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.     

Process optimization for methyl ester production from waste cooking oil using activated carbon supported potassium fluoride

This paper presents the transesterification of waste cooking palm oil (WCO) using activated carbon supported potassium fluoride catalyst. A central composite rotatable design was used to optimize the effect of molar ratio of methanol to oil, reaction period, catalyst loading and reaction temperature on the transesterification process. The reactor was pressurized up to 10 bar using nitrogen gas. All the variables were found to affect significantly the methyl ester yield where the most effective factors being the amount of catalyst and reaction temperature, followed by methanol to oil ratio. A quadratic polynomial equation was obtained for methyl ester yield by multiple regression analysis using response surface methodology (RSM). The optimum condition for transesterification of WCO to methyl ester was obtained at 3 wt.% amount of catalyst, 175 °C temperature, 8.85 methanol to oil molar ratio and 1 h reaction time. At the optimum condition, the predicted methyl ester yield was 83.00 wt.%. The experimental value was well within the estimated value of the model. The catalyst showed good performance with a high yield of methyl ester and the separation of the catalyst from the liquid mixture is easy.     

Transesterification of soybean oil with nano-MgO or not in supercritical and subcritical methanol

Nano-MgO can apparently improve the transesterification reaction of soybean oil with supercritical/subcritical methanol. The variables affecting the yield of methyl ester during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of methanol to soybean oil were investigated and compared with those of non-catalyst. When nano-MgO was added from 0.5 wt% to 3 wt%, the transesterification rate increased evidently, while the catalyst content was further enhanced to 5 wt%, little increased in yield. It was observed that increasing the reaction temperature had a favorable influence on methyl ester yield. In addition, for molar ratios of methanol to soybean oil ranging from 6 to 36, the higher molar ratios of methanol to oil was charged, the faster transesterification rate was obtained. When the temperature was increased to 533 K, the transesterification reaction was essentially completed within 10 min with 3 wt% nano-MgO and the methanol/oil molar rate 36:1. Such high reaction rate with nano-MgO was mainly owing to the lower activation energy (75.94 kJ/mol) and the higher stirring.     

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.     

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.     

Biodiesel production using alumina-supported calcium oxide: An optimization study

This study consists of the optimization of the methyl ester yields produced via transesterification of palm oil using CaO/Al₂O₃ solid base catalyst. Response Surface Methodology (RSM) in combination with Central Composite Design (CCD) was used to optimize the operating parameters. Alcohol/oil molar ratio, catalyst content in the reaction medium and reaction temperature were chosen as the variables and the response selected was the amount of methyl ester yields. All the reactions were performed in a batch laboratory scale reactor for 5 h; the optimum reaction conditions obtained were approximately alcohol/oil molar ratio of 12:1, catalyst content of 6 wt.% and reaction temperature of 65 °C. The results from ICP-MS exhibited insignificant leaching of the CaO active species into the reaction medium and the reusability of the catalyst was successfully tested in two subsequent cycles. Under certain reaction conditions the glycerol obtained was almost colorless.     

Conversion of waste cooking oil to biodiesel using ferric sulfate and supercritical methanol processes

In this comparative study, conversion of waste cooking oil to methyl esters was carried out using the ferric sulfate and the supercritical methanol processes. A two-step transesterification process was used to remove the high free fatty acid contents in the waste cooking oil (WCO). This process resulted in a feedstock to biodiesel conversion yield of about 85-96% using a ferric sulfate catalyst. In the supercritical methanol transesterification method, the yield of biodiesel was about 50-65% in only 15 min of reaction time. The test results revealed that supercritical process method is probably a promising alternative method to the traditional two-step transesterification process using a ferric sulfate catalyst for waste cooking oil conversion. The important variables affecting the methyl ester yield during the transesterification reaction are the molar ratio of alcohol to oil, the catalyst amount and the reaction temperature. The analysis of oil properties, fuel properties and process parameter optimization for the waste cooking oil conversion are also presented.     

Roselle (Hibiscus sabdariffa L.) oil as an alternative feedstock for biodiesel production in Thailand

The production of biodiesel fuel from crude roselle oil was evaluated in this study. The process of alkali-catalyzed transesterification with methanol was carried out to examine the effects of reaction variables on the formation of methyl ester: variables which included methanol-to-oil molar ratios of 4:1-10:1, catalyst concentrations of 0.25-2.0% w/w of oil, reaction temperatures of 32-60 °C, and reaction times of 5-80 min. The methyl ester content from each reaction condition was analyzed by gas chromatography (GC), the optimum condition having been achieved at a methanol-to-oil molar ratio of 8:1, a catalyst concentration of 1.5% w/w of oil, a reaction temperature of 60 °C, and a reaction time of 60 min. The resultant methyl ester content of 99.4% w/w, plus all of the other measured properties of the roselle biodiesel, met the Thai biodiesel (B100) specifications and international standards EN 14214:2008 (E) and ASTM D 6751-07b, with the exception of a higher carbon residue and lower oxidation stability.     

Optimization of polyol ester production by transesterification of Jatropha-based methyl ester with trimethylolpropane using Taguchi design of experiment

Polyol ester production from transesterification of Jatropha oil methyl ester (JOME) and trimethylolpropane (TMP) was investigated. The effects of temperature, pressure, ratio of JOME:TMP and catalyst amount were studied in optimization experiment, using Taguchi L9 experimental layout. The parameters explored were found to have a significant impact on the reaction. The order of importance of the variables was found to be pressure, temperature, JOME:TMP molar ratio and catalyst. The optimum reaction conditions were identified to be 483 K, 25 kPa; 1.0% w/w catalyst and JOME:TMP molar ratio of 4:1. At this optimum condition the JOME conversion obtained was 91.5%. Confirmation experiments were performed to demonstrate the effectiveness of this approach after the optimum levels of process parameters were determined.     

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.     

Production of biodiesel by ultrasound assisted esterification of Oreochromis niloticus oil

This paper evaluates the production of methyl esters from Oreochromis niloticus (Nile tilapia) oil and methanol. The reaction was carried out applying low-frequency high-intensity ultrasound (40 kHz) under atmospheric pressure and ambient temperature. Response surface methodology (RSM) was used to evaluate the influence of alcohol to oil molar ratio, catalyst concentration (sulfuric acid) and temperature on the yield of O. niloticus oil into methyl esters. Analysis of the operating conditions by RSM showed that the most important operating condition affecting the reaction was the alcohol to FFA molar ratio. The highest yield observed was of 98.2% after 90 min of reaction. The optimal operating condition was obtained applying an alcohol to oil molar ratio of 9.0 and a catalyst concentration of 2.0% w/w and temperature of 30 °C.     

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.     

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.     

Transesterification of sunflower oil catalyzed by flyash-based solid catalysts

Flyash-based base catalyst was used in the transesterification of sunflower oil with methanol to methyl esters in a heterogeneous manner. Catalyst preparation variables such as, the KNO₃ loading amount and calcination temperature were optimized. The catalysts were characterized by powder XRD. The catalyst prepared by loading of 5 wt.% KNO₃ on flyash followed by its calcination at 773 K has exhibited maximum oil conversion (87.5 wt.%). The influence of various reaction parameters such as % catalyst loading, methanol to oil molar ratio, reaction time, temperature, reusability of the catalyst on the catalytic activity was investigated. K₂O derived from KNO₃ might be an essential component in the catalyst for its efficiency.     

In-situ synthesis of MCM-41 on ceramic membranes and its application in transesterification as catalyst support for p-toluenesulfonic acid

In this study, a new kind of solid acid catalyst p-toluenesulfonic acid/MCM-41/ceramic membrane was synthesized by in situ synthesis and impregnation method, which has shown its favorable catalytic activity, as verified in the transesterification and catalyst characterization. The catalyst was characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared spectroscopy. The transesterification of palm oil and methanol results showed that p-toluenesulfonic acid/MCM-41/ceramic membrane had the highest catalytic activity with immersing p-toluenesulfonic acid solution concentration of 0.15 mol/L. Different operation parameters of the transesterification of palm oil with methanol, such as catalyst amount, catalytic mass ratio, reaction time, reaction temperature and methanol/palm oil molar ratio were investigated. Under the optimum conditions of 4 % of fresh catalyst (catalytic mass ratio is 4.37 %), 80 min of reaction time, reaction temperature of 120 °C and methanol to palm oil molar ratio of 12:1, a relatively high fatty acid methyl ester yield of 95.6 % was obtained.     

蓖麻油酸甲酯合成和高温裂解反应条件优化

先用蓖麻油和甲醇酯交换合成蓖麻油酸甲酯,再对蓖麻油酸甲酯进行高温裂解制备十一碳烯酸,探讨各种因素对蓖麻油酸甲酯合成和裂解的影响,得到较为适宜的反应条件。合成蓖麻油酸甲酯适宜的条件为:系统真空度0.095 MPa,反应时间4 h,甲醇钠催化剂质量为蓖麻油质量的3.00%,反应温度35 ℃,醇油物质的量比18∶1,该条件下,蓖麻油酸甲酯收率为86.4%;550 ℃裂解蓖麻油酸甲酯为最佳温度,十一碳烯酸收率为44.15%。     

Biodiesel production using supercritical methanol/carbon dioxide mixtures in a continuous reactor

Fatty acid methyl esters (biodiesel) were produced by the transesterification of triglycerides with compressed methanol (critical point at 240 °C and 81 bar) in the presence of solid acids as heterogeneous catalyst (SAC-13). Addition of a co-solvent, supercritical carbon dioxide (critical point at 31 °C and 73 bar), increased the rate of the supercritical alcohols transesterification, making it possible to obtain high biodiesel yields at mild temperature conditions. Experiments were carried out in a fixed bed reactor, and reactions were studied at 150-205 °C, mass flow rate 6-24 ml/min at a pressure of 250 bar. The molar ratio of methanol to oil, and catalyst amount were kept constant (9 g). The reaction temperature and space time were investigated to determine the best way for producing biodiesel. The results obtained show that the observed reaction rate is 20 time faster than conventional biodiesel production processes. The temperature of 200 °C with a reaction time of 2 min were found to be optimal for the maximum (88%) conversion to methyl ester and the free glycerol content was found below the specification limits.     

An ideal feedstock, kusum (Schleichera triguga) for preparation of biodiesel: Optimization of parameters

Kusum (Schleichera triguga), a non-edible oil bearing plant has been used as an ideal feedstock for biodiesel development in the present study. Various physical and chemical parameters of the raw oil and the fatty acid methyl esters derived have been tested to confirm its suitability as a biodiesel fuel. The fatty acid component of the oil was tested by gas chromatography. The acid value of the oil was determined by titration and was found to 21.30 mg KOH/g which required two step transesterification. Acid value was brought down by esterification using sulfuric acid (H₂SO₄) as a catalyst. Thereafter, alkaline transesterification was carried out using potassium hydroxide (KOH) as catalyst for conversion of kusum oil to its methyl esters. Various parameters such as molar ratio, amount of catalyst and reaction time were optimized and a high yield (95%) of biodiesel was achieved. The high conversion of the feedstock into esters was confirmed by analysis of the product on gas chromatograph-mass spectrometer (GC-MS). Viscosity and acid value of the product biodiesel were determined and found to be within the limits of ASTM D 6751 specifications. Elemental analysis of biodiesel showed presence of carbon, hydrogen, oxygen and absence of nitrogen and sulfur after purification. Molar ratio of methanol to oil was optimized and found to be 10:1 for acid esterification, and 8:1 for alkaline transesterification. The amounts of H₂SO₄ and KOH, 1% (v/v) and 0.7% (w/w), respectively, were found to be optimum for the reactions. The time duration of 1 h for acid esterification followed by another 1 h for alkaline transesterification at 50 ± 0.5 °C was optimum for synthesis of biodiesel.     

Ca and Zn mixed oxide as a heterogeneous base catalyst for transesterification of palm kernel oil

Transesterification of palm kernel oil with methanol over mixed oxides of Ca and Zn has been investigated batchwise at 60 °C and 1 atm. CaO·ZnO catalysts were prepared via a conventional co-precipitation of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at near neutral conditions. The catalysts were characterized by using techniques of X-ray diffraction (XRD), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The results indicated that the mixed oxides possess relatively small particle sizes and high surface areas, compared to pure CaO and ZnO. Moreover, the combination of Ca and Zn reduced the calcination temperature required for decomposition of metal carbonate precipitates to active oxides. Influences of Ca/Zn atomic ratio in the mixed oxide catalyst, catalyst amount, methanol/oil molar ratio, reaction time, and water amount on the methyl ester (ME) content were studied. Under the suitable transesterification conditions at 60 °C (catalyst amount = 10 wt.%, methanol/oil molar ratio = 30, reaction time = 1 h), the ME content of >94% can be achieved over CaO·ZnO catalyst with the Ca/Zn ratio of 0.25. The mixed oxide can be also applied to transesterification of palm olein, soybean, and sunflower oils. Furthermore, the effects of different regeneration methods on the reusability of CaO·ZnO catalyst were investigated.     

Production of biodiesel through transesterification of Jatropha oil using KNO3/Al2O3 solid catalyst

The purpose of the work to study biodiesel production by transesterification of Jatropha oil with methanol in a heterogeneous system, using alumina loaded with potassium nitrate as a solid base catalyst. Followed by calcination, the dependence of the conversion of Jatropha oil on the reaction variables such as the catalyst loading, the molar ratio of methanol to oil, reaction temperature, agitation speed and the reaction time was studied. The conversion was over 84% under the conditions of 70 °C, methanol/oil mole ratio of 12:1, reaction time 6 h, agitation speed 600 rpm and catalyst amount (catalyst/oil) of 6% (w). Kinetic study of reaction was also done.