Factors affecting the separation of the reaction mixture after transesterification of rapeseed oil

The most used method of biodiesel production is the transesterification of vegetable oils by a basic homogeneous catalyst. A heterogeneous reaction mixture is formed by this process which contains two phases: an ester phase and a glycerol phase. From this mixture, biodiesel is gained by sedimentation. The quality and quantity of both phases are affected by the conditions of the sedimentation process. It was studied how the conditions (independent variables: temperature of separation, amount of added water, time of sedimentation, etc.) affect the quantity and the quality of both phases (dependent variables). The Plackett–Burman statistic system was used for experiment planning. The relationship between independent and dependent variables was found and described by multidimensional linear regression. The created model allows the calculation of the optimum conditions of biodiesel production so that the quality of the biodiesel fulfills the EN 14214.     

Synthesis of Edible Vegetable Oils Enriched with Healthy 1,3-Diglycerides Using Crude Glycerol and Homogeneous/Heterogeneous Catalysis

Commercial edible vegetable oils in which part of their triglycerides are substituted with 1,3-diglycerides are healthier for human consumption than the original oils. This is because the human metabolism of 1,3-diglycerides is believed to occur through a distinct pathway with less probability of being deposited as fat in the body tissues. To obtain these enriched oils, conversion of triglycerides into diglycerides is carried out by glycerolysis using commercial crude glycerol containing dissolved alkali cations that homogeneously catalyze the reaction. The addition of a food production-compatible MgO as a supplementary solid basic catalyst, shortens the reaction time by half due to a combination of homogeneous and heterogeneous catalysis processes. In either homogeneously or homogeneous-heterogeneously catalyzed glycerolysis, the increase of the reaction temperature in the range of 453–493 K increases the final 1,3-diglyceride content. Furthermore, in both glycerolysis processes the triglyceride content can be decreased in more than 60% with the consequent increase of total diglycerides to 50%, 70% of which are the 1,3-isomers. The glycerolysis reaction proceeds without altering the fatty acid distribution of the original oils.     

甘油选择性脱水制备丙烯醛研究进展

生物柴油以其环保性和可再生性而被公认为是可替代石化柴油的新型能源,其迅猛发展将导致其副产物甘油的大量过剩,因此,开发和深度利用甘油,使其成为新一代从生物质到化学品的转化平台成为近期研究热点,其中,甘油脱水制丙烯醛是重要途径。综述了实现该过程的催化剂体系研究进展,探讨了催化剂结构和反应条件对甘油脱水反应性能的影响,分析了甘油脱水的反应路径,以期对开发高性能催化体系和合理工艺提供参考。由于匀相催化剂存在活性低、操作条件苛刻和设备腐蚀等缺点,开发的重点集中在固体酸催化剂上,虽然活性较高,但易失活,稳定性差。仍需进一步提高催化剂性能,同时结合反应器和工艺的设计和选择,综合考量。     

Waste Frying Oils as Substrate for Enzymatic Lipolysis: Optimization of Reaction Conditions in O/W Emulsion

Waste frying oils (WFO) can be both environmental pollutants and a source of valuable products. In this work we explore the conversion of WFO into surface‐active substances, such as FFA and partial glycerides, through enzymatic hydrolysis in O/W emulsion. Two different WFO and three lipases of different origin were tested. In addition, we optimized the conditions for the production of O/W emulsions to be used as reaction medium as well as several reaction parameters, such as the type of enzyme and its concentration, the pH, and the presence of Ca²⁺ ions. Gum arabic‐stabilized emulsions with an oil fraction of 0.15 proved to be the most adequate owing to their high interfacial area and short‐term stability. The physicochemical characterization of both WFO revealed the presence of an increased amount of surface‐active matter relative to food‐grade vegetable oils. These substances, mainly FFA, can interfere with lipase action and reduce the reaction rate. However, the extent of hydrolysis was only slightly affected by them, and remained fairly similar to that achieved with a control mixture of food‐grade vegetable oils. The product distribution depended on the enzyme used. Pseudomonas fluorescens lipase was found to be particularly suitable for the production of partial glycerides (mono‐ and diacylglycerols), which are in great demand by the food industry. In any case our results demonstrate that WFO are a good substrate for enzymatic hydrolysis, comparable to food‐grade vegetable oils, providing an alternative route for the valorization of this waste.     

Properties of a potential biofuel obtained from soybean oil by transmethylation with dimethyl carbonate

Biodiesel is a fuel generally consisting of a mixture of fatty acid methyl esters (FAMEs) which is used in alternative or in combination with petroleum diesel for its environmental benefits. Biodiesel is conveniently manufactured from vegetable oils by transesterification of triglycerides with methanol. However, the process brings about the concurrent formation of glycerol, which may become an oversupplied chemical if biodiesel production keeps growing. A novel biodiesel-like material (abbreviated as DMC-BioD) was developed by reacting soybean oil with dimethyl carbonate (DMC), which avoided the co-production of glycerol. The main difference between DMC-BioD and biodiesel produced from vegetable oil and methanol (MeOH-biodiesel) was the presence of fatty acid glycerol carbonate monoesters (FAGCs) in addition to FAMEs. In the following study, details regarding synthesis and composition of DMC-BioD are provided along with physical properties relevant for its use as a fuel. In addition, the production of potential pyrogenic contaminants was investigated by analytical pyrolysis and compared with those from MeOH-biodiesel, and the model compounds tristearin, triolein, trilinolein and oleic acid glycerol carbonate ester (OAGC). The presence of FAGCs influenced both fuel and flow properties, while the distribution of main pyrogenic compounds, including polycyclic aromatic hydrocarbons (PAHs), was little affected. Benefits and drawbacks of DMC as a candidate transmethylating reagent for producing biofuel from renewable resources and alternative co-products (glycerol carbonate and glycerol dicarbonate) are discussed.     

Studying the Influence of Alumina Catalysts Doped with Tin and Zinc Oxides in the Soybean Oil Pyrolysis Reaction

The pyrolysis of vegetable oils consists of cracking triglycerides to produce smaller molecules. A mixture of hydrocarbons and oxygenated compounds, such as carboxylic acids and aldehydes, is obtained as the product and which can be separated by fractional distillation. When the reaction is carried out in the absence of catalysts (thermal cracking), a great quantity of these oxygenated compounds is obtained. Thus, the presence of those oxygenated compounds in the products results in a high level of acidity, which can be a problem when using them as fuels in combustion engines. The aim of this work was to study the composition of the products obtained by cracking of vegetable oils assisted by γ-alumina doped with zinc and tin oxides. The products were analyzed by FT-IR, GC-MS and GC-FID and the acid number was determined by titration with alcoholic KOH solution. The acid number, infrared spectra and chromatograms of the resulting hydrocarbon mixtures indicated a significant reduction in oxygenated compounds when compared with the mixtures obtained by the thermal cracking process, thus decreasing the acidity of the mixture.     

Elimination of glycidyl palmitate in diolein by treatment with activated bleaching earth

In this study, activated bleaching earth (ABE) was used to eliminate glycidyl esters from both triacyl- and diacylglycerol oils. To investigate the mechanism, glycerol dioleate containing glycidyl palmitate (GP) was treated with ABE and the fate of the GP was monitored by analyzing the feed, treated, and ABE-absorbed oils using a gas-liquid chromatograph equipped with a flame-ionized detector. GP was completely removed from both the treated and absorbed oils. This indicates that this treatment is useful for GE removal from diacylglycerol oil, although it was not achieved by absorption of GE on ABE but rather by modification of GP. The results of composition analysis demonstrate that GP is transformed to glycerol monopalmitate, glycerol palmitate oleate, and glycerol dipalmitate at a recovery rate of 99.1 ± 1.3 %. An increase in glycerol monooleate and trace amounts of free glycerol and fatty acids were also observed after treatment. The transformation is proposed to involve a ring-opening reaction of GP with water contained in the ABE and in the bulk oil followed by an interesterification reaction among the resultant monopalmitate and the glycerol dioleate of the bulk oil. All the generated compounds were simple acylglycerols and glycerol. Therefore, ABE treatment could be useful for GE removal during the manufacture of edible oils.     

Advancements in Heterogeneous Catalysis for Biodiesel Synthesis

Heterogeneous catalysts are promising for the transesterification reaction of vegetable oils to produce biodiesel and have been studied intensively over the last decade. Unlike the homogeneous catalysts, heterogeneous catalysts can be easily separated from reaction mixture and reused for many times. They are environmentally benign and could be easily operated in continuous processes. This review classifies the solid catalysts into two categories based on their catalytic temperature, i.e. high temperature catalysts and low temperature catalysts. The nature of the catalysts can be specified into solid bases and solid acids. Three aspects, catalyst activity, catalyst life and oil flexibility, will be reviewed. Two kinds of heterogeneous catalysts, reported by IFP Inc. and by WSU, respectively, show a high catalytic activity, long catalyst life and low leaching of catalyst components. These two catalysts also show ability to simultaneously catalyze esterification and transesterification, and can be used in half-refined or crude oil system which provide a potential for greatly decrease the feedstock cost.     

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.     

Study on the glycerolysis reaction of high free fatty acid oils for use as biodiesel feedstock

Biodiesel is the main alternative to fossil diesel and it may be produced from different feedstocks such as semi-refined vegetable oils, waste frying oils or animal fats. However, these feedstocks usually contain significant amounts of free fatty acids (FFA) that make them inadequate for the direct base catalyzed transesterification reaction (where the FFA content should be lower than 4%). The present work describes a possible method for the pre-treatment of oils with a high content of FFA (20 to 50%) by esterification with glycerol. In order to reduce the FFA content, the reaction between these FFA and an esterification agent is carried out before the transesterification reaction. The reaction kinetics was studied in terms of its main factors such as temperature, % of glycerin excess, % of catalyst used, stirring velocity and type of catalyst used. The results showed that glycerolysis is a promising pre-treatment to acidic oils or fats (> 20%) as they led to the production of an intermediary material with a low content of FFA that can be used directly in the transesterification reaction for the production of biodiesel.     

Production of fatty acid methyl esters over a limestone-derived heterogeneous catalyst in a fixed-bed reactor

Production of fatty acid methyl esters (FAME) via the transesterification of different vegetable oils and methanol with a limestone-derived heterogeneous catalyst was investigated in a fixed-bed reactor at 65 °C and ambient pressure. This heterogeneous catalyst, as a 1 or 2 mm cross-sectional diameter extrudate, was prepared via a wet mixing of thermally treated limestone with Mg and Al compounds as binders and with or without hydroxyethyl cellulose (HEC) as a plasticizer, followed by calcination at 800 °C. The physicochemical properties of the prepared catalysts were characterized by various techniques. Palm kernel oil, palm oil, palm olein oil and waste cooking oil could be used as the feedstocks but the FFA and water content must be limited. The extrudate catalyst prepared with the HEC addition exhibited an enhanced formation of FAME due to an increased porosity and basicity of the catalyst. The FAME yield was increased with the methanol/oil molar ratio. The effect of addition of methyl esters as co-solvents on the FAME production was investigated. The structural and compositional change of the catalysts spent in different reaction conditions indicated that deactivation was mainly due to a deposition of glycerol and FFA (if present). The FAME yield of 94.1 wt.% was stably achieved over 1500 min by using the present fixed-bed system.     

Hydroxyl content and refractive index determinations on transesterified soybean oil

Biodiesel, a promising alternative diesel fuel, is produced by transesterification of vegetable oils or animal fats with methanol. One of the main problems in the industrial application of the transesterification process is how to determine the conversion of oils to methyl esters. In this work, a quick analytical method was developed for monitoring the transesterification reaction of soybean oil with methanol. The conversion of oils to methyl esters could be determined by applying a simple linear correlation with hydroxyl content of the transesterified mixture or refractive index of the product. The results were in agreement with the values measured by ¹H NMR spectroscopy. Compared with existing chromatographic and other methods, this method for monitoring the transesterification of vegetable oils with methanol is simple, rapid, and inexpensive and is especially suitable for process control purposes.     

Biodiesel processing and production

Biodiesel is an alternative diesel fuel that is produced from vegetable oils and animal fats. It consists of the monoalkyl esters formed by a catalyzed reaction of the triglycerides in the oil or fat with a simple monohydric alcohol. The reaction conditions generally involve a trade-off between reaction time and temperature as reaction completeness is the most critical fuel quality parameter. Much of the process complexity originates from contaminants in the feedstock, such as water and free fatty acids, or impurities in the final product, such as methanol, free glycerol, and soap. Processes have been developed to produce biodiesel from high free fatty acid feedstocks, such as recycled restaurant grease, animal fats, and soapstock.     

Interesterification of edible oils

Types of interesterification discussed are (a) interchange between a fat and free fatty acids, in which the most important reaction is the introduction of acids of low mol wt into a fat with higher fatty acids; (b) interchange between a fat and an alcohol, e.g., with glycerol, in order to produce emulsifiers like monoglycerides; (c) rearrangement of fatty acid radicals in triglycerides, the so-called transesterification which in recent years has taken on the same importance as hydrogenation or fractionation. In natural fats, the fatty acid radicals are not usually randomly distributed but become so by rearrangement; the distinctive physical properties of natural fats and oils can be changed within limits by this transesterification. Well-known examples are cocoa butter, palm oil, and lard. More important is the transesterification of a mixture of different fats and oils; e.g., the combination of hydrogenation and interesterification allows the production of a solid fat with high linoleic acid content. The composition of glycerides after random interesterification can be calculated by formulas. Distinct from random is such directed interesterification. This is done by working at low temperatures that glycerides with higher melting point crystallize from the reaction mixture. Directed interesterification can be combined with fractionation, for instance, to get a higher yield of liquid fraction from palm oil than is obtained by fractionation alone. The transesterification process can be performed in a batch or continuously. A small amount of metallic sodium or sodium ethylate is used as catalyst, which is destroyed by water or acid and removed after the reaction.     

Activity of solid catalysts for biodiesel production: A review

Heterogeneous catalysts are promising for the transesterification reaction of vegetable oils to produce biodiesel. Unlike homogeneous, heterogeneous catalysts are environmentally benign and could be operated in continuous processes. Moreover they can be reused and regenerated. However a high molar ratio of alcohol to oil, large amount of catalyst and high temperature and pressure are required when utilizing heterogeneous catalyst to produce biodiesel. In this paper, the catalytic activity of several solid base and acid catalysts, particularly metal oxides and supported metal oxides, was reviewed. Solid acid catalysts were able to do transesterification and esterification reactions simultaneously and convert oils with high amount of FFA (Free Fatty Acids). However, the reaction rate in the presence of solid base catalysts was faster. The catalyst efficiency depended on several factors such as specific surface area, pore size, pore volume and active site concentration.     

Lipase-catalyzed incorporation of n−3 polyunsaturated fatty acids into vegetable oils

The ability of immobilized lipases IM60 fromMucor miehei and SP435 fromCandida antarctica to modify the fatty acid composition of selected vegetable oils by incorporation of n−3 polyunsaturated fatty acids into the vegetable oils was studied. The transesterification was carried out in organic solvent with free acid and ethyl esters of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) as acyl donors. With free EPA as acyl donor, IM60 gave higher incorporation of EPA than SP435. However, when ethyl esters of EPA and DHA were the acyl donors, SP435 gave higher incorporation of EPA and DHA than IM60. When IM60 and free acid were used, the addition of 5 μL water increased EPA incorporation into soybean oil by 4.9%. With ethyl ester of EPA as acyl donor, addition of 2 μL water increased EPA incorporation by 3.9%. For SP435, addition of water up to 2μL resulted in increased EPA incorporation, but the incorporation declined when the added water exceeded this amount. The addition of water increased the EPA incorporation into Trisun 90 after 24 h reaction but not the reaction rate at early stages of the reaction.     

Some problems involved in the water wash of neutralized vegetable oils

Summary An investigation of the removal of soap from neutralized vegetable oils by washing with water has shown that some oils are obtained practically soap-free after only one water wash whereas the soap in other oils cannot be removed even by repeated washing. Coconut, palm, and olive oils are easily washed whereas linseed and rapeseed oils are not. Peanut, sunflowerseed, soybean, and cottonseed oils are sometimes washable and sometimes not. With unwashable oils different methods for soap determination give inconsistent results because calcium and magnesium soaps, or other naturally-occurring compounds of these metals, are not determined to the same extent by these methods. Calcium and magnesium in the crude oils are probably combined with phosphatides or other lipids and remain to some extent in this state after neutralization. Calcium and magnesium present as soaps or as any other compound may be detected easily in crude, neutralized, and washed oils by the titration method of Wolff. Washability of neutralized oils may be improved in a number of ways; the most efficient is pre-treatment with concentrated phosphoric acid or re-refining with a mixture of sodium hydroxide and sodium carbonate. Either of these treatments can be applied in batch or continuous refining processes. To prevent contamination of washable oils with calcium and magnesium, soft water should be used for washing and in preparation of refining solutions.     

Standard biodiesel from soybean oil by a single chemical reaction

Laboratory methods are described for producing standard biodiesel from low-acid-number vegetable oils in single-step reactions without distillation of the products. Either sodium hydroxide or methoxide is used as the catalyst. Biodiesel fuel is currently made from vegetable oils using basic catalysts. With this methodology, the oils must be reacted two or three times with methanol, in the presence of sodium methoxide, to make a product that meets the standard for the total chemically bound and unbound glycerol content. Previously it was thought that sodium hydroxide could never be used as the catalyst because it forms soap with the ester, which lowers the yield and makes product isolation difficult. Two of the described methods use sodium hydroxide as the catalyst and the other uses sodium methoxide. These methods rely on the use of oxolane as co-solvent to manipulate phase behavior during the reaction. Reactant molar ratios and base concentrations are also optimized to drive the reactions to the necessary degree of completion.     

Lipase-catalyzed interesterification of oils and fats

Extracellular microbial lipases can be used as catalysts for the interesterification of oils and fats. Use of specific lipases gives products which are unobtainable by chemical interesterification methods. Some of these products have properties of value to the oils and fats industry. The catalysts for enzymatic interesterification are prepared by coating inorganic support materials with the lipases. For batch interesterification reactions, the catalyst particles are activated by addition of a small amount of water and then stirred with a reactant mixture dissolved in petroleum ether. At the end of the reaction period, the catalyst particles are removed by filtration, and the interesterified triglycerides isolated by conventional fat fractionation techniques. The catalyst can be used in subsequent batch reactions. As an alternative to the batch reaction system, continuous enzymatic interesterification processes can be operated by pumping water containg feedstock through a packed bed of activated catalyst.