A hybrid feedstock for a very efficient preparation of biodiesel

Biodiesel has been synthesized from karanja, mahua and hybrid {karanja and mahua (50:50 v/v)} feedstocks. A high yield in the range of 95-97% was obtained with all the three feedstocks. Conversion of vegetable oil to fatty acid methyl esters was found to be 98.6%, 95.71% and 94% for karanja, mahua and hybrid feedstocks respectively. The optimized reaction parameters were found to be 6:1 (methanol to oil) molar ratio, H₂SO₄ (1.5% v/v), at 55 ± 0.5 °C for 1 h during acid esterification for the three feedstocks. During alkaline transesterification, a molar ratio of 8:1 (methanol to oil), 0.8 wt.% KOH (wt/wt) at 55 ± 0.5 °C for 1 h was found to be optimum to achieve high yield for karanja oil. For mahua oil and the hybrid feedstock, 6:1 (methanol to oil) molar ratio, 0.75 (w/w) KOH at 55 ± 0.5 °C for 1 h was optimum for alkaline transesterification to obtain a high yield. High yield and conversion from hybrid feedstock during transesterification reaction was an indication that the reaction was not selective for any particular oil. ¹H NMR has been used for the determination of conversion of the feedstock to biodiesel.     

Ethanolysis of used frying oil. Biodiesel preparation and characterization

The transesterification reaction of used frying oil by means of ethanol, using sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium methoxide as catalysts, was studied. The objective of the work was to characterize the ethyl esters for its use as biodiesels in compression ignition motors. The operation variables used were ethanol/oil molar ratio (6:1–12:1), catalyst concentration (0.1–1.5 wt.%), temperature (35–78 °C), and catalyst type. The evolution of the process was followed by gas chromatography, determining the concentration of the ethyl esters at different reaction times. The biodiesel was characterized by its density, viscosity, flash point, combustion point, cold filter plugging point, cloud and pour points, Conradson carbon residue, characteristics of distillation, cetane index and high heating value according to ISO norms. The biodiesel with the best properties was obtained using an ethanol/oil molar ratio of 12:1, potassium hydroxide as catalyst (1%), and 78 °C temperature. The density, viscosity, cetane index, Conradson carbon residue and calorific power of the biodiesel obtained had values close to those of a no. 2 diesel. On the contrary, the cold filter plugging point, and cloud and pour points are higher than the conventional diesel fuel. Although higher, flash and combustion points fulfil the norms for ethyl esters derived from vegetable oils. In consequence, the final product obtained had very similar characteristics to a no. 2 diesel oil, and therefore, these ethyl esters might be used as an alternative to fossil fuels. The two-stage transesterification was better than the one-stage process, and the yields of ethyl esters were improved 30% in relation with the one-stage transesterification.     

Optimization of biodiesel production from crude palm oil using ultrasonic irradiation assistance and response surface methodology

BACKGROUND: Production of biodiesel from crude palm oil (CPO) with 6 wt% of free fatty acid (FFA) using a low‐frequency ultrasonic irradiation (40 kHz) technique was investigated in the present work. The objective of this study was to determine the relationship between various important parameters of the alkaline catalyzed transesterification process to obtain a high conversion to biodiesel. Response surface methodology (RSM) was used to statistically analyze and optimize the operating parameters of the process. A central composite design (CCD) was adopted to study the effects of the methanol to oil molar ratio, the catalyst concentration, reaction temperature, and irradiation time on conversion to biodiesel. RESULTS: The result from the RSM analysis indicated that the methanol to oil molar ratio, catalyst concentration and irradiation time have the most significant effects on the conversion to biodiesel. Moreover, a coefficient of determination (R²) value of 0.93 shows the fitness of a second‐order model for the present study. Based on this second‐order model, the optimum conditions for alkaline catalyzed transesterification of CPO were found to be a methanol to oil molar ratio of 6.44:1, catalyst concentration 1.25 wt%, reaction temperature 38.44 °C and irradiation time 25.96 min. At the calculated optimum condition, the conversion to biodiesel reached 97.85%. Under these same conditions, the experimental value was 98.02 ± 0.6%. CONCLUSIONS: The mathematical model developed has been proven to adequately describe the range of the experimental parameters studied and provide a statistically accurate prediction of the optimum conversion to biodiesel. Copyright © 2011 Society of Chemical Industry     

Transesterification kinetics of palm olein oil using supercritical methanol

Continuous transesterification of palm olein oil using supercritical methanol was investigated in the absence of a catalyst. The variables studied were reaction temperature (270–350 °C), pressure (20–40 MPa), and residence time (5–25 min), with a methanol-to-oil molar ratio of 40. Preheating at 245 °C was used to form a homogeneous phase in the absence of thermal decomposition of palm olein oil. The activation energies and reaction activation volumes of the fatty acid methyl ester (FAME), and those of the individual components (C16:0, C18:0, C18:1, and C18:2 methyl esters), were calculated. The entropies of activation (ΔS^‡) of the transesterification reactions were also obtained. As the transesterification of vegetable oil in supercritical methanol included a strongly negative (−175 J/mol K) entropy of activation, transesterification required harsh conditions.     

Statistical optimization for biodiesel production from waste frying oil through two-step catalyzed process

The aim of this work was to investigate the optimum conditions in biodiesel production from waste frying oil using two-step catalyzed process. In the first step, sulfuric acid was used as a catalyst for the esterification reaction of free fatty acid and methanol in order to reduce the free fatty acid content to be approximate 0.5%. In the second step, the product from the first step was further reacted with methanol using potassium hydroxide as a catalyst. The Box-Behnken design of experiment was carried out using the MINITAB RELEASE 14, and the results were analyzed using response surface methodology. The optimum conditions for biodiesel production were obtained when using methanol to oil molar ratio of 6.1:1, 0.68 wt.% of sulfuric acid, at 51 °C with a reaction time of 60 min in the first step, followed by using molar ratio of methanol to product from the first step of 9.1:1, 1 wt.% KOH, at 55 °C with a reaction time of 60 min in the second step. The percentage of methyl ester in the obtained product was 90.56 ± 0.28%. In addition, the fuel properties of the produced biodiesel were in the acceptable ranges according to Thai standard for community biodiesel.     

Investigation of low-temperature methanol synthesis in a bubble column slurry reactor with a flash column

Reaction performance of a CuCr/CH₃ONa catalyst for the low-temperature methanol synthesis was examined in a bubble column slurry reactor with a flash column (BCSR/FC). The BCSR/FC was operated at 4.5 ± 0.2 MPa/110–120 °C for BCSR and 0.4 ± 0.1 MPa/80–90 °C for FC, although fluctuation of operation parameters was larger. Syngas conversion decreased from 71.0% to 19.8% during the operation test in 100 h, which was attributed to consumption of CH₃ONa and a negative effect of the emulsifier OP-10 used.     

Production of biodiesel from waste fryer grease using mixed methanol/ethanol system

Transesterification of waste fryer grease (WFG) containing 5–6 wt.% free fatty acid (FFA) was carried out with methanol, ethanol, and mixtures of methanol/ethanol maintaining the oil to alcohol molar ratio of 1:6, and initially with KOH as a catalyst. Mixtures of methanol and ethanol were used for transesterification in order to use the better solvent property of ethanol and rapid equilibrium using methanol. Formation of soap by reaction of FFA present in WFG with KOH instigated difficulty in the separation of glycerol from biodiesel ester. To untangle this problem, two-stage (acid and alkali catalyzed) method was used for biodiesel synthesis. More than 90% ester was obtained when two-stage method was used compared to ∼ 50% ester in single stage alkaline catalyst. In the case of mixed alcohol, a relatively smaller amount of ethyl esters was formed along with methyl esters. Acid value, viscosity, and cetane number of all the esters prepared from WFG were within the range of the ASTM standard. Esters obtained from WFG showed good performance as a lubricity additive.     

甲醇和甲醛催化合成聚甲氧基二甲醚

聚甲氧基二甲醚作为柴油添加剂,可以提高柴油的十六烷值(CN),提高燃油的利用率,作为甲醇大宗下游产品具有广阔的应用前景。在固定床管式反应器中,以改性大孔阳离子交换树脂为催化剂,在温度40～100℃、液相空速1.32～16.37 h^-1、甲醛/甲醇摩尔比1～4和反应压力0.1～3.0 MPa下,以单因素实验和正交实验相结合的方式,系统地研究了甲醛与甲醇缩醛化工艺条件,获得了较佳的工艺条件,在温度70℃、甲醛/甲醇摩尔比3:1、液相空速1.32 h^-1、反应压力2.0 MPa的条件下,甲醇的转化率为69.72%,DMM_3-8选择性为62.08%。     

In situ transesterification of coconut oil using mixtures of methanol and tetrahydrofuran

The conventional biodiesel production method requires oil extraction followed by transesterification with methanol. The solubility of vegetable oils in methanol is low which decreases the overall rate of reaction. To eliminate the oil extraction step and improve the overall reaction rate, simultaneous extraction, esterification and transesterification were conducted by directly mixing methanol and tetrahydrofuran (THF) co-solvent and sulfuric acid catalyst with ground, desiccated coconut meat (copra) in a batch process and continuing the reaction until the system reached steady state. After separation of the mixture, yield was obtained by measuring the content of triglycerides, diglycerides and monoglycerides in the biodiesel phase. The yield increases with THF:methanol ratio, methanol:oil molar ratio and temperature. Within the range of conditions tested, the highest yield achieved was 96.7% at 60 °C, THF:methanol volume ratio of 0.4 and methanol:oil molar ratio of 60:1. The methanol:oil molar ratio is necessarily high in order to completely wet the copra mass, but is still lower than in previous studies by other researchers on in situ transesterification. Product assays show that the resulting biodiesel product is similar to conventionally produced coconut biodiesel. The results indicate that the in situ transesterification of copra using methanol/THF mixtures merits further study.     

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.     

Improvement of the oxidation stability of biodiesel as prepared by supercritical methanol method with lignin

An antioxidation effect of lignin‐derived products in biodiesel prepared using supercritical methanol (300°C/20 MPa) with molar ratio between rapeseed oil and methanol of 1:42 was studied. It was found that lignin could be decomposed to low molecular compounds that have a free radical‐trapping effect after supercritical methanol treatment. However, longer treatment time decreased the antioxidation effect of the lignin‐derived compounds. Rapeseed biodiesel prepared by supercritical methanol method at 300°C/20 MPa for 20 min with a small amount of added lignin showed an induction period longer than 6 h at 110°C in a Rancimat test. In addition, it was found that lignin had a catalytic effect in biodiesel production using the supercritical methanol method without significantly affecting other fuel properties of the prepared biodiesel. Thus, the study proved that lignin addition provides an inexpensive and technically acceptable way to improve the oxidation stability of biodiesel prepared by the supercritical methanol method with satisfactory fuel properties.     

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.     

Evaluation of biodiesel obtained from cottonseed oil

Esters from vegetable oils have attracted a great deal of interest as substitutes for petrodiesel to reduce dependence on imported petroleum and provide a fuel with more benign environmental properties. In this work biodiesel was prepared from cottonseed oil by transesterification with methanol, using sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide as catalysts. A series of experiments were conducted in order to evaluate the effects of reaction variables such as methanol/oil molar ratio (3:1–15:1), catalyst concentration (0.25–1.50%), temperature (25–65 °C), and stirring intensity (180–600 rpm) to achieve the maximum yield and quality. The optimized variables of 6:1 methanol/oil molar ratio (mol/mol), 0.75% sodium methoxide concentration (wt.%), 65 °C reaction temperature, 600 rpm agitation speed and 90 min reaction time offered the maximum methyl ester yield (96.9%). The obtained fatty acid methyl esters (FAME) were analyzed by gas chromatography (GC) and ¹H NMR spectroscopy. The fuel properties of cottonseed oil methyl esters (COME), cetane number, kinematic viscosity, oxidative stability, lubricity, cloud point, pour point, cold filter plugging point, flash point, ash content, sulfur content, acid value, copper strip corrosion value, density, higher heating value, methanol content, free and bound glycerol were determined and are discussed in the light of biodiesel standards such as ASTM D6751 and EN 14214.     

Biodiesel production from waste cooking oil over alkaline modified zirconia catalyst

Screening and catalytic activity of alkaline modified zirconia i.e. Mg/ZrO₂, Ca/ZrO₂, Sr/ZrO₂, and Ba/ZrO₂ as heterogeneous catalyst in biodiesel production from waste cooking oil (WCO) have been investigated. The catalysts were prepared via wet impregnation of alkaline nitrate salts supported on zirconia. Physico-chemical characteristics of the catalysts were analyzed by BET surface area, XRD, FESEM and CO₂–NH₃–TPD. Among the catalysts screened, Sr/ZrO₂ exhibited higher catalytic activities. Characterization results disclosed Sr/ZrO₂ catalyst possessed balanced basic and acid site concentrations with its pore volume, surface area as well as pore diameters suitable for biodiesel production. The balanced active sites facilitated simultaneous transesterification and esterification of WCO. A plausible mechanism has been suggested for the simultaneous reactions. The effects of operating process conditions such as methanol to oil molar ratio, reaction temperature and catalyst loading on biodiesel production in the presence of Sr/ZrO₂ were investigated. Methyl ester (ME) yield at 79.7% was produced over 2.7 wt.% catalyst loading (Sr/ZrO₂), 29:1 methanol to oil molar ratio, 169 min of reaction time and 115.5 °C temperature.     

Rape oil transesterification over heterogeneous catalysts

This work studies the application of KNO₃/CaO catalyst in the transesterification reaction of triglycerides with methanol. The objective of the work was characterizing the methyl esters for its use as biodiesel in compression ignition motors. The variables affecting the methyl ester yield during the transesterification reaction, such as, amount of KNO₃ impregnated in CaO, the total catalyst content, reaction temperature, agitation rate, and the methanol/oil molar ratio, were investigated to optimize the reaction conditions.The evolution of the process was followed by gas chromatography, determining the concentration of the methyl esters at different reaction times. The biodiesel was characterized by its density, viscosity, cetane index, saponification value, iodine value, acidity index, CFPP (cold filter plugging point), flash point and combustion point, according to ISO norms. The results showed that calcium oxide, impregnated with KNO₃, have a strong basicity and high catalytic activity as a heterogeneous solid base catalyst.The biodiesel with the best properties was obtained using an amount of KNO₃ of 10% impregnated in CaO, a methanol/oil molar ratio of 6:1, a reaction temperature of 65 °C, a reaction time of 3.0 h, and a catalyst total content of 1.0%. In these conditions, the oil conversion was 98% and the final product obtained had very similar characteristics to a no. 2 diesel, and therefore, these methyl esters might be used as an alternative to fossil fuels.     

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.     

Dolomite as a heterogeneous catalyst for transesterification of canola oil

In this study, the catalytic activity of dolomite was evaluated for the transesterification of canola oil with methanol to biodiesel in a heterogeneous system. The influence of the calcination temperature of the catalyst and the reaction variables such as the temperature, catalyst amount, methanol/canola oil molar ratio, and time in biodiesel production were investigated. The maximum activity was obtained with the catalyst calcined at 850 °C. When the reaction was carried out at reflux of methanol, with a 6:1 molar ratio of methanol to canola oil and a catalyst amount of 3 wt.% the highest FAME yield of 91.78% was obtained after 3 h of reaction time.     

Continuous enzymatic production of biodiesel from virgin and waste sunflower oil in supercritical carbon dioxide

A continuous process for biodiesel production in supercritical carbon dioxide was implemented. In the transesterification of virgin sunflower oil with methanol, Lipozyme TL IM led to fatty acid methyl esters yields (FAME) that exceeded 98% at 20 MPa and 40 °C, for a residence time of 20 s and an oil to methanol molar ratio of 1:24. Even for moderate reaction conversions, a fractionation stage based on two separators afforded FAME with >96% purity. Lipozyme TL IM was less efficient with waste cooking sunflower oil. In this case, a combination of Lipozyme TL IM and Novozym 435 afforded FAME yields nearing 99%.     

Production of biodiesel through optimized alkaline-catalyzed transesterification of rapeseed oil

Present work reports an optimized protocol for the production of biodiesel through alkaline-catalyzed transesterification of rapeseed oil. The reaction variables used were methanol/oil molar ratio (3:1-21:1), catalyst concentration (0.25-1.50%), temperature (35-65 °C), mixing intensity (180-600 rpm) and catalyst type. The evaluation of the transesterification process was followed by gas chromatographic analysis of the rapeseed oil fatty acid methyl esters (biodiesel) at different reaction times. The biodiesel with best yield and quality was produced at methanol/oil molar ratio, 6:1; potassium hydroxide catalyst concentration, 1.0%; mixing intensity, 600 rpm and reaction temperature 65 °C. The yield of the biodiesel produced under optimal condition was 95-96%. It was noted that greater or lower the concentration of KOH or methanol than the optimal values, the reaction either did not fully occur or lead to soap formation.The quality of the biodiesel produced was evaluated by the determinations of important properties such as density, specific gravity, kinematic viscosity, higher heating value, acid value, flash point, pour point, cloud point, combustion point, cold filter plugging point, cetane index, ash content, sulphur content, water content, copper strip corrosion value, distillation temperature and fatty acid composition. The produced biodiesel was found to exhibit fuel properties within the limits prescribed by the latest American Standards for Testing Material (ASTM) and European EN standards.     

Transesterification of vegetable oil to biodiesel fuel using alkaline catalyst

Biodiesel is gaining more and more importance as an attractive fuel due to the depleting fossil fuel resources. 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 to give the corresponding monoalkyl esters. This article reports experimental data on the production of fatty acid methyl esters from vegetable oils, soybean and cottonseed oils using sodium hydroxide as alkaline catalyst. The variables affecting the yield and characteristics of the biodiesel produced from these vegetable oils were studied. The variables investigated were reaction time (1-3 h), catalyst concentration (0.5-1.5 w/wt%), and oil-to-methanol molar ratio (1:3-1:9). From the obtained results, the best yield percentage was obtained using a methanol/oil molar ratio of 6:1, sodium hydroxide as catalyst (1%) and 60 ± 1 °C temperature for 1 h. The yield of the fatty acid methyl ester (FAME) was determined according to HPLC. The composition of the FAME was determined according to gas chromatography. The biodiesel samples were physicochemically characterized. From the results it was clear that the produced biodiesel fuel was within the recommended standards of biodiesel fuel.