodiesel blends: An optimum mix for Asia

Biodiesel, an alternative renewable fuel made from transesterification of vegetable oil with alcohol, is becoming more readily available for use in blends with conventional diesel fuel for transportation applications. Soybean and Rapeseed are common feedstocks for Biodiesel production in USA and Europe, respectively. However, Asian countries are not self sufficient in edible oil and exploring non-edible seed oils, like Jatropha and Pongamia as biodiesel raw materials. However there is a gestation period of few years before these crops start yielding seeds and oil. On the other hand, South Eastern countries like Malaysia and Thailand have surplus Palm crops. But due to substantial amount of saturated fats in Palm, the Palm biodiesel has poor low temperature properties. In order to exploit the proximity of South Asian and South-East Asian countries, blends of Jatropha and Palm biodiesel have been examined to study their physico-chemical properties and to get an optimum mix of them to achieve better low temperature properties, with improved oxidation stability.     

Temperature-dependent kinematic viscosity of selected biodiesel fuels and blends with diesel fuel

The kinematic viscosities of four biodiesel fuels—two natural soybean oil methyl esters, one genetically modified soybean oil methyl ester, and one yellow grease methyl ester—and their 75, 50, and 25% blends with No. 2 diesel fuel were measured in the temperature range from 20 to 100°C in steps of 20°C. The measurements indicated that all these fuels had viscosity-temperature relationships similar to No. 2 diesel fuel, which followed the Vogel equation as expected. A weighted semilog blending equation was developed in which the mass-based kinematic viscosity of the individual components was used to compute the mixture viscosity. A weight factor of 1.08 was applied to biodiesel fuel to account for its effect on the mixture viscosity. The average absolute deviation achieved with this method was 2.1%, which was better than the uncorrected mass average blending equation that had an average absolute deviation of 4.5%. The relationship between the viscosity and the specific gravity of biodiesel fuels was studied. A method that could estimate the viscosity from the specific gravity of biodiesel fuel was developed. The average absolute deviation for all the samples using this method was 2.7%. The accuracy of this method was comparable to the weighted mass-based semilog blending equation.