Acid-catalyzed production of biodiesel from waste frying oil

The reaction kinetics of acid-catalyzed transesterification of waste frying oil in excess methanol to form fatty acid methyl esters (FAME), for possible use as biodiesel, was studied. Rate of mixing, feed composition (molar ratio oil:methanol:acid) and temperature were independent variables. There was no significant difference in the yield of FAME when the rate of mixing was in the turbulent range 100 to 600 rpm. The oil:methanol:acid molar ratios and the temperature were the most significant factors affecting the yield of FAME. At 70 °C with oil:methanol:acid molar ratios of 1:245:3.8, and at 80 °C with oil:methanol:acid molar ratios in the range 1:74:1.9–1:245:3.8, the transesterification was essentially a pseudo-first-order reaction as a result of the large excess of methanol which drove the reaction to completion (99±1% at 4 h). In the presence of the large excess of methanol, free fatty acids present in the waste oil were very rapidly converted to methyl esters in the first few minutes under the above conditions. Little or no monoglycerides were detected during the course of the reaction, and diglycerides present in the initial waste oil were rapidly converted to FAME.     

A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesterification from palm oil

The transesterification of palm oil to methyl esters (biodiesel) was studied using KOH loaded on Al₂O₃ and NaY zeolite supports as heterogeneous catalysts. Reaction parameters such as reaction time, wt% KOH loading, molar ratio of oil to methanol, and amount of catalyst were optimized for the production of biodiesel. The 25 wt% KOH/Al₂O₃ and 10 wt% KOH/NaY catalysts are suggested here to be the best formula due to their biodiesel yield of 91.07% at temperatures below 70 °C within 2–3 h at a 1:15 molar ratio of palm oil to methanol and a catalyst amount of 3–6 wt%. The leaching of potassium species in both spent catalysts was observed. The amount of leached potassium species of the KOH/Al₂O₃ was somewhat higher compared to that of the KOH/NaY catalyst. The prepared catalysts were characterized by using several techniques such as XRD, BET, TPD, and XRF.     

Effects of water on the esterification of free fatty acids by acid catalysts

To maximize the production of biodiesel from soybean soapstock, the effects of water on the esterification of high-FFA (free fatty acid) oils were investigated. Oleic acid and high acid acid oil (HAAO) were esterified by reaction with methanol in the presence of Amberlyst-15 as a heterogeneous catalyst or sulfuric acid as a homogeneous catalyst. The yield of fatty acid methyl ester (FAME) was studied at oil to methanol molar ratios of 1:3 and 1:6 and reaction temperatures of 60 and 80 °C. The rate of esterification of oleic acid significantly decreased as the initial water content increased to 20% of the oil. The activity of Amberlyst-15 decreased more rapidly than that of sulfuric acid, due to the direct poisoning of acid sites by water. Esterification using sulfuric acid was not affected by water until there was a 5% water addition at a 1:6 molar ratio of oil to methanol. FAME content of HAAO prepared from soapstock rapidly increased for the first 30 min of esterification. Following the 30-min mark, the rate of FAME production decreased significantly due to the accumulation of water. When methanol and Amberlyst-15 were removed from the HAAO after 30 min of esterification and fresh methanol and a catalyst were added, the time required to reach 85% FAME content was reduced from 6 h to 1.8 h.     

Biodiesel production by esterification of palm fatty acid distillate

Production of fatty acid methyl ester (FAME) from palm fatty acid distillate (PFAD) having high free fatty acids (FFA) was investigated in this work. Batch esterifications of PFAD were carried out to study the influence of: including reaction temperatures of 70–100 °C, molar ratios of methanol to PFAD of 0.4:1–12:1, quantity of catalysts of 0–5.502% (wt of sulfuric acid/wt of PFAD) and reaction times of 15–240 min. The optimum condition for the continuous esterification process (CSTR) was molar ratio of methanol to PFAD at 8:1 with 1.834 wt% of H₂SO₄ at 70 °C under its own pressure with a retention time of 60 min. The amount of FFA was reduced from 93 wt% to less than 2 wt% at the end of the esterification process. The FAME was purified by neutralization with 3 M sodium hydroxide in water solution at a reaction temperature of 80 °C for 15 min followed by transesterification process with 0.396 M sodium hydroxide in methanol solution at a reaction temperature of 65 °C for 15 min. The final FAME product met with the Thai biodiesel quality standard, and ASTM D6751-02.     

Biodiesel from palm oil via loading KF/Ca–Al hydrotalcite catalyst

The solid base catalyst KF/Ca–Al hydrotalcite was obtained from Ca–Al layered double hydroxides and successfully used in the transesterification of methanol with palm oil to produce biodiesel. With the load of KF, the activity of Ca–Al mixed-oxides had been improved much. For the mass ratio 80 wt.%(KF·6H₂O to Ca–Al mixed-oxides) catalyst, under the optimal condition: 338 K, catalyst amount 5%(wt./wt. oil) and methanol/oil molar ratio 12:1, after 5 h reaction, the fatty acid methyl esters yield could reach 97.98%; for the mass ratio 100 wt.%(KF·6H₂O to Ca–Al mixed-oxides) ones, under the same reaction condition, only needed 3 h to get the FAME yield of 99.74%, and even only reacted 1 h, the FAME yield could obtain 97.14%.     

Application of response surface methodology for optimizing transesterification of Moringa oleifera oil: Biodiesel production

Response surface methodology (RSM), with central composite rotatable design (CCRD), was used to explore optimum conditions for the transesterification of Moringa oleifera oil. Effects of four variables, reaction temperature (25–65 °C), reaction time (20–90 min), methanol/oil molar ratio (3:1–12:1) and catalyst concentration (0.25–1.25 wt.% KOH) were appraised. The quadratic term of methanol/oil molar ratio, catalyst concentration and reaction time while the interaction terms of methanol/oil molar ratio with reaction temperature and catalyst concentration, reaction time with catalyst concentration exhibited significant effects on the yield of Moringa oil methyl esters (MOMEs)/biodiesel, p < 0.0001 and p < 0.05, respectively. Transesterification under the optimum conditions ascertained presently by RSM: 6.4:1 methanol/oil molar ratio, 0.80% catalyst concentration, 55 °C reaction temperature and 71.08 min reaction time offered 94.30% MOMEs yield. The observed and predicted values of MOMEs yield showed a linear relationship. GLC analysis of MOMEs revealed oleic acid methyl ester, with contribution of 73.22%, as the principal component. Other methyl esters detected were of palmitic, stearic, behenic and arachidic acids. Thermal stability of MOMEs produced was evaluated by thermogravimetric curve. The fuel properties such as density, kinematic viscosity, lubricity, oxidative stability, higher heating value, cetane number and cloud point etc., of MOMEs were found to be within the ASTM D6751 and EN 14214 biodiesel standards.     

Biodiesel production from palm oil via heterogeneous transesterification

This paper presents the study of the transesterification of palm oil via heterogeneous process using montmorillonite KSF as heterogeneous catalyst. This study was carried out using a design of experiment (DOE), specifically response surface methodology (RSM) based on four-variable central composite design (CCD) with α (alpha) = 2. The transesterification process variables were reaction temperature, x₁ (50–190 °C), reaction period, x₂ (60–300 min), methanol/oil ratio, x₃ (4–12 mol mol^?1) and amount of catalyst, x₄ (1–5 wt%). It was found that the yield of palm oil fatty acid methyl esters (FAME) could reach up to 79.6% using the following reaction conditions: reaction temperature of 190 °C, reaction period at 180 min, ratio of methanol/oil at 8:1 mol mol^?1 and amount of catalyst at 3%.     

Lithium ion impregnated calcium oxide as nano catalyst for the biodiesel production from karanja and jatropha oils

Lithium impregnated calcium oxide has been prepared by wet impregnation method in nano particle form as supported by powder X-ray diffraction and transmission electron microscopy. Basic strength of the same was measured by Hammett indicators. Calcium oxide impregnated with 1.75 wt% of lithium was used as solid catalyst for the transesterification karanja and jatropha oil, containing 3.4 and 8.3 wt% of free fatty acids, respectively. The reaction parameters, viz., reaction temperature, alcohol to oil molar ratio, free fatty acid contents, amount of catalyst and amount of impregnated lithium ion in calcium oxide support, have been studied to establish the most suitable condition for the transesterification reaction. The complete transesterification of karanja and jatropha oils was achieved in 1 and 2 h, respectively, at 65 °C, utilizing 12:1 molar ratio of methanol to oil and 5 wt% (catalyst/oil, w/w) of catalyst. Few physicochemical properties of the prepared biodiesel samples have been studied and compared with standard values.     

Production of FAME by palm oil transesterification via supercritical methanol technology

The present study employed non-catalytic supercritical methanol technology to produce biodiesel from palm oil. The research was carried out in a batch-type tube reactor and heated beyond supercritical temperature and pressure of methanol, which are at 239 °C and 8.1 MPa respectively. The effects of temperature, reaction time and molar ratio of methanol to palm oil on the yield of fatty acid methyl esters (FAME) or biodiesel were investigated. The results obtained showed that non-catalytic supercritical methanol technology only required a mere 20 min reaction time to produce more than 70% yield of FAME. Compared to conventional catalytic methods, which required at least 1 h reaction time to obtain similar yield, supercritical methanol technology has been shown to be superior in terms of time and energy consumption. Apart from the shorter reaction time, it was found that separation and purification of the products were simpler since no catalyst is involved in the process. Hence, formation of side products such as soap in catalytic reactions does not occur in the supercritical methanol method.     

Synthesis of fatty acid methyl esters via the transesterification of waste cooking oil by methanol with a barium-modified montmorillonite K10 catalyst

The transesterification of waste cooking oil (WCO) with methanol to produce fatty acid methyl esters (FAMEs) in the presence of barium-modified montmorillonite K10 (BMK10) catalyst was investigated in a batch reactor. The influence of the reaction parameters on the yield of FAME was investigated. The highest value of 83.38% was obtained with 3.5 wt% catalyst loading at 150 °C with a methanol: oil molar ratio of 12:1 during a reaction time of 5 h. BMK10 is a promising low-cost catalyst for the transesterification of WCO to produce FAME.     

Biodiesel from Jojoba oil-wax: Transesterification with methanol and properties as a fuel

The Jojoba oil-wax is extracted from the seeds of the Jojoba (Simmondsia chinensis Link Schneider), a perennial shrub that grows in semi desert areas in some parts of the world. The main uses of Jojoba oil-wax are in the cosmetics and pharmaceutical industry, but new uses could arise related to the search of new energetic crops.This paper summarizes a process to convert the Jojoba oil-wax to biodiesel by transesterification with methanol, catalysed with sodium methoxide (1 wt% of the oil). The transesterification reaction has been carried out in an autoclave at 60 °C, with a molar ratio methanol/oil 7.5:1, and vigorous stirring (600 rpm), reaching a quantitative conversion of the oil after 4 h. The separation of the fatty acid methyl esters (the fraction rich in FAME, 79% FAME mixture; 21% fatty alcohols; 51% of methyl cis-11-eicosenoate) from the fatty alcohols rich fraction (72% fatty alcohols; 28% FAME mixture; 26% of cis-11-eicosen-1-ol, 36% of cis-13-docosen-1-ol) has been accomplished in a single crystallization step at low temperature (−18 °C) from low boiling point petroleum ether.The fraction rich in FAME has a density (at 15 °C), a kinematic viscosity (at 40 °C), a cold filter plugging point and a high calorific value in the range of the European standard for biodiesel (EN 14214).     

Kinetic model for the esterification of oleic acid catalyzed by zinc acetate in subcritical methanol

The esterification of oleic acid in subcritical methanol catalyzed by zinc acetate was investigated in a batch-type autoclave. The effect of reaction conditions such as temperature, pressure, reaction time and molar ratio of oleic acid to methanol on the esterification was examined. The oleic acid conversion reached 95.0% under 220 °C and 6.0 MPa with the molar ratio of methanol to oleic acid being 4 and 1.0 wt% zinc acetate as catalyst. A kinetic model for the esterification was established. By fitting the kinetic model with the experimental results, the reaction order n = 2.2 and activation energy E_a = 32.62 KJ/mol were obtained.     

Optimization of transesterification conditions for the production of fatty acid methyl ester (FAME) from Chinese tallow kernel oil with surfactant-coated lipase

Surfactant-coated lipase was used as a catalyst in preparing fatty acid methyl ester (FAME) from Chinese tallow kernel oil from Sapium sebiferum (L.) Roxb. syn. Triadica sebifera (L.) small. FAME transesterification was analyzed using response surface methodology to find out the effect of the process variables on the esterification rate and to establish prediction models. Reaction temperature and time were found to be the main factors affecting the esterification rate with the presence of surfactant-coated lipase. Developed prediction models satisfactorily described the esterification rate as a function of reaction temperature, time, dosage of surfactant-coated lipase, ratio of methanol to oil, and water content. The FAME mainly contained fatty acid esters of C16:0, C18:0, C18:1, C18:2, and C18:3, determined by a gas chromatograph. The optimal esterification rate was 93.86%. The optimal conditions for the above esterification ratio were found to be a reaction time of 9.2 h, a reaction temperature of 49 °C, dosage of surfactant-coated lipase of 18.5%, a ratio of methanol to oil of 3:1, and water content of 15.6%. Thus, by using the central composite design, it is possible to determine accurate values of the transesterification parameters where maximum production of FAME occurs using the surfactant-coated lipase as a transesterification catalyst.     

Synthesis of fatty acid methyl esters via the methanolysis of palm oil over Ca3.5xZr0.5yAlxO3 mixed oxide catalyst

Novel mixed metal oxide catalyst Ca_3.5xZr_0.5yAl_xO₃ was synthesized through the coprecipitation of metal hydroxides. The textural, morphological, and surface properties of the synthesized catalysts were characterized via Brunauer–Emmett–Teller method, X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy. The catalytic performance of the as-synthesized catalyst series was evaluated during the transesterification of cooking palm oil with methanol to produce fatty acid methyl esters (FAME). The influence of different parameters, including the calcination temperature (300–700 °C), methanol to oil molar ratio (6:1–25:1), catalyst amount (0.5–6.5 wt%), reaction time (0.5–12 h) and temperature (70–180 °C), on the process was thoroughly investigated. The metal oxide composite catalyst with a Ca:Zr ratio of 7:1 showed good catalytic activity toward methyl esters. Over 87% of FAME content was obtained when the methanol to oil molar ratio was 12:1, reaction temperature 150 °C, reaction time 5 h and 2.5 wt% of catalyst loading. The catalyst could also be reused for over four cycles.     

Continuous esterification for biodiesel production from palm fatty acid distillate using economical process

An overflow system for continuous esterification of palm fatty acid distillate (PFAD) using an economical process was developed using a continuous stirred tank reactor (CSTR). Continuous production compared to batch production at the same condition had higher product purity. The optimum condition for the esterification process was a 8.8:1:0.05 molar ratio of methanol to PFAD to sulfuric acid catalyst, 60 min of residence time at 75 °C under its own pressure. The free fatty acid (FFA) content in the PFAD was reduced from 93 to less than 1.5%wt by optimum esterification. The esterified product had to be neutralized with 10.24%wt of 3 M sodium hydroxide in water solution at a reaction temperature of 80 °C for 20 min to reduce the residual FFA and glycerides. The components and properties of fatty acid methyl ester (FAME) could meet the standard requirements for biodiesel fuel. Eventually the production costs were calculated to disclose its commercialization.     

Esterification of high FFA tung oil with solid acid catalyst in fixed bed reactor

The effect of molar ratio of methanol to oil, temperature and space velocity (SV) on pre-esterification of Tung oil was carried out in pilot-scale fixed bed reactor, with solid acid catalysts. The molar ratio results showed the maximum acid value reduction efficiency (90.21%) was obtained at the molar ratio of 8:1, the acid value decreased sharply to 0.70 g kg^?1 of KOH. And esterification reaction attained balance when space velocity was enough, so 0.029 h^?1 was optimal space velocity. Furthermore, activity of reactant and rate of reaction increase with temperature increased, and the maximum conversion was achieved at 65 °C, the acid value of Tung oil could be reduced to 1.4 g kg^?1 of KOH.     

The nanometer magnetic solid base catalyst for production of biodiesel

Nanometer magnetic solid base catalysts were prepared by loading CaO on Fe₃O₄ with Na₂CO₃ and NaOH as precipitator, respectively. The optimum conditions for preparation of this catalyst were investigated. The influence of the proportion of Ca²⁺ to Fe₃O₄ on the catalytic performance has been studied. The catalyst with highest catalytic activity has been obtained when the proportion of Ca²⁺ to Fe₃O₄ is 7:1; the catalytic activity of the catalyst calcined from Ca(OH)₂ to Fe₃O₄ is better than that calcined from CaCO₃ to Fe₃O₄; under the conditions of methanol/oil molar ratio of 15:1, catalyst dosage of 2 wt% and temperature of 70 °C, the biodiesel yield reaches to 95% in 80 min, even to 99% finally. The catalytic activity and recovery rate of the nanometer magnetic solid base catalysts are much better than those of CaO. Calcination temperature was determined by differential thermogravimetric analysis. Ca₂Fe₂O₅, a kind of new metal multiple oxide, was found in the catalyst through X-ray diffraction. At the end, these catalysts were characterized by scanning electronic microscope (SEM), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM).     

Study on the use of MgAl hydrotalcites as solid heterogeneous catalysts for biodiesel production

This paper, reports experimental work on the use of new heterogeneous solid basic catalysts for biodiesel production: double oxides of Mg and Al, produced by calcination, at high temperature, of MgAl lamellar structures, the hydrotalcites (HT). The most suitable catalyst system studied are hydrotalcite Mg:Al 2:1 calcinated at 507 °C and 700 °C, leading to higher values of FAME also in the second reaction stage. One of the prepared catalysts resulted in 97.1% Fatty acids methyl esters (FAME) in the 1st reaction step, 92.2% FAME in the 2nd reaction step and 34% FAME in the 3rd reaction step. The biodiesel obtained in the transesterification reaction showed composition and quality parameters within the limits specified by the European Standard EN 14214. 2.5% wt catalyst/oil and a molar ratio methanol:oil of 9:1 or 12:1 at 60–65 °C and 4 h of reaction time are the best operating conditions achieved in this study. This study showed the potential of Mg/Al hydrotalcites as heterogeneous catalysts for biodiesel production.     

Comparison of biodiesel production from crude Jatropha oil and Krating oil by supercritical methanol transesterification

This work compared the production of biodiesel from two different non-edible oils with relatively high acid values (Jatropha oil and Krating oil). Using non-catalytic supercritical methanol transesterification, high methyl ester yield (85–90%) can be obtained in a very short time (5–10 min). However, the dependence of fatty acid methyl ester yield on reaction conditions (i.e., temperature and pressure) and the optimum conditions were different by the source of oils and were correlated to the amount of free fatty acids (FFAs) and unsaturated fatty acid content in oils. Krating oil, which has higher FFAs and unsaturated fatty acid content, gave higher fatty acid methyl ester yield of 90.4% at 260 °C, 16 MPa, and 10 min whereas biodiesel from Jatropha oil gave fatty acid methyl ester yield of 84.6% at 320 °C, 15 MPa and 5 min using the same molar ratio of methanol to oil 40:1. The product quality from crude Krating oil met the biodiesel standard. Pre-processing steps such as degumming or oil purification are not necessary.     

Biodiesel production from soybean and Jatropha oils using cesium impregnated sodium zirconate as a heterogeneous base catalyst

Cesium modified sodium zirconate (Cs-Na₂ZrO₃) was prepared by ionic exchange from sodium zirconate (Na₂ZrO₃), which was synthesized via a solid state reaction. Both ceramics, i.e., pristine Na₂ZrO₃ and the Cs-Na₂ZrO₃, were used as basic heterogeneous catalysts in biodiesel production. Soybean and Jatropha oils were used as triglyceride sources for transesterification reactions. Parameters, such as catalyst concentration (between 0.5 and 3 wt%), reaction time, different methanol/vegetable oil molar ratios, and temperature of the reaction, were evaluated. The cesium cation influence was evaluated from the basic transesterification reactivity. The results showed that the introduction of cesium significantly modified the catalytic activity in biodiesel production. Cs enhanced the reaction kinetics in obtaining biodiesel and reduced the reaction time in comparison with pristine Na₂ZrO₃. The results showed that Cs-Na₂ZrO₃ as a basic heterogeneous catalyst exhibited the best fatty acid methyl esters (FAME) conversion for soybean oil (98.8%) at 1 wt%, 30:1 methanol/oil ratio, 65 °C, and 15 min. The best conditions for Jatropha oil (90.8%) were 3 wt%, 15:1 methanol/oil ratio, 65 °C, and 1 h. The impregnation of Na₂ZrO₃ with cesium represents a very exciting alternative heterogeneous base catalyst for biodiesel production.