Synthesis of biodiesel from edible and non-edible oils in supercritical alcohols and enzymatic synthesis in supercritical carbon dioxide

Biodiesel is an attractive alternative fuel because it is environmentally friendly and can be synthesized from edible and non-edible oils. The synthesis of biodiesel from edible oils like palm oil and groundnut oil and from crude non-edible oils like Pongamia pinnata and Jatropha curcas was investigated in supercritical methanol and ethanol without using any catalyst from 200 to 400 °C at 200 bar. The variables affecting the conversion during transesterification, such as molar ratio of alcohol to oil, temperature and time were investigated in supercritical methanol and ethanol. Biodiesel was also synthesized enzymatically with Novozym-435 lipase in presence of supercritical carbon dioxide. The effect of reaction variables such as temperature, molar ratio, enzyme loading and kinetics of the reaction was investigated for enzymatic synthesis in supercritical carbon dioxide. Very high conversions (>80%) were obtained within 10 min and nearly complete conversions were obtained at within 40 min for the synthesis of biodiesel in supercritical alcohols. However, conversions of only 60–70% were obtained in the enzymatic synthesis even after 8 h.     

Process optimization for biodiesel production from Jatropha, Karanja and Polanga oils

Petroleum sourced fuels is now widely known as non-renewable due to fossil fuel depletion and environmental degradation. Renewable, carbon neutral, transport fuels are necessary for environmental and economic sustainability. Biodiesel derived from oil crops is a potential renewable and carbon neutral alternative to petroleum fuels. Chemically, biodiesel is monoalkyl esters of long chain fatty acids derived from renewable feed stock like vegetable oils and animal fats. It is produced by transesterification in which, oil or fat is reacted with a monohydric alcohol in presence of a catalyst. The process of transesterification is affected by the mode of reaction condition, molar ratio of alcohol to oil, type of alcohol, type and amount of catalysts, reaction time and temperature and purity of reactants. In the present paper various methods of preparation of biodiesel from non-edible filtered Jatropha (Jatropha curcas), Karanja (Pongamia pinnata) and Polanga (Calophyllum inophyllum) oil have been described. Mono esters (biodiesel) produced and blended with diesel were evaluated. The technical tools and processes for monitoring the transesterification reactions like TLC, GC and HPLC have also been used.     

Optimization of two step karanja biodiesel synthesis under microwave irradiation

The free fatty acid of crude karanja oil (Pongamia pinnata) was reduced and biodiesel was synthesized from pretreated oil under microwave irradiation. The process variables such as irradiation time, methanol-oil ratio and sulfuric acid concentration for pretreatment step; irradiation time, methanol-oil ratio and KOH concentration were optimized through the Box-Behnken experimental design. The free fatty acid of crude karanja oil was reduced to 1.11 ± 0.07% with an optimal combination of 190 s irradiation time (180 W), 33.83 (w/w)% methanol-oil ratio and 3.73 (w/w)% sulfuric acid concentration. An optimal combination of 150 s irradiation time, 33.4 (w/w)% methanol-oil ratio and 1.33 (w/w)% KOH concentration yielded 89.9 ± 0.3% biodiesel. The model was validated by conducting experiments at optimal design conditions. The present work confirmed that the microwave energy has a significant effect on esterification and transesterification reaction.     

Two-step biodiesel production from Jatropha curcas crude oil using SiO2·HF solid catalyst for FFA esterification step

A high quality biodiesel was produced from Mexican Jatropha curcas crude oil (JCCO) by a two step catalyzed process. The free fatty acids (FFA) were first esterified with methanol, catalyzed by a solid catalyst: SiO₂ pretreated with HF. The catalyst showed a high number of Lewis acid surface sites, and no CO₂ or H₂O adsorption activity. This catalyst showed a high FFA esterification activity and high stability. After 30 esterification runs, the catalyst activity remained unchanged. During the second step, the triglycerides present in the JCCO were transesterified with methanol catalyzed by NaOH. The chromatographic analysis of the biodiesel obtained, revealed that the process proposed in this investigation led to a very high quality biodiesel, meeting the international requirements for its utilization as a fuel. The combustion gas emissions of the JCCO biodiesel were studied by FTIR spectroscopy using a laboratory combustor. These preliminary results showed low amounts of aromatic and sulfur containing compounds. However, halogenated compounds and dicyclopentadiene were also detected at the combustor exhaust.     

The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives

At present, the homogeneous base-catalyzed methanolysis reaction of vegetable oils is a most often used process for the industrial biodiesel production. The toxicity of methanol, the risk of the methanol vapor explosion and the possibility of the ethanol production from biorenewable resources have contributed to the development of a vegetable oil ethanolysis process for the biodiesel production. In the reaction of vegetable oils and ethanol in the presence of a catalyst, completely agricultural fuels consisted of fatty acid ethyl esters (FAEE) are obtained having physico-chemical properties similar to those of the appropriate methyl esters and diesel fuel. The ethanolysis reaction of various oily feedstocks has been widely studied to optimize the reaction conditions and to develop new catalytic systems and processes based on chemical and biological catalysts, as well as the development of non-catalytic processes. Most researches investigate the application of homogeneous base catalysts. This paper studies the review of vegetable oil ethanolysis investigations for the biodiesel production done so far. The goals of the paper are to present the development of FAEE synthesis by catalytic and non-catalytic processes, their advantages and disadvantages, the influence of some operating and reaction conditions on the process rate and ethyl esters yield, the kinetics models describing the ethanolysis process rate, the process optimization and the possibilities for improving the FAEE synthesis process.     

Intensification of biodiesel production from vegetable oils using ultrasonic-assisted process: Optimization and kinetic

Intensification of biodiesel production process using low frequency ultrasonic irradiation (20 kHz, 200 W) is elucidated in this study. Effects of five process variables in an ultrasonic-assisted reactor catalyzed by SrO through transesterification of vegetable oils are investigated. RSM was employed and the optimum conditions were at an ultrasonic pulse on of 9 s followed by 2 s of pulse off within a reaction time of 30.7 min. The optimum ultrasonic power was found to be 130 W using an oil amount of 52 g (R² = 0.97). The model was applicable to different types of oil with errors less than 10%. FFA content was responsible for the different yields obtained with different oils. Three steps of the transesterification process were measured to obtain the kinetic study. The results revealed that the reaction followed a second-order kinetic. The activation energies varied between 70.63 kJ/mol and 136.93 kJ/mol showing relatively high coefficient of determinations.     

Analysis of parameters and interaction between parameters of the microwave-assisted continuous transesterification process of Jatropha oil using response surface methodology

A simple continuous process was designed for the transesterification of Jatropha curcas (J. curcas) oil to alkyl esters using microwave-assisted method. The product with purity above 96.5% of alkyl ester is called the biodiesel fuel. Using response surface methodology, a series of experiments with three reaction factors at three levels were carried out to investigate the transesterification reaction in a microwave and conversion of alkyl ester from J. curcas oil with NaOH as the catalyst. The results showed that the ratio of methanol to oil, amount of catalyst and flow rate have significant effects on the transesterification and conversion of alkyl ester. Based on the response surface methodology using the selected operating conditions, the optimal ratio of methanol to oil, amount of catalyst and flow rate of transesterification process were 10.74, 1.26 wt% and 1.62 mL/min, respectively. The largest predicted and experimental conversions of alkyl esters (biodiesel) under the optimal conditions are 99.63% and 99.36%, respectively. Our findings confirmed the successful development of a two-step process for the transesterification reaction of Jatropha oil by microwave-assisted heating, which is effective and time-saving for alkyl ester production.     

Biodiesel production from supercritical carbon dioxide extracted Jatropha oil using subcritical hydrolysis and supercritical methylation

This study investigates supercritical carbon dioxide (SC-CO₂) extraction of triglycerides from powdered Jatropha curcas kernels followed by subcritical hydrolysis and supercritical methylation of the extracted SC-CO₂ oil to obtain a 98.5% purity level of biodiesel. Effects of the reaction temperature, the reaction time and the solvent to feed ratio on free fatty acids in the hydrolyzed oil and fatty acid esters in the methylated oil via two experimental designs were also examined. Supercritical methylation of the hydrolyzed oil following subcritical hydrolysis of the SC-CO₂ extract yielded a methylation reaction conversion of 99%. The activation energy of hydrolysis and trans-esterified reactions were 68.5 and 45.2 kJ/mole, respectively. This study demonstrates that supercritical methylation preceded by subcritical hydrolysis of the SC-CO₂ oil is a feasible two-step process in producing biodiesel from powdered Jatropha kernels.     

Transesterification of edible and non-edible oils over basic solid Mg/Zr catalysts

A series of Mg–Zr catalysts with varying Mg to Zr ratios was prepared by co-precipitation method. These catalysts were characterized by BET surface area, X-ray diffraction, X-ray photo electron spectroscopy and temperature programmed desorption of CO₂. The catalytic activity of these catalysts was evaluated for the room temperature transesterification of both edible and non-edible oils to their corresponding fatty acid methyl esters. The catalyst with Mg/Zr (2:1 wt./wt.%) exhibited exceptional activity towards transesterification reaction within short reaction time. The effects of different reaction parameters such as catalyst to oil mass ratio, reaction temperature, reaction time and methanol to oil molar ratio were studied to optimize the reaction conditions. The reasons for the observed activity of these catalysts are discussed in terms of their basicity and other physico-chemical properties.     

Karanja (Pongamia Pinnata) biodiesel production in Bangladesh, characterization of karanja biodiesel and its effect on diesel emissions

This paper presents production of biodiesel (BD) from non-edible renewable karanja (Pongamia Pinnata) oil, determination of BD properties and influence of BD on engine performance and emissions. Bangladesh imports 2.4 million metric ton (MT) DF each year [M.N. Nabi, M.S. Akhter, K.M.F. Islam, Prospect of biodiesel production from jatropha curcas, a promising non edible oil seed in Bangladesh, International Conference on Mechanical Engineering (ICME, Dhaka, Bangladesh) Proceedings 2007, paper no. ICME07-TH-06. [1]]. It has 0.32 million hectare of unused land [M.N. Nabi, S.M.N. Hoque, M.S. Uddin, Prospect of Jatropha curcas and pithraj cultivation in Bangladesh, Journal of Engineering and Technology, IUT, Dhaka, Bangladesh, 7 (1) (2009) 41–54. [2]]. It has been found that cultivating of karanja plant in such unused land; Bangladesh can reduce DF import by 28%. Karanja methyl ester (KME), which is termed as BD, has been produced by well-known transesterification process. The properties of B100 (B100) and its blends were determined mainly according to ASTM standard and some of them were as per EN14214 standard. The Fourier transform infrared (FTIR) analysis showed that the DF fuel contained mainly alkanes and alkens, while the B100 contained mainly esters. The gas chromatography (GC) of B100 revealed that a maximum of 97% methyl ester was produced from karanja oil. Engine experiment result showed that all BD blends reduced engine emissions including carbon monoxide (CO), smoke and engine noise, but increased oxides of nitrogen (NOx). Compared to DF, B100 reduced CO, and smoke emissions by 50 and 43%, while a 15% increase in NOx emission was observed with the B100. Compared to DF, engine noise with B100 was reduced by 2.5 dB.     

Mixing characteristics of the oil-methanol system in the production of biodiesel using edible and non-edible oils

Production of biodiesel from rice bran and karanja oils was studied in a stirred tank reactor at different agitator speeds. The reaction system involves two immiscible phases: oil and methanol. The minimum critical speed and the emulsion properties for the reacting system were measured. Based on these values the sauter mean diameter, interfacial area and flow regime were obtained. The minimum critical speed of agitator for rice bran was 700-750 rpm and for karanja was 550-650 rpm. The lower rpm for karanja oil is due to the presence of gums in the non-edible oils. The flow regime for the non-reacting system was found to be transitional and turbulent for reacting. The sauter mean diameter decreased to 7-8 times, from 2010 to 240 μm with increased agitator speed in the initial stages of the reaction and then was found to be constant with further increase. The specific interfacial area obtained from sauter mean diameter showed an increase accordingly. The economics of the biodiesel process depends on the conversions which also dictate the yield. The characteristics determined in the present work are useful in understanding the biodiesel process and help in the scale up of the reactor using different feed-stocks.     

Reduction of high content of free fatty acid in sludge palm oil via acid catalyst for biodiesel production

In this study, sulphuric acid (H₂SO₄) was used in the pretreatment of sludge palm oil for biodiesel production by an esterification process, followed by the basic catalyzed transesterification process. The purpose of the pretreatment process was to reduce the free fatty acids (FFA) content from high content FFA (> 23%) of sludge palm oil (SPO) to a minimum level for biodiesel production (> 2%). An acid catalyzed esterification process was carried out to evaluate the low content of FFA in the treated SPO with the effects of other parameters such as molar ratio of methanol to SPO (6:1-14:1), temperature (40-80 °C), reaction time (30-120 min) and stirrer speed (200-800 rpm). The results showed that the FFA of SPO was reduced from 23.2% to less than 2% FFA using 0.75% wt/wt of sulphuric acid with the molar ratio of methanol to oil of 8:1 for 60 min reaction time at 60 °C. The results on the transesterification with esterified SPO showed that the yield (ester) of biodiesel was 83.72% with the process conditions of molar ratio of methanol to SPO 10:1, reaction temperature 60 °C, reaction time 60 min, stirrer speed 400 rpm and KOH 1% (wt/wt). The biodiesel produced from the SPO was favorable as compared to the EN 14214 and ASTM D 6751 standard.     

Optimization of process conditions using response surface methodology for the microwave-assisted transesterification of Jatropha oil with KOH impregnated CaO as catalyst

A transesterification reaction of Jatropha curcas oil with methanol in the presence of KOH impregnated CaO catalyst was performed in a simple continuous process. The process variables such as methanol/oil molar ratio (X₁), amount of catalyst (X₂) and total reaction time (X₃) were optimized through response surface methodology, using the Box–Behnken model. Within the range of the selected operating conditions, the optimal ratio of methanol to oil, amount of catalyst and total reaction time were found to be 8.42, 3.17% and 67.9 min, respectively. The results showed that the amount of catalyst and total reaction time have significant effects on the transesterification reaction. For the product to be accepted as a biodiesel fuel, its purity must be above 96.5% of alkyl esters. Based on the optimum condition, the predicted biodiesel conversion was 97.6% while the actual experimental value was 97.1%. The above mentioned results demonstrated that the response surface methodology (RSM) based on Box–Behnken model can well predict the optimum condition for the biodiesel production.     

Extraction,transesterification and process control in biodiesel production from Jatropha curcas

Biodiesel has gained worldwide popularity as an alternative energy source due to its renewable, non‐toxic, biodegradable and non‐flammable properties. It also has low emission profiles and is environmentally beneficial. Biodiesel can be used either in pure form or blended with conventional petrodiesel in automobiles without any major engine modifications. Various non‐edible and edible oils can be used for the preparation of biodiesel. With no competition with food uses, the use of non‐edible oils as alternative source for engine fuel will be important. Among the non‐edible oils, such as Pongamia, Argemone and Castor, Jatropha curcas has tremendous potential for biodiesel production. J. curcas, growing mainly in tropical and sub‐tropical climates across the developing world, is a multipurpose species with many attributes and considerable potentials. In this article, we review the oil extraction and characterization, the role of different catalysts on transesterification, the current state‐of‐the‐art in biodiesel production, the process control and future potential improvement of biodiesel production from J. curcas.     

Effect of methanol content on enzymatic production of biodiesel from waste frying oil

The enzymatic production of biodiesel from waste frying oil with methanol has been studied using immobilized lipase Novozym 435 as catalyst. The effects of methanol to oil molar ratio, dosage of enzyme and reaction time were investigated. The optimum reaction conditions were methanol to oil molar ratio of 25:1, 10% of Novozym 435 based on oil weight and reaction period of 4 h at 50 °C obtaining a biodiesel yield of 89.1%. Moreover, the reusability of the lipase over repeated cycles was also investigated under standard conditions.     

Optimization of the production of biodiesel from soybean oil by ultrasound assisted methanolysis

This paper evaluates and optimizes the production of biodiesel from soybean oil and methanol using sodium hydroxide as catalyst. The study and optimization was carried out at low catalyst concentration (0.2 to 0.6 w/w). The reaction was carried out with application of low-frequency high-intensity ultrasound under atmospheric pressure and ambient temperature in a batch reactor. Response surface methodology (RSM) was used to evaluate the influence of methanol to oil ratio and catalyst concentration on soybean oil conversion into biodiesel. Analysis of the operating conditions by RSM showed that the most important operating condition affecting the reaction was the methanol to oil ratio, while catalyst amount showed little significance in the transesterification reaction. Total consumption of oil was obtained when alcohol to oil ratio of 9:1 and catalyst concentration of 0.2 w/w were applied.     

Solubility of Jatropha and Aquilaria oils in supercritical carbon dioxide at elevated pressures

This study investigated experimental equilibrium solubilities of Jatropha curcas and Aquiliaria crassna oils dissolved in supercritical carbon dioxide at temperatures of 318-338 K and pressures of 20, 25, 30, 35 MPa. The highest solubility of J. curcas and A. crassna oil were 29.8 and 28.4 mg L⁻¹, respectively, at 338 K and 35 MPa. The oil solubilities and the concentration of triglycerides both increased with increasing temperature and pressure. Triglyceride molecules surrounded by carbon dioxide molecules may be proposed since solubilities increased with the flux of supercritical carbon dioxide. The solubility of these two oils linearly increased with the density of supercritical carbon dioxide. Experimental data of the oil solubility were successfully correlated by the Chrastil equation.     

Obtaining and characterization of biodiesel from jupati (Raphia taedigera Mart.) oil

The search for alternative triglyceride sources for biodiesel production is a widely discussed issue in Brazil because of the initiation of the Brazilian biofuel program. The viability of biodiesel production from the oil of Raphia taedigeraMart., commonly known as jupati, is studied in this work. This paper presents the obtention and characterization of biodiesel from jupati using an ethylic route with a methane sulfonic acid reaction catalyst. The alcohol:oil molar ratio was 9:1, and the catalyst concentration was 2% of the oil mass. The yield of the process was 92% by mass, and the oil conversion into jupati ethylic biodiesel was 99.6%. The physical and chemical parameters of jupati ethylic biodiesel were within the limits set by the National Agency of Petroleum, Natural Gas and Biofuels (ANP).     

Application of N-methylimidizolium functionalized anion exchange resin containing NaOH for production of biodiesel

Biodiesel produced by vegetable oil transesterification is a potential alternative fuel to diesel regarding the limited resources of fossil fuel and its environmental concerns. In this paper, N-methylimidazole functionalized anion exchange resin (R⁺-OH⁻) containing NaOH was synthesized through two-step method and applied for transesterification of soybean oil. R⁺-OH⁻ was found to show some polarity due to the functional groups of N-methylimidazole and hydroxyl, and NaOH could be absorbed in R⁺-OH⁻ to form R⁺OH⁻ (Na). Both soybean oil and methanol will be compatible to the partly-polar R⁺OH⁻ (Na), and the reaction will be enhanced by the co-catalysis of R⁺-OH⁻ with NaOH. The properties of R⁺-OH⁻ (Na) were studied, such as ion exchange capacity, stability and microstructure. The influences of the molar ratio of methanol to soybean oil, stirring speed and the amount of R⁺-OH⁻ (Na) were investigated. The conversion of soybean oil was up to 97.25% at the optimal condition: molar ratio of methanol to soybean oil 12:1, the amount of catalyst 2.5%, reaction temperature 50 °C, stirring speed 570 rpm and reaction time 10 h. The co-catalysis of R⁺-OH⁻ with NaOH improved the yield of biodiesel greatly, and R⁺-OH⁻ (Na) could be reused after regeneration.     

脂肪酶催化非食用植物油制备生物柴油的过程优化

以麻疯树油、亚麻油、乌柏油为原料油,采用固定化脂肪酶Lipozyme TL IM,在3.0 g油、1 mL正己烷、醇油摩尔比为3.5∶1、固定化酶质量为油质量20%的条件下进行生物柴油的制备,通过脂肪酸甲酯产率和组成分析,以考察生物柴油制备的影响因素,进行反应时间优化.结果表明,酶的催化作用对脂肪酸组分不存在选择性,且...