Thermodynamic analysis of fatty acid esterification for fatty acid alkyl esters production

The development of renewable energy source alternatives has become a planet need because of the unavoidable fossil fuel scarcity and for that reason biodiesel production has attracted growing interest over the last decade. The reaction yield for obtaining fatty acid alkyl esters varies significantly according to the operating conditions such as temperature and the feed reactants ratio and thus investigation of the thermodynamics involved in such reactional systems may afford important knowledge on the effects of process variables on biodiesel production. The present work reports a thermodynamic analysis of fatty acid esterification reaction at low pressure. For this purpose, Gibbs free energy minimization was employed with UNIFAC and modified Wilson thermodynamic models through a nonlinear programming model implementation. The methodology employed is shown to reproduce the most relevant investigations involving experimental studies and thermodynamic analysis.     

Potential of waste palm cooking oil for catalyst-free biodiesel production

Disposal of waste palm cooking oil (WPCO) via an environmental-friendly route is of major importance in the quest for sustainable development. In this study, WPCO was utilized instead of refined vegetable oils as the source of triglycerides for biodiesel production. WPCO contains several impurities, such as water and free fatty acids, which limit its application in catalytic transesterification processes. Consequently, a catalyst-free process using supercritical methanol was employed to investigate the potential of WPCO as an economical feedstock for biodiesel production. The parameters that influence the reaction, including reaction time, temperature and the molar ratio of alcohol to oil, were investigated. For comparison purposes, refined palm oil (RPO) was also subjected to supercritical methanol reaction and it was found that both processes produced comparable optimum yields of 80% at their respective optimum conditions. Hence, it can be concluded that WPCO has high potential as an economical and practical future source of biodiesel.     

以棉籽油皂脚为原料制备生物柴油

文章探讨了在酸性催化剂作用下以酸化的棉籽油皂脚为原料制备生物柴油的工艺,为棉籽油生产过程中产生的废料--棉籽油皂脚的回收利用开辟了一条新的途径.试验考察了催化剂用量、反应时间、投料比等因素对反应收率的影响,并通过正交试验优化得到了最佳工艺条件:催化剂(浓硫酸)用量4%(以脂肪物质量计),反应时间10 h,脂肪物与甲醇物质的量比为1:10.在上述最优条件下产品收率可达83%.     

Production of biodiesel from high free fatty acid Karanja (Pongamia pinnata) oil

Non-edible oil contains several unsaponifiable and toxic components, which make them unsuitable for human consumption. Karanja (Pongamia pinnata) is an underutilized plant which is grown in many parts of India. Sometimes the oil is contaminated with high free fatty acids (FFAs) depending upon the moisture content in the seed during collection as well as oil expression. The present study deals with production of biodiesel from high FFA Karanja oil because the conventional alkali-catalyzed route is not the feasible route. This paper discusses the mechanism of a dual process adopted for the production of biodiesel from Karanja oil containing FFA up to 20%. The first step is acid-catalyzed esterification by using 0.5% H₂SO₄, alcohol 6:1 molar ratio with respect to the high FFA Karanja oil to produce methyl ester by lowering the acid value, and the next step is alkali-catalyzed transesterification. The yield of biodiesel from high FFA Karanja oil by dual step process has been observed to be 96.6–97%.     

Fuel properties of blend and biodiesel generated from acid oil using whole cell biocatalyst

Biodiesel was generated through whole cell catalyzed transesterification of acid oil, to the extent of up to 92%. The fuel properties of biodiesel (B100) and its blend (B20) were determined and compared with standard biodiesel as per American Society for Testing and Materials (ASTM) standard (ASTM D6751). B100 and B20 showed good pour point of ?26°C and ?29°C, respectively, indicating their operation viability in colder environment. Other properties of biodiesel are quite similar to petroleum diesel and ASTM standard. The results of this study reveal the potential use of acid oil as feedstock for generation of fuel grade biodiesel through biocatalyzed transesterification.     

Homogeneous borotungstic acid and heterogeneous micellar borotungstic acid catalysts for biodiesel production by esterification of free fatty acid

A highly negatively charged borotungstic acid H₅BW₁₂O₄₀ had been tested as homogeneous catalyst in esterification. Compared with common used H₃PW₁₂O₄₀, it displayed a higher conversion (98.7%) and excellent efficiency (96.2%) due to its high amount of protons in methanol. In order to overcome the drawbacks of homogeneous heteropolyacid H₅BW₁₂O₄₀, a Brønsted-surfactant-combined (C₁₆TA)H₄BW₁₂O₄₀ (C₁₆TA = cetyltrimethyl ammonium) had been fabricated with strong acidity and nano-size micellar structure resulting in enhanced activity and stability during the reaction, which exhibited consistent activity during recycling in esterification reaction.     

氨基磺酸非均相催化菜籽油及废油脂制备生物柴油

采用正交试验和单因素试验的方法研究了氨基磺酸催化菜籽油及废油脂与甲醇的酯交换过程,考察了醇油物质的量比、催化剂用量、反应温度和反应时间对反应收率的影响。结果表明:菜籽油酯交换的最佳反应条件为醇油物质的量比6∶1,氨基磺酸用量为原料油质量的1.0%,反应温度60℃,反应时间20 min,此工艺条件下,脂肪酸甲酯的收率达到95.6%;废油脂酯交换的最佳反应条件为醇油物质的量比8∶1,氨基磺酸用量为原料油质量的1.0%、反应温度65℃,反应时间30 min,此工艺条件下,脂肪酸甲酯的收率达到87.5%。利用红外光谱表征了菜籽油和生物柴油的结构,气相色谱分析了生物柴油的组成。     

Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst

A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized vegetable oil asphalt. This catalyst was employed to simultaneously catalyze esterification and transesterification to synthesis biodiesel when a waste vegetable oil with large amounts of free fatty acids (FFAs) was used as feedstock. The physical and chemical properties of this catalyst were characterized by a variety of techniques. The maximum conversion of triglyceride and FFA reached 80.5 wt.% and 94.8 wt.% after 4.5 h at 220 °C, when using a 16.8 M ratio of methanol to oil and 0.2 wt.% of catalyst to oil. The high catalytic activity and stability of this catalyst was related to its high acid site density (–OH, Brönsted acid sites), hydrophobicity that prevented the hydration of –OH species, hydrophilic functional groups (–SO₃H) that gave improved accessibility of methanol to the triglyceride and FFAs, and large pores that provided more acid sites for the reactants.     

One-step production of biodiesel through simultaneous esterification and transesterification from highly acidic unrefined feedstock over efficient and recyclable ZnO nanostar catalyst

Zinc oxide (ZnO) nanostar synthesized by simple and up-scalable microwave-assisted surfactant free hydrolysis method was applied as catalyst for biodiesel synthesis through one-step simultaneous esterification and transesterification from high free fatty acid (FFA) contaminated unrefined feedstock. It was found that ZnO nanostar catalyst was reacted with FFA to yield zinc oleate (ZnOl) as intermediate and finally became zinc glycerolate (ZnGly). With the re-deposition of ZnGly back to the ZnO nanostar catalyst at the end of the reaction, the catalyst can be easily recovered and stay active for five cycles. Furthermore, the rate of transesterification is highly promoted by the presence of FFA (6 wt.%) which makes it an efficient catalyst for low grade feedstock like waste cooking oil and crude plant oils.     

大豆酸化油制备生物柴油的研究

试验研究了大豆酸化油在复合酸催化剂的作用下与甲醇发生转酯化和酯化反应生成脂肪酸甲酯(生物柴油)的最佳反应条件.试验结果表明,该酯化及转酯化反应的最佳操作条件:复合酸催化剂的用量为大豆油质量的5%、油醇摩尔比为1:6、反应时间为6h、反应温度为65℃.     

Chlorella sp.: A new strain with highly saturated fatty acids for biodiesel production in bubble-column photobioreactor

The biodiesel production from a naturally isolated strain of Chlorella in 2 L bubble-column photobioreactor was studied. The microalgal strain was isolated from the rice paddy-field soil samples during a screening program. After 17 days, at the end of exponential phase of growth, the total content of the lipids was extracted. The extracted fatty acids were first esterified and then identified using GC/MS analysis. Several types of fatty acid methyl esters (FAMEs) were identified in the isolated microalga and the presence of saturated fatty acids in Chlorella sp. MCCS 040 was approved. The composition of fatty acids in the studied species of microalga was mainly palmitic acid methyl ester, myristic acid methyl ester, stearic acid methyl ester and undecanoic acid methyl ester. This strain because of its highly saturated fatty acids content can be an ideal candidate for biodiesel production.     

The influence of molecular structure of fatty acid monoalkyl esters on diesel combustion

The subject of this paper is a series of experiments conducted on a single-cylinder research engine investigating the influence of molecular structure on the combustion behaviour of fatty acid alcohol ester (biodiesel) molecules under diesel engine conditions. The fuels employed in these experiments comprised various samples of pure individual fatty acid alcohol ester molecules of different structure, as well as several mixtures of such molecules. The latter consisted in biodiesel fuels produced by the transesterification of naturally occurring plant oils or animal fat with a monohydric alcohol. It was observed that the molecular structure of the fuel significantly influenced the formation of NO_x and particulate matter and their respective concentration in the exhaust gas. The influence on the formation of NO_x in particular, appeared to be exerted first through the effect which the molecular structure had on the auto-ignition delay occurring after the fuel was injected into the combustion chamber, and second through the flame temperature at which the various molecules burned. The emission of particulates on the other hand showed correlation with the number of double bonds in the fuel molecules for the case of larger accumulation mode particles, and with the boiling point of the fuel samples for the case of the smaller, nucleation mode particles. The effect of ignition delay on the exhaust emissions of these pollutants was isolated by adding the ignition promoting molecule 2-ethylhexyl nitrate to some of the fuel samples in closely specified concentrations, so as to equalise the ignition delay for the relevant fuel samples. The removal of the ignition delay as a main influence on the combustion process enabled the observation of the lesser effects of adiabatic flame temperature.     

Periodic variation in kernel oil content and fatty acid profiles of Calophyllum innophyllm L.: A potential biodiesel feedstock in Australia

Variation in oil content and fatty acid profiles of a native Australian biodiesel feedstock species Calophyllum inophyllum were studied in two different fruiting periods (winter 2008 and autumn 2009) and in three different northern Queensland provenances (Cardwell, Townsville, Yeppoon). Oils were extracted by standard n-hexane double extraction and fatty acid profiles were determined by ISO 5508 and 5509 methods using gas chromatography. C. inophyllum provenances have demonstrated a significant periodic variation in oil content and fatty acid profile, and as a result alter the quality of fatty acid methyl esters (biodiesel). FAP of majority of kernel oil sources were found to vary significantly (P < 0.05) with seasonal variation in temperature and longterm average rainfall.     

Biodiesel production from degummed Jatropha curcas oil using constant-temperature ultrasonic water bath

This paper studied tri-basic potassium phosphate for transesterification process with degummed crude Jatropha curcas oil using constant-temperature, ultrasonic water bath generating low-intensity pulses with good energy distribution converting the maximum amount of biodiesel. Tri-basic potassium phosphate is suitable for J. curcas oil when the free fatty acid (FFA) content is less than 2%. The optimal reaction levels are catalyst 1.0 wt%, temperature of 50°C, and methanol-to-oil molar ratio of 12:1. The yield is 98% after 45 min, at 20 kHz frequency. The catalytic activity is found similar to potassium hydroxide and the catalyst solubility is only 4.27 ppm.     

Preparation, characterization and application of heterogeneous solid base catalyst for biodiesel production from soybean oil

A solid base catalyst was prepared by neodymium oxide loaded with potassium hydroxide and investigated for transesterification of soybean oil with methanol to biodiesel. After loading KOH of 30 wt.% on neodymium oxide followed by calcination at 600 °C, the catalyst gave the highest basicity and the best catalytic activity for this reaction. The obtained catalyst was characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Thermogravimetric analysis (TGA), N₂ adsorption-desorption measurements and the Hammett indicator method. The catalyst has longer lifetime and maintained sustained activity after being used for five times, and were noncorrosive and environmentally benign. The separate effects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and reaction time were investigated. The experimental results showed that a 14:1 M ratio of methanol to oil, addition of 6.0% catalyst, 60 °C reaction temperature and 1.5 h reaction time gave the best results and the biodiesel yield of 92.41% was achieved. The properties of obtained biodiesel are close to commercial diesel fuel and is rated as a realistic fuel as an alternative to diesel.     

Studies on the performance of tubular flow reactor for esterification of free fatty acid from used cooking oil using highly porous cation exchange resin as catalyst

Semi-batch esterification of free fatty acid (FFA) from used cooking oil with methanol was carried out using RCP160M cation exchange resin in a tubular flow reactor (TFR). The results revealed that the conversion of FFA increased with the increase of catalyst bed height, methanol to oil mass ratio and decreases with increase of feedstock flow rates. However, the FFA conversion was decreased upon further increases of methanol to oil mass ratio from 6:1 to 12:1. This might possibly happen due to several factors such as mass transfer limitation between reactants and catalyst and inhomogeneity of the reactants during the reaction.     

Biodiesel production by esterification of oleic acid over zeolite Y prepared from kaolin

Zeolite Y, with a Si/Al ratio 3.1, was prepared using Iraqi kaolin and tested as a catalyst in the liquid-phase esterification of oleic acid (a simulated free fatty acid frequently used as a model reaction for biodiesel production). XRD confirmed the presence of the characteristic faujasite structure of zeolite Y, and further analysis was conducted using BET adsorption, FTIR spectroscopy, XRF, DLS particle size and SEM. A range of experimental conditions were employed to study the reaction; alcohol/oleic acid molar ratio, temperature, and catalyst mass loading. The optimum conditions for the reaction were observed at 70 °C, 5 wt% catalyst loading and 6:1 ethanol to oleic acid molar ratio. The oleic acid conversion using the zeolite prepared from kaolin was 85% after 60 min, while the corresponding value for a commercial sample of HY zeolite was 76%. Our findings show that low Si/Al ratio zeolite Y is a suitable catalyst for esterification, which is in contrast to the widespread view of the unsuitability of zeolites, in general, for such applications.     

Effect of injection parameters on the combustion and emission characteristics in a common-rail direct injection diesel engine fueled with waste cooking oil biodiesel

The objective of this paper was to study the effects of the injection pressure and injection timing on the combustion and emission characteristics in a single-cylinder common-rail direct injection (CRDI) diesel engine fueled with waste cooking oil (WCO) biodiesel and commercial diesel fuel. The fuel property including fatty acid composition for the biodiesel were measured and compared with those of the conventional diesel fuel. The engine tests were conducted at two injection pressures (80 and 160 MPa) and different injection timings from −25 to 0 crank angle degree (CAD) after top dead center (aTDC) under two different engine loads. The results showed that the indicated specific fuel consumption (ISFC) with respect to the injection timings of the biodiesel was higher than that of the diesel fuel under all experimental conditions. The peak cylinder pressure and the peak heat release rate of the biodiesel were slightly lower, while the ignition delay was slightly longer under all operating conditions. In terms of emissions, the biodiesel had benefits in reduction of smoke, carbon monoxide (CO), hydrocarbon (HC) emissions especially with high fuel injection pressure. The nitrogen oxide (NO_x) emissions of the biodiesel were relatively higher than those of the diesel under all experimental conditions.     

A novel one-pot synthesis of tetragonal sulfated zirconia catalyst with high activity for biodiesel production from the transesterification of soybean oil

A sulfated zirconia catalyst has been prepared by a novel one-pot vapor-controlled synthesis route using ammonium persulphate as sulfate agent. A possible formation mechanism of the catalyst is proposed. The effect of calcination temperature and S/Zr molar ratio on the structural, textural and catalytic properties of the prepared catalyst were investigated in detail using X-ray diffraction (XRD), N₂ adsorption–desorption, ammonia temperature programmed desorption (NH₃-TPD), Fourier transform infrared spectroscopy (FTIR) and a scanning electron microscope (SEM) which was equipped with an energy dispersive spectroscope (EDS). The results indicated that the samples calcined at 500 °C possessed zirconia of pure tetragonal structure, more content of sulfur and better distribution of acid sites on the surface of zirconia compared with the samples calcined at 600  °C at fixed S/Zr molar ratio. Moreover, they showed excellent catalytic activity with 100% yields of biodiesel for the transesterification of soybean oil with methanol.