Two-stage processes of homogenous catalysed transesterification of high free fatty acid crude oil of rubber seed

Biodiesel is a diesel replacement and renewable fuel that is manufactured from vegetable oils, animal fats or waste cooking oils. The production of biodiesel from edible oil is currently much more expensive than hydrocarbon-based fuel, due to the relatively high cost of edible oils. The cost of biodiesel can be reduced by using non-edible oils instead of edible oils. The purpose of the present study was to develop a method of esterification of non-edible oil like rubber seed oil (Hevea brasiliensis). The high free fatty acid content oil reacts quickly with alkaline catalysts to form soap, which prevents the separation of biodiesel and glycerol. A two-step process was used instead of the simple alkaline catalysed transesterification process. It consisted of an acid catalysed pre-processing followed by the usual alkaline catalysed process. The physical and chemical properties of biodiesel were analysed. The quantification of methyl esters were done by high-performance liquid chromatography.     

Biodiesel production from renewable feedstocks: Status and opportunities

The increased demand for energy, climate change, and energy security concerns has driven the research interest for the development of alternative fuel from plant origin. Biodiesel derived from plant oils, which include edible and non-edible oil have gained interest for the last two decades as alternative for diesel around the world. Among these plant origin oils more than 95% of biodiesel production feedstocks come from edible oils, because they are readily available in many regions. The major advantage of these feedstocks is the properties of biodiesel produced from them are suitable to be used as diesel fuel substitute. But the consequence is the increase demand of the feedstock for food as well as fuel. A sustainable alternative fuel should be derived from renewable non-food biomass sources. The main objective of this review is to give an overview on the synthesis of biodiesel through esterification and transesterification using non-edible oil resources which are available in India, and available processes for synthesis of biodiesel (acid-, base-catalyzed transesterification reactions (homogeneous and heterogeneous), their importance, and which is the commercial process also discussed here.     

Performance and emission evaluation of a diesel engine fueled with methyl esters of rubber seed oil

Recent concerns over the environment, increasing fuel prices and scarcity of its supply have promoted the interest in development of the alternative sources for petroleum fuels. At present, biodiesel is commercially produced from the refined edible vegetable oils such as sunflower oil, palm oil and soybean oil, etc. by alkaline-catalyzed esterification process. This process is not suitable for production of biodiesel from many unrefined non-edible vegetable oils because of their high acid value. Hence, a two-step esterification method is developed to produce biodiesel from high FFA vegetable oils. The biodiesel production method consists of acid-catalyzed pretreatment followed by an alkaline-catalyzed transesterification. The important properties of methyl esters of rubber seed oil are compared with other esters and diesel. Pure rubber seed oil, diesel and biodiesel are used as fuels in the compression ignition engine and the performance and emission characteristics of the engine are analyzed. The lower blends of biodiesel increase the brake thermal efficiency and reduce the fuel consumption. The exhaust gas emissions are reduced with increase in biodiesel concentration. The experimental results proved that the use of biodiesel (produced from unrefined rubber seed oil) in compression ignition engines is a viable alternative to diesel.     

Biodiesel from cotton seed oil and its effect on engine performance and exhaust emissions

The use of biodiesel is rapidly expanding around the world, making it imperative to fully understand the impacts of biodiesel on the diesel engine combustion process and pollutant formation. Biodiesel is known as the mono-alkyl-esters of long chain fatty acids derived from renewable feedstocks, such as, vegetable oils or animal fats, for use in compression ignition engines. Different parameters for the optimization of biodiesel production were investigated in the first phase of this study, while in the next phase of the study performance test of a diesel engine with neat diesel fuel and biodiesel mixtures were carried out. Biodiesel was made by the well known transesterification process. Cottonseed oil (CSO) was selected for biodiesel production. Cottonseed is non-edible oil, thus food versus fuel conflict will not arise if this is used for biodiesel production. The transesterification results showed that with the variation of catalyst, methanol or ethanol, variation of biodiesel production was realized. However, the optimum conditions for biodiesel production are suggested in this paper. A maximum of 77% biodiesel was produced with 20% methanol in presence of 0.5% sodium hydroxide. The engine experimental results showed that exhaust emissions including carbon monoxide (CO) particulate matter (PM) and smoke emissions were reduced for all biodiesel mixtures. However, a slight increase in oxides of nitrogen (NO_x) emission was experienced for biodiesel mixtures.     

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.     

Biodiesel production from non-edible plant oils

Because of biodegradability and nontoxicity biodiesel has become more attractive as alternative fuel. Biodiesel is produced mainly from vegetable oils by transesterification of triacylglycerols. From economic and social reasons, edible oils should be replaced by lower-cost and reliable feedstocks for biodiesel production such as non-edible plant oils. This paper reviews various methods for biodiesel production from common non-edible oils employing alcoholysis reactions. The aim of this paper is to present the possibilities of the use of non-edible oils into biodiesel production, to consider the various methods for treatment of non-edible oils and to emphasize the influence of the operating and reaction conditions on the process rate and the ester yield. The special attention is paid to the possibilities of optimization, kinetics and improvement of biodiesel production from non-edible oils.     

Comparison of biodiesel production from crude Jatropha oil and Krating oil by supercritical methanol transesterification

This work compared the production of biodiesel from two different non-edible oils with relatively high acid values (Jatropha oil and Krating oil). Using non-catalytic supercritical methanol transesterification, high methyl ester yield (85–90%) can be obtained in a very short time (5–10 min). However, the dependence of fatty acid methyl ester yield on reaction conditions (i.e., temperature and pressure) and the optimum conditions were different by the source of oils and were correlated to the amount of free fatty acids (FFAs) and unsaturated fatty acid content in oils. Krating oil, which has higher FFAs and unsaturated fatty acid content, gave higher fatty acid methyl ester yield of 90.4% at 260 °C, 16 MPa, and 10 min whereas biodiesel from Jatropha oil gave fatty acid methyl ester yield of 84.6% at 320 °C, 15 MPa and 5 min using the same molar ratio of methanol to oil 40:1. The product quality from crude Krating oil met the biodiesel standard. Pre-processing steps such as degumming or oil purification are not necessary.     

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.     

Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: An optimized process

Response surface methodology (RSM) based on central composite rotatable design (CCRD) was used to optimize the three important reaction variables—methanol quantity (M), acid concentration (C) and reaction time (T) for reduction of free fatty acid (FFA) content of the oil to around 1% as compared to methanol quantity (M′) and reaction time (T′) and for carrying out transesterification of the pretreated oil. Using RSM, quadratic polynomial equations were obtained for predicting acid value and transesterification. Verification experiments confirmed the validity of both the predicted models. The optimum combination for reducing the FFA of Jatropha curcas oil from 14% to less than 1% was found to be 1.43% v/v H₂SO₄ acid catalyst, 0.28 v/v methanol-to-oil ratio and 88-min reaction time at a reaction temperature of 60 °C as compared to 0.16 v/v methanol-to-pretreated oil ratio and 24 min of reaction time at a reaction temperature of 60 °C for producing biodiesel. This process gave an average yield of biodiesel more than 99%. The fuel properties of jatropha biodiesel so obtained were found to be comparable to those of diesel and confirming to the American and European standards.     

Biodiesel production from mixture of mahua and simarouba oils with high free fatty acids

A suitable process comprising acid pretreatment followed by main base transesterification reaction was developed to produce biodiesel from mixture of Mahua (M) and Simarouba (S) oils with high free fatty acids (FFA). The acid pretreatment reduced the high FFAs of the mixture of oils to around 1% which were then transesterified with methanol and KOH as catalyst at a reaction temperature of 60 °C. A genetic algorithm coupled with artificial neural network (ANN-GA) model to obtain the best pretreatment process parameters for bringing down the FFA level of individual vegetable oils to around 1% was modified to include the wide range of oils and validated for mixtures of M and S oils. The quality of biodiesel produced was analyzed by gas chromatography (GC), which indicated above 90% ester conversion. The fuel properties of biodiesel were found to be comparable to diesel and were conforming to the latest biodiesel standards.     

Analysis and evaluation of operating variables for the yield of Karanja and neem oil-based biodiesel production

The aim of this research is to present the possibilities of the use of non-edible oils in biodiesel production, to consider the various methods for treatment of non-edible oils and to emphasise the influence of the operating and reaction conditions on the process rate and the ester yield. Because of biodegradability and non-toxicity biodiesel has become more attractive as alternative fuel. Biodiesel is produced mainly from vegetable oils by transesterification. For economic and social reasons, edible oils should be replaced by lower-cost and reliable feedstock for biodiesel production, such as non-edible plant oils. In this work biodiesel is produced from neem and Karanja by using butanol, propanol, ethanol and methanol as alcohols and KOH and NaOH as alkali catalysts by the transesterification process. The aim of this research is to analyse the different reaction parameters such as catalyst concentration, type of catalyst, types of alcohol, alcohol to oil molar ratio, reaction time and reaction temperature on the yield of biodiesel from non-edible oils. The maximum yield obtained was 95% with Karanja as oil with methanol and KOH as alkali catalyst at oil to alcohol molar ratio of 6:1 in 1 h at 60°C. Special attention is paid to the possibilities of producing biodiesel from non-edible oils.     

New Options for Conversion of Vegetable Oils to Alternative Fuels

Biodiesel from transesterification of vegetable oils is an excellent alternative fuel. There is, however, a need to develop a direct process for conversion of vegetable oils into gasoline-competitive biodiesel and other petroleum products. Methyl esters of vegetable oils have several outstanding advantages among other new-renewable and clean engine fuel alternatives. The purpose of the transesterification process is to lower the viscosity of vegetable oil. Compared to No. 2 diesel fuel, all of the vegetable oils are much more viscous, whereas methyl esters of vegetable oils are slightly more viscous. The methyl esters are more volatile than those of the vegetable oils. Conversion of vegetable oils to useful fuels involves the pyrolysis and catalytic cracking of the oils into lower molecular products. Pyrolysis produces more biogasoline than biodiesel fuel. Soap pyrolysis products of vegetable oils can be used as alternative diesel engine fuel. The soaps obtained from the vegetable oils can be pyrolyzed into hydrocarbon-rich products. Zinc chloride catalyst contributed greatly to high amounts of hydrocarbons in the liquid product. The yield of ZnCl ₂ catalytic conversion of the soybean oil reached the maximum 79.9% at 660 K.     

Biodiesel production by esterification of palm fatty acid distillate

Production of fatty acid methyl ester (FAME) from palm fatty acid distillate (PFAD) having high free fatty acids (FFA) was investigated in this work. Batch esterifications of PFAD were carried out to study the influence of: including reaction temperatures of 70–100 °C, molar ratios of methanol to PFAD of 0.4:1–12:1, quantity of catalysts of 0–5.502% (wt of sulfuric acid/wt of PFAD) and reaction times of 15–240 min. The optimum condition for the continuous esterification process (CSTR) was molar ratio of methanol to PFAD at 8:1 with 1.834 wt% of H₂SO₄ at 70 °C under its own pressure with a retention time of 60 min. The amount of FFA was reduced from 93 wt% to less than 2 wt% at the end of the esterification process. The FAME was purified by neutralization with 3 M sodium hydroxide in water solution at a reaction temperature of 80 °C for 15 min followed by transesterification process with 0.396 M sodium hydroxide in methanol solution at a reaction temperature of 65 °C for 15 min. The final FAME product met with the Thai biodiesel quality standard, and ASTM D6751-02.     

Activity of homogeneous and heterogeneous catalysts,spectroscopic and chromatographic characterization of biodiesel: A review

Biofuel has got tremendous attraction for the last decade as an alternative source of energy. Bioethanol and biodiesel are two main products of first generation biofuel. Biodiesel is chemically fatty acid methyl esters prepared from various edible and non-edible oils. It has been used as a substitute to mineral diesel during the last decade. This review is about generation, transesterification, factors affecting transesterification, catalysts (homogeneous and heterogeneous) and physico-chemical characterization of biodiesel by chromatographic and spectroscopic techniques. The alkaline homogeneous catalysts (NaOH or KOH) have been used on commercial scale for production of biodiesel because these are cheap and reaction occurs in less time. The heterogeneous catalysts such as metal oxides, e.g., CaO, MgO, SrO, ZnO, La₂O₃, Mg–Al hydrolalcite have been used for transesterification of vegetable oil due to their easy separation and reuse but these catalysts take more time for completion of reaction. The yield of biodiesel may be affected by alcohol/oil ratio, concentration of catalyst, time required for reaction, temperature free fatty acid moisture. The prepared biodiesel has been characterized by chromatographic techniques like gas chromatography, gas chromatography–mass spectroscopy, high performance liquid chromatography and spectroscopic techniques like nuclear magnetic resonance and infrared spectroscopy.     

An experimental comparison of transesterification process with different alcohols using acid catalysts

Vegetable oils and animal fats in their raw form have high viscosities that makes them unsuitable as fuels for diesel engines. Transesterification is one of the well-known processes by which fats and oils are converted into biodiesel. The reaction often makes use of acid/base catalyst. If the material possesses high free fatty acid then acid catalyst gives better results. In the present investigation, Mahua oil having 14% free fatty acid was transesterifed to obtain biodiesel using acid catalysts with different alcohols. The alcohols used were Methanol, Ethanol and Butanol. The objective of using higher alcohol is to find their effect on ester yield. The process optimization was made based on the maximum ester yield. The results show that transesterification with butanol gives a better yield compared to methanol and ethanol. The transesterification results show that higher catalyst concentration by 6–10% Vol. produces biodiesel with lower viscosity, lower specific gravity with a higher yield (short reaction time of 5 hours). The best process condition with butanol was found to be 6% Vol. of sulfuric acid with 150% excess butanol, which gave an yield of around 95.4% in a reaction time of 5 hours. The prepared biodiesels were tested as per the standard and were found to be satisfactory.     

Biodiesel fuel production with solid amorphous-zirconia catalysis in fixed bed reactor

Amorphous zirconia catalysts, titanium-, aluminum-, and potassium-doped zirconias, were prepared and evaluated in the transesterification of soybean oil with methanol at 250 °C, and the esterification of n-octanoic acid with methanol at 175–200 °C. Titanium- and aluminum-doped zirconias are promising solid catalysts for the production of biodiesel fuels from soybean oil because of their high performance, with over 95% conversion in both of the esterifications.     

Diesterol: An environment-friendly IC engine fuel

Diesterol is a new specific term which denotes a mixture of fossil diesel fuel (D), vegetable oil methyl ester called biodiesel (B) and plant derived ethanol (E). In the context of the present paper, this term refers specifically to the combination of diesel fuel, bioethanol produced from potato waste, dehydrated in a vapor phase using 3A Zeolite, and sunflower methyl ester produced through transesterification. The mixture of DBE, i.e. diesterol, was patented under the Iranian patent No. 39407, dated 12-3-2007. The main purpose of this research work was to reduce engine exhaust NO_x, CO, HC and smoke emissions due to application of biofuel and the increase of fuel oxygen content. It was needed to prepare suitable low cost and renewable additives. The diesterol properties such as pour point, viscosity, flash point, copper strip corrosion, ash content, sulfur content and cetane number were determined experimentally. The optimum ratio of bioethanol and biodiesel was found to be 40/60 considering fuel oxygen content, fuel price and mixture properties. Bioethanol was added to enhance the oxygenated component in the fuel, while the sunflower methyl ester was added to maintain the fuel stability at low temperatures. The parameters considered for investigation are the engine power, torque, specific fuel consumption and exhaust emissions for various mixture proportions. The experimental results showed that bioethanol plays an important role in determining the flash point of the blends. By adding 3% bioethanol to diesel and sunflower methyl ester, the flash point was reduced by 16 °C. The viscosity of the blend was also reduced by increasing the amount of bioethanol. The sulfur content of bioethanol and sunflower methyl ester is very low compared to diesel fuel. The sulfur content of diesel is 500 ppm whereas that of bioethanol and sunflower methyl ester is 0 and 15 ppm, respectively. This lower sulfur content is another factor enhancing the use of fuel blends in diesel engines. The bioethanol and sunflower methyl ester combination has sulfur content less than 20 ppm. The maximum power and torque using diesel fuel were 17.75 kW and 64.2 Nm at 3600 and 2400 rpm, respectively. Adding oxygenated compounds to the new blend seems to slightly reduce the engine power and torque and increased the average sfc for various speeds. The experimental measurement and observation of smoke concentration, NO_x, CO and HC concentration indicated that both of these pollutants reduced by increasing the biofuel composition of diesterol throughout the engine operating range.     

Emission analysis of Azolla methyl ester with BaO nano additives for IC engine

The aim of this work is to decrease emissions in diesel engines fueled with diesel and algae biodiesel blends and also addition of BiO nanoparticles. Azolla algae can be used to produce biodiesel, because of high oil content. The biodiesel was prepared by using Azolla algae non-edible oil through transesterification process. In the present study, the BaO nano additives into the algae oil-based methyl ester blend and its diesel blends are analyzed the emission characteristic at different load. Addition of BaO nanoparticle was a strategy to reduce emission (CO, HC, and O₂) of the biodiesel.     

Lithium ion impregnated calcium oxide as nano catalyst for the biodiesel production from karanja and jatropha oils

Lithium impregnated calcium oxide has been prepared by wet impregnation method in nano particle form as supported by powder X-ray diffraction and transmission electron microscopy. Basic strength of the same was measured by Hammett indicators. Calcium oxide impregnated with 1.75 wt% of lithium was used as solid catalyst for the transesterification karanja and jatropha oil, containing 3.4 and 8.3 wt% of free fatty acids, respectively. The reaction parameters, viz., reaction temperature, alcohol to oil molar ratio, free fatty acid contents, amount of catalyst and amount of impregnated lithium ion in calcium oxide support, have been studied to establish the most suitable condition for the transesterification reaction. The complete transesterification of karanja and jatropha oils was achieved in 1 and 2 h, respectively, at 65 °C, utilizing 12:1 molar ratio of methanol to oil and 5 wt% (catalyst/oil, w/w) of catalyst. Few physicochemical properties of the prepared biodiesel samples have been studied and compared with standard values.     

Evaluation of the performance of biodiesel from waste vegetable oil in a flame tube furnace

This work presents a theoretical and experimental study of the biodiesel (ethyl ester from a waste vegetable oil) performance in a flame tube furnace. The heat transfer rate was analysed in several sections along the furnace and the performance of the biodiesel was compared to that of diesel oil. The flow of heat from the burn of each fuel in the direction of the walls of the combustion chamber was evaluated under the same fuel injection pressure. The peak of the heat transfer occurred around 0.45 m far from the fuel injection nozzle in a 0.305 m inner diameter combustion chamber. The diesel oil showed a higher heat transfer rate in most parts exposed to the flame. In the region where the body of the flame is not present, the heat transfer of biodiesel becomes higher.