Transesterification of palm oil and esterification of palm fatty acid in near- and super-critical methanol with SO4-ZrO2 catalysts

Sulfated zirconia (SO₄-ZrO₂) catalysts, prepared with three different sulfur loading contents (0.75%, 1.8% and 2.5%) at two calcination temperatures (500 °C and 700 °C), were tested for use in the transesterification of purified palm oil (PPO) and the esterification of palm fatty acid (PFA) in near-critical and super-critical methanol. Techniques including BET, XRD, NH₃- and CO₂-TPD revealed that the sulfur content and calcination temperature strongly affects the catalyst base-acid site, specific surface area, average pore size, phase structure, and thus the catalytic reactivity. The most suitable sulfur loading content was found to be 1.8% and the optimum calcination temperature 500 °C. The results show that the use of SO₄-ZrO₂ reduces esterification reaction times, the amount of methanol necessary and the required reaction temperature. The reactions at 250 °C in the presence of the SO₄-ZrO₂ catalyst at 0.5 w/w% catalyst to PPO or PFA were found to give the highest FAMEs conversions. Under these conditions, 90% and 75% conversions were achieved within 10 and 1 min from PPO (at 25:1 MeOH:PPO molar ratio) and PFA (at 6:1 MeOH:PFA molar ratio), respectively.     

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.     

Esterification of industrial-grade palm fatty acid distillate over modified ZrO2 (with WO3-, SO4 -and TiO2-): Effects of co-solvent adding and water removal

The esterification of palm fatty acid distillate (PFAD), a by-product from palm oil industry, in the presence of three modified zirconia-based catalysts i.e. SO₄-ZrO₂, WO₃-ZrO₂ and TiO₂-ZrO₂ (with several sulfur- and tungsten-loading contents, Ti/Zr molar ratios, and calcination temperatures) was studied. It was found that, among all synthesized catalysts, the reaction in the presence of SO₄-ZrO₂ and WO₃-ZrO₂ (with 1.8%SO₄ calcined at 500 °C and/or 20%WO₃ calcined at 800 °C) enhances relatively high fatty acid methyl ester (FAME) yield (84.9-93.7%), which was proven to relate with the high acid site density and specific surface area as well as the formation of tetragonal phase over these catalysts. The greater benefit of WO₃-ZrO₂ over SO₄-ZrO₂ was its high stability after several reaction cycles, whereas significant deactivation was detected over SO₄-ZrO₂ due to the leaching of sulfur from catalyst. For further improvement, the addition of toluene as co-solvent was found to increase the FAME yield along with reduce the requirement of methanol to PFAD molar ratio (while maintains the FAME yield above 90%). Furthermore, it was observed that the presence of water in the feed considerably lower the FAME yield due to the catalyst surface interfering by water and the further hydrolysis of FAME back to fatty acids. We proposed here that the negative effect can be considerably minimized by adding molecular sieve to remove water from the feed and/or during the reaction.     

Sulfonated Beet Pulp as Solid Catalyst in One-Step Esterification of Industrial Palm Fatty Acid Distillate

In this research a new heterogeneous catalyst has been prepared for biodiesel production. The catalyst was prepared by sulfonating industrial sugar waste. Unlike homogeneous catalysts, which require further purification and separation from the biodiesel production reaction media, this inexpensive synthetic catalyst does not need to go through an additional separation process. This advantage consequently minimizes the total application costs. The catalyst was prepared by partially carbonizing sugar beet pulp at 400 °C. The carbonization product was then sulfonated with concentrated H₂SO₄ vapor in order to produce a solid catalyst. The prepared catalyst was used in the esterification reaction between palm fatty acid distillate (PFAD) and methanol. The effects of the temperature, methanol/PFAD ratio, reaction time and catalyst dosage on the efficiency of the production were individually investigated. The optimum biodiesel production occurred at 85 °C, a reaction time of 300 min, catalyst dosage of 3 g and methanol/PFAD ratio of 5:1 (mol/mol), lowering the acid value from 198 to 13.1 (mg KOH/g oil) or the equivalent, with a fatty acid methyl ester yield of around 92 %. The results suggest that the synthesized inexpensive catalyst is useful for biodiesel production from PFAD.     

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.     

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.     

Kinetics of methyl ester production from mixed crude palm oil by using acid-alkali catalyst

The production of biodiesel from high free fatty acid mixed crude palm oil using a two-stage process was investigated. The kinetics of the reactions was determined in a batch reactor at various reaction temperatures. It was found that the optimum conditions for reducing high free fatty acid (FFA) in MCPO (8-12 wt.%/wt oil) using esterification was a 10:1 molar ratio of methanol to FFA and using 10 wt.%/wt of sulfuric acid (based on FFA) as catalyst. The subsequent transesterification reaction to convert triglycerides to the methyl ester was found to be optimal using 6:1 molar ratio of methanol to the triglyceride (TG) in MCPO and using 0.6 wt.%/vol_TG sodium hydroxide as catalyst. Both reactions were carried out in a stirred batch reactor over a period of 20 min at 55, 60 and 65 °C. The concentration of compounds in each sample was analyzed by Thin Layer Chromatography/Flame Ionization Detector (TLC/FID), Karl Fischer, and titration techniques. The results were used for calculating the rate coefficients by using the curve-fitting tool of MATLAB. Optimal reaction rate coefficients for the forward and reverse esterification reactions of FFA were 1.340 and 0.682 l mol⁻¹ min⁻¹, respectively. The corresponding optimal transesterification, rate coefficients for the forward reactions of TG, diglyceride (DG), and monoglyceride (MG) of transesterification were 2.600, 1.186, and 2.303 l mol⁻¹ min⁻¹, and for the reverse reactions were 0.248, 0.227, and 0.022 l mol⁻¹ min⁻¹, respectively.     

Production of ethyl ester from crude palm oil by two-step reaction with a microwave system

The production of ethyl esters of fatty acids from a feed material of crude palm oil (CPO) with a high free fatty acid (FFA) content under microwave assistance has been investigated. Parametric studies have been carried out to investigate the optimum conditions for the esterification process (amount of ethanol, amount of catalyst, reaction time, and microwave power). As a result, a molar ratio of FFA to ethanol of 1:24 with 4% wt./wt. of H₂SO₄/FFA, a microwave power of 70 W, and a reaction time of 60 min have been identified as optimum reaction parameters for the esterification process aided by microwave heating. At the end of the esterification process, the amount of FFA had been reduced from 7.5 wt.% to less than 2 wt.%. Similar results were obtained following conventional heating at 70 °C, but only after a reaction time of 240 min. Transesterification of the esterified palm oil has been accomplished with a molar ratio of CPO to ethanol of 1:4, 1.5 wt.% KOH as a catalyst, a microwave power of 70 W, and a reaction time of 5 min. This two-step esterification and transesterification process provided a yield of 80 wt.% with an ester content of 97.4 wt.%. The final ethyl ester product met with the specifications stipulated by ASTM D6751-02.     

An empirical approach in predicting biodiesel viscosity at various temperatures

A thermodynamic model is proposed for the determination of kinematic viscosities of saturated fatty acid methyl esters (FAMEs) of various chain lengths at different temperatures. The linearity of the natural logarithm of viscosity-carbon number, plot is limited to a narrow carbon number range. The predicted viscosities of FAMEs of C_12:0-C_18:0, which are commonly found in vegetable oils and used as biodiesels, agree well with the experimental values. The highest difference is 0.354 cSt (5.60%), for methyl stearate at 40 °C. When the proposed method for viscosity calculation of saturated FAMEs are used in combination with the methods for viscosities of biodiesel the mixtures, the predicted viscosities agree well with the values reported in the literatures and the measured values. The differences between the predicted viscosities and those reported in the literatures (at 40 °C) are 1.08 to 8.56% (for eight different vegetable oil methyl esters). The differences between the predicted viscosities and the measured values for coconut methyl esters, at 25, 40 and 50 °C are 9.20, 5.53 and 5.57%, respectively. The differences are slightly higher than those of palm oil methyl esters (4.48, 2.06 and 2.48%, respectively).The proposed method can also be applied to predict the viscosities of free fatty acids and it is speculated it may be applied to other homologous series as well.     

Thermal stability of biodiesel in supercritical methanol

Non-catalytic biodiesel production technologies from oils/fats in plants and animals have been developed in our laboratory employing supercritical methanol. Due to conditions in high temperature and high pressure of the supercritical fluid, thermal stability of fatty acid methyl esters and actual biodiesel prepared from various plant oils was studied in supercritical methanol over a range of its condition between 270 °C/17 MPa and 380 °C/56 MPa. In addition, the effect of thermal degradation on cold flow properties was studied. As a result, it was found that all fatty acid methyl esters including poly-unsaturated ones were stable at 270 °C/17 MPa, but at 350 °C/43 MPa, they were partly decomposed to reduce the yield with isomerization from cis-type to trans-type. These behaviors were also observed for actual biodiesel prepared from linseed oil, safflower oil, which are high in poly-unsaturated fatty acids. Cold flow properties of actual biodiesel, however, remained almost unchanged after supercritical methanol exposure at 270 °C/17 MPa and 350 °C/43 MPa. For the latter condition, however, poly-unsaturated fatty acids were sacrificed to be decomposed and reduced in yield. From these results, it was clarified that reaction temperature in supercritical methanol process should be lower than 300 °C, preferably 270 °C with a supercritical pressure higher than 8.09 MPa, in terms of thermal stabilization for high-quality biodiesel production.     

Continuous production of fatty acid methyl esters from corn oil in a supercritical carbon dioxide bioreactor

Continuous production of fatty acid methyl esters (FAMEs) from corn oil was studied in a supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Response surface methodology (RSM) based on central composite rotatable design (CCRD) was employed to investigate and optimize the reaction conditions: pressure (11-35 MPa), temperature (35-63 °C), substrate mole ratio (methanol:corn oil 1-9) and CO₂ flow rate (0.4-3.6 L/min, measured at ambient conditions). Increasing the substrate mole ratio increased the FAME content, whereas increasing pressure decreased the FAME content. Higher conversions were obtained at higher and lower temperatures and CO₂ flow rates compared to moderate temperatures and CO₂ flow rates. The optimal reaction conditions generated from the predictive model for the maximum FAME content were 19.4 MPa, 62.9 °C, 7.03 substrate mole ratio and 0.72 L/min CO₂ flow rate. The optimum predicted FAME content was 98.9% compared to an actual value of 93.3 ± 1.1% (w/w). The SC-CO₂ bioreactor packed with immobilized lipase shows great potential for biodiesel production.     

Production of biodiesel from palm fatty acid distillate using sulfonated-glucose solid acid catalyst:Characterization and optimization

A palm fatty acid distillate (PFAD) has been used for biodiesel production. An efficient sulfonated-glucose acid catalyst (SGAC) was prepared by sulfonation to catalyze the esterification reaction. The effect of three variables i.e. methanol-to-PFAD molar ratio, catalyst amount and reaction time, on the yield of PFAD esters was studied by the response surface methodology (RSM). The optimum reaction conditions were:12.2:1 methanol-to-PFAD molar ratio, 2.9%catalyst concentration and 134 min of time as predicted by the RSM. The reaction under the optimum conditions resulted in 94.5%of the free fatty acid (FFA) conversion with 92.4%of the FAME yield. The properties of the PFAD esters were determined according to biodiesel standards.     

Non-catalytic biodiesel process with adsorption-based refining

Different feedstocks of varying acidity ranks and water contents were subjected to a series of discontinuous steps that simulated a biodiesel production process. The three steps comprised: (i) the non-catalytic transesterification with supercritical methanol at 280 °C; (ii) the distillation of the unreacted methanol, water and volatile products; and (iii) the adsorption of the impurities with adequate adsorbents. Refined soy oil, chicken oil and waste cooking oil were subjected to the same simple procedure. The process produced biodiesel complying with the water, acid, glycerides and methyl esters content specifications of the EN 14214 standard.Biodiesel production by the reaction of oils in supercritical methanol at 280 °C and methanol-to-oil molar ratios of 15 and 20 produced amounts of glycerol as small as 0.02%. This simplified the subsequent refining of the biodiesel and is considered an advantage over the classic alkali-catalyzed process (that produces 10% of glycerol by-product) because washing steps can be spared.The contents of methyl esters, water and free fatty acids showed a volcano pattern when plotted as a function of the reaction time. In the case of the free fatty acids this was attributed to the initial reaction of water and triglycerides to form acids and glycerol that increased the acidity of the product mixture. At longer reaction times these acids were likely transformed into methyl esters or were decarboxylated to hydrocarbons and CO₂. Water formation was attributed to glycerol decomposition and esterification of free fatty acids.The design of a simple process for biodiesel production using a single reaction step with negligible glycerol production and an adsorption-based refining step was thus studied. A possible scheme integrating reaction, methanol recycling, biodiesel purification and heat recovery was discussed. Advantages and disadvantages of process units were analyzed on terms of operating cost and simplicity.     

In situ production of fatty acid methyl ester from low quality rice bran: An economical route for biodiesel production

Low quality rice bran was used to produce fatty acid methyl ester (FAME) via in situ extraction, esterification and transesterification process. The effects of the acid and alkaline catalysts on the ester yield, esterification and transesterification process were studied. When 75 ml of absolute methanol, 150 ml of petroleum ether, 0.75 g of concentrated sulfuric acid and 0.71 g of sodium hydroxyl were used, 16.69% (w_FAME/w_{rice bran}) of FAME was obtained. The esterification rate and the transesterification rate reached 98.83% and 80.47%. Based on the proposed route, the production process of FAME (biodiesel) could be simplified and the production cost could be reduced.     

Potassium hydroxide catalyst supported on palm shell activated carbon for transesterification of palm oil

In this study, potassium hydroxide catalyst supported on palm shell activated carbon was developed for transesterification of palm oil. The Central Composite Design (CCD) of the Response Surface Methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst loading and methanol to oil molar ratio on the production of biodiesel using activated carbon supported catalyst. The highest yield was obtained at 64.1 °C reaction temperature, 30.3 wt.% catalyst loading and 24:1 methanol to oil molar ratio. The physical and chemical properties of the produced biodiesel met the standard specifications. This study proves that activated carbon supported potassium hydroxide is an effective catalyst for transesterification of palm oil.     

Synthesis and component confirmation of biodiesel from palm oil and dimethyl carbonate catalyzed by immobilized-lipase in solvent-free system

The transesterification of palm oil and dimethyl carbonate (DMC) for preparing biodiesel has been carried out at the catalysis of immobilized-lipase in solvent-free system. The components were all confirmed by GC and GC–MS analysis. The fatty acid methyl esters (FAMEs) were analyzed with internal standard method. The fatty acids glycerol carbonate esters (FAGCs) were characterized as the intermediates. And, glycerol dicarbonate (GDC) was confirmed as the byproduct by comparing with the model compound. Moreover, the effects of the reaction conditions (type of lipases, molar ratio of DMC and palm oil, amount of catalyst, reaction temperature and time) on the yield of FAMEs were investigated. The yield of FAMEs could reach 90.5% at 55 °C for 24 h with the molar ratio of DMC to oil 10:1 and the catalyst amount of 20% Novozym 435 (based on the oil weight). There was no obvious loss in the FAMEs yield after Novozym 435 having been used for eight cycles.     

Continuous production of biodiesel fuel from vegetable oil using supercritical methanol process

A system for continuous transesterification of vegetable oil using supercritical methanol was developed using a tube reactor. Increasing the proportion of methanol, reaction pressure and reaction temperature can enhance the production yield effectively. However, side reactions of unsaturated fatty acid methyl esters (FAME) occur when the reaction temperature is over 300 °C, which lead to much loss of material. There is also a critical value of residence time at high reaction temperature, and the production yield will decrease if the residence time surpasses this value. The optimal reaction condition under constant reaction temperature process is: 40:1 of the molar ratio of alcohol to oil, 25 min of residence time, 35 MPa and 310 °C. However, the maximum production yield can only be 77% in the optimal reaction condition of constant reaction temperature process because of the loss caused by the side reactions of unsaturated FAME at high reaction temperature. To solve this problem, we proposed a new technology: gradual heating that can effectively reduce the loss caused by the side reactions of unsaturated FAME at high reaction temperature. With the new reaction technology, the methyl esters yield can be more than 96%.     

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.     

Biodiesel synthesis via homogeneous Lewis acid-catalyzed transesterification

Lewis acids (AlCl₃ or ZnCl₂) were used to catalyze the transesterification of canola oil with methanol in the presence of terahydrofuran (THF) as co-solvent. The conversion of canola oil into fatty acid methyl esters was monitored by ¹H NMR. NMR analysis demonstrated that AlCl₃ catalyzes both the esterification of long chain fatty acid and the transesterification of vegetable oil with methanol suggesting that the catalyst is suitable for the preparation of biodiesel from vegetable oil containing high amounts of free fatty acids. Optimization by statistical analysis showed that the conversion of triglycerides into fatty acid methyl esters using AlCl₃ as catalyst was affected by reaction time, methanol to oil molar ratio, temperature and the presence of THF as co-solvent. The optimum conditions with AlCl₃ that achieved 98% conversion were 24:1 molar ratio at 110 °C and 18 h reaction time with THF as co-solvent. The presence of THF minimized the mass transfer problem normally encountered in heterogeneous systems. ZnCl₂ was far less effective as a catalyst compared to AlCl₃, which was attributed to its lesser acidity. Nevertheless, statistical analysis showed that the conversion with the use of ZnCl₂ differs only with reaction time but not with molar ratio.     

Direct synthesis of poly(l-lactic acid) in supercritical carbon dioxide with dicyclohexyldimethylcarbodiimide and 4-dimethylaminopyridine

The direct synthesis of poly(l-lactic acid) (PLLA) from an l-lactic acid oligomer has been performed in supercritical carbon dioxide (scCO₂) using an esterification promoting agent, dicyclohexyldimethylcarbodiimide (DCC), and 4-dimethylaminopyridine (DMAP) as a catalyst. PLLA within M_n of 13,500 g/mol was synthesised in 90% yield at 3500 psi and 80 °C after 24 h. The molecular weight distribution of the products was narrower than PLLA prepared with melt-solid phase polymerisation under conventional conditions. Both DCC and DMAP showed high solubility in scCO₂ (DCC: 7.6 wt% (1.63×10⁻² mol/mol CO₂) at 80 °C, 3385 psi, DMAP: 4.5 wt% (1.62×10⁻²mol/mol CO₂) at 80 °C, 3386 psi) and supercritical fluid extraction was found to be effective at removing excess DMAP and DCC after the polymerisation was complete. We show that DCC and DMAP are effective esterification promoting reagents with further applications for condensation polymerisations in scCO₂.