Renewable energy sources from Michelia champaca and Garcinia indica seed oils: A rich source of oil

Michelia champaca and Garcinia indica seeds yielded 45.0% and 45.5% of oil. The fatty acid profiles of both the seed oils were examined. The saponification value (SV), iodine value (IV) and cetane number (CN) of fatty acid methyl esters of both the seed oils were empirically determined. The saponification value (SV) and iodine value (IV) are in good agreement with the experimentally observed values. The fatty acid compositions, iodine value and cetane number were used to predict the quality of fatty acid methyl esters of oil for use as biodiesel. Thus, the fatty acid methyl esters of seed oils of M. champaca and G. indica were found to be the most suitable biodiesel and they meet the major specification of biodiesel standards. The selected plants M. champaca and G. indica have great potential for biodiesel. M. champaca and G. indica seed oils were found to contain keto fatty acids along with the other normal fatty acids, respectively. These fatty acids have been detected and characterized by UV, FTIR, ¹H NMR, ¹³C NMR, MS, GC techniques and chemical transformations.     

Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran and co-workers for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet-stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO₂ production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.     

Mathematical Relationships Derived from Biodiesel Fuels

Abstract

The objective of this study was to estimate mathematical relationships derived from biodiesel fuels from various vegetable oils by non-catalytic supercritical methanol and ethanol method. The vegetable oils are all extremely viscous with viscosities ranging from 10 to 20 times greater than petroleum diesel fuel. The aim of the transesterification process is to lower the viscosity of the oil. Methyl and ethyl esters as biodiesels were prepared from vegetable oils through transesterification by non-catalytic supercritical fluids. The biodiesels were characterized for their physical and main fuel properties including viscosity, density, flash point and higher heating value (HHV). The viscosities of biodiesels (3–5 mm²/s at 311 K) were much less than those of pure oils (27–54 mm²/s at 311 K), and their HHVs of approximately 40.5 MJ/kg were 10% less than those of petrodiesel fules (～45 MJ/kg). The most important variables affecting the ester yield during the transesterification reaction are molar ratio of alcohol to vegetable oil and reaction temperature. The viscosity values of vegetable oil methyl esters highly decreases after transesterification process. Compared to no. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. The flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. 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.     

Transesterification of jojoba oil,sunflower oil,neem oil,rocket seed oil and linseed oil by tin catalysts

The methanolysis of jojoba oil has been studied in the presence of tin powder, dibutyltin diacetate (C₄H₉)₂Sn(OOCCH₃)₂, dioctyltin diacetate (C₈H₁₇)₂Sn(OOCCH₃)₂, dibutyltin oxide (C₄H₉)₂SnO, dioctyltin oxide (C₈H₁₇)₂SnO, diphenyltin oxide (C₆H₅)₂SnO, dibutyltin chloride dihydroxide (C₄H₉)₂Sn(OH)₂Cl, butyltinhydroxide hydrate (C₄H₉)Sn(=O)OH.xH₂O, Ni nanoparticles and Pd nanoparticles act as catalysts. Among these, 1 weight % of dibutyltin diacetate shows the maximum conversion. Then, methanolysis of sunflower oil, neem oil, rocket seed oil and linseed oil into methyl esters studied in the presence of 1% dibutyltin diacetate as a catalyst and was compared their percentage conversions. The experimental yield for the conversion of jojoba oil, sunflower oil, neem oil, rocket seed oil and linseed oil into biodiesel was found to be 71%, 51%, 50.78%, 40.90% and 39.66%, respectively. The experimental yield of the conversion of jojoba oil into methyl esters was found to be increased up to 96% by increasing reaction time, without emulsion formation. The synthesis of jojoba seed oil biodiesel (JSOB), soybean oil biodiesel (SOB), neem oil biodiesel (NOB), rocket seed oil biodiesel (RSOB) and linseed oil biodiesel (LSOB) was confirmed by NMR (¹H & ¹³C) and FT-IR analyses of biodiesel.     

Production of biodiesel fuels from linseed oil using methanol and ethanol in non-catalytic SCF conditions

Methyl and ethyl esters as biodiesel fuels were prepared from linseed oil with transesterification reaction in non-catalytic supercritical fluids conditions. Biodiesel fuel is a renewable substitute fuel for petroleum diesel fuel made from vegetable or animal fats. Biodiesel fuel has better properties than that of petroleum diesel fuel such as renewable, biodegradable, non-toxic, and essentially free of sulfur and aromatics. The purpose of the transesterification process is to lower the viscosity of the oil. The viscosity values of linseed oil methyl and ethyl esters highly decreases after transesterification process. The viscosity values of vegetable oils vary between 27.2 and 53.6 mm² s^?1, whereas those of vegetable oil methyl esters between 3.59 and 4.63 mm² s^?1. Compared with no. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. The transesterification of linseed oil in supercritical fluids such as methanol and ethanol has proved to be the most promising process. Methanol is the commonly used alcohol in this process, due in part to its low cost. Methyl esters of vegetable oils have several outstanding advantages among other new-renewable and clean engine fuel alternatives. The most important variables affecting the methyl ester yield during the transesterification reaction are molar ratio of alcohol to vegetable oil and reaction temperature. Biodiesel has become more attractive recently because of its environmental benefits. Biodiesel is an environmentally friendly fuel that can be used in any diesel engine without modification.     

Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate

Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet-stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines.     

Coriander seed oil methyl esters as biodiesel fuel: Unique fatty acid composition and excellent oxidative stability

Coriander (Coriandrum sativum L.) seed oil methyl esters were prepared and evaluated as an alternative biodiesel fuel and contained an unusual fatty acid hitherto unreported as the principle component in biodiesel fuels: petroselinic (6Z-octadecenoic; 68.5 wt%) acid. Most of the remaining fatty acid profile consisted of common 18 carbon constituents such as linoleic (9Z,12Z-octadeca-dienoic; 13.0 wt%), oleic (9Z-octadecenoic; 7.6 wt%) and stearic (octadecanoic; 3.1 wt%) acids. A standard transesterification procedure with methanol and sodium methoxide catalyst was used to provide C. sativum oil methyl esters (CSME). Acid-catalyzed pretreatment was necessary beforehand to reduce the acid value of the oil from 2.66 to 0.47 mg g^?1. The derived cetane number, kinematic viscosity, and oxidative stability (Rancimat method) of CSME was 53.3, 4.21 mm² s^?1 (40 °C), and 14.6 h (110 °C). The cold filter plugging and pour points were ?15 °C and ?19 °C, respectively. Other properties such as acid value, free and total glycerol content, iodine value, as well as sulfur and phosphorous contents were acceptable according to the biodiesel standards ASTM D6751 and EN 14214. Also reported are lubricity, heat of combustion, and Gardner color, along with a comparison of CSME to soybean oil methyl esters (SME). CSME exhibited higher oxidative stability, superior low temperature properties, and lower iodine value than SME. In summary, CSME has excellent fuel properties as a result of its unique fatty acid composition.     

Relationships between Viscosity and Density Measurements of Biodiesel Fuels

Abstract

The viscosity values of vegetable oils vary between 27.2 and 53.6 mm²/s, whereas those of vegetable oil methyl esters between 3.59 and 4.63 mm²/s. The viscosity values of vegetable oil methyl esters highly decreases after transesterification process. Compared to no. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. The flash point values of vegetable oil methyl esters are highly lower than those of vegetable oils. An increase in density from 860 to 885 kg/m³ for vegetable oil methyl esters or biodiesels increases the viscosity from 3.59 to 4.63 mm²/s, 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 irregular. An increase in density from 860 to 885 kg/m³ for vegetable oil methyl esters increases the flash point from 401 to 453 K, and the increases are slightly regular.     

Periodic variation in kernel oil content and fatty acid profiles of Calophyllum innophyllm L.: A potential biodiesel feedstock in Australia

Variation in oil content and fatty acid profiles of a native Australian biodiesel feedstock species Calophyllum inophyllum were studied in two different fruiting periods (winter 2008 and autumn 2009) and in three different northern Queensland provenances (Cardwell, Townsville, Yeppoon). Oils were extracted by standard n-hexane double extraction and fatty acid profiles were determined by ISO 5508 and 5509 methods using gas chromatography. C. inophyllum provenances have demonstrated a significant periodic variation in oil content and fatty acid profile, and as a result alter the quality of fatty acid methyl esters (biodiesel). FAP of majority of kernel oil sources were found to vary significantly (P < 0.05) with seasonal variation in temperature and longterm average rainfall.     

Property modification of jatropha oil biodiesel by blending with other biodiesels or adding antioxidants

The feasibility of biodiesel production from jatropha (Jatropha curcas) oil was investigated with respect to the biodiesel blending properties and its oxidation stability with antioxidants. The JME (jatropha oil methyl esters) had the cetane number of 54, cold filter plugging point of −2 °C, density of 881 kg/m³ at 15 °C, ester content of 99.4 wt.%, iodine value of 96.55 g I₂/100 g, kinematic viscosity of 4.33 mm²/s at 40 °C, and oxidation stability of 3.86 h. Furthermore, the JME was blended with palm oil biodiesel and soybean oil biodiesel at various weight ratios and evaluated for fuel properties as compared to the relevant specifications. In addition, several antioxidants at concentrations between 100 and 1000 ppm were studied for their potential to improve the oxidation stability of the JME. The relationship between the IP (induction period) in the measurement of the oxidation stability associated with the antioxidant consumption in the JME was described by first-order reaction rate kinetics. Moreover, the ln IP (natural logarithm of the IP) at various concentrations of pyrogallol showed a linear relationship with the test temperature. The oxidation stability at ambient temperatures was predicted on the basis of an extrapolation of the temperature-dependent relationship.     

Biodiesel production from swine manure via housefly larvae (Musca domestica L.)

Although biodiesel is a sustainable and renewable diesel fuel, the current feedstock predominantly from edible oils limits the economic feasibility of biodiesel production and thus the development of a cost-effective non-food feedstock is really essential. In this study, approximately 21.6% of crude grease was extracted from housefly (Musca domestica L.) larvae reared on swine manure, and the extracted grease was evaluated for biodiesel production concerning the variables affecting the yield of acid-catalyzed production of methyl esters and the properties of the housefly larvae-based biodiesel. The optimized process of 8:1 methanol/grease (mol/mol) with 2 vol% H₂SO₄ reacted at 70 °C for 2 h resulted in a 95.7% conversion rate from free fatty acid (FFA) into methyl esters. A 90.3% conversion rate of triglycerides (crude grease) to its esters was obtained from alkaline trans-esterification using sodium hydroxide as catalyst. The major fatty acid components of this larvae grease were palmitic (29.1%), oleic (23.3%), palmitoletic (17.4%) and linoleic (17.2%). The housefly larvae-based biodiesel has reached the ASTM D6751-10 standard in density (881 kg/m³), viscosity (5.64 mm²/s), ester content (96.8%), flash point (145 °C), and cetane number (52). These findings suggest that the grease derived from swine manure-grown housefly larvae can be a feasible non-food feedstock for biodiesel production.     

Biodiesel production from inedible animal tallow and an experimental investigation of its use as alternative fuel in a direct injection diesel engine

In this study, a substitute fuel for diesel engines was produced from inedible animal tallow and its usability was investigated as pure biodiesel and its blends with petroleum diesel fuel in a diesel engine. Tallow methyl ester as biodiesel fuel was prepared by base-catalyzed transesterification of the fat with methanol in the presence of NaOH as catalyst. Fuel properties of methyl ester, diesel fuel and blends of them (5%, 20% and 50% by volume) were determined. Viscosity and density of fatty acid methyl ester have been found to meet ASTM D6751 and EN 14214 specifications. Viscosity and density of tallow methyl esters are found to be very close to that of diesel. The calorific value of biodiesel is found to be slightly lower than that of diesel. An experimental study was carried out in order to investigate of its usability as alternative fuel of tallow methyl ester in a direct injection diesel engine. It was observed that the addition of biodiesel to the diesel fuel decreases the effective efficiency of engine and increases the specific fuel consumption. This is due to the lower heating value of biodiesel compared to diesel fuel. However, the effective engine power was comparable by biodiesel compared with diesel fuel. Emissions of carbon monoxide (CO), oxides of nitrogen (NO_x), sulphur dioxide (SO₂) and smoke opacity were reduced around 15%, 38.5%, 72.7% and 56.8%, respectively, in case of tallow methyl esters (B100) compared to diesel fuel. Besides, the lowest CO, NO_x emissions and the highest exhaust temperature were obtained for B20 among all other fuels. The reductions in exhaust emissions made tallow methyl esters and its blends, especially B20 a suitable alternative fuel for diesel and thus could help in controlling air pollution. Based on this study, animal tallow methyl esters and its blends with petroleum diesel fuel can be used a substitute for diesel in direct injection diesel engines without any engine modification.     

Lipase immobilization and production of fatty acid methyl esters from canola oil using immobilized lipase

Lipase enzyme from Aspergillus oryzae (EC 3.1.1.3) was immobilized onto a micro porous polymeric matrix which contains aldehyde functional groups and methyl esters of long chain fatty acids (biodiesel) were synthesized by transesterification of crude canola oil using immobilized lipase. Micro porous polymeric matrix was synthesized from styrene-divinylbenzene (STY-DVB) copolymers by using high internal phase emulsion technique and two different lipases, Lipozyme TL-100L^® and Novozym 388^®, were used for immobilization by both physical adsorption and covalent attachment. Biodiesel production was carried out with semi-continuous operation. Methanol was added into the reactor by three successive additions of 1:4 M equivalent of methanol to avoid enzyme inhibition. The transesterification reaction conditions were as follows: oil/alcohol molar ratio 1:4; temperature 40 °C and total reaction time 6 h. Lipozyme TL-100L^® lipase provided the highest yield of fatty acid methyl esters as 92%. Operational stability was determined with immobilized lipase and it indicated that a small enzyme deactivation occurred after used repeatedly for 10 consecutive batches with each of 24 h. Since the process is yet effective and enzyme does not leak out from the polymer, the method can be proposed for industrial applications.     

Optimisation of base-catalysed transesterification of Simarouba glauca oil for biodiesel production

Biodiesel was prepared from the crude oil of Simarouba glauca by transesterification with methanol in the presence of KOH as a catalyst. The reaction parameters such as catalyst concentration, alcohol to oil molar ratio, temperature and rate of mixing were optimised for the production of Simarouba oil methyl ester. The yield of methyl esters from Simarouba oil under the optimal condition was 94–95%. Important fuel properties of methyl esters of Simarouba oil (biodiesel) was compared with ASTM and DIN EN 14214. The viscosity was found to be 4.68 Cst at 40°C and the flashpoint was 165°C.     

High quality biodiesel from yellow oleander (Thevetia peruviana) seed oil

Yellow oleander (Thevetia peruviana Schum.) seed oil has been investigated to produce biodiesel. Transesterification of the oil to biodiesel was carried out in methanol by batch reaction using a heterogeneous catalyst derived from the trunk of Musa balbisiana Colla (one variety of banana plant). 96 wt.% of the oil is converted to biodiesel at 32 °C in 3 h. The wt.% composition of the biodiesel is methyl oleate 43.72, methyl palmitate 23.28, methyl linoleate 19.85, methyl stearate 10.71 and methyl arachidate 2.41. Fuel properties conform to standards set for ASTM D6751, EN 14214, BS II and BS III, and in certain aspects better. The biodiesel is free from sulfur and has exhibited a high cetane number of 61.5.     

Pumpkin (Cucurbita pepo L.) seed oil as an alternative feedstock for the production of biodiesel in Greece

In recent years, the acceptance of fatty acid methyl esters (biodiesel) as a substitute to petroleum diesel has rapidly grown in Greece. The raw materials for biodiesel production in this country mainly include traditional seed oils (cotton seed oil, sunflower oil, soybean oil and rapeseed oil) and used frying oils. In the search for new low-cost alternative feedstocks for biodiesel production, this study emphasizes the evaluation of pumpkin seed oil. The experimental results showed that the oil content of pumpkin seeds was remarkably high (45%). The fatty acid profile of the oil showed that is composed primarily of linoleic, oleic, palmitic and stearic acids. The oil was chemically converted via an alkaline transesterification reaction with methanol to methyl esters, with a yield nearly 97.5 wt%. All of the measured properties of the produced biodiesel met the current quality requirements according to EN 14214. Although this study showed that pumpkin oil could be a promising feedstock for biodiesel production within the EU, it is rather difficult for this production to be achieved on a large scale.     

Opium poppy (Papaver somniferum L.) oil for preparation of biodiesel: Optimization of conditions

Opium poppy, Papaver somniferum L., is one of the ancient herbal medicines. In addition to this medical use of latex, opium that is extracted from the immature seed capsule, it is also used illegally for pleasure. It is being produced in great quantities in Turkey especially in Afyonkarahisar city. The seeds of opium poppy plant have high ratio oil content. The opium poppy seeds and oil of these seeds are purely used as an ingredient in production of bakery products. In this study, biodiesel evaluation of the opium poppy seeds that have a high oil ratio is aimed. Alkali catalyzed (NaOH) single-phase reaction was preferred to produce biodiesel from opium poppy oil. The parameters like catalyst concentration, methanol ratio, reaction temperature were optimized and biodiesel production was obtained with high yield in reaction time of 75 min. The methyl ester content in the opium poppy oil biodiesel was determined with Gas Chromatography–Frame Ionized Detector (GC–FID). In optimum conditions, methanol ratio and catalyst concentration was determined as 20 wt% and 0.5 wt%, respectively. The reaction temperature was optimized as 60 °C. Biodiesel was obtained from the opium poppy oil under optimum conditions. Some basic features of the produced methyl esters were determined.     

A bronsted basic ionic liquid as an efficient and environmentally benign catalyst for biodiesel synthesis from soybean oil and methanol

Morpholine basic ionic liquid was synthesized with N-methyl morpholine, N-butyl bromide, and KOH by two-step method and was used to catalyze the transesterification of soybean oil with methanol to biodiesel. The structure of the catalyst were examined by ¹H nuclear magnetic resonance. The effects of the molar ratio of methanol to oil, reaction temperature, and amount of catalyst on the biodiesel yield were investigated. Optimized biodiesel yield of 94.5% was achieved with catalyst amount of 3.0 wt%, and methanol to soybean oil molar ratio of 14:1 at reaction temperature of 60 °C for 6 h. The catalyst has maintained sustained activity after being employed to six cycles. The prepared biodiesel component was analyzed by gas chromatography-mass spectrometry (GC-MS) and the results showed that the biodiesel comprised of hexadecanoic acid methyl ester, 10, 13-octadecadienoic acid methyl ester, 9-octadecenoic acid methyl ester, and octadecanoic acid methyl ester, illustrating that fatty acids of soybean oil were converted completely.     

Application of response surface methodology for optimizing transesterification of Moringa oleifera oil: Biodiesel production

Response surface methodology (RSM), with central composite rotatable design (CCRD), was used to explore optimum conditions for the transesterification of Moringa oleifera oil. Effects of four variables, reaction temperature (25–65 °C), reaction time (20–90 min), methanol/oil molar ratio (3:1–12:1) and catalyst concentration (0.25–1.25 wt.% KOH) were appraised. The quadratic term of methanol/oil molar ratio, catalyst concentration and reaction time while the interaction terms of methanol/oil molar ratio with reaction temperature and catalyst concentration, reaction time with catalyst concentration exhibited significant effects on the yield of Moringa oil methyl esters (MOMEs)/biodiesel, p < 0.0001 and p < 0.05, respectively. Transesterification under the optimum conditions ascertained presently by RSM: 6.4:1 methanol/oil molar ratio, 0.80% catalyst concentration, 55 °C reaction temperature and 71.08 min reaction time offered 94.30% MOMEs yield. The observed and predicted values of MOMEs yield showed a linear relationship. GLC analysis of MOMEs revealed oleic acid methyl ester, with contribution of 73.22%, as the principal component. Other methyl esters detected were of palmitic, stearic, behenic and arachidic acids. Thermal stability of MOMEs produced was evaluated by thermogravimetric curve. The fuel properties such as density, kinematic viscosity, lubricity, oxidative stability, higher heating value, cetane number and cloud point etc., of MOMEs were found to be within the ASTM D6751 and EN 14214 biodiesel standards.     

Fuel properties of Brassica juncea oil methyl esters blended with ultra-low sulfur diesel fuel

Brassica juncea is a drought-tolerant member of the Brassicaceae plant family with high oil content and a short growing season that is tolerant of low quality soils. It was investigated as a feedstock for production of biodiesel along with evaluation of subsequent fuel properties, both neat and in blends with petroleum diesel fuel. These results were compared against relevant fuel standards such as ASTM D6751, EN 14214, ASTM D975, EN 590, and ASTM D7467. Crude B. juncea oil was extracted from unconditioned seeds utilizing a continuous tubular radial expeller. The oil was then chemically refined via degumming, neutralization and bleaching to render it amenable to direct homogeneous sodium methoxide-catalyzed transesterification. The principal fatty acid detected in B. juncea oil was erucic acid (44.1%). The resulting biodiesel yielded fuel properties compliant with the biodiesel standards with the exception of oxidative stability and kinematic viscosity in the case of EN 14214. Addition of tert-butylhydroquinone and blending with soybean oil-derived biodiesel ameliorated these deficiencies. The fuel properties of B5 and B20 blends of B. juncea oil methyl esters (BJME) in ultra-low sulfur (<15 ppm S) diesel (ULSD) fuel were within the ranges specified in the petrodiesel standards ASTM D975, EN 590 and ASTM D7467 with the exception of derived cetane number in the case of EN 590. This deficiency was attributed to the inherently low cetane number of the certification-grade ULSD, as it did not contain performance-enhancing additives. In summary, this study reports new fuel property data for BJME along with properties of B5 and B20 blends in ULSD. Such results will be useful for the development of B. juncea as an alternative source of biodiesel fuel.