Biodiesel fuels

The mono-alkyl esters, most commonly the methyl esters, of vegetable oils, animal fats or other materials consisting mainly of triacylglycerols, often referred to as biodiesel, are an alternative to conventional petrodiesel for use in compression-ignition engines. The fatty acid esters that thus comprise biodiesel largely determine many important fuel properties. In turn, the composition of the biodiesel depends on the composition of the parent feedstock because feedstocks with widely varying fatty acid composition can be used for biodiesel production. The use of different feedstocks is also significant under aspects of increasing biodiesel supply and socio-economic issues. In this article, biodiesel production is briefly described, followed by a discussion of biodiesel fuel properties and the influence of varying fatty acid profiles and feedstocks. It is shown that the properties of biodiesel least influenced by minor components can be determined by a straightforward equation in which the properties of the biodiesel fuel are calculated from the amounts of the individual component fatty esters and their properties. Optimizing biodiesel composition is also addressed.     

Free lipase-catalyzed biodiesel production from phospholipids-containing oils

Free lipase-catalyzed biodiesel has drawn more and more attentions in recent years because of its advantages of lower cost and faster reaction rate. Utilizing free lipase to convert low quality oils such as crude vegetable oils and microbial oils is beneficial to further reduce the cost of biodiesel production. However, these oils typically contain some amount of phospholipids. Phospholipids were found to affect the lipase-catalyzed process and further influence the enzyme's thermal stability in biodiesel production process. In this work, free lipase NS81006-mediated biodiesel production from oils containing phospholipids at varied temperature was investigated systematically. It was found that the presence of phospholipids at high temperature led to a decreased fatty acid methyl esters (FAME) yield and poor reuse stability of the lipase during NS81006-catalyzed biodiesel production process. The higher the temperature was, the greater negative effect was observed. This inhibitory effect was found to be mainly caused by the coexistence of phospholipids and methanol in the system. Based on this finding, a novel two-step enzyme-mediated process was further developed, with which the above-mentioned inhibitory effect was eliminated, and a FAME yield of 95.1% could be obtained with oils containing 10% phospholipids even at high temperature of 55 °C.     

Comparative assessment of sal and kusum biodiesel properties

This paper focuses on the use of kusum and sal oils found abundantly in India, yet unexplored for biodiesel production. The fatty acid profiles of the feedstocks suggest that sal oil has 56.8% saturated fatty acid whereas kusum oil has 34.8%. The kinematic viscosities of methyl ester of sal and kusum oils were higher and the calorific values were lower than those of diesel. The oxidation stability of both the esters is more than 6 h. The physicochemical properties of the two esters were within permissible limits of ASTM standard. The blending of ester in diesel has resulted in better performance and lower emissions.     

Biodiesel and renewable diesel: A comparison

The search for alternatives to petroleum-based fuels has led to the development of fuels from various sources, including renewable feedstocks such as fats and oils. Several types of fuels can be derived from these triacylglycerol-containing feedstocks. One of them is biodiesel, which is defined as the mono-alkyl esters of vegetable oils or animal fats. Biodiesel is produced by transesterifying the oil or fat with an alcohol such as methanol under mild conditions in the presence of a base catalyst. Another kind of product that can be obtained from lipid feedstocks is a fuel whose composition simulates that of petroleum-derived diesel fuel. This kind of fuel, probably best termed “renewable diesel”, is produced from the fat or oil by a hydrodeoxygenation reaction at elevated temperature and pressure in the presence of a catalyst. This article discusses in a general and comparative fashion aspects such as fuel production and energy balance, fuel properties, environmental effects including exhaust emissions and co-products. Among the questions that are addressed are if these fuels compete with or complement each other and what the effect of production scale may be.     

Inorganic heterogeneous catalysts for biodiesel production from vegetable oils

Biofuels are renewable solutions to replace the ever dwindling energy reserves and environmentally pollutant fossil liquid fuels when they are produced from low cost sustainable feedstocks. Biodiesel is mainly produced from vegetable oils or animal fats by the method of transesterification reaction using catalysts. Homogeneous catalysts are conventionally used for biodiesel production. Unfortunately, homogeneous catalysts are associated with problems which might increase the cost of production due to separation steps and emission of waste water. Inorganic heterogeneous catalysts are potentially low cost and can solve many of the problems encountered in homogeneous catalysts. Many solid acid and base inorganic catalysts have been studied for the transesterification of various vegetables oils. The work of many researchers on the development of active, tolerant to water and free fatty acids (FFA), as well as stable inorganic catalysts for biodiesel production from vegetable oils are reviewed and discussed.     

Correlation for the estimation of the cetane number of biodiesel fuels and implications on the iodine number

Some European experts on normalization of transport fuels have recently suggested the suppression of the cetane-number limitation from the European biodiesel norm when its final destination is blending with diesel fuel. Although this measure should not affect the range of oils used for biodiesel production (only few of them lead to biodiesel fuels with cetane numbers below this limit), the trend of cetane number to decrease with increasing unsaturation could reinforce the arguments to maintain the iodine-number limitation as an indirect limit for the cetane number.The iodine number has frequently been subjected to controversy because its stringent limitation in Europe prevents from using differently unsaturated fatty oils for biodiesel production. Some of the arguments in favour of extending or eliminating the iodine-number limitation in the norm are exposed here. Previously, a correlation for the estimation of the cetane number based on a literature review is proposed. From this correlation, a procedure is proposed for the estimation of the limiting effect of the current cetane-number limitation on the unsaturation degree of biodiesel fuels. Finally, the impact of the elimination of the cetane-number limitation on the use of different oils for biodiesel production is analyzed.     

Ethyl levulinate: A potential bio-based diluent for biodiesel which improves cold flow properties

Biodiesel, defined as mono-alkyl esters of long-chain fatty acids derived from vegetable oils or animal fats, is an attractive renewable fuel alternative to conventional petroleum diesel fuel. Biodiesel produced from oils such as cottonseed oil and poultry fats suffer from extremely poor cold flow properties because of their high saturated fatty acid content. In the current study, Ethyl Levulinate (ethyl 4-oxopentanoate) was investigated as a novel, bio-based cold flow improver for use in biodiesel fuels. The cloud (CP), pour (PP), and cold filter plugging points (CFPP) of biodiesel fuels prepared from cottonseed oil and poultry fat were improved upon addition of ethyl levulinate at 2.5, 5.0, 10.0, and 20.0% (vol). Reductions of 4-5 °C in CP, 3-4 °C in PP and 3 °C in CFPP were observed at 20 vol % ethyl levulinate. The influence of ethyl levulinate on acid value, induction period, kinematic viscosity and flash point was determined. The kinematic viscosities and flash points decreased with increasing content of ethyl levulinate. All samples (≤15 vol % ethyl levulinate) satisfied the ASTM D6751 limit with respect to flash point, but none of the 20 vol % blends were acceptable when compared to the higher EN 14214 specification. Acid value and oxidative stability were essentially unchanged upon addition of ethyl levulinate. In summary, ethyl levulinate appears acceptable as a diluent for biodiesel fuels with high saturated fatty acid content.     

Kapok oil methyl esters

The increased need for biodiesel feedstocks has caused various vegetable oils to be examined for this purpose. In the present work, the methyl esters of kapok (Ceiba pentandra) oil were prepared. The essential fuel properties were comprehensively determined and evaluated in comparison to specifications in biodiesel standards and some prior results. The kinematic viscosity of kapok oil methyl esters was greater than expected, an observation traced to the elevated amounts of methyl esters with cyclic moieties. Overall, kapok oil is a potential biodiesel feedstock. The ¹H and ¹³C NMR spectra of kapok methyl esters are reported.     

Performance and emission evaluation of a diesel engine fueled with methyl esters of rubber seed oil

Recent concerns over the environment, increasing fuel prices and scarcity of its supply have promoted the interest in development of the alternative sources for petroleum fuels. At present, biodiesel is commercially produced from the refined edible vegetable oils such as sunflower oil, palm oil and soybean oil, etc. by alkaline-catalyzed esterification process. This process is not suitable for production of biodiesel from many unrefined non-edible vegetable oils because of their high acid value. Hence, a two-step esterification method is developed to produce biodiesel from high FFA vegetable oils. The biodiesel production method consists of acid-catalyzed pretreatment followed by an alkaline-catalyzed transesterification. The important properties of methyl esters of rubber seed oil are compared with other esters and diesel. Pure rubber seed oil, diesel and biodiesel are used as fuels in the compression ignition engine and the performance and emission characteristics of the engine are analyzed. The lower blends of biodiesel increase the brake thermal efficiency and reduce the fuel consumption. The exhaust gas emissions are reduced with increase in biodiesel concentration. The experimental results proved that the use of biodiesel (produced from unrefined rubber seed oil) in compression ignition engines is a viable alternative to diesel.     

单酯类燃料组成与结构对燃料特性的影响

生物柴油是一种可再生的国产绿色替代能源，来自于植物油单酯衍生物。脂肪酸酯作为发动机燃料的可行性来自于其分子结构和较高的能量密度。燃料的热值主要取决于燃料中C、H、O等元素的质量分数。作为柴油的品质参数之一，十六烷值同样适用于替代燃料生物柴油。脂肪酸链中的不饱和键是导致CN下降的最重要因素。不饱和键的数目及位置对燃料特性参数CN、IV、低温流动性和氧化安定性等都具有重要的影响。     

Performance characteristics of a low heat rejection diesel engine operating with biodiesel

Vegetable oils are a promising alternative among the different diesel fuel alternatives. However, the high viscosity, poor volatility and cold flow characteristics of vegetable oils can cause some problems such as injector coking, severe engine deposits, filter gumming, piston ring sticking and thickening of lubrication oil from long-term use in diesel engines. These problems can be eliminated or minimized by transesterification of the vegetable oils to form monoesters. These monoesters are known as biodiesel. The important advantages of biodiesel are lower exhaust gas emissions and its biodegradability and renewability compared with petroleum-based diesel fuel. Although the transesterification improves the fuel properties of vegetable oil, the viscosity and volatility of biodiesel are still worse than that of petroleum diesel fuel. The energy of the biodiesel can be released more efficiently with the concept of low heat rejection (LHR) engine. The aim of this study is to apply LHR engine for improving engine performance when biodiesel is used as an alternative fuel. For this purpose, a turbocharged direct injection (DI) diesel engine was converted to a LHR engine and the effects of biodiesel (produced from sunflower oil) usage in the LHR engine on its performance characteristics have been investigated experimentally. The results showed that specific fuel consumption and the brake thermal efficiency were improved and exhaust gas temperature before the turbine inlet was increased for both fuels in the LHR engine.     

Progress in biodiesel processing

Biodiesel is a notable alternative to the widely used petroleum-derived diesel fuel since it can be generated by domestic natural sources such as soybeans, rapeseeds, coconuts, and even recycled cooking oil, and thus reduces dependence on diminishing petroleum fuel from foreign sources. The injection and atomization characteristics of the vegetable oils are significantly different than those of petroleum-derived diesel fuels, mainly as the result of their high viscosities. Modern diesel engines have fuel-injection system that is sensitive to viscosity change. One way to avoid these problems is to reduce fuel viscosity of vegetable oil in order to improve its performance. The conversion of vegetable oils into biodiesel is an effective way to overcome all the problems associated with the vegetable oils. Dilution, micro-emulsification, pyrolysis, and transesterification are the four techniques applied to solve the problems encountered with the high fuel viscosity. Transesterification is the most common method and leads to monoalkyl esters of vegetable oils and fats, now called biodiesel when used for fuel purposes. The methyl ester produced by transesterification of vegetable oil has a high cetane number, low viscosity and improved heating value compared to those of pure vegetable oil which results in shorter ignition delay and longer combustion duration and hence low particulate emissions.     

Screening of marine microalgae for biodiesel feedstock

Biodiesel production from microalgae lipids is increasingly regarded as a more sustainable and feasible alternative to conventional biodiesel feedstocks derived from terrestrial bioenergy crops. A total of ninety-six strains of marine microalgae, with an elevated biomass productivity and intracellular lipid content, were isolated from the coastal waters of Singapore using an automated flow cytometric cell-sorting technique. Cell sorting was based on the two-dimensional distribution of algal cells for red fluorescence (representing chlorophyll auto-fluorescence) against forward-light scatter (representing cell size) and red vs. green fluorescence. Twenty-one of the strains were further characterized with respect to cell growth rate, biomass concentration, lipid content (total and neutral lipid) and fatty acid profile. The growth rates of Skeletonema costatum, Chaetoceros and Thalassiosira species were greatest among the entire strains, but in terms of absolute lipid yield Nannochloropsis strains predominated. Nannochloropsis strains had a lipid content ranging from 39.4% to 44.9% of dry weight biomass. Transesterification of the lipids yielded 25-51% of fatty acid methyl ester (FAME) i.e. biodiesel, where total FAME content ranged between 11 and 21% of dry weight biomass. This study describes the microalgae screening process and demonstrates that Nannochloropsis is a promising species for biodiesel feedstock.     

Potential hybrid feedstock for biodiesel production in the tropics

Recently, mixture of different oils at various proportions have been used as feedstock for biodiesel production. The primary aim is to improve fuel properties which are strongly influenced by the fatty acid composition of the individual oil that makes up the feedstock mix. The tropics are renowned for abundant oil-bearing crops of which palm kernel oil (PKO) from palm seed and groundnut oil (GNO) are prominent. This present paper investigated biodiesel production from hybrid oil (HO) of PKO (medium carbon chain and highly saturated oil) and GNO (long carbon chain and highly unsaturated oil) at 50/50 (v/v) blending. The principal fatty acids (FAs) in the HO are oleic (35.62%) and lauric acids (24.23%) with 47.80% of saturated FA and 52.26% of unsaturated FA contents. The chemical conversion of the oil to methyl ester (ME) gave 86.56% yield. Fuel properties of hybrid oil methyl ester (the HOME) were determined in accordance with standard test methods and were found to comply with both ASTM D6751 and EN 14214 standards. The oxidative stability, cetane number and kinematic viscosity (KV) of HOME were observed to be improved when compared with those of GNO methyl ester from single parent oil, which could be accredited to the improved FA composition of the HO. The KV (3.69 mm²/s) of HOME obtained in this paper was remarkably low compared with those reported in literature for most biodiesels. This value suggests better flow, atomization, spray and combustion of this fuel. Conclusively, the binary blend of oils can be a viable option to improve the fuel properties of biodiesel feedstock coupled with reduced cost.     

History and policy of biodiesel in Brazil

Historically, during petroleum shortage, vegetable oils and their derivatives have been proposed as alternatives to petroleum diesel fuel. Since 1930, different approaches have been proposed by Brazilian's universities and research institutes, including the use of neat vegetable oils (pure or in blends) or their derivatives, such as hydrocarbons obtained by thermal-catalytic cracking and fatty acids’ methyl or ethyl esters (nowadays known as “biodiesel”) produced by alcoholysis. Recently, the external dependence on imported diesel fuel and the present petroleum crisis have increased the discussion in Brazil in the sense of starting to use alternatives to diesel fuel, biodiesel being the main alternative for a large petroleum diesel substitution program.     

A comprehensive review on biodiesel as an alternative energy resource and its characteristics

As the fossil fuels are depleting day by day, there is a need to find out an alternative fuel to fulfill the energy demand of the world. Biodiesel is one of the best available resources that have come to the forefront recently. In this paper, a detailed review has been conducted to highlight different related aspects to biodiesel industry. These aspects include, biodiesel feedstocks, extraction and production methods, properties and qualities of biodiesel, problems and potential solutions of using vegetable oil, advantages and disadvantages of biodiesel, the economical viability and finally the future of biodiesel. The literature reviewed was selective and critical. Highly rated journals in scientific indexes were the preferred choice, although other non-indexed publications, such as Scientific Research and Essays or some internal reports from highly reputed organizations such as International Energy Agency (IEA), Energy Information Administration (EIA) and British Petroleum (BP) have also been cited. Based on the overview presented, it is clear that the search for beneficial biodiesel sources should focus on feedstocks that do not compete with food crops, do not lead to land-clearing and provide greenhouse-gas reductions. These feedstocks include non-edible oils such as Jatropha curcas and Calophyllum inophyllum, and more recently microalgae and genetically engineered plants such as poplar and switchgrass have emerged to be very promising feedstocks for biodiesel production.It has been found that feedstock alone represents more than 75% of the overall biodiesel production cost. Therefore, selecting the best feedstock is vital to ensure low production cost. It has also been found that the continuity in transesterification process is another choice to minimize the production cost. Biodiesel is currently not economically feasible, and more research and technological development are needed. Thus supporting policies are important to promote biodiesel research and make their prices competitive with other conventional sources of energy. Currently, biodiesel can be more effective if used as a complement to other energy sources.     

生物柴油特性分析与应用

生产生物柴油的主要原料是可再生的生物资源,生物柴油含氧而基本不合硫和芳香烃,具有良好的燃料品质和环境友好性,从能源战略角度分析,生物柴油是最为重要的代用燃料之一.柴油机不需改动即可使用生物柴油,柴油机使用生物柴油不仅利于改善燃料结构,而且可以降低有害排放.本文对比了生物柴油与矿物柴油的燃料特性,分析了柴油机燃用生物柴油的好处,介绍了生物柴油在国内外的发展情况,指出发展生物柴油的目的并不是要取代矿物柴油,而在于改善矿物柴油的性能,以满足不断严格的排放标准,并对推动我国生物柴油的发展提出了建议.     

Biodiesel fuels from palm oil via the non-catalytic transesterification in a bubble column reactor at atmospheric pressure: A kinetic study

Biodiesel has become more attractive recently because of its environmental benefits and the fact that it is made from renewable resources. Transesterification of vegetable oils with short-chain alcohol has long been a preferred method for producing biodiesel fuel. A new reactor was developed to produce fatty acid methyl esters (FAME) by blowing bubbles of superheated methanol vapor continuously into vegetable oil without using any catalysts. A kinetic study on the non-catalytic transesterification of palm oil was made in a reactor without stirring at atmospheric pressure. The effects of reaction temperatures (523, 543, and 563 K) on the rate constant, conversion, yield of methyl esters (ME) and composition of the reaction product under semi-batch mode operation are investigated. The activation energy and the frequency factor values of the transesterification reaction obtained in this experiment are 31 kJ/mol and 4.2, respectively. The optimum reaction temperature which gives the highest ME content (95.17% w/w) in the reaction product is 523 K, while the rate constant of the total system increased with reaction temperature.     

Simulation study of the production of biodiesel using feedstock mixtures of fatty acids in complex reactive distillation columns

Biodiesel can be produced from a number of natural, renewable sources, but vegetable oils are the main feedstocks. The current manufacturing biodiesel processes, however, have several disadvantages: expensive separation of products from the reaction mixture, and high costs due to relatively complex processes involving one to two reactors and several separation units. Therefore, to solve these problems, in recent years several researchers have developed a sustainable biodiesel production process based on reactive distillation. In this paper the production of biodiesel using feedstock mixtures of fatty acids is explored using reactive distillation sequences with thermal coupling. The results indicate that the complex reactive distillation sequences can produce a mixture of esters as bottoms product that can be used as biodiesel. In particular, the thermally coupled distillation sequence involving a side rectifier can handle the reaction and complete separation in accordance with process intensification principles.     

Experimental and chemical kinetic modeling study of small methyl esters oxidation: Methyl (E)-2-butenoate and methyl butanoate

This study examines the effect of unsaturation on the combustion of fatty acid methyl esters (FAME). New experimental results were obtained for the oxidation of methyl (E)-2-butenoate (MC, unsaturated C₄ FAME) and methyl butanoate (MB, saturated C₄ FAME) in a jet-stirred reactor (JSR) at atmospheric pressure under dilute conditions over the temperature range 850-1400 K, and two equivalence ratios (Φ=0.375,0.75) with a residence time of 0.07 s. The results consist of concentration profiles of the reactants, stable intermediates, and final products, measured by probe sampling followed by on-line and off-line gas chromatography analyses. The oxidation of MC and MB in the JSR and under counterflow diffusion flame conditions was modeled using a new detailed chemical kinetic reaction mechanism (301 species and 1516 reactions) derived from previous schemes proposed in the literature. The laminar counterflow flame and JSR (for ?=1.13) experimental results used were from a previous study on the comparison of the combustion of both compounds. Sensitivity analyses and reaction path analyses, based on rates of reaction, were used to interpret the results. The data and the model show that MC has reaction pathways analogous to that of MB under the present conditions. The model of MC oxidation provides a better understanding of the effect of the ester function on combustion, and the effect of unsaturation on the combustion of fatty acid methyl ester compounds typically found in biodiesel.