The effect of natural and synthetic antioxidants on the oxidative stability of palm diesel

Crude and distilled palm oil methyl esters conveniently known as palm diesel have been successfully evaluated as diesel substitute. Crude palm oil methyl esters are produced from transesterification of crude palm oil with minor components such as carotenes and vitamin E still intact and they are reddish in colour. The distilled palm oil methyl esters are obtained after the recovery of minor components (e.g. Carotenes and vitamin E) From the crude palm oil methyl esters. These valuable minor components are preferably to be recovered as they can be sold as value-added products before they are burnt together with the methyl esters as fuel. Although both possesses fuel characteristics which are comparable to those of petroleum diesel, crude palm oil methyl esters are found to exhibit better oxidative stability (rancimat induction period >25 h) than distilled palm oil methyl esters (about 3.5 h). It is attributed to the presence of vitamin E (about 600 ppm), a natural antioxidant in the former. While the distilled palm oil methyl esters contain practically no vitamin E (<50 ppm) and as a result, they exhibit poor oxidative stability. Thus, the crude palm oil methyl esters meet the european standard for biodiesel (EN 14214) which has set a minimum rancimat induction period of 6 h. In the present study, research was conducted to enhance the oxidative stability of distilled palm oil methyl esters in order to meet the aforementioned standard. Natural and synthetic antioxidants were used in the present study to investigate their effect on the oxidative stability of distilled palm oil methyl esters. It was found that both types of antioxidant showed beneficial effects in inhibiting the oxidation of distilled palm oil methyl esters. Comparatively, the synthetic antioxidants were found to be more effective than the natural antioxidants as lower dosage (17 times less) was needed to achieve the minimum rancimat induction period of 6 h.     

Transesterified milkweed (Asclepias) seed oil as a biodiesel fuel

The methyl and ethyl esters of milkweed (Asclepias) seed oil were prepared and compared to soybean esters in laboratory tests to determine biodiesel fuel performance properties. The pour points of the methyl and ethyl milkweed esters measured −6 °C and −10 °C, respectively, which is consistent with the high levels of unsaturation characteristic of milkweed seed oil. The oxidative stabilities measured by OSI at 100 °C were between 0.8 and 4.1 h for all samples tested. The kinematic viscosities determined at 40 °C by ASTM D 445 averaged 4.9 mm²/s for milkweed methyl esters and 4.2 mm²/s for soybean methyl esters. Lubricity values determined by ASTM D 6079 at 60 °C were comparable to the corresponding soybean esters with average ball wear scar values of 118 μm for milkweed methyl esters and 200 μm for milkweed ethyl esters.     

Biodiesel production from waste tallow

In the present investigation an attempt has been made to use waste tallow as low cost sustainable potential feed stock for biodiesel production. Effect of various process parameters such as amount of catalyst, temperature and time on biodiesel production was investigated. The optimal conditions for processing 5 g of tallow were: temperature, 50 and 60 °C; oil/methanol molar ratio 1:30 and 1:30, amount of H₂SO_4, 1.25 and 2.5 g for chicken and mutton tallow, respectively. Under optimal conditions, chicken and mutton fat methyl esters formation of 99.01 ± 0.71% and 93.21 ± 5.07%, was obtained after 24 h in the presence of acid. The evaluation of transesterification process was followed by gas chromatographic analysis of tallow fatty acid esters. A total of 98.29% and 97.25% fatty acids were identified in chicken and mutton fats, respectively. Both fats were found highly suitable to produce biodiesel with recommended fuel properties.     

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.     

Nitration of biodiesel of waste oil: Nitrated biodiesel as a cetane number enhancer

Biodiesel has been produced by transesterification of waste frying oil with methanol catalysed by sodium methoxide. The unsaturated fatty acid methyl esters of the biodiesel produced have been nitrated by two alternative nitration methods, showing an incorporation of nitrogen between 3.43 and 5.10 wt.%, in the chemical form of nitro, nitrate and acetoxy functional groups. A detailed gas chromatography–mass spectrometry analysis has been carried out on the nitrated biodiesel samples in order to identify the nitration products of this complex mixture. The nitrated biodiesel has been added to a base diesel fuel in a 1000 mg L⁻¹ concentration resulting in an increase of the cetane number of the fuel by more than five points, from 54.7 to 60.5.     

Biodiesel preparation,optimization, and fuel properties from non-edible feedstock,Datura stramonium L.

This is a study on the feasibility of biodiesel preparation from a new and promising non-edible feedstock, Datura stramonium L. oil (DSO). First, important physical–chemical properties, such as oil content of seed (21.4 wt%), acid value (7.93 mg KOH/g) and fatty acid composition of expressed oil, were determined. Second, under the optimal two-step catalyzed reaction conditions, the maximum fatty acid methyl ester (FAME) yield (87%) and FAME content of more than 98 wt% were obtained. Furthermore, the fuel properties of DSO biodiesel were determined and evaluated. Compared with Jatrpha curcas L. (JC) and beef tallow (BT) biodiesel, DSO biodiesel possessed the best kinematic viscosity (4.33 mm²/s) and cold filter plug point (?5 °C). Based on the results, D. stramonium L. was identified as a promising species for biodiesel feedstock.     

Biodiesel synthesis combining pre-esterification with alkali catalyzed process from rapeseed oil deodorizer distillate

A two-step technique combining pre-esterification catalyzed by cation exchange resin with transesterification catalyzed by base alkali was developed to produce biodiesel from rapeseed oil deodorizer distillate (RDOD). The free fatty acids (FFAs) in the feedstock were converted to methyl esters in the pre-esterification step using a column reactor packed with cation exchange resin. The acid value of oil was reduced from the initial 97.60 mg-KOH g^? 1 oil to 1.12 mg-KOH g^? 1 oil under the conditions of cation exchange resin D002 catalyst packed dosage 18 wt.% (based on oil weight), oil to methanol molar ratio 1:9, reaction temperature 60 °C, and reaction time 4 h. The biodiesel yield by transesterification was 97.4% in 1.5 h using 0.8 wt.% KOH as catalyst and a molar ratio of oil to methanol 1:4 at 60 °C. The properties of RDOD biodiesel production in a packed column reactor followed by KOH catalyzed transesterification were measured up the standards of EN14214 and ASTM6751-03.     

Biodiesel production from tall oil with synthesized Mn and Ni based additives: Effects of the additives on fuel consumption and emissions

In this study, biodiesel fuel and fuel additives were produced from crude tall oil that is a by-product in the pulp manufacturing by craft or sulphate pulping process. Fatty acids and resinic acids were obtained from crude tall oil by distillation method. Tall oil methyl ester (biodiesel) was produced from fatty acids. Resinic acids were reacted with NiO and MnO₂ stoichiometrically for production of metallic fuel additives. Each metallic fuel additive was added at the rate of 8 μmol/l and 12 μmol/l to make mixtures of 60% tall oil methyl ester/40% diesel fuel (TE60) for preparing test fuels. Metallic fuel additives improved properties of biodiesel fuels, such as pour point and viscosity values. Biodiesel fuels were tested in an unmodified direct injection diesel engine at full load condition. Specific fuel consumption of biodiesel fuels increased by 6.00%, however, in comparison with TE60, it showed trend of decreasing with adding of additives. Exhaust emission profile of biodiesel fuels improved. CO emissions and smoke opacity decreased up to 64.28% and 30.91% respectively. Low NO_x emission was also observed in general for the biodiesel fuels.     

Biodiesel production from highly unsaturated feedstock via simultaneous transesterification and partial hydrogenation in supercritical methanol

In this study, a supercritical one-pot process combining transesterification and partial hydrogenation was proposed to test its technical feasibility. Simultaneous transesterification of soybean oil and partial hydrogenation of polyunsaturated compounds over Cu catalyst in supercritical methanol was performed at 320 °C and 20 MPa. Hydrogenation proceeded simultaneously during the transesterification of soybean oil in supercritical methanol, and hydrogenation occurred during the reaction despite the absence of hydrogen gas. The polyunsaturated methyl esters obtained in the biodiesel were mainly converted to monounsaturated methyl esters by partial hydrogenation. Key properties of the partially hydrogenated methyl esters were improved and complied with standard specifications for biodiesel.     

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.     

Optimization of pretreatment reaction for methyl ester production from chicken fat

In biodiesel production, to use low cost feedstock such as rendered animal fats may reduce the biodiesel cost. One of the low cost animal fats is the chicken fat for biodiesel production. It is extracted from feather meal which is prepared from chicken wastes such as chicken feathers, blood, offal and trims after rendering process. However, chicken fats often contain significant amounts of FFA which cannot be converted to biodiesel using an alkaline catalyst due to the formation of soap. Therefore, the FFA level should be reduced to desired level (below 1%) by using acid catalyst before transesterification. For this aim, sulfuric, hydrochloric and sulfamic (amidosulfonic) acids were used for pretreatment reactions and the variables affecting the FFA level including alcohol molar ratio, acid catalyst amount and reaction time were investigated by using the chicken fat with 13.45% FFA. The optimum pretreatment condition was found to be 20% sulfuric acid and 40:1 methanol molar ratio based on the amount of FFA in the chicken fat for 80 min at 60 °C. After transesterification, the methyl ester yield was 87.4% and the measured fuel properties of the chicken fat methyl ester met EN 14214 and ASTM D6751 biodiesel specifications.     

Enzymatic conversion of corn oil into biodiesel in a batch supercritical carbon dioxide reactor and kinetic modeling

Synthesis of fatty acid methyl esters (FAME) as biodiesel from corn oil was studied in a batch supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Effects of reaction conditions on the contents of FAME, monoacylglycerols (MAG), diacylglycerols (DAG), and triacyglycerols (TAG) were investigated at various enzyme loads (5–15%), temperatures (40–60 °C), substrate mole ratios (corn oil:methanol; 1:3–1:9), pressures (10–30 MPa), and times (1–8 h). The highest FAME content (81.3%) was obtained at 15% enzyme load, 60 °C, 1:6 substrate mole ratio, and 10 MPa in 4 h. A reaction kinetic model was used to describe the system, and the activation energy of the system was calculated as 72.9 kJ/mol. Elimination of the use of organic solvents, chemical catalysts and wastewater as well as reasonably high yields make the enzymatic synthesis of biodiesel in SC-CO₂ a promising green alternative to conventional biodiesel process.     

Transesterification of soybean oil and analysis of bioproduct

Biodiesel produced by the transesterification reaction of soybean oil using potassium hydroxide (KOH) catalytic is a promising alternative fuel to diesel regarding the limited resources of fossil fuel and the environmental concerns. In order to decrease the operational temperature and increase the conversion efficiency of methanol, a novel idea was presented in which a co-solvent dichloromethane was added to the reactants. The results showed that the yield of methyl ester was improved when dichloromethane was coexistence. The effects of the co-solvent, molar ratio of methanol/oil, reaction temperature, and catalyst on the biodiesel conversion were investigated. With the optimal reaction temperature of 45 °C, methanol to oil ratio of 4.5:1, co-solvent dichloromethane of 4.0%, a 96% yield of methyl esters was observed in 2.0 h at the condition with 1.0 wt.% potassium hydroxide. The characterization and analysis of biodiesel were obtained by FT-IR, gas chromatograph and inductively coupled plasma atomic emission (ICP–OES) spectroscopy methods. The cetane number, flash point, cold filter plugging point, acid number, water content, ash content and total glycerol content were investigated.     

Fundamental combustion characteristics of palm methyl ester (PME) as alternative fuel for gas turbines

To investigate the combustion characteristics of palm methyl ester (PME) as an alternative fuel for gas turbines, combustion experiments at atmospheric pressure using high-temperature air (673 K) were performed. Chemical equilibrium calculations and investigations of fuel atomizing characteristics using a laser diffraction spray analyzer (LDSA) were also conducted. The results show that combustion characteristics of PME are similar to those of diesel fuel. Furthermore, it is indicated that NO_x emissions can be reduced by using PME instead of diesel fuel for gas turbines.     

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.     

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.     

Production of high-quality biodiesel fuels from various vegetable oils over Ti-incorporated SBA-15 mesoporous silica

Ti-incorporated SBA-15 mesoporous silica (shortly termed Ti-SBA-15) was a highly efficient and recyclable solid acid to synthesize high-quality biodiesel fuel (BDF) derived from various vegetable oils at moderate reaction condition, in comparison to siliceous SBA-15 and commercial TiO₂ catalysts with different anatase sizes, where the catalytically active sites mainly related to the tetrahedral-coordinated Ti(IV) species with weak Lewis acid nature. The TOF values of Ti-SBA-15 catalysts were around 18–166 h^− 1, an order of magnitude larger than those of commercial TiO₂ catalysts. A high-quality BDF containing more than 98.4 mass% of fatty acid methyl ester (FAME), which met with international fuel standard, was obtained over 3Ti-SBA-15 catalyst at 200 °C using a methanol/oil ratio of 108. Most importantly, the 3Ti-SBA-15 catalyst showed extremely high water and free fatty acid (FFA) tolerance levels, which were several ten times better than homogeneous and heterogeneous catalysts in conventional BDF production technology.     

An efficient method for the enrichment of the arachidonic acid methyl ester from Mortierella alpina-derived crude oils

An improved method was developed for enriching arachidonic acid (AA) methyl ester from microbial oil by two-step low-temperature wet fractionation. The effects of solvent, operating temperature, and solvent-to-fatty acid methyl esters (FAMEs) ratio on the enrichment of AA were investigated. The best results were achieved when n-hexane was used as solvent. With operating temperatures in the range ?30 °C to ?80 °C and a FAMEs-to-solvent ratio of 1:5 (v/v), the proportion of AA methyl ester isolated could be increased to 83.76 ± 2.78% with a yield of 52.89%. The total recovery of AA methyl ester would be further increased to 90.84% by recrystallization of the solid phases. The 20C, 22C saturated fatty acids were enriched by n-hexane or petroleum ether at ?30 °C, with concentrations increased 7.5-fold or 7.2-fold compared with their original levels, respectively. In addition, a method that combined alkali and acid catalysis of the transmethylation was the most conducive to the preparation of polyunsaturated fatty acid methyl esters.     

The densities of three biodiesel fuels at temperatures up to 300 °C

In order to obtain the densities of biodiesel fuels at temperatures up to 300 °C, a capacitance type liquid level meter was designed to measure the increase in volume of 50 ml of three commercial biodiesel fuels over the temperature range of 20–300 °C. Densities were measured for methyl esters of canola and soy and ethyl esters of fish-oil. The frequency output from the meter was linear with temperature and liquid level. Frequencies were recorded in kHz to within three decimal places and had sensitivities of 0.040 kHz/°C and −2.740 kHz/cm for temperature and submergence depth, respectively. Derived densities were found to be linear with temperature over the measured range. Used in this fashion, the level meter can be considered a precise densitometer with a repeatability of 1%.