Energy Conversion and Management 52 (2011) 27412751

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Energy Conversion and Management

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Overview on the current trends in biodiesel production

N.N.A.N. Yusuf, S.K. Kamarudin , Z. Yaakub
Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

a r t i c l e

i n f o

a b s t r a c t
The nite nature of fossil fuels necessitates consideration of alternative fuels from renewable sources. The term biofuel refers to liquid, gas and solid fuels predominantly produced from biomass. Biofuels include bioethanol, biomethanol, biodiesel and biohydrogen. Biodiesel, dened as the monoalkyl esters of vegetable oils or animal fats, is an attractive alternative fuel because it is environmentally friendly and can be synthesized from edible and non-edible oils. Here, we review the various methods for the production of biodiesel from vegetable oil, such as direct use and blending, microemulsion, pyrolysis and transesterication. The advantages and disadvantages of the different biodiesel-production methods are also discussed. Finally, we analyze the economics of biodiesel production using Malaysia as a case study. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 18 March 2010 Accepted 5 December 2010 Available online 29 March 2011 Keywords: Biodiesel Biofuel Economy

1. Introduction The world is currently facing the worst energy crisis in history. Many countries worldwide are still heavily dependent on petroleum as their main source of electricity and transportation fuel, and its price has been setting record highs in recent days. Thus, the only possible solution to this crisis is to nd a sustainable (renewable) and economically feasible source of alternative energy. There are many alternative energy sources such as wind, solar, geothermal and biomass that fulll the rst criterion (sustainability). However, few of these can fulll the second criterion (economic feasibility). The best option, fullling both criteria, is biofuel, particularly that made from readily available biomass feedstock [13]. Biomass refers to all the vegetable matter that can be obtained from photosynthesis. The great versatility of biomass as a feedstock is evident from the range of materials that can be converted into various solid, liquid and gaseous fuels using biological and thermochemical conversion processes. Biomass energy is by far the largest renewable energy source, representing 10.4% of the worlds total primary energy supply or 77.4% of global renewable energy supply [4]. The concept of using biofuels in diesel engines originated with the demonstration of the rst diesel engine by its inventor, Rudolf Diesel, at the World Exhibition in Paris in 1900, using peanut oil as the fuel. However, due to the then-abundant supply of petroleum diesel, research and development activities on vegetable-oil fuels were not seriously pursued. These fuels received attention only recently, when it was realized that petroleum fuels were fast dwindling and environmentally friendly renewable substitutes must be identied [5,6]. Biofuels are liquid or gaseous fuels for the
Corresponding author. Tel.: +60 389216422; fax: +60 389216148.
E-mail address: ctie@eng.ukm.my (S.K. Kamarudin). 0196-8904/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.enconman.2010.12.004

transport sector that are predominantly produced from biomass. Biofuels can be produced from a variety of bio-feedstocks, they are renewable, sustainable, biodegradable, carbon neutral for the whole life cycle and environmentally friendly; they encourage green industries and agriculture and are applicable as motor fuels, without or with slight engine modications. Several biofuels, including bioethanol, biomethanol, biodiesel and biohydrogen, appear to be attractive options for the future of the transport sector. The production of biofuels is expected to rise steadily in the next few decades [7]. At present, several countries such Brazil, the United States, Germany, Australia, Italy and Austria are already using biofuels such as bioethanol and biodiesel. It is expected that this trend will continue to grow and more countries will use biofuels [8,9]. Bioethanol is an alternative fuel based on alcohol produced by the fermentation and distillation of raw materials with high sugars and starch contents. Besides these raw materials, ethanol can be obtained from lignocellulosic biomass from trees and some annual plants. Ethanol can be produced from any organic matter of biological origin with considerable amounts of sugars and/or materials that can be converted into sugar such as starch or cellulose. Sugarcane, sugar beetroot, and sugar sorghum are examples of raw materials with high sugar contents which thus can be used for ethanol production. Wheat, barley, and corn are raw materials containing starch, which can easily be converted into sugar using available technologies. A signicant part of the woody part of trees and annuals is composed of cellulose, which can also be converted into sugar, but the process is more complicated than that required for starch [10]. Biomethanol is another alcohol fuel produced from biomass. A new study patented in Sweden concluded that methanol can be produced from biomass via black-liquor gasication at a cost competitive with gasoline and diesel [11]. A recent study on oil-palm

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N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 27412751 Table 1 Physical properties of biodiesel [1]. Common name Common chemical name Chemical formula range Kinematic viscosity range (mm2/s, at 313 K) Density range (kg/m3, at 288 K) Boling-point range (K) Flash-point range (K) Distillation range (K) Vapor pressure (mm Hg, at 295 K) Solubility in water Physical appearance Odor Biodegradability Reactivity Biodiesel Fatty acid (m)ethyl ester C14C24 methyl esters or C1525H28 48O2 3.35.2 860894 >457 420450 470600 <5 Insoluble in water Light to dark yellow, clear liquid Light musty/soapy odor More biodegradable than petroleum diesel Stable, but avoid strong oxidizing agents

biomass waste showed that black liquor can be produced from the trunk of the oil palm, but at present the black liquor is used to produce pulp and paper [12]. Biological hydrogen-generation (biohydrogen) technologies provide a wide range of approaches to generate hydrogen and are potentially more environmentally friendly and less energy intensive than thermochemical or electrochemical processes. There are three types of microorganisms used for hydrogen generation: cyanobacteria, anaerobic bacteria and fermentative bacteria. The cyanobacteria directly decompose water into hydrogen and oxygen in the presence of light energy by photosynthesis. Photosynthetic bacteria use organic substrates such as organic acids. Anaerobic bacteria use organic substances as the sole source of electrons and energy, converting them into hydrogen. Biohydrogen can be generated using bacteria such as Clostridia by controlling temperature, pH, reactor hydraulic-retention time (HRT), and other operating parameters of the fermentation system. Biohydrogen can be generated by direct biophotolysis, indirect biophotolysis, photofermentations and dark fermentation [13]. Among all the biofuels, biodiesel has been receiving perhaps the most attention, due to the similarity between biodiesel and conventional diesel in terms of chemical structure and energy content. Additionally, no modication of the diesel engine is required, as biodiesel is compatible with existing engine models and has been commercially blended with diesel as a transportation fuel in a number of countries including Germany, Italy and Malaysia [3].

2. Biodiesel Biodiesel is an alternative fuel for diesel engines produced by chemically reacting a vegetable oil or animal fat with an alcohol. Alcohols are the most frequently used acyl acceptors, particularly methanol and, to a lesser extent, ethanol. Other alcohols can also be used, e.g., propanol, butanol, isopropanol, tert-butanol, branched alcohols and octanol but the cost is much higher. Regarding the choice between methanol and ethanol, the former is cheaper, more reactive and the fatty-acid methyl esters (FAME) produced are more volatile than fatty-acid ethyl esters (FAEE). However, ethanol is less toxic and is considered more renewable because it can be easily produced from renewable sources by fermentation. In contrast, methanol is currently mainly produced from non-renewable fossil sources, such as natural gas. Regarding their characteristics as fuels, FAME and FAEE show slight differences; for example, FAEE have slightly higher viscosities and slightly lower cloud and pour points than the corresponding FAME [14]. The reaction requires a catalyst, usually a strong base, such as sodium or potassium hydroxide, and produces new chemical compounds called methyl esters. It is these esters that have come to be known as biodiesel [15,16]. The physical properties of biodiesel are given in Table 1. Biodiesel is a clear amber-yellow liquid with a viscosity similar to that of petroleum diesel. Biodiesel is non-ammable and, in contrast to petroleum diesel, is non-explosive, with a ash point of 423 K for biodiesel as compared to 337 K for petroleum diesel. Unlike petroleum diesel, biodiesel is biodegradable and non-toxic, and it significantly reduces toxic and other emissions when burned as a fuel. International practice led to the adoption of a single nomenclature to identify the concentration of biodiesel in the blends, known as the BXX nomenclature, where XX is the percentage in volume of the biodiesel in the diesel/biodiesel blend. For example, B2, B5, B20 and B100 are fuels with a concentration of 2%, 5%, 20% and 100% biodiesel, respectively. Currently, there are four main concentrations of biodiesel used in the fuel market, namely, pure (B100), blends (B20B30), additive (B5) and lubricity-additive (B2). The blends in volumetric proportions between 5% and 20% are the most

common. The B5 blend does not require any engine modication. Biodiesel is perfectly miscible with, and also physically and chemically similar to, mineral diesel and so can be used in compression ignition engines without signicant or onerous adjustments [1,10]. Biodiesel can be pumped, stored and handled using the same infrastructure, devices and procedure usually employed for conventional diesel fuel. In fact, as biodiesel does not produce explosive vapors and has a relatively high ash point (close to 150 C), transportation, handling and storage are safer than with conventional diesel [17]. 2.1. Various raw materials used as feedstock Vegetable oils are becoming a promising alternative to diesel fuel because they are renewable in nature and can be produced locally and in environmentally friendly ways. Edible vegetable oils such as canola [1822] and soybean oil [2327] in the USA, palm oil [2833] in Malaysia, rapeseed oil [26,3438] in Europe and corn oil [39,40] have been used for biodiesel production and found to be good diesel substitutes [15]. Non-edible vegetable oils, such as Pongamia pinnata (Karanja or Honge) [4145], Jatropha curcas (Jatropha or Ratanjyote) [43,44,4648] and Madhuca iondica (Mahua) [49,50] have also been found to be suitable for biodiesel production. The oil yield from the crop itself is always the key factor in deciding the suitability of a feedstock for biodiesel production. Oil crops with higher oil yields are more preferable in the biodiesel industry because they can reduce the production cost. Generally, the cost of raw materials accounts for about 7080% of the total production cost of biodiesel. Table 2 shows the oil yields in terms of kg/ha and wt.% and also the prices for various types of edible and
Table 2 Oil yields for major non-edible and edible oil sources [2]. Type of oil Non-edible oil Jatropha Rubber seed Castor Pongamia pinnata Sea mango Edible oil Soybean Palm Rapeseed Oil yield (kg oil/ha) 1590 80120 1188 2252250 N/A 375 5000 1000 Oil yield (wt.%) Seed: 3540, kernel: 5060 4050 53 3040 54 20 20 3750 Price (USD/ton) N/A N/A N/A N/A N/A 684 478 683

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non-edible oils grown worldwide. It is clear that higher oil yield always corresponds to lower cost. Some of the costs of the non-edible oils were not obtained as they are not currently traded on the open market [2]. From Table 2, it is observed that palm oil has the highest oil yield at 5000 kg of oil per hectare; this value is far higher than other oils, which are only in the range of hundreds to 2000 kg of oil per hectare. Among the various non-edible oils shown in Table 2, jatropha has the highest yield, followed by P. pinnata and castor. However, the oil yield in P. pinnata is not constant, depending on many factors such as plantation type and oil-extraction technique [2]. 2.2. The production of biodiesel Considerable efforts have been made to develop vegetable-oil derivatives that approximate the properties and performance of hydrocarbon-based diesel fuels. The problems with substituting triglycerides for diesel fuels are mostly associated with their (i) high viscosity; (ii) low stability against oxidation (and the subsequent polymerization reactions); and (iii) low volatility, which inuences the formation of a relatively high amount of ash due to incomplete combustion [51]. These can be changed in at least four ways, as follows. 2.2.1. Direct use and blending Vegetable oil can be mixed with diesel fuel and used directly for running an engine. The successful experimental blending of vegetable oil with diesel fuel has been done by various researchers. A diesel eet was powered with a blend of 95% ltered used cooking oil and 5% diesel in 1982. In 1980, Caterpillar Brazil Company used pre-combustion chamber engines with a mixture of 10% vegetable oil to maintain total power without any modication to the engine. A blend of 20% oil and 80% diesel was found to be successful [52]. Pramanik [53] found that a 50% blend of Jatropha oil can be used in diesel engines without any major operational difculties but further study is required to determine the long-term durability of the engine. The direct use of vegetable oils and/or the use of oil blends have generally been considered to be unsatisfactory and impractical for both direct and indirect diesel engines. The high viscosity, acid composition, free fatty-acid content, gum formation due to oxidation, polymerization during storage and combustion, carbon deposits and lubricating-oil thickening are the obvious problems (see Table 3). It has been proven that the use of 100% vegetable oil was also possible with some minor modications to the fuel system. Major
Table 3 Problems and potential solutions for using vegetable oils as engine fuels [53]. Problem Short-term 1. Cold-weather starting 2. Plugging and gumming of lters, lines and injector 3. Engine knocking Long-term 4. Coking of injectors and carbon deposits on piston and head of engine 5. Excessive engine wear Probable cause

problems have been associated with the use of pure vegetable oils as fuels in compressionignition engines, mainly due to the increased viscosity. Micro-emulsication, pyrolysis and transesterication have been used as remedies to solve the problems encountered due to high fuel viscosity [54]. 2.2.2. Microemulsion Microemulsions are isotropic, clear or translucent, thermodynamically stable dispersions of oil, water, surfactant, and often a small amphiphilic molecule, called a cosurfactant. The droplet diameters in microemulsions range from 100 to 1000 . A microemulsion can be made of vegetable oils with an ester and dispersant (cosolvent), or of vegetable oils, an alcohol and a surfactant, with or without diesel fuels. Because of their alcohol contents, microemulsions have lower volumetric heating values than diesel fuels, but these alcohols have high latent heats of vaporization and tend to cool the combustion chamber, which reduces nozzle coking. A microemulsion of methanol with vegetable oils can perform nearly as well as diesel fuels. The use of 2-octanol as an effective amphiphile in the micellar solubilization of methanol in triolein and soybean oil has been demonstrated; the viscosity was reduced to 11.2 cSt at 25 C. The reported engine tests on a microemulsion consisting of soybean oil:methanol:2-octanol:cetane improver (52.7:13.3:33.3:1) indicated the accumulation of carbon around the orices of the injector nozzles and heavy deposits on exhaust valves [55]. Wellert et al. [56] studied the phase behavior of a microemulsion and a bi-continuous phase was identied using small-angle neutron scattering (SANS) and freeze-fracture electron microscopy (FFEM); the inuence of choice of co-surfactant on the structural parameters was also studied. Jesus et al. [57] introduced the use of a microemulsion method for the determination of sodium and potassium in biodiesel using a water-in-oil emulsion process for biodiesel produced from different sources such as soybeans, castor, sunower oil, animal fat and other vegetable oils. 2.2.3. Thermal cracking (pyrolysis) Pyrolysis is the conversion of one organic substance into another by means of heat or by heat in the presence of a catalyst. The pyrolyzed material can be vegetable oil, animal fat, natural fatty acids or methyl esters of fatty acids. The pyrolysis of fats has been investigated for more than 100 years, especially in those areas of the world that lack deposits of petroleum. Many investigators have studied the pyrolysis of triglycerides to obtain products suitable for diesel engines. Thermal decomposition of triglycerides

Potential solution Preheat fuel prior to injection; chemically alter fuel to an ester Partially rene the oil to remove gums; lter to 4 lm Adjust injection timing; preheat fuel prior to injection; chemically alter fuel to an ester Heat fuel prior to injection; switch engine to diesel when operating at part load; chemically alter the vegetable oil to an ester

High viscosity, low cetane, and low ash point of vegetable oils Natural gums (phosphatides) and ash in vegetable oil Very low cetane of some oils. Improper injection timing

High viscosity of vegetable oil, incomplete combustion of fuel; poor combustion at partial load

High viscosity, incomplete combustion of fuel, poor combustion at partial load; possibly free fatty acids in vegetable oil; dilution of engine-lubricating oil due to blow-by of vegetable oil Collection of poly-unsaturated vegetable oil blow-by in crank-case to the point where polymerization occurs

Heat fuel prior to injection; switch engine to diesel when operating at partial load; chemically alter the vegetable oil to an ester; increase frequency of lubricating-oil changes; lubricating-oil additives to inhibit oxidation

6. Failure of enginelubricating oil due to polymerization

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produces alkanes, alkenes, alkadienes, aromatics and carboxylic acids [53,68]. 2.2.4. Transesterication Transesterication is a process of reacting a triglyceride such as vegetable oil with an alcohol in the presence of an alkaline catalyst to produce fatty-acid esters and glycerol. Among the alcohols, methanol and ethanol are used commercially because of their low cost and their physical and chemical advantages. They are easily dissolved in and react quickly with tri-glycerides and NaOH. A catalyst is used to improve the reaction rate and yield. An alkaline-catalyzed transesterication process is normally adopted for biodiesel production because alkaline metal alkoxides and hydroxides are more effective than acid catalysts. Sodium and potassium methoxide are much more effective catalysts for the base-catalyzed transesterication of triglycerides [5861]. Darnoko and Cheryan [62] studied the kinetics of palm-oil transesterication in a batch reactor. Their study illustrated that while the overall conversion of the process did not change with temperature, the rate of the transesterication process was increased with temperature. The overall reaction kinetics is dependent on the individual rate constants for the conversion of triglycerides to diglycerides, monoglycerides and alcohol esters. Based on the rate constants obtained, the conversion of triglycerides to diglycerides was the slowest reaction in transesterication. The time needed for the mass transfer to occur is shortened as temperature is increased, leading to a higher rate of transesterication at higher temperatures. Figs. 13 represent the different transesterication reactions. Fig. 1 shows the production of biodiesel via an alkaline catalyst. The commonly used catalysts are sodium and potassium hydroxides. These reactions are operated at 25125 C. Fig. 2 presents the production of biodiesel using an acid catalyst. The reaction is similar to the alkaline reaction but the alcohol reactants are fed in excess in order to increase the conversion rate. This reaction is

operated at 5580 C. The other type of reaction for transesterication is enzymatic, using lipase in hydrolysis, alcoholysis and acidolysis reactions. The advantage of this reaction is the ease of product separation; however, the cost of the biocatalyst is very expensive compared to other catalysts and so it is not yet a viable process for commercial biodiesel production. Lastly, Fig. 3 presents the production of biodiesel via a supercritical reaction with alcohol. This reaction uses methanol as alcohol and is capable of producing high conversions in a short period of time. However the operating temperature is very high, around 350 C [63,64]. Table 4 summarizes the advantages and disadvantages of the different transesterication reactions. 2.3. Advantages of biodiesel 2.3.1. Availability and renewability of biodiesel Biodiesel is the only alternative fuel with the property that lowconcentration biofuelpetroleum fuel blends will run well in unmodied conventional engines. It can be stored anywhere petroleum diesel fuel is stored. Biodiesel can be made from domestically produced, renewable oilseed crops such as soybean, rapeseed and sunower. The risks of handling, transporting and storing biodiesel are much lower than those associated with petroleum diesel. Biodiesel is safe to handle and transport because it is as biodegradable as sugar and has a high ash point compared to petroleum diesel fuel. Biodiesel can be used alone or mixed in any ratio with petroleum diesel fuel. The most common blend is a mix of 20% biodiesel with 80% petroleum diesel, or B20 in recent scientic investigations; however, for future commercial applications in Europe the current regulation foresees a maximum of 5.75% biodiesel [66]. 2.3.2. Lower emissions from biodiesel The European Transportation Policy for 2010 created by the European White Paper Commission projects an increase in carbon dioxide emissions from vehicles of about 50% from the years 2000

Fig. 1. Production of biodiesel via alkaline catalysis.

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Fig. 2. Production of biodiesel via acidic catalysis.

Fig. 3. Production of biodiesel via supercritical-alcohol transesterication.

Table 4 Comparison of transesterication reactions [65]. Technique Acidic-catalyst transesterication Alkaline-catalyst transesterication Lipase-catalyst transesterication Biodiesel (%) 99% after 4 h of reaction 99% after 2 h of reaction 95% after 105 h of reaction Advantage High production of biodiesel High and rapid production of biodiesel in a short period of time Can be operated at room temperature Disadvantage Acidic catalyst Formation of calcium foam at initial stage of transesterication Slow reaction

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to 2010. The White Paper states that the only way around this problem is to develop clean alternative fuels so that the greenhouse effects can be decreased [67]. The best potential future energy source in the transportation sector is biodiesel. Biodiesel mainly emits carbon monoxide, carbon dioxide, oxides of nitrogen, sulfur oxides and smoke. Combustion of biodiesel alone provides over a 90% reduction in total unburned hydrocarbons (HC) and a 7590% reduction in polycyclic aromatic hydrocarbons (PAHs). Biodiesel further provides signicant reductions in particulates and carbon monoxide over petroleum diesel fuel. Biodiesel provides a slight increase or decrease in nitrogen oxides depending on engine family and testing procedures [66]. Currently, global warming caused by CO2 is the main climatic problem in the world. Therefore, environmental protection is important for the future of the world. Because biodiesel is made from renewable sources, it presents a convenient way to provide fuel while protecting the environment from unwanted emissions. Biodiesel is an ecological and non-hazardous fuel with low emission values, and therefore it is environmentally useful. Using biodiesel as an alternative fuel is a way to minimize global air pollution and in particular reduce the emission levels of potential or probable carcinogens [68]. Carraretto et al. [69] investigated the emission of unburned hydrocarbons, carbon dioxide, carbon monoxide, sulfates, polycyclic aromatic hydrocarbons, nitrated polycyclic aromatic hydrocarbons and particulate matter from biodiesel; the net emission of CO2 was considerably lower than that of diesel oil. Kegl [70] stressed the importance of fuel-injection system to reduce engine emissions as well as fuel consumption. The author suggested that pressure squareness (ratio of mean to maximum injection pressure) should be at a maximum, and fuelling in the rst part of the injection should be reduced to reduce NOx emission. Simultaneously, the fuelling in the last part of the injection should be lowered to reduce smoke emissions. Pradeep and Sharma [71] studied the use of hot-exhaust-gas recirculation for the control oxides of nitrogen in a compression ignition engine fuelled with biodiesel from Jatropha oil. Exhaustgas recirculation was shown to be an effective method for NOx control. The exhaust gases mainly consist of inert carbon dioxide and nitrogen and possess a high specic heat. When recirculated to the engine inlet, they reduce oxygen concentration and act as a heat sink. This process reduces oxygen concentration and peak combustion temperature, which results in reduced NOx. Exhaust-gas recirculation is not free from demerits. It can signicantly increase smoke and fuel consumption and reduce thermal efciency unless suitably optimized. 2.3.3. Biodegradability of biodiesel The biodegradability of biodiesel has been proposed as a solution for the waste problem. Biodegradable fuels such as biodiesels have an expanding range of potential applications and are environmentally friendly. Therefore, there is growing interest in degradable diesel fuels that degrade more rapidly than conventional petroleum fuels. Biodiesel is non-toxic and degrades about four times faster than petroleum diesel. Its oxygen content improves the biodegradation process, leading to an increased level of quick biodegradation [72]. Vegetable-oil methyl esters are reported to be non-toxic and easily biodegradable in an aquatic environment. It was determined that during a 21-day period, 98% of pure rapeseed oil methyl ester (RME) was biologically decomposed, while only 60% of pure fossil diesel fuel decomposed. This means that RME fully meets the main requirements of international standards for biological degradation (more than 90% degraded within 21 days for biofuels) [73]. Pasqualino et al. [74] reported more than 98% degradation of pure biodiesel after 28 days in comparison to 50% and 56% for diesel fuel and

gasoline respectively. Also, the time taken to reach 50% biodegradation was reduced from 28 to 22 days in 5% biodiesel mixture and from 28 to 16 days in the case of a 20% biodiesel mixture at room temperature. The biodegradability of the mixture was reported to increase with the addition of biodiesel. 2.3.4. Higher lubricity Biodiesel has good lubricant properties compared to petroleum diesel oil, in particular very-low-sulfur diesel. This is very important to reduce wear in the engine and the injection system [69]. Demirbas [68] stated that the oxygen content of biodiesel improves the combustion process and decreases its oxidation potential. The structural oxygen content of a fuel improves combustion efciency due to the increase of the homogeneity of oxygen with the fuel during combustion. Due to this, the combustion efciency of biodiesel is higher than petroleum diesel, and the combustion efciency of methanol/ethanol is higher than that of gasoline. A visual inspection of the injector types would indicate no difference between the biodiesel fuels when tested on petroleum diesel. The overall injector coking is considerably low. Biodiesel contains 11% oxygen by weight and contains no sulfur. The use of biodiesel can extend the life of diesel engines because it is more lubricating than petroleum diesel fuel. The higher heating values (HHVs) of biodiesels are relatively high. The HHVs of biodiesels (3941 MJ/kg) are slightly lower than that of gasoline (46 MJ/kg), petroleum diesel (43 MJ/kg) or petroleum (42 MJ/kg), but higher than coal (3237 MJ/kg). Table 5 shows a comparison of the chemical properties and HHVs of biodiesel and petroleumdiesel fuels. 2.3.5. Engine-performance evaluation using biodiesel Cetane number (CN) is widely used as a dieselfuel quality parameter. It is related to the ignition-delay time and combustion quality; a higher cetane number indicates better ignition properties [16]. CN is measured by the ISO 5156 test method. This test method is recommended for diesel and biodiesel and the passing limits are 46 and 51, respectively. However, there are reports of the theoretical estimation of cetane numbers without running extensive engine tests. The cetane number of biodiesel from various sources has been estimated to vary from 48 (grape biodiesel) to 61 (palm biodiesel) [75]. The CN of biodiesel is generally higher than for conventional diesel. The longer the fatty-acid carbon chains and the more saturated the molecules are, the higher the CN is. The CN of biodiesel from animal fats is higher than those of vegetable oils [76]. Altn et al. [77] studied a single-cylinder engine fueled with various types of vegetable oils. The results obtained gave a very good comparison of engine performance when various vegetable oils are used as fuel. The engine was operated at 1300 rpm and a torque of 35 Nm. Petroleum dieselfuel performance was used as a reference. The observed maximum torque differences between the reference value and peak values of the vegetable-oil fuels were about 10% with raw sunower oil, raw soybean oil and opium-poppy oil fuels. The maximum power differences between the reference

Table 5 Comparison of chemical properties and higher heating values (HHVs) of biodiesel and petroleumdiesel fuels [63]. Chemical property Ash (wt.%) Sulfur (wt.%) Nitrogen (wt.%) Aromatics (vol.%) Iodine number HHV (MJ/kg) Biodiesel (methyl ester) 0.0020.036 0.0060.020 0.0020.007 0 65156 39.240.6 Diesel 0.0060.010 0.0200.050 0.00010.003 2838 0 45.145.6

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value and peak values of the vegetable-oil fuels were about 18% with raw cottonseed oil and raw soybean oil. The minimum torque and power difference was about 3% between the reference value and the oils. These results may be due to the higher viscosity and lower heating values of vegetable oils. The specic fuel consumption of petroleum diesel was very low in comparison with all vegetable oils and their esters. Specic fuel-consumption values of methyl esters were generally less than those of the raw oil fuels. The higher specic fuel-consumption values of vegetable oils are due to their lower energy contents. Relatively low CO emissions were obtained with the esters in comparison with raw vegetable oils. Maximum CO2 emissions were about 10.5% with petroleum diesel fuel and slightly lower with vegetable oil. This was due to the better spraying qualities and more uniform mixture preparation of these esters. NOx emissions with vegetable-oil fuels were lower than those with petroleum diesel fuel and the NOx values of the methyl esters were higher than those of the raw fuels. NOx formation is related to maximum combustion temperature. As the injected particle size of the vegetable oils was greater than with petroleum diesel fuel, the combustion efciency and maximum combustion temperatures with each of the vegetable oils were lower and NOx emissions were reduced. Smoke-opacity percentages during each of the vegetable-oil operations were greater than that with petroleum diesel fuel. The opacity values of methyl esters were between those of diesel fuel and raw vegetable-oil fuels. The greater smoke-opacity percentages of the vegetable-oil fuels were mainly due to the contents of heavier hydrocarbon molecules. Acceleration tests indicated that maximum engine-power output depended on the biodiesel content in the fuel and decreased as the biodiesel concentration increased. It was observed that with pure biodiesel the acceleration time increased by approximately 8% compared to the baseline petroleum diesel fuel, while B50 led to an increase of 4.1%. These differences were expected due to the lower energy content of the blends. Poorer atomization may also explain reductions in maximum engine-power output [78]. 2.4. Disadvantages of biodiesel The main problem associated with the use of biodiesel, especially that prepared from palm oil, is its poor low-temperature ow properties, measured in terms of cloud point, pour point and CFPP. The low-temperature properties are very critical for the use of biofuels in aviation applications. The low-temperature properties can be improved by blending with biodiesel from unsaturated feedstocks [79]. Other major disadvantages of biodiesel are its higher viscosity, lower energy content, higher nitrogen-oxides (NOx) emissions, lower engine speed and power, injector coking, engine compatibility, high price and higher engine wear. Table 6 shows the ASTM fuel standards for biodiesel and petroleum-diesel fuels. Important operating disadvantages of biodiesel in comparison with petroleum diesel include cold-start problems, the lower energy content, higher copper-strip corrosion and fuel-pumping difculty due to the higher viscosity. This increases fuel consumption when biodiesel is used, in comparison with pure petroleum diesel and in blends, in direct proportion to the share of the biodiesel content. Taking into account the higher production costs of biodiesel compared to petroleum diesel, this increase in fuel consumption compounds the overall increased cost of application of biodiesel as an alternative to petroleum diesel [63]. As more than 95% of biodiesel is made from edible oil, there have been many claims that this may give rise to further economic problems. By converting edible oils into biodiesel, food resources are being used as automotive fuels. It is believed that large-scale production of biodiesel from edible oils may bring about a global

Table 6 ASTM standards of biodiesel and petroleumdiesel fuels. Property Flash point Water and sediment Kinematic viscosity (at 313 K) Sulfated ash Ash Sulfur Sulfur Test method D 93 D 2709 D 445 D 874 D 482 D 5453 D 2622/ 129 D 130 D 613 D 1319 D 4530 D 524 D 1160 ASTM D975 (petroleum diesel) 325 K min 0.05 max vol.% 1.34.1 mm2/s 0.01 max wt.% 0.05 max wt.% ASTM D6751 (biodiesel, B100) 403 K 0.05 max vol.% 1.96.0 mm2/s 0.02 max wt.% 0.05 max wt.%

Copper-strip corrosion Cetane number Aromaticity Carbon residue Carbon residue Distillation temp. (90% volume recycle)

No. 3 max 40 min 35 max vol.% 0.35 max mass% 555 K min 611 K max

No. 3 max 47 min 0.05 max mass%

Fig. 4. Global vegetable-oil blending stock and biodiesel production [2].

imbalance in the food supply-and-demand market. Recently, environmentalists have cited the negative impact on the planet of biodiesel production from edible oils, especially deforestation and the destruction of ecosystems. EEB, claimed that the expansion of oilcrop plantations for biodiesel production on a large scale has caused deforestation in countries such as Malaysia, Indonesia and Brazil because more and more forest has been cleared for plantation purposes. Furthermore, the line between food and fuel economies is blurred as both of the elds are competing for the same oil resources. In other words, biodiesel is competing with the food industry for limited land availability for the plantation of oil crops. Arable land that would otherwise have been used to grow food would instead be used to grow fuel [80]. There has been signicant expansion in the plantation of oil crops for biodiesel in the past few years in order to fulll the continuously increasing demand for biodiesel. Fig. 4 shows the trend in global vegetable-oil blending stocks due to the production of biodiesel in the years 19912010 [2]. Although there is continuous increase in the production of vegetable oil, the blending stocks of vegetable oils are continuously decreasing due to increasing production of biodiesel. Eventually, with the implementation of biodiesel as a substitute fuel for petroleum-derived diesel oil, this may lead to the depletion of edible-oil supply worldwide.

3. Current trends in biodiesel The international biofuel market is still at an early and very dynamic stage. Future conditions for an international biofuel market in Europe will largely be decided by the European Union (EU)

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policies on renewable energy and their interplay with national energy policies. So far, the Commission has indicated that biomass will play an important role in the future. In that context, the biofuel trade seems to be a plausible scenario for Europe. It is likely that novel trade ows will appear and disappear as this new fuel market evolves [81]. European research and testing indicate that, when used as a diesel fuel substitute, biodiesel can replace petroleum diesel. Fig. 5 shows the world biodiesel capacity between 1991 and 2010. In the EU, biodiesel is by far the biggest biofuel and represents 82% of the biofuel production. Biodiesel has become more attractive recently because of its environmental benets. The cost of biodiesel, however, is the main obstacle to commercialization of the product. Biodiesel reduces carbon dioxide, carbon monoxide, PAH and nitrated PAH emissions. The use of biodiesel decreases the solid-carbon fraction of PM and reduces the sulfate fraction, while the soluble, or HC, fraction stays the same or increases. Emissions of nitrogen oxides increase with the concentration of biodiesel in the fuel. Some biodiesel produces more nitrogen oxides than others, and some additives have shown promise in moderating the increases. Germany produced 1.9 billion liters or more than half the world total. Other countries with signicant biodiesel markets in 2005 included France, the United States, Italy and Brazil. All other countries combined accounted for only 11% of world biodiesel consumption in 2005. In Germany biodiesel is also sold at a lower

Fig. 5. World biodiesel capacity, 19912010 [82].

price than fossil diesel fuel. Biodiesel is treated like any other vehicle fuel in the UK. In February 2006, the European Union set the goal of fullling 5.75% of transportation-fuel needs with biofuels in all member states by 2010. Many countries have adopted various policy initiatives. Specic legislation to promote and regulate the use of biodiesel is in force in Germany, Italy, France, Austria and Sweden [68]. By 2010, the United States is expected to become the worlds largest single biodiesel market, accounting for roughly 18% of world biodiesel consumption, followed by Germany. New and large single markets for biodiesel are expected to emerge in China, India and Brazil [83]. Demand for energy is increasing every day due to the rapid growth of population and urbanization. As the major conventional energy resources such as coal, petroleum and natural gas are at the verge of becoming extinct; biomass can be considered as one of the promising environmentally friendly renewable energy options [13]. The biomass-intensive future energy-supply scenario includes 385 million hectares of biomass-energy plantations globally in 2050, with three quarters of this area established in developing countries [84]. Based on a study conducted by the 9th National Plan of Malaysia, the demand for fossil fuel is increasing continuously. In the term of the 8th National plan of Malaysia, which ranged from 2000 to 2005, the demand for energy in the commercial sector increased from 1244 PJ to 1632 PJ. The energy intensity increased from 5.9 GJ in the year 2000 to 6.2 GJ in the year 2005. Petroleum is the main source of energy, and, as shown in Table 7a, the percentage from other energy sources is very low (46%). The increasing demand for natural gas (79%) parallels the policy of fuelsource diversity. From Table 7b, it can also be observed that the transportation sector is the primary energy consumer in Malaysia, accounting for 40.5% of the total energy demand in the commercial sector in the 2005. The industrial sector comprises 38% of the total demand while domestic and other sources account for about 13.1%. Based on these gures, Malaysia is predicted to become a net importer of fossil fuels by the year 2015. However, the introduction of alternative fuels such as hydrogen, ethanol and biodiesel, will reduce the dependence on imported fuel sources. Malaysia is capable of generating its own alternative fuels, as mentioned previously, using domestic renewable resources [65]. The potential future use of biodiesel in the transportation sector necessitates a shift in the current energy supply from petroleum products such as gasoline and diesel, to biodiesel.

Table 7a Final demand of commercial energy by source, 20002010 [65]. Source Petajoules 2000 Petroleum products Natural gas Electricity Coal Total 820.0 161.8 220.4 41.5 1243.7 2005 1023.1 246.6 310.0 52.0 1631.7 2010 1372.9 350.0 420.0 75.0 2217.9 Percentage of the total 2000 65.9 13.0 17.7 3.4 100.0 2005 62.7 15.1 19.0 3.2 100.0 2010 61.9 15.8 18.9 3.4 100.0 Average annual growth rate (%) RMKe-8 4.5 8.8 7.1 4.6 5.6 RMKe-9 6.1 7.3 6.3 7.6 6.3

Table 7b Final demand of commercial energy by sector, 20002010 [65]. Source Petajoules 2000 Industrial Transportation Residential and commercial Agricultural Total 477.6 505.5 162.0 4.4 1243.7 2005 630.7 661.3 213.0 8.0 2217.9 2010 859.9 911.7 284.9 16.7 1631.7 Percentage of the total 2000 38.4 40.6 13.0 0.4 100.0 2005 38.6 43.5 13.1 0.5 100.0 2010 38.8 41.1 12.8 0.8 100.0 Average annual growth rate (%) RMKe-8 5.7 5.5 5.6 12.9 5.6 RMKe-9 6.4 6.6 6.0 15.9 6.3

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The large-scale use of biomass energy in the EU would be facilitated by a European market for biofuels. Regions rich in biomass resources could become net exporters of biofuels to regions with fewer opportunities for biofuel production, which would increase the Unions total use of biomass energy. Inter-regional and international biofuel trade is also a likely consequence of the growing use of biomass energy. At the moment, there is a mounting interest in the biofuel trade in Europe [81]. Kartha and Larson [84] reported that various scenarios have been proposed in estimating the yields of biofuels from biomass sources in the future energy system. The availability of resources is an important factor in cogenerative use of biofuel in the electricity, heat or liquid-fuel market. There are currently two global biomass-based liquid transportation fuels that might replace gasoline and diesel fuel, bioethanol and biodiesel. Transport is one of the main energy-consuming sectors. It is assumed that biodiesel will be used as a fossil diesel replacement and that bioethanol used as a gasoline replacement. Biomass-based energy sources for heat, electricity and transportation fuels are potentially carbon dioxide neutral and recycle the same carbon atoms. Due to the widespread availability of biomass resources, opportunities for biomass-based fuel technology will potentially employ more people than current fossil-fuel based technology. About 60% of current world ethanol production is from sugarcrop feedstocks. Ethanol is a well-established biofuel for transport and industry sectors in several countries, notably in Brazil. The United States has used ethanol produced from maize (corn) in fuel blends since the 1980s. The United States ethanol production, with corn as the primary feedstock, totaled 2821 million gallons in 2003 and is projected to increase to 4544 million gallons in 2025. In 2004, 3.4 billion gallons of fuel ethanol were produced from over 10% of the corn crop. Ethanol demand is expected to more than double in the next ten years. For the supply to be available to meet this demand, new technologies must be moved from the laboratory to commercial reality [82].

Table 8 Comparison of estimated costs for producing biodiesel from palm, rapeseed and soybean oils. Cost component (US$/ ton) Palm oil from Malaysia 547 47 35 55 Rapeseed oil from the EU 800 Soybean oil from the US 601

Feedstock (FOB at producing country) Biodiesel production cost: Solvents, acids and chemicals Other costs Adjustment for energy parity with petroleum diesel (based on 90% of kJ/kg of energy of petroldiesel) Total Cost of biodiesel Estimated freight and insurance cost to Rotterdam Total cost in EU Local distribution (approximation) Total cost at petrol kiosk in EU Price of retail biodiesel (Germany)a

137 684 70 754 3050 784804 1322

196 996 996 3050 10291046

150 751 50 801 3050 831851

Assuming production plant with capacity > 100,000 ton/annum; other gures based on pricing as of March 2007. a FO Licht based on UFOP Marktinformation (three-month average retail prices from November 2006 to January 2007).

4. Economic analysis One of the main limiting factors for the market diffusion of biodiesel is the high economic cost of production compared to petroleum diesel oil. Currently, the cost of biodiesel is competitive only when excise tax is not applied. Nevertheless, the promotion of biodiesel is justied by the fact that the global emission of CO2 is greatly reduced and that the net energy yield is positive. In addition, the use of biodiesel involves an appreciable reduction of some emitted pollutants. This could be a key solution to reduce urban pollution [69]. The major economic factor to consider for the input costs of biodiesel production is the feedstock, which is about 80% of the total operating cost. Other important costs are labor, methanol and catalyst. In some countries, lling stations sell biodiesel more cheaply than conventional diesel. The cost of biodiesel fuels varies depending on the base stock, geographic area, variability in crop production from season to season, the price of crude petroleum and other factors. Biodiesel has sold for over twice the price of petroleum diesel. The high price of biodiesel is in large part due to the high price of the feedstock. Biodiesel is becoming of interest to companies for commercial-scale production as well as the more usual home-brew biodiesel user and the user of straight vegetable oil or waste vegetable oil in diesel engines. Biodiesel is commercially available in most oilseed-producing countries. Biodiesel is a technologically feasible alternative to petroleum diesel, but currently biodiesel cost is 1.53 times higher than the fossil diesel cost in developed countries. Biodiesel is more expensive than petroleum diesel, although it is still commonly produced in

relatively small quantities (in comparison to petroleum products and ethanol). The competitiveness of biodiesel versus petroleum diesel depends greatly on fuel-taxation approaches and levels. Generally, the production costs of biodiesel remain much higher than for petroleum diesel. Therefore, biodiesel is not competitive to petroleum diesel under current economic conditions. The competitiveness of biodiesel relies on the prices of biomass feedstock and costs as well as the conversion technology [63]. The price of the feedstock will become a more important factor as it represents 80% of the cost of biodiesel production. Even at current vegetable oil prices this is an advantage for palm oil which trades at a considerable discount compared to rapeseed oil and soybean oil. Rabobank [85] estimates that the price of palm biodiesel in the EU if produced in Malaysia will be about US$784804/ton (Table 8). The estimated theoretical production cost for rapeseed biodiesel is US$1035/tonne and US$840 for soybean biodiesel. These gures are based on the average prices of each vegetable oil, including an approximately 20% cost of production, international freight and domestic distribution charges. The reported consumer biodiesel price in Germany, based on a three-month average up to January, was US$1332/ton. Palm biodiesel from Malaysia is still competitively priced although this estimate does not consider any potential excise nor import duty that could be imposed by the EU member-states on palm methyl ester. 5. Conclusions The term biofuel refers to liquid or gaseous fuels for the transport sector that are predominantly produced from biomass. Biofuels including bioethanol, biomethanol, biodiesel and biohydrogen appear to be attractive options for the future transport sector. Biodiesel is better than diesel fuel in terms of sulfur content, ash point, aromatic content and biodegradability. Biodiesel, dened as the monoalkyl esters of fatty acids derived from vegetable oil or animal fat, has demonstrated a number of promising characteristics in applications as an extender for combustion in compressionignition engines (CIEs), including a reduction of exhaust emissions. Biodiesel is much less polluting than petroleum diesel, resulting in much lower emissions of almost every pollutant: carbon dioxide, sulfur oxide, particulates, carbon monoxide, air toxics and unburned hydrocarbons. Biodiesel does,

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N.N.A.N. Yusuf et al. / Energy Conversion and Management 52 (2011) 27412751 [29] Moser BR, Vaughn SF. Evaluation of alkyl esters from Camelina sativa oil as biodiesel and as blend components in ultra low-sulfur diesel fuel. Bioresour Technol 2010;101:64653. [30] Lozada I, Islas J, Grande G. Environmental and economic feasibility of palm oil biodiesel in the Mexican transportation sector. Renew Sustain Energy Rev 2010;14:48692. [31] Boey PL, Maniam GP, Abd Hamid S. Biodiesel production via transesterication of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst. Bioresour Technol 2009;100:63628. [32] Abdullah AZ, Salamatinia B, Mootabadi H, Bhatia S. Current status and policies on biodiesel industry in Malaysia as the worlds leading producer of palm oil. Energy Policy 2009;37:54408. [33] Kansedo J, Lee KT, Bhatia S. Biodiesel production from palm oil via heterogeneous transestericatio. Biomass Bioenergy 2009;2:2716. [34] Shi H, Bao Z. 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however, have nitrogen oxide emissions that are about 10 percent higher than petroleum diesel. Blending biodiesel into petroleum diesel can help reduce emissions. It is well known that transport is almost totally dependent on fossil fuels. Biodiesel is one of the feasible alternatives. The biodiesel fuels have not been widely accepted in the market because they are more expensive than petroleum fuels. With recent increases in petroleum prices and uncertainties concerning petroleum availability, there is renewed interest in biodiesel fuels for diesel engines [37].

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