Quality survey of biodiesel blends sold at retail stations

A quality survey of the biodiesel blends sold in 24 retail stations in March and April 2007 was performed. The main feedstock for the biodiesel blends sold was determined to be soybean oil based. The total acid numbers (TAN) for all of the samples were below 0.3 mg/g, and the derived cetane numbers (DCN) were above 40 for all but one of the samples. The viscosity of all the samples was within the proposed ASTM range for B20. The cold-flow properties were adequate, with the pour point (PP) being below ?36 °C for most samples, suggesting the presence of a pour point depressant. However, the oxidative stability for the samples is of concern, with over 45% having an induction period (IP) of less than 6 h. Moreover, the actual blending level of the biodiesel blends generally differed from the blending level on the pump label, and fuel properties varied over a wide range even for the same blend composition.     

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     

Quality analysis of wintertime B6-B20 biodiesel blend samples collected in the United States

A survey of the quality of biodiesel blends in the United States was conducted in the winter of 2009-2010. Forty samples were collected in the study; two-thirds of the samples collected were from areas with a 10th percentile minimum ambient temperature below − 12 °C. Fuel properties were measured and compared to the relevant ASTM D7467-09 specification properties. The B6-B20 study shows increased compliance with the blend level requirements to 72.5% of samples tested, with a cold state average biodiesel content of 12% and a warm state average biodiesel content of 19%. The decreased biodiesel content in cold states is likely to due to deliberate reductions to meet the cloud point expectations. Continuing problems were noted with induction period stability for B6-B20 blends, with a failure rate of 24%. Samples collected from cold weather states had a failure rate of only 18%, likely because of the reduced biodiesel content; the failure rate from warm weather states rose to 57%. Samples failed the induction period stability specification before the acid value increased to the point of failure and no acid value failures were recorded. No failures were observed water and sediment. A single failure was noted for flash point, likely due to external contamination during fuel handling. Cloud point and cold filter plugging points are reported.     

Quality characteristics of edible vegetable oil blends

Two edible oil blends, namely groundnut oil:rice-bran oil and mustard oil:rice-bran oil, were prepared in different proportions and stored for a period of three years. Their physicochemical characteristics were determined. The results agreed with expected values except for free fatty acid percents and butyrorefrac-tometer readings, presumably due to rancidity. Fatty acid compositions of the blends were determined and ratios of characteristic fatty acids, like lignoceric to palmitic for groundnut oil:rice-bran oil blends, and erucic to palmitic for mustard oil:rice-bran oil blends, were calculated to identify individual oils in the blend.     

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.     

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.     

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.     

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.     

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.     

Comparison of PAH and regulated harmful matter emissions from biodiesel blends and paraffinic fuel blends on engine accumulated mileage test

This study investigated polycyclic aromatic hydrocarbon (PAH) and regulated harmful matter (traditional pollutant) emissions, fuel consumption, and the assessment of the inferior condition of engine oil from heavy-duty diesel engines (HDDEs) fueled with palmbiodiesel–PDF (premium diesel fuel) blends and paraffinic–palmbiodiesel blends under brand-new (the mileage was zero) engines accumulated mileage test. Experimental results indicated that the emissions of THC and CO increased with operation time but the emissions of NO_x and PAHs decreased with operation time between 0 and 300 h (18,000 km). Using palmbiodiesel–PDF blends or paraffinic–palmbiodiesel blends instead of PDF in HDDEs reduced the emissions of THC (10.7–44.2%), CO (0.664–15.6%), CO₂ (0.763–2.55%), NO_x (1.25–4.97%), PM (6.11–26.8%), total PAHs (43.0–90.2%) and total BaP_eq (63.1–89.6%) significantly.     

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.     

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.     

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.     

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.     

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.     

Effect of biodiesel blends on North American heavy‐duty diesel engine emissions

We conducted an assessment of North American heavy‐duty engine emission test results for biodiesel from 49 experimental studies, including both engine dynamometer and vehicle test results. Comparison with a commercial database showed that the engines in the emissions database are not representative of the existing North American in‐use fleet as of 2007; more than 50% of the tested engines were of 1995 or earlier vintage. Nevertheless, the results show that the use of a common biodiesel blend (B20) consistently reduces emissions of particulate matter, hydrocarbons, and carbon monoxide by 10–20%. Tests with B20 show varying effects on oxides of nitrogen (NO_x). If results for pre‐1992 two‐cycle 6V‐92TA(E) engines (which represent 0.2% of the 2007 in‐use fleet but 28% of the engines tested) are removed, then there is no statistical evidence that the average NO_x emissions from B0 and B20 are different (p value of 0.50 for an estimated average increase of 1%). Several researchers have used changes in engine calibration to eliminate any NO_x penalty associated with B20 (in engines that show an increase in NO_x with B20), while still maintaining the advantages of B20 in reducing other pollutants. The emissions effect of B20 on heavy‐duty diesel truck emissions did not show any correlation with model year or type of fuel injection equipment.     

Prediction of properties of diesel/biodiesel blends by infrared spectroscopy and multivariate calibration

Partial least squares models (PLS) using near and middle infrared spectrometry were developed to predict quality parameters of diesel/biodiesel blends (density, sulphur content and distillation temperatures). Practical aspects are discussed, such as calibration set composition; model efficiency using different infrared regions and spectrometers; and the calibration transfer problem. The root mean square errors of prediction, employing both regions and equipment, were comparable with the reproducibility of the corresponding standard method for the properties investigated. Calibration transfer between the two instruments, using direct standardization (DS), yielded prediction errors comparable to those obtained with complete recalibration of the secondary instrument.     

生物柴油特性及作为混合燃料添加剂的研究

论述了生物柴油优越的理化特性,可作为柴油的替代燃料,并讨论了生物柴油作为乙醇（甲醇）与柴油或汽油混合燃料的添加剂情况.通过溶解度测定及三相图实验数据表明生物柴油作为乙醇与柴油添加剂,促溶效果较好;对于生物柴油-汽油-乙醇体系来讲,三者可以任意比例混合,可改善汽油的燃烧性能;对于生物柴油-柴油-甲醇体系,效果不理想.     

A review of laboratory-scale research on lipid conversion to biodiesel with supercritical methanol (2001-2009)

Biodiesel production from lipids (vegetable oils and animal fats) with non-catalytic supercritical methanol (SCM) has several advantages over that of homogeneous catalytic process, including a high production efficiency, environmentally friendliness and a wide range of possible feedstocks. This article reviews the effect of the operating parameters on the lipid conversion to biodiesel with SCM, such as the temperature, pressure, methanol to oil molar ratio, and reaction time, for both batch and continuous systems, including the effect of the mixing intensity and dispersion in tubular reactors. The operating temperature is the key parameter to control either extent of reaction or other parameters. Studies on evaluating the chemical kinetics, phase behavior, binary vapor-liquid equilibrium (VLE) of lipid conversion in SCM are summarized. The pseudo-first order model is suitable to simplify the system at high methanol to oil molar ratios, but it is inadequate at a low methanol concentration which instead requires the second order model. Transition temperatures of reaction mixture depend on the critical point of reaction mixture which is assigned by methanol to oil molar ratio and amount of co-solvents in the system. For binary VLE studies, no single thermodynamic model for the overall process is available, probably because of the differences in the polarity between the initial and the final state of the reaction system. Since traditional operating parameters of the lipid conversion in SCM involve elevated temperatures and pressures, techniques for allowing milder operating conditions that employ the addition of co-solvents or catalysts are discussed. The ongoing and more extensive research on co-solvents, heterogeneous catalysts, phase behavior and multicomponent VLE of lipid conversion to biodiesel with SCM should provide a better understanding and achieve the goal of green biodiesel production technology in the near future.     

Design and improvement of biodiesel fuels blends by optimization of their molecular structures and compositions

Biodiesel is a renewable alternative to petroleum-based diesel fuel that could potentially still prove to be substantially more environmentally friendly than their fossil alternatives. It is obtained by a transesterification reaction from any triglyceride material (edible and non-edible oils, animal fats, lipid algae, etc.) being a potential tool for sustainable development. Its properties as fuel are strongly linked to the molecular structure of its species composition: profile, chemical structure and quantity of fatty acids alkyl esters contained. Hence the manipulation of this composition could lead to improve different kinds of fuel properties. In this work we implement a group contribution approach of the Statistical Associating Fluid Theory, named SAFT-γ to describe the molecular structure of each fatty ester and to evaluate the influence of its chemical framework in the behavior of biodiesel as fuel by predicting the more relevant thermophysical properties. Parameters for the biodiesel model were obtained by experimental data fitting. Optimal fatty ester composition and potential FAMEs profile were obtained by implementing an Evolutionary Genetic Algorithms (EGA). Biodiesel blends found in this work were compared with two commercial B100 stock in order to analyze its thermodynamical behavior which would be a powerful tool for clean combustion analysis differences.