Effect of methanol content on enzymatic production of biodiesel from waste frying oil

The enzymatic production of biodiesel from waste frying oil with methanol has been studied using immobilized lipase Novozym 435 as catalyst. The effects of methanol to oil molar ratio, dosage of enzyme and reaction time were investigated. The optimum reaction conditions were methanol to oil molar ratio of 25:1, 10% of Novozym 435 based on oil weight and reaction period of 4 h at 50 °C obtaining a biodiesel yield of 89.1%. Moreover, the reusability of the lipase over repeated cycles was also investigated under standard conditions.     

Microwave assisted in continuous biodiesel production from waste frying palm oil and its performance in a 100 kW diesel generator

A household microwave (800W) was modified as a biodiesel reactor for continuous transethylation of waste frying palm oil. The high free fatty acid oil was simultaneously neutralized and transesterified with sodium hydroxide. With the ethanol to oil molar ratio of 12:1, 3.0% NaOH (in ethanol) and 30s residence time, the continuous conversion of waste frying palm oil to ethyl ester was over 97%. The waste palm oil biodiesel was then tested in a 100 kW diesel generator as a neat fuel (B100) and 50% blend with diesel No. 2 fuel (B50). The engine performance and emission are recorded. At the engine loads varied from 0 kW to 75 kW (at 25 kW intervals) of the maximum electrical rating, the performance of the neat and B50 are slightly lower than diesel No. 2 fuel. Emissions of NO_x, CO and HC from B100 and B50 are lower than those of diesel No. 2 fuel, except that at the 75 kW engine load, where the B100 emits higher levels of NO_x than the diesel No. 2 fuel.     

甲醇钠催化地沟油制备生物柴油研究

以浓硫酸为催化剂,高酸值地沟油与甲醇酯化反应降酸的最优工艺条件为:n(甲醇):n(地沟油)=9:1,m(浓硫酸):m(地沟油)=1.1％,反应温度60℃,反应时间5h.制备生物柴油的最优工艺条件为:以甲醇钠为催化剂,反应时间2h,反应温度65℃,n(甲醇):n(地沟油)=7:1,m(甲醇钠):m(地沟油)=0.8％.制...     

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.     

Physical-chemical properties of waste cooking oil biodiesel and castor oil biodiesel blends

This work presents the physical-chemical properties of fuel blends of waste cooking oil biodiesel or castor oil biodiesel with diesel oil. The properties evaluated were fuel density, kinematic viscosity, cetane index, distillation temperatures, and sulfur content, measured according to standard test methods. The results were analyzed based on present specifications for biodiesel fuel in Brazil, Europe, and USA. Fuel density and viscosity were increased with increasing biodiesel concentration, while fuel sulfur content was reduced. Cetane index is decreased with high biodiesel content in diesel oil. The biodiesel blends distillation temperatures T₁₀ and T₅₀ are higher than those of diesel oil, while the distillation temperature T₉₀ is lower. A brief discussion on the possible effects of fuel property variation with biodiesel concentration on engine performance and exhaust emissions is presented. The maximum biodiesel concentration in diesel oil that meets the required characteristics for internal combustion engine application is evaluated, based on the results obtained.     

Statistical optimization for lithium silicate catalyzed production of biodiesel from waste cooking oil

Lithium silicate is one of the suitable heterogeneous catalysts for biodiesel production. The possibilities of large number of combinations of different reaction parameters make the optimization of biodiesel production process over various heterogeneous catalysts highly tedious, necessitating the development of alternate strategies for parameter optimization. Here, Box-Behnken design (BBD) coupled with response surface methodology (RSM) is employed to optimize the process parameters required for the production of biodiesel from waste cooking oil using lithium silicate as catalyst. Simple method of impregnation was performed for the material preparation and the catalyst was analyzed using different techniques. It was found that the activity is directly proportional to the basicity data obtained from temperature programmed desorption (TPD) of CO₂ over various catalyst systems. The material exhibits macroporous morphology and the major crystalline phase of the most active catalyst was found to be Li₂SiO₃. The effects of different reaction parameters were studied and a biodiesel yield of 100% was obtained under the predicted optimum reaction conditions of methanol : oil molar ratio 15 : 1, catalyst amount 7 wt%, reaction temperature 55 °C and reaction time 2.5 h. The validation experiments showed a correlation coefficient of 0.95 between the predicted and experimental yield of biodiesel, which indicates the high significance of the model. The fuel properties of biodiesel obtained under the optimum conditions met the specifications as mentioned in ASTM D6751 and EN 14214 standards. Catalyst heterogeneity and low reaction temperature are the major attractions of the present biodiesel preparation strategy.     

Biodiesel production from Croton megalocarpus oil and its process optimization

Production of biodiesel from non-edible feedstocks is attracting more attention than in the past, for the purpose of manufacturing alternative fuels without interfering with the food chain. Biodiesel was produced using Croton megalocarpus oil as a non-edible feedstock. C. megalocarpus oil was obtained from north Tanzania. This study aimed at optimizing the biodiesel production process parameters experimentally. The parameters involved in the optimization process were the amount of the catalyst, of alcohol, temperature, agitation speed and reaction time. The optimum biodiesel conversion efficiency obtained was 88% at the optimal conditions of 1.0 wt.% amount of potassium hydroxide catalyst, 30 wt.% amount of methanol, 60 °C reaction temperature, 400 rpm agitation rate and 60 min reaction time. The properties of croton biodiesel which were determined fell within the recommended biodiesel standards. Croton oil was found with a free fatty acid content of 1.68% which is below the 2% recommended for the application of the one step alkaline transesterification method. The most remarkable feature of croton biodiesel is its cold flow properties. This biodiesel yielded a cloud and pour point of −4 °C and −9 °C, respectively, while its kinematic viscosity lay within the recommended standard value. This points to the viability of using croton biodiesel in cold regions.     

Long storage stability of biodiesel made from rapeseed and used frying oil

The degree of physical and chemical deterioration of biodiesel produced from rapeseed and used frying oil was studied under different storage conditions. These produced drastic effects when the fuel was exposed to daylight and air. However, there were no significant differences between undistilled biodiesel made from fresh rapeseed oil and used frying oil. The viscosity and neutralization numbers rose during storage owing to the formation of dimers and polymers and to hydrolytic cleavage of methyl esters into fatty acids. However, even for samples studied under different storage conditions for over 150 d the specified limits for viscosity and neutralization numbers had not been reached. In European biodiesel specifications there will be a mandatory limit for oxidative stability, because it may be a crucial parameter for injection pump performance. The value for the induction period of the distilled product was very low. The induction period values for the undistilled samples decreased very rapidly during storage, especially with exposure to light and air.     

The use of a modified TDSP for biodiesel production from soybean, linseed and waste cooking oil

In this study, the Transesterification Double Step Process (TDSP) for the production of biodiesel from vegetable oil was modified to yield a shorter reaction time and products with improved quality. TDSP consists in a two step transesterification procedure which starts with a basic catalysis, followed by an acidic catalysis. The process modifications included a reduction in the concentration of catalysts, a reduction in the reaction time of the first step and the direct mixing of methanol/acid solution, without cooling the system between the first and second step. A comparison between washed and unwashed biodiesel demonstrates that the final washing and drying procedure is necessary for satisfactory results. The products were analyzed by ¹H-NMR and nineteen different biodiesel analyses specific for international quality certification. The modified procedure resulted in a high conversion index (97% for waste cooking oil and soybean oil and 98% for linseed oil) and high yield (87 ± 5% for waste cooking oil, 92 ± 3% for soybean and 93 ± 3% for linseed oil). The biodiesel produced by the modified TDSP met ASTM, EN ISO and ABNT standards before the addition of stabilizer.     

Long storage stability of biodiesel from vegetable and used frying oils

Biodiesel is defined as the mono-alkyl esters of vegetable oils. Production of biodiesel has grown tremendously in European Union in the last years. Though the commercial prospects for biodiesel have also grown, there remains some concern with respect to its resistance to oxidative degradation during storage. Due to the chemical structure of biodiesel the presence of the double bond in the molecule produce a high level of reactivity with the oxygen, especially when it placed in contact with air. Consequently, storage of biodiesel over extended periods may lead to degradation of fuel properties that can compromise fuel quality.This study used samples of biodiesel prepared by the process of transesterification from different vegetable oils: high oleic sunflower oil (HOSO), high and low erucic Brassica carinata oil (HEBO and LEBO) respectively and used frying oil (UFO). These biodiesels, produced from different sources, were used to determine the effects of long storage under different conditions on oxidation stability. Samples were stored in white (exposed) and amber (not exposed) glass containers at room temperature.The study was conducted for a period of 30-months. At regular intervals, samples were taken to measure the following physicochemical quality parameters: acid value (AV), peroxide value (PV), viscosity (ν), iodine value (IV) and insoluble impurities (II). Results showed that AV, PV, ν and II increased, while IV decreased with increasing storage time of biodiesel samples. However, slight differences were found between biodiesel samples exposed and not exposed to daylight before a storage time of 12 months. But after this period the differences were significant.     

Current scenario and potential of biodiesel production from waste cooking oil in Pakistan: An overview

Biodiesel utilization has been rapidly growing worldwide as the prime alternative to petrodiesel due to a global rise in diesel fuel demand along with hazardous emissions during its thermochemical conversion. Although, several debatable issues including feedstock availability and price, fuel and food competition, changes in land use and greenhouse gas emission have been raised by using edible as well as inedible feedstocks for the production of biodiesel. However, non-crop feedstocks could be a promising alternative. In this article, waste cooking oils have been recommended as a suitable option for biodiesel production bearing in mind the current national situation. The important factors such as the quantity of waste cooking oil produced, crude oil and vegetable oil import expenses, high-speed diesel imports, waste management issues and environmental hazards are considered. Moreover, process simulation and operating cost evaluation of an acid catalyzed biodiesel production unit are also conducted. The simulation results show that the production cost of waste cooking oil-based biodiesel is about 0.66USD·L^-1. We believe that the present overview would open new pathways and ideas for the development of biofuels from waste to energy approach in Pakistan.     

Improving the cold flow properties of biodiesel from waste cooking oil by surfactants and detergent fractionation

The use of surfactants and detergent fractionation to improve the cold flow properties of biodiesel from waste cooking oil (BWCO) was investigated. The effect of five types of surfactants, including sugar esters (S270 and S1570), silicone oil (TSA 750S), polyglycerol ester (LOP-120DP) and diesel conditioner (DDA) on the reduction of the cold filter plugging point (CFPP) of the BWCO, was evaluated, with the greatest reduction to the CFPP of the BWCO (from −10 °C to −16 °C) being was achieved by the addition of 0.02 wt% of polyglycerol ester (LOP-120P). Detergent fractionation of the BWCO was performed by first mixing partially crystallized biodiesel with a chilled detergent (sodium dodecylsulfate) solution accompanied by an electrolyte (magnesium sulfate), and then separating the mixture by centrifugation to obtain the BWCO liquid. An orthogonal experimental design was utilized to investigate the effects of the various parameters on detergent fractionation. The optimal parameters, as obtained by range analysis, were as follows: detergent loading 0.3 wt%, electrolyte loading 1.0 wt%, and water loading 150 wt%. The CFFP of the liquid biodiesel from waste cooking oil (LBWCO) was −17 °C with a yield of 73.1% when the detergent fractionation was performed under these conditions. A limited number of biodiesel physical and chemical properties were analyzed before and after the addition of surfactants and detergent fractionation.     

Synthesis of economically viable biodiesel from waste frying oils (WFO)

In present communication, waste frying oil (WFO) has been used as a feedstock for biodiesel synthesis. WFO, procured from a local Indian restaurant possessed an acid value of 0.84 mg KOH/g, which is low enough for single step transesterification reaction. Biodiesel (fatty acid methyl esters) was washed after transesterification reaction and the yield got lowered substantially (from 96% to 86.36%) after water washing owing to loss of esters. 30:100 vol% (methanol to oil), 0.6 wt% NaOCH₃, 60°C temperature and 600 rpm agitation in 1 h reaction time was found to be optimum for transesterification reaction. ¹H NMR spectrum showed a high conversion (95.19%) of fatty acids in WFO to biodiesel in 2 h reaction time. Almost complete conversion (99.68%) was attained in 2 h reaction time. © 2011 Canadian Society for Chemical Engineering     

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

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

Small scale biodiesel synthesis from waste frying oil and crude methanol in Morocco

Biodiesel was produced at small scale by transesterification of used frying oil(UFO) recovered from Moroccan pastry shops and fish frying restaurants. Biodiesel was first synthesised at laboratory scale in order to optimize the transesterification parameters. The cost of the final product was also optimized using low-cost raw materials.The UFO and the produced biodiesel were characterized with several techniques including gas chromatography,1H NMR,13 C NMR, FTIR, and TGA–TDA techniques.1H NMR gas chromatographic analyses of the final product confirmed that the transesterification in the chosen experimental conditions was completed. These results were confirmed by TGA–TDA analysis used as new techniques to monitoring triglyceride conversion. The biodiesel did not contain any trace of glycerol, and it did meet the international standards. The transesterification at low cost in small scale conditions was performed at 60 °C using 1.2% of KOH and a methanol/oil molar ratio of 6:1. A yield of 80.8% was achieved. The properties of the produced biodiesel were found to be as good as those of biodiesels obeying to European standards. The biodiesel production was also performed at small-scale for individual utilisation. Thus, the product was tested in a kerosene stove for heating and non-modified commercial diesel engine producing electricity.     

An enzymatic/acid-catalyzed hybrid process for biodiesel production from soybean oil

The present study is aimed at developing an enzymatic/acid-catalyzed hybrid process for biodiesel production using soybean oil as feedstock. In the enzymatic hydrolysis, 88% of the oil taken initially was hydrolyzed by binary immobilized lipase after 5 h under optimal conditions. The hydrolysate was further used in acid-catalyzed esterification for biodiesel production and the effects of temperature, catalyst concentration, feedstock to methanol molar ratio, and reaction time on biodiesel conversion were investigated. By using a feedstock to methanol molar ratio of 1:15 and a sulfuric acid concentration of 2.5%, a biodiesel conversion of 99% was obtained after 12 h of reaction at 50 °C. The biodiesel produced by this process met the American Society for Testing and Materials (ASTM) standard. This hybrid process may open a way for biodiesel production using unrefined and used oil as feedstock.     

Exhaust emissions from a Diesel engine fueled with transesterified waste olive oil

The exhaust emissions of a Diesel direct injection Perkins engine fueled with waste olive oil methyl ester were studied at several steady-state operating conditions. Emissions were characterized with neat biodiesel from used olive oil and conventional Diesel fuel. Results revealed that the use of biodiesel resulted in lower emissions of CO (up to 58.9%), CO₂ (up to 8.6%, excepting a case which presented a 7.4% increase), NO (up to 37.5%), and SO₂ (up to 57.7%), with increase in emissions of NO₂ (up to 81%, excepting a case which presented a slight reduction). Biodiesel also presented a slight increase in brake-specific fuel consumption (lower than 8.5%) that may be tolerated due to the exhaust emission benefits. Combustion efficiency remained constant using either biodiesel or Diesel fuel. The proposed alternative for Diesel fuel could significantly decrease the enormous amount of waste frying oil, furthermore becoming less dependent on fossil oil imports and decreasing environmental pollution.     

Heterogeneous catalyzed biodiesel production from Moringa oleifera oil

In this study, biodiesel was produced from Moringa oleifera oil using sulfated tin oxide enhanced with SiO₂ (SO₄²⁻/SnO₂-SiO₂) as super acid solid catalyst. The experimental design was done using design of experiment (DoE), specifically, response surface methodology based on three-variable central composite design (CCD) with alpha (α) = 2. The reaction parameters studied were reaction temperature (60 °C to 180 °C), reaction period (1 h to 3 h) and methanol to oil ratio (1:6 to 1:24). It was observed that the yield up to 84 wt.% of Moringa oleifera methyl esters can be obtained with reaction conditions of 150 °C temperature, 150 min reaction time and 1:19.5 methanol to oil ratio, while catalyst concentration and agitation speed are kept at 3 wt.% and 350-360 rpm respectively. Therefore this study presents the possibility of converting a relatively new oil feedstock, Moringa oleifera oil to biodiesel and thus reducing the world's dependency on existing edible oil as biodiesel feedstock.     

Application of response surface methodology for optimization of biodiesel production by transesterification of soybean oil with ethanol

In this paper, the transesterification of soybean oil with ethanol is studied. The transesterification process can be affected by differing parameters. The biodiesel production process was optimized by the application of factorial design 2⁴ and response surface methodology. The combined effects of temperature, catalyst concentration, reaction time and molar ratio of alcohol in relation to oil were investigated and optimized using response surface methodology. Optimum conditions for the production of ethyl esters were the following: mild temperature at 56.7 °C, reaction time in 80 min, molar ratio at 9:1 and catalyst concentration of 1.3 M.     

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.