Techno-economic analysis of a biodiesel production process from vegetable oils

Biodiesel, which is defined as the monoalkyl esters of long chain fatty acids derived from a renewable lipid feedstock, has received considerable attention worldwide as a medium-term alternative to diesel fuel obtained from petroleum. Biodiesel can be produced by the transesterification of vegetable oils or animal fats using short-chain alcohols in the presence of a suitable catalyst and glycerol is the only byproduct obtained in significant quantities. In this work a techno-economic analysis of a process that produces biodiesel from vegetable oils is presented with the aim to investigate the dependence of the critical profitability indicators on the production capacity.     

Utilization of ethyl ester of waste vegetable oils as fuel in diesel engines

Jordan relies heavily on expensive and unreliable imported oil. Therefore, this study was initiated to investigate the potential of ethyl ester used as vegetable oil (VO; biodiesel) to substitute oil-based diesel fuel. The fuels tested were several ester/diesel blends including 100% ester in addition to diesel fuel, which served as the baseline fuel. Variable-speed tests were run on all fuels on a standard test rig of a single-cylinder, direct-injection diesel engine. Tests were conducted to compare these blends with the baseline local diesel fuel in terms of engine performance and exhaust emissions. The results indicated that the blends burned more efficiently with less specific fuel consumption, and therefore, resulted in higher engine thermal efficiency. Furthermore, the blends produced less carbon monoxide and unburned hydrocarbons than diesel fuel. The 100% ester fuel and the blend of 75:25 ester/diesel gave the best performance while the 50:50 blend consistently resulted in the lowest amounts of emissions over the whole speed range tested.     

Intensification of biodiesel production from vegetable oils using ultrasonic-assisted process: Optimization and kinetic

Intensification of biodiesel production process using low frequency ultrasonic irradiation (20 kHz, 200 W) is elucidated in this study. Effects of five process variables in an ultrasonic-assisted reactor catalyzed by SrO through transesterification of vegetable oils are investigated. RSM was employed and the optimum conditions were at an ultrasonic pulse on of 9 s followed by 2 s of pulse off within a reaction time of 30.7 min. The optimum ultrasonic power was found to be 130 W using an oil amount of 52 g (R² = 0.97). The model was applicable to different types of oil with errors less than 10%. FFA content was responsible for the different yields obtained with different oils. Three steps of the transesterification process were measured to obtain the kinetic study. The results revealed that the reaction followed a second-order kinetic. The activation energies varied between 70.63 kJ/mol and 136.93 kJ/mol showing relatively high coefficient of determinations.     

Optimization of biodiesel production from edible and non-edible vegetable oils

The non-edible vegetable oils such as Jatropha curcas and Pongamia glabra (karanja) and edible oils such as corn and canola were found to be good viable sources for producing biodiesel. Biodiesel production from different edible and non-edible vegetable oils was compared in order to optimize the biodiesel production process. The analysis of different oil properties, fuel properties and process parameter optimization of non-edible and edible vegetable oils were investigated in detail. A two-step and single-step transesterification process was used to produce biodiesel from high free fatty acid (FFA) non-edible oils and edible vegetable oils, respectively. This process gives yields of about 90-95% for J. curcas, 80-85% for P. glabra, 80-95% for canola, and 85-96% for corn using potassium hydroxide (KOH) as a catalyst. The fuel properties of biodiesel produced were compared with ASTM standards for biodiesel.     

Transesterification processes for vegetable oils: A simple control method of methyl ester content

One of the main problems in the study or industrial application of transesterification processes for vegetable oils is how to measure the methyl ester content. In this work, a quick analytical method was developed for assessing the methyl ester content of purified “fuel grade” transesterification products by applying a simple correlation with viscosity. The correlation was tested on a wide range of samples with various methyl ester contents; the results were in agreement with the values measured by gas-chromatographic analysis. In a defined range of weight fractions the correlation allows for the determination of the methyl ester content of purified transesterification products by a single viscosity measurement. This method is especially suitable for process control purposes as it determines the methyl ester content quickly and simply.     

Increased yields in biodiesel production from used cooking oils by a two step process: Comparison with one step process by using TGA

Short chain alcohol esters of fatty acids can be used as diesel fuel. In this study, one step and two step base catalyzed room temperature transesterification reaction of used cooking oil was compared. In the two step base catalyzed process, for 1000 g of used cooking oil 4.2 g NaOH and 140 ml MeOH was used in the first step and 1.8 g NaOH and 60 ml MeOH was used in the second step. All reactions were done at 25 °C; the effects of water content and suspended particles on the yield were studied. The yields were easily determined by Thermo Gravimetric Analysis (TGA) instead of the usual Gas chromatography (GC) and the viscosity of products was measured by Ubbelohde type viscosimeter. It was found that two step processes gives a better yield (96%) than the one step process (86%).     

Transesterification of Camellia japonica and Vernicia fordii seed oils on alkali catalysts for biodiesel production

Camellia japonica and Vernicia fordii seed oils were employed as a feedstock for production of biodiesel by transesterification with methanol on alkali catalysts. The composition and physicochemical properties were investigated in the raw seed oils and the biodiesel products. The fatty acid methyl ester (FAME) contents in the biodiesel produced from the seed oils were above 96% on KOH catalyst in the reaction. It was acceptable for the limit of European biodiesel qualities for BD100. Other qualities such as cetane number, acid value, density, and kinematic viscosity, of the produced biodiesels also matched the biodiesel qualities.     

The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives

At present, the homogeneous base-catalyzed methanolysis reaction of vegetable oils is a most often used process for the industrial biodiesel production. The toxicity of methanol, the risk of the methanol vapor explosion and the possibility of the ethanol production from biorenewable resources have contributed to the development of a vegetable oil ethanolysis process for the biodiesel production. In the reaction of vegetable oils and ethanol in the presence of a catalyst, completely agricultural fuels consisted of fatty acid ethyl esters (FAEE) are obtained having physico-chemical properties similar to those of the appropriate methyl esters and diesel fuel. The ethanolysis reaction of various oily feedstocks has been widely studied to optimize the reaction conditions and to develop new catalytic systems and processes based on chemical and biological catalysts, as well as the development of non-catalytic processes. Most researches investigate the application of homogeneous base catalysts. This paper studies the review of vegetable oil ethanolysis investigations for the biodiesel production done so far. The goals of the paper are to present the development of FAEE synthesis by catalytic and non-catalytic processes, their advantages and disadvantages, the influence of some operating and reaction conditions on the process rate and ethyl esters yield, the kinetics models describing the ethanolysis process rate, the process optimization and the possibilities for improving the FAEE synthesis process.     

Graphical method to select vegetable oils as potential feedstock for biodiesel production

Chemical compositions of 80 vegetable oils were collected from literature and the properties of the obtainable biodiesel (methyl esters) have been predicted by empirical relationships. The purpose has been to check the viability of predicting if a biodiesel could meet the EN 14214 standards knowing only the fatty acid profile (FAP) of the parent oil. Two parameters were used in this investigation: (i) average number of carbon atoms in the fatty acid chains, (ii) average number of double bonds (C?C) per molecule. Two new empirical relationships have been proposed to predict the viscosity and the cetane number of biodiesel from the two parameters. The range of values of the two parameters leading to biodiesel meeting the EN 14214 standard for viscosity, cetane number, iodine value, and cold filter plugging point have been graphically obtained by overlapping the corresponding level surfaces. Practical applications: This work provides biodiesel producers with indications of the quality of biodiesel without the need for analytical testing of the product (indeed, of the product itself). Only the fatty acid profile of the starting vegetable oil is required. The quality of biodiesel can be estimated by using a chart developed in this work, allowing to estimate, e.g. if the biodiesel meets the European standards. The work can be useful to rapidly screen oil seed crops in studies of genetic engineering that require high throughput.     

棕榈油酯交换制备生物柴油的反应动力学

在甲醇与棕榈油的摩尔比为6∶1和催化剂KOH用量为棕榈油质量1.0%的条件下,研究不同温度下棕榈油制备生物柴油的酯交换反应动力学,采用Origin软件拟合曲线方程,建立棕榈油酯交换反应的宏观动力学模型。研究结果表明:棕榈油制备生物柴油的酯交换反应遵循1.40级动力学方程,反应速率随温度的升高而加快,二者符合Arrhenius方程,该反应的活化能为27.23 kJ/mol,频率因子为1.4×103。文中研究建立的反应动力学模型将对扩大试验研究提供理论依据和基础数据支持。     

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%.     

从废酯液中回收醋酸乙酯的分离技术

介绍了以废酯液为原料分离生产醋酸乙酯的工艺过程。利用废酯液中各组分在水中溶解特性的不同,水洗沉降对酸性物质与酯进行初步分离。依据精馏理论,确定分离初始方案。选择合适的热力学方程,利用模拟软件模拟分离过程;根据总费用最小,优化操作条件和塔设备参数,确定最优分离条件。模拟计算结果表明:采用2个塔流程可有效分离生产出合格品醋酸乙酯,年收益达500.1万元。     

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.     

An original transesterification route for fatty acid ester production from vegetable oils in a solvent-free system

Wax ester production from a long-chain alcohol and methyl ester has been investigated with an immobilized thermostable lipase (lipozyme IM from Novo Nordisk). The transesterification reaction rate was monitored in solvent-free medium that was exclusively composed of the reactants and the enzyme. The transesterification is performed by simply mixing the two substrates in various stoichiometric amounts at a temperature range from 55 to 65°C under constant stirring in the presence of low concentrations of enzyme preparation (0.12 to 2%, w/w). Long-chain reactants produce waxes of high molecular mass that induce low solubility and high viscosity. On average, high transesterification yields are obtained (around 95%). Thermodynamic parameters involving substrate concentration and temperature have also been investigated. The balance between optimal working temperature and the molar ratio of substrates in such a complex medium appears to be 60°C, with a molar ratio methyl oleate/stearyl alcohol of 1:0.5. Substrate inhibition due to stearyl alcohol has been observed. A study of kinetic parameters has confirmed these results.     

废动植物油生产生物柴油的工程设计

介绍了以废动植物油为原料,在自制新型微酸性DYD催化剂的作用下,通过酯交换反应生成生物柴油的设计过程。根据各个步骤的反应条件及其生产物的特性,结合工业化生产流程的一般规律,通过物性计算,设计出工业化生产工艺流程。结果表明:醇解与酯化转化率达到95.9%,无污染物排放,生物柴油的各项性能指标均达到美国同类产品的标准(D6751-03a),为发展生物柴油探索了一条切实可行的途径。     

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.     

Biodiesel production from non-degummed vegetable oils: Phosphorus balance throughout the process

In this work, the biodiesel production process using high-phosphorous content raw materials is studied. The objective is to determine the phosphorous mass balances, in order to determine the amount of this element in each stream of an integrated process including esterification, transesterification, and glycerin purification. It was found that up to 97% of the initial phosphorous content in the oil is accumulated in the glycerin phase. The small amount of phosphorous left in the biodiesel phase after decantation is eliminated during the acid extraction carried out to purify the biodiesel. The evaporation of methanol after the reaction plays a major role in the quantity of phosphorous and soaps left in the biodiesel phase. For example, with a crude soybean oil containing 226 ppm of phosphorous, the methanol content at the end of the reaction in the biodiesel phase is 4.6 wt.%, being the phosphorous content 7.1 ppm, and the soap concentration 3.89 g/kg. The methanol was evaporated in such a way that its concentration dropped to 0.35 wt.%, and the phosphorous and soaps concentrations decreased to 4 ppm and 0.7 g/kg respectively. This has a direct impact in the quality of the final biodiesel. During the esterification, also an important amount of phosphorous is eliminated from the biodiesel phase.     

Chemical modification of vegetable oils for lubricant applications

Owing to the unfavorable impact on the environment of mineral oil-based lubricants, there has been a steady increase in the demand for biodegradable, environment-friendly lubricants. However, development of a biodegradable base fluid that could replace or partially substitute conventional mineral oil is a big challenge. Vegetable oils are recognized as rapidly biodegradable and are thus promising candidates as base fluids in environment-friendly lubricants. Vegetble oils have excellent lubricity, but poor oxidation and low-temeprature stability. This paper presents a series of structural modifications of vegetable oils using anhydrides of different chain lengths. The reaction was monitored and products were confirmed by NMR, FTIR, gel permeation chromatography, and thermogravimetric analysis (TGA). Experimental conditions were optimized for research quantity and for laboratory scale-up (up to 4 lb=1.8 kg). The thermo-oxidation stability of these new lubricant base fluids was tested using pressure differential scanning calorimetry and TGA. The chemically modified base fluids exhibit superior oxidation stability in comparison with unmodified vegetable oils. These base fluids in combination with suitable additives exhibit equivalent oxidation stability compared with mineral oil-based formulations.     

Process optimization for biodiesel production from Jatropha, Karanja and Polanga oils

Petroleum sourced fuels is now widely known as non-renewable due to fossil fuel depletion and environmental degradation. Renewable, carbon neutral, transport fuels are necessary for environmental and economic sustainability. Biodiesel derived from oil crops is a potential renewable and carbon neutral alternative to petroleum fuels. Chemically, biodiesel is monoalkyl esters of long chain fatty acids derived from renewable feed stock like vegetable oils and animal fats. It is produced by transesterification in which, oil or fat is reacted with a monohydric alcohol in presence of a catalyst. The process of transesterification is affected by the mode of reaction condition, molar ratio of alcohol to oil, type of alcohol, type and amount of catalysts, reaction time and temperature and purity of reactants. In the present paper various methods of preparation of biodiesel from non-edible filtered Jatropha (Jatropha curcas), Karanja (Pongamia pinnata) and Polanga (Calophyllum inophyllum) oil have been described. Mono esters (biodiesel) produced and blended with diesel were evaluated. The technical tools and processes for monitoring the transesterification reactions like TLC, GC and HPLC have also been used.     

Transesterification for biodiesel production catalyzed by combined lipases: Optimization and kinetics

Preparation of biodiesel from waste cooking oil catalyzed by combined lipases in tert‐butanol medium was investigated. Several crucial parameters affecting biodiesel yield were optimized by response surface methodology, such as dosage of combined lipases of Novozym 435 and Lipozyme TLIM, weight ratio of Novozym 435 to Lipozyme TLIM, amount of tert‐butanol, reaction temperature, and molar ratio of oil to methanol. Under the optimized conditions, the highest biodiesel yield was up to 83.5% The proposed model on biodiesel yield had a satisfactory coefficient of R² (= 94.02%), and was experimentally verified. The combined lipases exhibited high‐operational stability. After 30 cycles (300 h) successively, the activity of combined lipases maintained 85% of its original activity. A reaction kinetic model was proposed to describe the system and deduced to be a pseudo‐first‐order reaction, and the calculated activation energy was 51.71 kJ/mol. © 2009 American Institute of Chemical Engineers AIChE J, 2010