Kinetic studies on the esterification of free fatty acids in jatropha oil

Kinetic studies have been carried out on the esterification of free fatty acids (FFAs) in jatropha oil with methanol in the presence of sulphuric acid catalyst at 5 and 10 wt% concentrations relative to free fatty acids (0.4–0.8 wt% relative to oil) and methanol–FFA mole ratios ranging from 20:1 to 80:1. It has been found that a 60:1 methanol–FFA mole ratio and 5 wt% catalyst at 60°C and 500 rpm or above provided a final acid value lower than 1 mg KOH/g oil within 60 min. A kinetic model has been proposed with second‐order kinetics for both the forward and backward reactions. The effect of temperature on the reaction rate constants and equilibrium constant has been determined using Arrhenius and von't Hoff equations, respectively. The heat of reaction was found to be ?11.102 kJ/mol.     

Design and testing of continuous acid-catalyzed esterification reactor for high free fatty acid mixed crude palm oil

Using acid-catalyzed esterification, a continuous reactor, containing four separate continuous stirred tank reactors (CSTR's), was designed and used to reduce the free fatty acid (FFA) content of mixed crude palm oil (MCPO). A six-blade disk turbine and four baffles were installed in each of the four reactors to enhance mixing. The complete reactor was tested using response surface methodology (RSM). A 5-level, 4-factor, central composite design (CCD) was employed to optimize the four important reaction variables (methanol/oil ratio; sulfuric acid/oil ratio; speed of the stirrer; and residence time) to reduce the FFA content of the MCPO to less than 1 wt.% of oil. Multiple regression analysis was used to derive a polynomial equation to predict the FFA content of the product. This was then used to indicate optimal conditions for reducing the FFA in mixed crude palm oil to less than 1 wt.%.     

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.     

Solid superacid catalyzed glycerol esterification of free fatty acids in waste cooking oil for biodiesel production

The free fatty acids (FFAs) of waste cooking oil (WCO) are readily esterified with crude glycerol in the presence of the solid superacid SO/ZrO₂–Al₂O₃. This reaction lowers the acidity of WCO before biodiesel production. The solid superacid SO/ZrO₂–Al₂O₃ catalyzes both FFA esterification and TAG glycerolysis during the reaction. The conversion of FFA in the WCO with an acid value of 88.4 ± 0.5 mg KOH/g to acylglycerols was 98.4% under optimal conditions (mole ratio of glycerol to FFA = 1.4:1; reaction time = 4 h; reaction temperature = 200°C; catalyst loading = 0.3 wt%) obtained through an orthogonal experiment. The final FAME product with a FAME content of 96.9 ± 0.3 wt% yield was 94.8 wt%, after transesterification of the esterified WCO with methanol, catalyzed by potassium hydroxide. The FAME composition of the products produced by transesterification were identified and quantified by GC–MS. The results suggest that this new glycerol esterification process, using a solid superacid catalyst, affords a promising method to convert oils with high FFA levels, like WCO, to biodiesel. The process has the inherent advantage of easy separation steps for removing excess alcohol and significant savings in energy, when compared to acid catalyzed reactions with methanol to lower acidity. Practical applications : In this work, WCO with a high acid value was esterified with crude glycerol catalyzed by solid super acid, whose formula was expressed as SO/ZrO₂–Al₂O₃. There are distinct advantages to this new esterification process, which include easy separation of the excess crude glycerol by sedimentation or centrifugation, the use of the low cost reactant crude glycerol direct from the byproducts of transesterification, the potential to achieve a very low content of FFAs by post‐refining to improve the yield of the final product, and time and energy saving are found as compared to the traditional methanol esterification process. This new technology provides a promising alternative method for processing feedstocks of high acid value, such as WCO, for the production of biodiesel.     

Producing biodiesel from high free fatty acids waste cooking oil assisted by radio frequency heating

Efficient biodiesel conversion from waste cooking oil with high free fatty acids (FFAs) was achieved via a two-stage procedure (an acid-catalyzed esterification followed by an alkali-catalyzed transesterification) assisted by radio frequency (RF) heating. In the first stage, with only 8-min RF heating the acid number of the waste cooking oil was reduced from 68.2 to 1.64 mg KOH/g by reacting with 3.0% H₂SO₄ (w/w, based on oil) and 0.8:1 methanol (weight ratio to waste oil). Then, in the second stage, the esterification product (primarily consisting of triglycerides and fatty acid methyl esters) reacted with 0.91% NaOH (w/w, based on triglycerides) and 14.2:1 methanol (molar ratio to triglycerides) under RF heating for 5 min, and an overall conversion rate of 98.8 ± 0.1% was achieved. Response surface methodology was employed to evaluate the effects of RF heating time, H₂SO₄ dose and methanol/oil weight ratio on the acid-catalyzed esterification. A significant positive interaction between RF heating time and H₂SO₄ concentration on the esterification was observed.     

Optimization of pretreatment of Jatropha oil with high free fatty acids for biodiesel production

A central composite rotatable design and response surface methodology were used in order to investigate the individual and combined effects of the ethanol-to-oil ratio, H₂SO₄ concentration, temperature and time of reaction on the reduction of free fatty acid (FFA) in jatropha oil. A quadratic polynomial model relating the reaction variables with FFA reduction was developed, presenting a good coefficient of determination (R²= 0.893). For reducing FFA to less than 1%, the optimal combination was found to be 0.62 v·v^-1 ethanol-to-oil ratio (14.9 v·v^-1 ethanol-to-FFA ratio), 1.7% v·v^-1 H₂SO₄ concentration, and 79 min reaction time at a reaction temperature of 54°C. These results are of great relevance to maximize methyl esters formation by transesterification using an alkaline catalyst.     

A kinetic study of the esterification of free fatty acids (FFA) in sunflower oil

The kinetics of the esterification of free fatty acids (FFA) in sunflower oil with methanol in the presence of sulphuric acid at concentrations of 5 and 10 wt% relative to free acids as catalyst and methanol/oleic acid mole ratios from 10:1 to 80:1 was studied. The experimental results were found to fit a first-order kinetic law for the forward reaction and a second-order one for the reverse reaction.The influence of temperature on the kinetic constants was determined by fitting the results to the Arrhenius equation. The energy of activation for the forward reaction decreased with increasing catalyst concentration from 50 745 to 44 559 J/mol.Based on the experimental results, a methanol/oleic acid mole ratio of 60:1, a catalyst (sulphuric acid) concentration of 5 wt% and a temperature of 60 °C provided a final acid value for the oil lower than 1 mg KOH/g oil within 120 min. This is a widely endorsed limit for efficient separation of glycerin and biodiesel during production of the latter.     

制备生物柴油用高游离脂肪酸花椒籽油的酯化法降酸

花椒籽油要达到制备生物柴油的要求,必须进行降酸处理。简单介绍了降酸前处理中的脱胶和脱色,甲醇酯化降酸的较优工艺为:催化剂浓硫酸浓度为2%,醇油摩尔比为30∶1,反应时间为2.5 h,反应温度为60℃。在此条件下,花椒籽油酸值可由78.91 mg KOH/g降到1.56 mg KOH/g,可以满足后期制备生物柴油要求。     

Determination of free fatty acids in palm oil by near-infrared reflectance spectroscopy

A near-infrared (NIR) spectroscopy calibration was developed for the determination of free fatty acids (FFA) in crude palm oil and its fractions based on the NIR reflectance approach. A range of FFA concentrations was prepared by hydrolyzing oil with 0.15% (w/w) lipase in an incubator at 60°C (200 rpm). Sample preparation was performed in Dutch cup, and the spectra were measured in duplicate for each sample. The optimized calibration models were constructed with multiple linear regression analysis based on C=O overtone regions from 1850–2050 nm. The best wavelength combinations were 1882, 2010, and 2040 nm. Multiple correlation coefficients squared (R ²) were: 0.994 for crude palm oil, 0.961 for refined-bleached-deodorized (RBD) palm olein, and 0.971 for RBD palm oil. Calibrations were validated with an independent set of 8–10 samples. R ² of validation were 0.997, 0.943, and 0.945, respectively. The developed method was rapid, with a total analysis time of 5 min, and environmentally friendly, and its accuracy was generally good for raw-material quality control.     

Oxidation stability of biodiesel derived from free fatty acids associated with kinetics of antioxidants

Biodiesel derived from free fatty acids (FFAs), which has the advantage of not competing with the edible-oil market, exhibited poor oxidation stability. The induction period (IP) of the FFA-based biodiesel determined by the Rancimat method at 110 °C was 0.20 h. This study investigates the effectiveness of one natural and ten synthetic antioxidants, including α-tocopherol (α-T); butylated hydroxyanisole (BHA); butylated hydroxytoluene (BHT); 2, 5-di-tert-butylhydroquinone (DTBHQ); Ethanox 4740; Ethanox 4760E; 2,2′-methylene-bis-(4-methyl-6-tert-butylphenol) (MBMTBP); N,N′-di-sec-butyl-p-phenylenediamine (PDA); propyl gallate (PG); pyrogallol (PY); and tert-butylhydroquinone (TBHQ), at concentrations between 100 and 1000 ppm to improve the oxidation stability of the FFA-based biodiesel. The order of antioxidant effectiveness with respect to the oxidation stability of the FFA-based biodiesel was PY > Ethanox 4760E > PG > Ethanox 4740 > PDA ~ BHA > BHT > MBMTBP ~ TBHQ > DTBHQ > α-T. The IP of the FFA-based biodiesel increased as the antioxidant concentration was increased and decreased at high test temperatures. Furthermore, the relationship between the IP values associated with the consumption of antioxidants in the FFA-based biodiesel was described by first-order reaction rate kinetics. However, the natural logarithm of IP (ln IP) at various concentrations of Ethanox 4760E showed a linear relation with the test temperature. The IP at ambient temperature was predicted based on the extrapolation method of the temperature dependence relation. After long-term storage at room temperature, the IP and acid value of the original FFA-based biodiesel significantly decreased and increased, respectively, with storage time, while the addition of antioxidants ensured the oxidation stability of the FFA-based biodiesel over 6 months of storage.     

Enzymatic epoxidation of soybean oil methyl esters in the presence of free fatty acids

Epoxides of soybean oil methyl esters (SMEs) are biodegradable, non‐toxic, and renewable epoxy plasticizers. The objective of the present work was to investigate the effects of free fatty acids on the enzymatic epoxidation of SMEs. The results showed that the epoxidation of SMEs depended on the type of the added free fatty acid. For saturated (≤C_18:0) and monounsaturated free fatty acids, the epoxy oxygen group content (EOC) of SMEs increased with increasing carbon chain length of free fatty acids; for branched‐chain unsaturated free fatty acids, the EOC of SMEs decreased in the presence of hydroxyl group (OH) and hydroperoxide (OOH) of free fatty acids; the EOC of SMEs decreased with increasing number of double bonds of free fatty acids. The maximum EOC and the initial epoxidization rate (V₀) linearly decreased with increasing peroxide value of SMEs. The highest EOC (6.87 ± 0.3%) of SMEs was obtained using behenic acid as reaction material, which was similar with that of stearic acid (EOC 6.75 ± 0.2%).     

Influence of free fatty acid content of coconut oil on deposit and performance of plant oil pressure stoves

In tropical and subtropical countries, utilization of unprocessed plant oil or used frying oil as household cooking fuel promises to be a competitive alternative to well known fuels like wood and kerosene. However, the use of unprocessed plant oil in plant oil pressure stoves leads to the formation of deposits inside the vaporizer, which have to be removed from time to assure a proper operation of the plant oil pressure stove.Therefore, the objective of this study was to investigate the effect of free fatty acid content of coconut oil on performance and deposit formation in plant oil pressure stoves. Test fuels with different levels of free fatty acid content were prepared by aerating the coconut oil with dry air (5.04 l O₂/kg h) at a temperature of 85 °C. Experiments were performed with the plant oil pressure stove ’Protos’ (BSH Bosch und Siemens Hausgeräte GmbH).As a result, 0.15 g of deposits per kg of consumed oil was found for fresh coconut oil with free fatty acid content of 0.03%, which served as control. Aged oil with a free fatty acid content of 23.1% resulted in 6.48 g deposits per kg of consumed test fuel. Conradson carbon residue CCR of 0.18% was low for control and increased to 0.82% for aged oil. Specific fuel consumption was in a range between 0.284 and 0.304 kg/h without significant differences between the fuels. Performance of the plant oil pressure stove was not affected by the amount of free fatty acids in the plant oil. However, lower heating value decreased from initial 35 MJ/kg for control to 30 MJ/kg for aged fuel, and as consequence power output from plant oil pressure stove decreased. Therefore, plant oils with free fatty acid content below 5%, which is equivalent to an acid value of 10 mg KOH/g, are recommended as fuels for plant oil pressure stoves.     

Biodiesel production from high FFA rubber seed oil

Currently, most of the biodiesel is produced from the refined/edible type oils using methanol and an alkaline catalyst. However, large amount of non-edible type oils and fats are available. The difficulty with alkaline-esterification of these oils is that they often contain large amounts of free fatty acids (FFA). These free fatty acids quickly react with the alkaline catalyst to produce soaps that inhibit the separation of the ester and glycerin. A two-step transesterification process is developed to convert the high FFA oils to its mono-esters. The first step, acid catalyzed esterification reduces the FFA content of the oil to less than 2%. The second step, alkaline catalyzed transesterification process converts the products of the first step to its mono-esters and glycerol. The major factors affect the conversion efficiency of the process such as molar ratio, amount of catalyst, reaction temperature and reaction duration is analyzed. The two-step esterification procedure converts rubber seed oil to its methyl esters. The viscosity of biodiesel oil is nearer to that of diesel and the calorific value is about 14% less than that of diesel. The important properties of biodiesel such as specific gravity, flash point, cloud point and pour point are found out and compared with that of diesel. This study supports the production of biodiesel from unrefined rubber seed oil as a viable alternative to the diesel fuel.     

Sulfonated polystyrene: A catalyst with acid and superabsorbent properties for the esterification of fatty acids

In this work, catalysts with acid and superabsorbent properties were obtained by sulfonation of expanded polystyrene and used to promote the esterification of oleic acid with ethanol. The prepared superabsorbent polymers (SAP) showed high concentration of active sulfonic acid sites (0.7-5.9 mmol acid sites g⁻¹) and high water absorption capacity (445-900 g_water g⁻¹). It was observed that the catalytic activity increased with the number of acid site and water absorption capacity. Turnover frequencies suggested that the catalytic activity depends on the accessibility/diffusion processes determined by the crosslinks in the polymer. Commercial sulfonic acid resins and polyacrylate based superabsorbent polymers showed very low activities compared with the SAP produced. The SAP also showed higher activity compared to the homogeneous catalyst p-toluenesulfonic acid. The higher activity of the prepared SAP is discussed in terms of the acidity of sulfonic groups combined with the water absorption which shifts the esterification equilibrium.     

Metal oxides as heterogeneous catalysts for esterification of fatty acids obtained from soybean oil

The growing demand for renewable energy sources stimulates the development of new technologies for biofuel production. Biodiesel synthesis by esterification of fatty acids is a favorable route, because, differently from transesterification, it does not produce glycerin and uses cheaper raw materials. In this work the study of metal oxides and their performance as Lewis acid catalysts in the esterification of fatty acids obtained from soybean oil presented promising results in heterogeneous catalysis, with reaction yields as high as 89%. The influence of variables such as temperature, reaction time and the amount of catalyst in the reaction yield was also evaluated. The possibility of recycling tin oxide was also studied, showing that it was possible to reuse the catalyst up to ten times without significant losses in its catalytic activity.     

Structural effects of WO3 incorporation on USY zeolite and application to free fatty acids esterification

Zeolites have occupied a distinguished position due to their unique properties as solid acids and catalytic results achieved in several industrial reactions. This work studied the influence of supported WO₃ on USY zeolite structure, acidity and activity towards an esterification reaction. High dispersion of WO₃ species on USY was achieved, but at higher loading (?11.4%), microcrystalites of WO₃ were detected below the theoretical monolayer coverage (∼32%). Tungsten species were deposited preferentially inside the zeolite structure and interacted with the Brønsted sites of USY as well as on silanol surface groups with the formation of small aggregates. In addition, dealumination took place, especially in the samples with high WO₃ loading. USY had the most and the strongest acidic sites (Brønsted type), but the incorporation of WO₃ decreased the amount and the strength of the new sites. However, all WO₃/USY catalysts were more active than USY in the esterification of oleic acid with ethanol (conversion above 74%, 2 h at 200 °C). The calculation of the TOF for a 1 h reaction demonstrated that 11.4% WO₃/USY was the most active catalyst. Furthermore, it had the lowest rate of deactivation of acid sites after the reaction (∼13% after four cycles). The better performance of the 11.4% WO₃/USY sample was also attributed to a better distribution of strength of the acidic sites and a more hydrophobic character of the synthesized material.     

Biodiesel production from tobacco (Nicotiana tabacum L.) seed oil with a high content of free fatty acids

The production of fatty acid methyl esters (FAME) from crude tobacco seed oil (TSO) having high free fatty acids (FFA) was investigated. Due to its high FFA, the TSO was processed in two steps: the acid-catalyzed esterification (ACE) followed by the base-catalyzed methanolysis (BCM). The first step reduced the FFA level to less than 2% in 25 min for the molar ratio of 18:1. The second step converted the product of the first step into FAME and glycerol. The maximum yield of FAME was about 91% in about 30 min. The tobacco biodiesel obtained had the fuel properties within the limits prescribed by the latest American (ASTM D 6751-02) and European (DIN EN 14214) standards, except a somewhat higher acid value than that prescribed by the latter standard (<0.5). Thus, tobacco seeds (TS), as agricultural wastes, might be a valuable renewable raw material for the biodiesel production.     

Heterogeneous esterification of oil with high amount of free fatty acids

Frying oils have become the newest raw material for the transesterification reaction for the production of biodiesel. However, these compounds usually come with a certain amount of free fatty acids. These impurities can be transformed into esters and the production of biodiesel could be increased.The use of basic resins to perform the esterification reaction into biodiesel is studied in this work. The effect of the most relevant variables of the process such as reaction temperature, molar ratio between alcohol and oil, amount of catalyst and amount of free fatty acids fed with the oil have been analyzed. For this purpose, an ideal frying oil using oleic acid and soybean oil was made. The alcohol used was ethanol.The esterification of free fatty acid using this heterogeneous catalyst appears as a great alternative to purify frying oil; in this case, the final conversion achieved was around 80%.