Biodiesel from corn germ oil catalytic and non-catalytic supercritical methanol transesterification

Transesterifications of grain of corn oil samples in KOH catalytic and in supercritical methanol were studied without using any catalyst. Biodiesel, an alternative biodegradable diesel fuel, is derived from triglycerides by transesterification with methanol and ethanol. The transesterification reaction is affected by the molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. It was observed that increasing the reaction temperature, especially to supercritical temperatures, had a favorable influence on methyl ester (biodiesel) conversion. The molar ratio of methanol to corn germ oil is also one of the most important variables affecting the yield of methyl esters. Higher molar ratios result in greater ester production in a shorter time. In the transesterification, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalysts, and reduces catalyst effectiveness, all of which result in a low conversion.     

Biodiesel production through the use of different sources and characterization of oils and their esters as the substitute of diesel: A review

The world is confronted with the twin crises of fossil fuel depletion and environmental degradation. The indiscriminate extraction and consumption of fossil fuels have led to a reduction in petroleum reserves. Petroleum based fuels are obtained from limited reserves. These finite reserves are highly concentrated in certain region of the world. Therefore, those countries not having these resources are facing a foreign exchange crisis, mainly due to the import of crude petroleum oil. Hence it is necessary to look for alternative fuels, which can be produced from materials available within the country. Although vegetative oils can be fuel for diesel engines, but their high viscosities, low volatilities and poor cold flow properties have led to the investigation of its various derivatives. Among the different possible sources, fatty acid methyl esters, known as Biodiesel fuel derived from triglycerides (vegetable oil and animal fates) by transesterification with methanol, present the promising alternative substitute to diesel fuels and have received the most attention now a day. The main advantages of using Biodiesel are its renewability, better quality exhaust gas emission, its biodegradability and the organic carbon present in it is photosynthetic in origin. It does not contribute to a rise in the level of carbon dioxide in the atmosphere and consequently to the green house effect. This paper reviews the source of production and characterization of vegetable oils and their methyl ester as the substitute of the petroleum fuel and future possibilities of Biodiesel production.     

Biodiesel production from mixed soybean oil and rapeseed oil

The biodiesel (fatty acid methyl esters, FAME) was prepared by transesterification of the mixed oil (soybean oil and rapeseed oil) with sodium hydroxide (NaOH) as catalyst. The effects of mole ratio of methanol to oil, reaction temperature, catalyst amount and reaction time on the yield were studied. In order to decrease the operational temperature, a co-solvent (hexane) was added into the reactants and the conversion efficiency of the reaction was improved. The optimal reaction conditions were obtained by this experiment: methanol/oil mole ratio 5.0:1, reaction temperature 55 °C, catalyst amount 0.8 wt.% and reaction time 2.0 h. Under the optimum conditions, a 94% yield of methyl esters was reached ∼94%. The structure of the biodiesel was characterized by FT-IR spectroscopy. The sulfur content of biodiesel was determined by Inductively Coupled Plasma emission spectrometer (ICP), and the satisfied result was obtained. The properties of obtained biodiesel from mixed oil are close to commercial diesel fuel and is rated as a realistic fuel as an alternative to diesel. Production of biodiesel has positive impact on the utilization of agricultural and forestry products.     

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.     

Biodiesel production from refined sunflower vegetable oil over KOH/ZSM5 catalysts

ZSM5 zeolite was impregnated with different KOH loadings (15 wt.%, 25 wt.% and 35 wt.%) to prepare a series of KOH/ZSM5 catalysts. The catalysts were calcined at 500 °C for 3 h and then characterized by N₂ adsorption–desorption and X-ray diffraction (XRD) techniques. The catalysts were tested in the transesterification reaction in a batch reactor at 60 °C and under atmospheric pressure. It was found that KOH/ZSM5 with 35 wt.% loading showed the best catalytic performance. The best reaction conditions in the presence of KOH/ZSM5 (35 wt.%) were determined while modifying the catalyst to oil ratio and the reaction time. The highest methyl ester yield (>95%) was obtained for a reaction time of 24 h, a catalyst to oil ratio of 18 wt.%, and a methanol to oil molar ratio of 12:1. The properties of produced biodiesel complied with the ASTM specifications. The catalytic stability test showed that 35KOH/ZSM5 was stable for 3 consecutive runs. Characterization of the spent catalyst indicated that a slight deactivation might be due to the leaching of potassium oxides active sites.     

Use of vegetable oils as I.C. engine fuels—A review

The increasing industrialization and motorization of the world has led to a steep rise for the demand of petroleum products. Petroleum based fuels are obtained from limited reserves. These finite reserves are highly concentrated in certain regions of the world. Therefore, those countries not having these resources are facing a foreign exchange crisis, mainly due to the import of crude oil. Hence, it is necessary to look for alternative fuels, which can be produced from materials available within the country. In addition, the use of vegetable oil as fuel is less polluting than petroleum fuels. This paper reviews the production and characterization of vegetable oil as well as the experimental work carried out in various countries in this field. In addition, the scope and challenges being faced in this area of research are clearly described.     

Biodiesel fuels from palm oil via the non-catalytic transesterification in a bubble column reactor at atmospheric pressure: A kinetic study

Biodiesel has become more attractive recently because of its environmental benefits and the fact that it is made from renewable resources. Transesterification of vegetable oils with short-chain alcohol has long been a preferred method for producing biodiesel fuel. A new reactor was developed to produce fatty acid methyl esters (FAME) by blowing bubbles of superheated methanol vapor continuously into vegetable oil without using any catalysts. A kinetic study on the non-catalytic transesterification of palm oil was made in a reactor without stirring at atmospheric pressure. The effects of reaction temperatures (523, 543, and 563 K) on the rate constant, conversion, yield of methyl esters (ME) and composition of the reaction product under semi-batch mode operation are investigated. The activation energy and the frequency factor values of the transesterification reaction obtained in this experiment are 31 kJ/mol and 4.2, respectively. The optimum reaction temperature which gives the highest ME content (95.17% w/w) in the reaction product is 523 K, while the rate constant of the total system increased with reaction temperature.     

Biodiesel production by ultrasound-assisted transesterification: State of the art and the perspectives

In the present paper state-of-the art and perspectives of ultrasound-assisted (UA) biodiesel production from different oil-bearing materials using acid, base and enzyme catalysts are critically discussed. The ultrasound action in biodiesel production is primarily based on the emulsification of the immiscible liquid reactants by microturbulence generated by radial motion of cavitation bubbles and the physical changes on the surface texture of the solid catalysts generating new active surface area. The importance of ultrasound characteristics and other process variables for the biodiesel yield and the reaction rate is focused on. UA transesterification is compared with other techniques for biodiesel production. Several different developing methods reducing the biodiesel production costs such as the optimization of process factors, the development of the process kinetic models, the use of phase transfer catalysts, the application of the continuous process, the design of novel types of ultrasonic reactors and the in situ ultrasound application in transesterification of oily feedstocks are also discussed.     

Biodiesel production from crude rice bran oil and properties as fuel

This research reported on the successfully production of biodiesel by transesterification of crude rice bran oil (RBO). The process included three-steps. Firstly, the acid value of RBO was reduced to below 1 mg KOH/g by two-steps pretreatment process in the presence of sulfuric acid catalyst. Secondly, the product prepared from the first process was carried out esterification with an alkaline catalyst. The influence of four variables on conversion efficiency to methyl ester, i.e., methanol/RBO molar ratio, catalyst amount, reaction temperature and reaction time, was studied at this stage. The content of methyl ester was analyzed by chromatographic analysis. Through orthogonal analysis of parameters in a four-factor and three-level test, the optimum reaction conditions for the transesterification were obtained: methanol/RBO molar ratio 6:1, usage amount of KOH 0.9% w/w, reaction temperature 60 °C and reaction time 60 min. In the third step, methyl ester prepared from the second processing step was refined to become biodiesel. Fuel properties of RBO biodiesel were studied and compared according to ASTM D6751-02 and DIN V51606 standards for biodiesel. Most fuel properties complied with the limits prescribed in the aforementioned standards. The consequent engine test showed a similar power output compared with regular diesel but consumption rate was slightly higher. Emission tests showed a marked decrease in CO, HC and PM, however, with a slight increase in NO_X.     

Inorganic heterogeneous catalysts for biodiesel production from vegetable oils

Biofuels are renewable solutions to replace the ever dwindling energy reserves and environmentally pollutant fossil liquid fuels when they are produced from low cost sustainable feedstocks. Biodiesel is mainly produced from vegetable oils or animal fats by the method of transesterification reaction using catalysts. Homogeneous catalysts are conventionally used for biodiesel production. Unfortunately, homogeneous catalysts are associated with problems which might increase the cost of production due to separation steps and emission of waste water. Inorganic heterogeneous catalysts are potentially low cost and can solve many of the problems encountered in homogeneous catalysts. Many solid acid and base inorganic catalysts have been studied for the transesterification of various vegetables oils. The work of many researchers on the development of active, tolerant to water and free fatty acids (FFA), as well as stable inorganic catalysts for biodiesel production from vegetable oils are reviewed and discussed.     

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.     

Performance evaluation of a vegetable oil fuelled compression ignition engine

Fuel crisis because of dramatic increase in vehicular population and environmental concerns have renewed interest of scientific community to look for alternative fuels of bio-origin such as vegetable oils. Vegetable oils can be produced from forests, vegetable oil crops, and oil bearing biomass materials. Non-edible vegetable oils such as linseed oil, mahua oil, rice bran oil, etc. are potentially effective diesel substitute. Vegetable oils have high-energy content. This study was carried out to investigate the performance and emission characteristics of linseed oil, mahua oil, rice bran oil and linseed oil methyl ester (LOME), in a stationary single cylinder, four-stroke diesel engine and compare it with mineral diesel. The linseed oil, mahua oil, rice bran oil and LOME were blended with diesel in different proportions. Baseline data for diesel fuel was collected. Engine tests were performed using all these blends of linseed, mahua, rice bran, and LOME. Straight vegetable oils posed operational and durability problems when subjected to long-term usage in CI engine. These problems are attributed to high viscosity, low volatility and polyunsaturated character of vegetable oils. However, these problems were not observed for LOME blends. Hence, process of transesterification is found to be an effective method of reducing vegetable oil viscosity and eliminating operational and durability problems. Economic analysis was also done in this study and it is found that use of vegetable oil and its derivative as diesel fuel substitutes has almost similar cost as that of mineral diesel.     

Synthesis of biodiesel from vegetable oils wastewater sludge by in-situ subcritical methanol transesterification: Process evaluation and optimization

Biodiesel are gaining increased public and scientific attention as an alternative to petroleum diesel fuel, driven by factors such as oil price spikes, energy security and environmental concerns. In this study, low grade wastewater sludge originated from wastewater treatment unit of vegetable oil factory as a viable alternative lipid source for biodiesel production was evaluated. The lipid mass fraction of the dry and ash-free sludge was 12.44 ± 0.87%, which mainly comprised of C16–C18 fatty acids. The in-situ transesterification process under subcritical water and methanol conditions was applied as a green pathway to convert lipids into fatty acid methyl esters (FAMEs). The reaction parameters investigated were temperatures (155–215 °C), pressures (5.5–6.5 MPa) and methanol to lipid mass ratios (1:1, 5:1 and 9:1). The highest FAME yield of 92.67 ± 3.23% was obtained at 215 °C, 6.5 MPa and methanol to lipid mass ratio of 5:1. Statistical analysis based on response surface methodology in 3-factor-3-level central composite designed experiments and analysis of variance were applied to examine the relation between input parameters and the response and to locate the optimum condition. Results showed that 98% of the variability in the response could be adequately explained by the second-order polynomial model. The optimum FAME yield (90.37%) was obtained at 215 °C, 6.5 MPa and methanol to lipid mass ratio of 5.12:1. Experimental validation (N = 3) demonstrated satisfactory agreement between the observed and predicted values with an error of at most 3.3%.     

Evaluation of the dielectric properties of biodiesel fuels produced from different vegetable oil feedstocks through electrochemical impedance spectroscopy

Biodiesel fuels were prepared from different vegetable oil sources (canola, soybean, sunflower, and corn) and studied through electrochemical impedance spectroscopy. The dielectric constant from these biofuels evidenced no important dependence on feedstock, suggesting basically no change in fuels' polarity from varying the raw materials. In a different way, huge variations of the electrical resistivity and relaxation frequency were found when comparing among the studied biodiesels. Our findings demonstrate that these variations are closely associated with changes in the biodiesel viscosity, which is known to modulate charge mobility and was feedstock dependent. Accordingly, the impedance spectroscopy is here revealed to be a sensitive, alternative and reliable analytical approach for distinguishing among different feedstock-related biodiesels and monitoring certain biofuels' properties, like viscosity and interrelated parameters, usually connected with fatty acid structural profiles in biodiesel fuels.     

Biodiesel production from olive–pomace oil of steam-treated alperujo

Recently interest has been revived in the use of plant-derived waste oils as renewable replacements for fossil diesel fuel. Olive–pomace oil (OPO) extracted from alperujo (by-product of processed olives for olive oil extraction), and produced it in considerable quantities throughout the Mediterranean countries, can be used for biodiesel production. A steam treatment of alperujo is being implemented in OPO extraction industry. This steam treatment improves the solid–liquid separation by centrifugation and facilitates the drying for further extraction of OPO. It has been verified that the steam treatment of this by-product also increases the concentration of OPO in the resulting treated solid, a key factor from an economic point of view. In the present work, crude OPO from steam-treated alperujo was found to be good source for producing biodiesel. Oil enrichment, acidity, biodiesel yield and fatty acid methyl ester composition were evaluated and compared with the results of the untreated samples. Yields and some general physicochemical properties of the quality of biodiesel were also compared to those obtained with other oils commonly used in biodiesel production. As for biodiesel yield no differences were observed. A transesterification process which included two steps was used (acid esterification followed by alkali transesterification). The maximum biodiesel yield was obtained using molar ratio methanol/triglycerides 6:1 in presence of sodium hydroxide at a concentration of 1% (w/w), reaction temperature 60 °C and reaction time 80 min. Under these conditions the process gave yields of about 95%, of the same order as other feedstock using similar production conditions.     

Biodiesel production from residual oils recovered from spent bleaching earth

This work was to study technical and economic feasibilities of converting residual oils recovered from spent bleaching earth generated at soybean oil refineries into useable biodiesel. Experimental results showed that fatty acids in the SBE residual oil were hexadecenoic acid (58.19%), stearic acid (21.49%) and oleic acid (20.32%), which were similar to those of vegetable oils. The methyl ester conversion via a transesterification process gave a yield between 85 and 90%. The biodiesel qualities were in reasonable agreement with both EN 14214 and ASTM D6751 standards. A preliminary financial analysis showed that the production cost of biodiesel from SBE oils was significantly lower than the pre-tax price of fossil diesel or those made of vegetable oils or waste cooking oils. The effects of the crude oil price and the investment on the production cost and the investment return period were also conducted. The result showed that the investment would return faster at higher crude oil price.     

Tetramethylguanidine as an efficient catalyst for transesterification of waste frying oils

New catalysts and environmentally benign processes may lead to methyl ester production with improved properties at competitive costs. In this study, transesterification of waste frying oil to biodiesel using tetramethylguanidine as a strong base catalyst was conducted. The influence of catalyst concentration and of certain physicochemical properties of waste frying oil was investigated. Experiments were also performed on a semi-refined cottonseed oil for comparison purposes. Experimental results showed that methyl ester conversion was dependent on the type of oil, catalyst concentration and reaction time.     

Characterization and transesterification of Iranian bitter almond oil for biodiesel production

In the present work the production of biodiesel using bitter almond oil (BAO) in a potassium hydroxide catalyzed transesterification reaction was investigated. The BAO was obtained from resources available in Iran and its physical and chemical properties including iodine value, acid value, density, kinematic viscosity, fatty acid composition and mean molecular weight were specified. The low acid value of BAO (0.24 mg KOH/g) indicated that the pretreatment of raw oil with acid was not required. The fatty acid content analysis confirmed that the contribution of unsaturated fatty acids in the BAO is high (84.7 wt.%). Effect of different parameters including methanol to oil molar ratio (3–11 mol/mol), potassium hydroxide concentration (0.1–1.7% w/w) and reaction temperature (30–70 °C) on the production of biodiesel were investigated. The results indicated that these parameters were important factors affecting the tranesterification reaction. The fuel properties of biodiesel including iodine value, acid value, density, kinematic viscosity, saponification value, cetane number, flash point, cloud point, pour point and distillation characteristics were measured. The properties were compared with those of petroleum diesel, EN 14214 and ASTM 6751 biodiesel standards and an acceptable agreement was observed.     

Kinetic models of transesterification of vegetable oils with methyl ethanoate under sub/supercritical conditions

Environmentally friendly fuel is produced from plants and trees and can fix CO₂ in a season or yearly depending on the crop yield. The growth of fast food restaurants in the State of Kuwait has resulted in the accumulation of large quantities of partially oxidized vegetable oil used in frying burgers, breaded chicken pieces, and chips. In this publication, kinetics of the transesterification reaction is discussed in great depth to understand the true mechanism and to determine the optimum conditions for the maximum yield for the commercially viable esterification process of used oil/fat with supercritical methyl ethanoate.     

Free lipase-catalyzed biodiesel production from phospholipids-containing oils

Free lipase-catalyzed biodiesel has drawn more and more attentions in recent years because of its advantages of lower cost and faster reaction rate. Utilizing free lipase to convert low quality oils such as crude vegetable oils and microbial oils is beneficial to further reduce the cost of biodiesel production. However, these oils typically contain some amount of phospholipids. Phospholipids were found to affect the lipase-catalyzed process and further influence the enzyme's thermal stability in biodiesel production process. In this work, free lipase NS81006-mediated biodiesel production from oils containing phospholipids at varied temperature was investigated systematically. It was found that the presence of phospholipids at high temperature led to a decreased fatty acid methyl esters (FAME) yield and poor reuse stability of the lipase during NS81006-catalyzed biodiesel production process. The higher the temperature was, the greater negative effect was observed. This inhibitory effect was found to be mainly caused by the coexistence of phospholipids and methanol in the system. Based on this finding, a novel two-step enzyme-mediated process was further developed, with which the above-mentioned inhibitory effect was eliminated, and a FAME yield of 95.1% could be obtained with oils containing 10% phospholipids even at high temperature of 55 °C.