Applied Energy 88 (2011) 10201031

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Opportunities and challenges for biodiesel fuel

Lin Lin a,, Zhou Cunshan b, Saritporn Vittayapadung c, Shen Xiangqian d, Dong Mingdong e,
a

School of Food & Biological Engineering, Jiangsu University, Zhenjiang 212013, PR China School of Agriculture and Food Science, Zhejiang A & F University, Linan 311300, PR China c Faculty of Industrial Technology, Chiangrai Rajabhat University, Chiangrai 57100, Thailand d School of Material Science & Engineering, Jiangsu University, Zhenjiang 212013, PR China e Interdisciplinary Nanoscience Center, Aarhus University, Aarhus 8000, Denmark
b

a r t i c l e

i n f o

a b s t r a c t
Fossil fuel resources are decreasing daily. As a renewable energy, biodiesel has been receiving increasing attention because of the relevance it gains from the rising petroleum price and its environmental advantages. This review highlights some of the perspectives for the biodiesel industry to thrive as an alternative fuel, while discussing opportunities and challenges of biodiesel. This review is divided in three parts. First overview is given on developments of biodiesel in past and present, especially for the different feedstocks and the conversion technologies of biodiesel industry. More specically, an overview is given on possible environmental and social impacts associated with biodiesel production, such as food security, land change and water source. Further emphasis is given on the need for governments incentives and public awareness for the use and benets of biodiesel, while promoting policies that will not only endorse the industry, but also promote effective land management. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 7 July 2010 Received in revised form 28 September 2010 Accepted 28 September 2010 Available online 30 October 2010 Keywords: Biodiesel Energy security Environment Food Land change Policy

Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Profile of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Historical background and development of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Feedstocks of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Biodiesel conversion technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Key drivers and challenges of biodiesel industry development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Security of energy supply . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Environmental effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Food security, land use changes and water source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Policy and government incentives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1020 1021 1021 1022 1025 1026 1026 1027 1027 1028 1028 1028 1028

3.

4. 5.

1. Introduction Since the commencement of industrial revolution in the late 18th and early 19th century, energy has become an indispensable factor for mankind to preserve economic growth and maintain standard of living. The most of global primary energy production
Corresponding authors. Tel.: +45 8942 3702 (L. Lin).
E-mail addresses: Lin780530@126.com (L. Lin), dong@inano.au.dk (D. Mingdong). 0306-2619/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.apenergy.2010.09.029

derives from fossil energy. As shown in Fig. 1, fossil fuels accounted for 88% of the primary energy consumption, with oil (35% share), coal (29%) and natural gas (24%) as the major fuels, while nuclear energy and hydroelectricity account for 5% and 6% of the total primary energy consumption, respectively [1]. However, due to the limited traditional fossil energy resources and increased environmental concerns, a requirement for alternative energy sources has been paid a great attention in recent years. Developing alternative energy is an inevitable choice for sustainable economic growth

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Fig. 1. World primary energy production in 2009 by source [1].

in human society. In addition, it is also important for the harmonious coexistence of human and environment as well as for the sustainable development [2]. Considerable attention was focused on the development of biofuel, with particular referring to the biodiesel. Biodiesel offers a number of technical and environmental benets over conventional fossil-based fuels. Especially, similarities between the combustion properties of biodiesel and fossil-based diesel have made the former one of the most promising alternatives to a renewable and sustainable fuel for the automobile. In recent years, the biodiesel industry developed rapidly. According to the International Energy Agencys (IEA) report on biodiesel production that looked at the 21 leading biofuel producing countries, global biodiesel production has increased tenfold from 2000 to 2008 and could be doubled to 21.8 bn liters by 2012 [3]. The motivations for governments to aggressively pursue biodiesel development are complex and multidimensional. The key driving force behind the government policies to develop biodiesel can be divided into three points as follow: Firstly, with the global energy crisis approaching, biodiesel fuel will play a more important role in strengthening a nations energy security. Secondly, as a renewable energy, biodiesel is derived from plant materials which can contribute to the reduction of greenhouse gas (GHG) emissions when replacing fossil oil if they are sustainably managed. Thirdly, the increased demand for oil crops for biodiesel production clearly has a positive effect on net farm income and also reduces government outlays to farmers by raising the market price of oil crops. However, biodiesel could be a double-edged sword. While we focused on the advantages of biodiesel, the debates on biodiesel have been intensively discussed in both the scientic world and the media. With the global increase in the scale of biodiesel production, biodiesel has become a systemic risk with respect to its economic, ecological, and socio-political impacts. Opportunities, challenges, and even threats have been raised. Especially those

linked to rst-generation biodiesel, have received considerable criticisms recentlymost notably the biodiesel potential to increase food prices and damage biodiversity; their relatively low GHG abatement capacity yet high marginal carbon abatement costs; their continuing need for signicant government support and subsides; their direct and indirect impacts on land use change and related greenhouse gas emissions [4,5] Here we highlight the important aspects of the biodiesel which will reveal the perspective as the next generation green fuel. Three major areas are discussed in the following: (1) Prole of biodiesel. (2) Key drivers and challenges of biodiesel industry development. (3) Policy and government incentives. 2. Prole of biodiesel 2.1. Historical background and development of biodiesel Biodiesel, which can also be known as fatty acid methyl ester (FAME), is produced from transesterication of vegetable oils or animal fats with the addition of methanol as shown in Fig. 2 [6]. Biodiesel is quite similar to petroleum-derived diesel in its main characteristics such as cetane number, energy content, viscosity and phase changes [7]. Biodiesel contains no petroleum products, but it is compatible with conventional diesel and can be blended in any proportion with fossil-based diesel to create a stable biodiesel blend. Therefore, biodiesel has become one of the most common biofuels in the world. The key milestones in the development of biodiesel industry were shown in Table 1. In fact, the usage of vegetable oils in diesel engine could be dated back to August 10, 1893. In this day, Rudolf Diesel, the inventor

Fig. 2. Transesterication of triacylglycerols to yield fatty acid alkyl esters (biodiesel).

1022 Table 1 Key milestones in the development of biodiesel industry. Date August 10, 1893 1900 August 31, 1937 Event

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1977 1979

1983 November, 1987 April, 1989 1991 1997 2002 October, 2003 September, 2005 October, 2008 November, 2008

Rudolf Diesels prime diesel engine model, which was fueled by peanut oil, ran on its own power for the rst time in Augsburg, Germany Rudolf Diesel showed his engine at the world exhibition in Paris, his engine was running on 100% peanut oil A Belgian scientist, G. Chavanne, was granted a patent for a Procedure for the transformation of vegetable oils for their uses as fuels. The concept of what is known as biodiesel today was proposed for the rst time A Brazilian scientist, Expedito Parente, applied for the rst patent of the industrial process for biodiesel Research into the use of transesteried sunower oil, and rening it to diesel fuel standards, was initiated in South Africa The process for producing fuel-quality, engine-tested biodiesel was completed and published internationally An Austrian company, Gaskoks established the rst biodiesel pilot plant Gaskoks established the rst industrial-scale plant Austrias rst biodiesel standard was issued A German standard, DIN 51606, was formalized ASTM D6751 was rst published A new Europe-wide biodiesel standard, DIN EN14214 was published Minnesota became the rst US state to mandate that all diesel fuel sold in the state contain part biodiesel, requiring a content of at least 2% biodiesel ASTM published new Biodiesel Blend Specications Standards The current version of the European Standard EN 14214 was published and supersedes EN 14214:2003

of the engine that beared his name, ran on his prime engine model in Augsburg, Germany. The engine model has been fueled nothing but peanut oil. In remembrance of this event, August 10 has been declared International Biodiesel Day. Dr. Diesel was visionary. Away back in 1912, he has long predicated that the use of vegetable oils for engine fuels would one day become as important as petroleum and the coaltar products of the present time. His usage continued until 1920s before fossil-based diesel almost completely eliminated vegetable oils in the market due to cheaper price, higher availability and government subsidies. The diesel engine has been modied to run on the lower viscosity petroleum fuel, now known as diesel. Nevertheless, Diesels ideas on agriculture and his invention provided the foundation for a society fueled with clean, renewable, locally grown fuel [8]. In 1970s, fossil fuels supply shortage and security had prompted new interest in developing vegetable oils as alternative energy. However, the altered diesel engine is no longer suitable for high viscosity and low volatility vegetable oils to be applied directly. Some operational problems were reported due to the high viscosity of vegetable oils compared to fossil-based diesel, which results in poor atomization of the fuel in the fuel spray and often leads to deposits and coking of the injectors, combustion chamber and valves. Renement has to be made in order to turn those vegetable oils into quality fuel. Attempts to overcome these problems included pyrolysis, blending [9,10] and microemulsication [11]. Yet, problems were still found with carbon deposition and contamination [12,13]. Transesterication of a vegetable oil was conducted as early as 1853 by scientists E. Duffy and J. Patrick, many years before the rst diesel engine became functional. The transesterication process can convert the vegetable oils to their alkyl esters and reduce the viscosity to diesel fuel level, which produced biodiesel with properties that were similar to petroleum-based diesel fuel. Therefore, it has become the most viable process to transform the vegetable oils to be used in existing engines without modications.

A Belgian scientist, G. Chavanne was granted a patent for a Procedure for the transformation of vegetable oils for their uses as fuels in 1937. The concept of what is known as biodiesel today was proposed for the rst time [14]. After that, a Brazilian scientist, Expedito Parente, applied for the rst patent of the industrial process for biodiesel in 1977 [15]. Meanwhile research for the production and rening of biodiesel using sunower oil was initiated in South Africa in 1979. By 1983, the process for producing fuelquality, engine-tested biodiesel was completed and published internationally [16]. An Austrian company, Gaskoks, obtained the technology from the South African Agricultural Engineers, sequently established the rst biodiesel pilot plant and the rst industrial-scale plant in 1987 and 1989, respectively. However, increasing subsidization in petroleum market had impeded any other signicant breakthrough being achieved. Not until in the late 1990s that growing concerns about the environment sustainability and decreasing cost differential had driven the growth in commercial production of biodiesel [7]. During that period, biodiesel plants were opened in many European countries, including the Czech Republic, Germany and Sweden. France launched the local production of biodiesel fuel known as diester from rapeseed oil. By 1998, the Austrian Biofuels Institute had identied 21 countries with commercial biodiesel projects. During the same period, nations in other parts of the world also saw local production of biodiesel starting up: In 2004, the government of Philippines had made it compulsory for the incorporation of 1% of coconut biodiesel blend in diesel fuel for use in government vehicles. In 2005, Minnesota became the rst US state to mandate that all diesel fuel sold in the state contain part of biodiesel, requiring a content of at least 2% biodiesel. For strengthening the quality control requirements of engine and equipment manufacturers, and allowing further companies to issue biodiesel engine warranties for the use of biodiesel fuels, a series of biodiesel standards were issued in succession, such as DIN 51606 (Germany), EN 14214 (Europe), ASTM D6751 (USA and Canada). Other countries have also established or are planning to adopt similar standards for the use of biodiesel as a motor fuel. Those standards have been periodically revised and updated. In 2008, the current version of EN 14214 and ASTM D6751 were published respectively, and superseded previous standards [17]. Now, biodiesel blend fuel is available at many normal service stations across Europe and US. With the quick development of biodiesel industry, biodiesel is playing a more and more important role in globe primary energy. 2.2. Feedstocks of biodiesel A variety of biolipids can be used to produce biodiesel. As shown in Fig. 3, the feedstock of biodiesel depends greatly on climate, local soil conditions and availability; consequently different regions are focusing their efforts on different types of oil. Typical raw materials of biodiesel are rapeseed oil, canola oil, soybean oil, sunower oil and palm oil. Beef and sheep tallow and poultry oil from animal sources and waste cooking oil are also sources of raw materials. There are various other biodiesel sources: jatropha, almond, barley, camelina (Camelina sativa), coconut, copra, sh oil, groundnut, karanja (Pongamia glabra), laurel, oat, poppy seed, okra seed, rice bran, sesame, sorghum and wheat [1821]. The common fatty acids, which exist in biolipid, are shown in Tables 2 and 3. The physical and chemical fuel properties of biodiesel basically depend on the fatty acids distribution of the triglyceride used in the production. The fatty acid distributions of some feedstocks commonly used in biodiesel production are shown in Table 2. In Table 4, some critical fuel properties of biodiesel (methyl ester, ME) fuels produced from different feedstocks are shown,

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Fig. 3. FAME around the world.

Table 2 The chemical structures of common fatty acids. Fatty acid Lauric (12:0) Myristic (14:0) Palmitic (16:0) Stearic (18:0) Oleic (18:1) Linoleic (18:2) Linolenic (18:3) Arachidic (20:0) Behenic (22:0) Erucic (22:1) Chemical structure CH3(CH2)10COOH CH3(CH2)12COOH CH3(CH2)14COOH CH3(CH2)16COOH CH3(CH2)7CH@CH(CH2)7COOH CH3(CH2)4CH@CHCH2CH@CH(CH2)7COOH CH3CH2CH@CHCH2CH@CHCH2CH@CH(CH2)7COOH CH3(CH2)18COOH CH3(CH2)20COOH CH3(CH2)7CH@CH(CH2)11COOH

respectively. In this section, the fuel properties of diesel and fatty acid alkyl mono-esters are compared to each other. It is easy to nd that biodiesel has better fuel properties than diesel, such as higher cetane number, higher ash point, and better lubrication. However, rst generation biodiesel is mainly produced from food-grade oils. According to some researches, feedstock acquisition currently accounts for over 75% of biodiesel production expenses, which is a serious threat to the economic viability of the

biodiesel industry as depicted in Fig. 4 [36]. Accordingly, the end cost of the biodiesel mainly depends on the price of feedstock. The international market prices of main oil crops were shown in Table 5. With vegetable oil price soaring high in recent years, the cost of producing biodiesel will keep raising. Biodiesel will lose its competitive advantage due to high price. Furthermore, problems associated with the impacts on food security and land change have also arisen. Base on the above, scientists are developing a new generation of biodiesel to help avoid such problems. One potential solution to this problem is employment of alternative feedstocks of varying type, quality, and cost. These feedstocks may include soapstocks, acid oils, tall oils, used cooking oils, and waste restaurant greases, various animal fats, non-food vegetable oils, and oils obtained from trees and microorganisms such as algae. Additionally, genetic modication is also being used to introduce favorable traits into biodiesel crops, such as higher yields or the ability to grow on non-arable land [3845]. In all new generation feedstocks of biodiesel, microalgae are the most promising one. Like plants, microalgae use sunlight, carbon dioxide and water to produce oils but they do so more efciently than crop plants. The process of making biodiesel fuel

Table 3 The fatty acid distributions of some biodiesel feedstocks. Feedstock Fatty acids (% w/w) 12:0 Sunower Rapeseed Soybean Palm Peanut Coconut Soybean soapstock Used frying oil Tallow Lard 46.5 14:0 1 0.3 19.2 36 12 16:0 6.08 3.49 10.58 42.8 12.3 9.8 17.2 12 2432 2830 18:0 3.26 0.85 4.76 4.5 4.6 3 4.4 2025 1218 18:1 16.93 64.40 22.52 40.5 53.6 6.9 15.7 53 3743 450 18:2 73.73 22.30 52.34 10.1 29 2.2 55.6 33 23 713 18:3 8.23 8.19 0.2 0.1 7.1 1 [22] [22] [23] [24] [24] [24] [25] [26] [27,28] [27,28] References

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Table 4 Some properties of diesel and biodiesel produced from different feedstocks. Fuel Diesel Soybean ME Rapeseed ME Palm ME Sunower ME Jatropha ME Tallow ME Soapstock ME Kin. viscosity (mm2/s, at 40 C) 2.04.5 4.08 4.83 4.71 4.60 4.4 5.00 4.30 Density (g/cm3, at 21 C) 0.8200.860 0.884 0.882 0.864 0.880 0.875 0.877 0.885 Cetane number 51.0 50.9 52.9 57.3 49.0 57.1 58.8 51.3 Flash point (C) 55 131 155 135 183 163 150 169 Cloud point (C) 18 0.5 4 16 1 4 12 6 Pour point (C) 25 4 10.8 12 7 9 References [29] [30,25] [30,31] [32,33] [30,34] [33] [30,34,35] [25]

Fig. 4. General cost breakdown for production of biodiesel [36].

Table 5 Price of main oil crops (US$/tonne) [37]. Date 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Soybean 483 356 336 412 534 633 545 573 771 1327 826 919 Sunower 560 413 428 587 592 663 703 635 846 1639 837 937 Groundnut 801 744 685 659 1139 1178 1102 931 1219 2018 1339 1255 Palm 486 309 235 329 421 481 392 416 655 1058 633 749 Rapeseed 482 359 372 451 588 670 660 770 852 1410 868 912 Coconut 748 539 323 388 449 630 636 583 812 1306 735 784

Table 6 The oil productivity of different crops (from Ref. [48]). Oil crops Corn Soybeans Safower Sunower Rapeseed Oil palm Microalgae Productivity (gallons per acre per year) 18 48 83 102 127 635 500015,000

Fig. 5. Simplied systems block diagram of the algae to biodiesel process (from Ref. [46]).

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1025

from microalgae involves several steps. Fig. 5 is a simplied block diagram of the entire system operation, which includes growth, harvest, extraction and conversion four major steps. Different algae species produce different amounts of oil. Some species of algae are ideally suited to biodiesel production due to their high oil content in some species, topping out near 50%. As Table 6 shows, oil productivity of many microalgae greatly exceeds the oil productivity of the best producing oil crops [4750]. Meanwhile, microalgae are the fastest-growing photosynthesizing organisms. They can complete an entire growing cycle every few days. Approximately 46 tons of oil/hectare/year can be produced from diatom algae. The production of algae to harvest oil for biodiesel has not been undertaken on a commercial scale, but working feasibility studies have been conducted to arrive at the above number. Specially bred mustard varieties can produce reasonably high oil yields and have the added benet that the meal left over after the oil has been pressed out can act as an effective and biodegradable pesticide [51]. Furthermore, algae can be grown almost anywhere, even on sewage or salt water, and does not require fertile land or food crops, and processing requires less energy than the algae provides [52]. 2.3. Biodiesel conversion technologies As mentioned above, diesel engine is not suitable for high viscosity, low volatility and polyunsaturated character vegetable oils to be applied directly [53]. Renement has to be made in order to turn those vegetable oils into quality fuel. Conventional methods of the application of vegetable oil in diesel engines are direct mixing and micro-emulsion. These two physical methods do not require any chemical process and can lower the viscosity of vegetable oil, but they cannot solve the problem of carbon deposits and lube pollution, and the high temperature pyrolysis cracking is hard to be controlled by its reactant at high temperature. The most relevant process parameters in these kinds of operation are reaction temperature, ratio of alcohol to vegetable oil, amount of catalyst, mixing intensity (RPM), catalyst, and the raw oils used [5457].

Table 7 Comparison of main preparation technologies. Technologies Dilution or microemulsion [58 61] Advantage Simple process Disadvantage 1. High viscosity

2. Bad volatility 3. Bad stability Pyrolysis [62,63] 1. Simple process 2. No-polluting 1. Fuel properties is closer to diesel 2. High conversion efciency 3. Low cost 4. It is suitable for industrialized production Supercritical methanol [66,67] 1. No catalyst 1. High temperature is required 2. Equipment is expensive 3. Low purity 1. Low free fatty acid and water content are required (for base catalyst) 2. Pollutants will be produced because products must be neutralized and washed 3. Accompanied by side reactions 4. Difcult reaction products seperation 1. High temperature and pressure are required 2. Equipment cost is high 3. High energy consumption

Aimed at problems in dilution and micro-emulsion methods, some new techniques were applied to solve the problems encountered with the high fuel viscosity. These methods include pyrolysis, transesterication and supercritical methanol. The comparison of main biodiesel preparation technologies was shown in Table 7. Amongst the four techniques, transesterication is the most promising solution to the high viscosity problem. Now, transesterication is widely available technique for industrialized biodiesel production due to its high conversion efciency and low cost. In transesterication, the triglyceride can be transformed into monoester. Due to the transesterication in the ester exchange process, the viscosity of vegetable oil is reduced and heat values maintained. The cetane number increases because the molecular chain is cut into 1/3. Transesterication is the chemical reaction between triglycerides and short-chain alcohol in the presence of a catalyst to produce mono-esters. The long- and branched-chain triglyceride molecules are transformed to mono-esters and glycerin [42]. Commonly-used short-chain alcohols are methanol, ethanol, propanol and butanol. Methanol is used commercially because of its low price [40]. Because this process is a reversible reaction, the output of biodiesel will be directly inuenced by the proportion of reactants, the type and the dosage of the catalyst, and the reaction conditions. From the principle of reversible reaction, it follows that a higher usage of methanol leads to a higher output of biodiesel. However, the higher density of methanol can cause a polycondensation reaction; as a result, it will reduce the effective concentration of methanol, and cause difculties for the separation of biodiesel. Furthermore, more methanols are associated with higher costs. In the process of batch reaction or continuous reaction activated by an alkalescence catalyst, a 6:1 mol ratio has been used widely [6871]. There are three common kinds of catalysts in the ester reaction: lipase catalysts, acid catalysts, and alkali catalysts. Each catalyst has its own advantages and disadvantages in the whole reaction process. The transesterication is typically catalyzed by lipases such as Candida antartica, Candida rugasa, Pseudomonas cepacia, immobilized lipase (Lipozyme RMIM), Pseudomonas spp. or Rhizomucar miehei. The yield of biodiesel from this process can vary depending on the type of enzyme used [72]. As the catalyst, enzyme is restricted to rigorous reaction condition and activity lose of lipase, etc., it cannot be used on the large commercial production until now. In catalytic transesterication using homogeneous acid catalyst, the reaction is catalyzed by sulphuric [73,74], hydrochloric [74] or sulphonic acids [75]. Homogeneous acid catalysts are less sensitive

Transesterication [64,65]

Table 8 Comparison of homogeneously and heterogeneously catalyzed transesterication (from Ref. [72]). Factors Reaction rate Post-treatment Homogeneous catalysis Fast and high conversion Catalyst cannot be recovered, must be neutralized leading to waste chemical production Limited used of Heterogeneous catalysis Moderate conversion Catalyst can be recovered Continuous x bed continuous methodology operation possible Not sensitive

Processing methodology Presence of water/free fatty acids Catalyst reuse Cost

2. Short reaction time 3. High conversion 4. Good adaptability

Sensitive

Not possible Comparatively costly

Possible Potentially cheaper

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to FFAs and can simultaneously conduct esterication and transesterication. However, acid-catalyzed transesterication has been largely ignored mainly because they are slower and necessitate higher reaction temperatures. Most of the commercial biodiesel is produced from plant oils using very effective homogeneous alkali catalysts such as sodium or potassium hydroxides, carbonates or alkoxides [72,75,76]. The speed of the alkali catalyzing process is higher than that in the acid activating process. This, together with the good corrosion resistance properties, promoted the alkali catalysts to be widely used in industry. However, the alkali catalyzing process is very sensitive to the presence of water and free fatty acids and needs lots of methanol. When the raw feedstocks have a high percentage of free fatty acids or water, the alkali catalyst will react with the free fatty acids to form soaps. The water can hydrolyze the triglycerides into diglycerides and form more free fatty acids. Both of the above reactions are undesirable and reduce the yield of the biodiesel product. Moreover, since the alkali catalysts must be neutralized, giving rise to wastewater that cannot be reutilized, and glycerol is obtained as an aqueous solution of relatively low purity [7779]. These problems can be alleviated by using heterogeneous transesterication catalysts. A comparison between homogeneous and heterogeneous catalysis is summarized in Table 8. The advantage of heterogeneous catalyst usage is its fast and easy separation from the reaction mixture without requiring the use of neutralization agent. Furthermore such type of catalyst could be regenerated and reused, and it has a less corrosive character, leading to safer, cheaper and more environment-friendly operation [80]. Therefore, there is an increasing interest in the possibility of replacing the homogeneous alkaline hydroxides, carbonates or metal alkoxides by heterogeneous solid catalysts insoluble in methanol [8185]. Many different types of solid catalysts were applied in transesterication of vegetable oils to produce biodiesel, such as alkali earth metal oxides and transition metal oxides [8692]. Despite the solid phase catalytic methods are intensively studied, the industrial applications are limited. The advantages of solid catalysts are easy separation and simple post treatments. Nevertheless, heterogeneous catalytic methods are usually mass transfer resistant, time consuming and inefcient [93]. One of the ways to minimize the mass transfer limitation for heterogeneous catalysts in liquid phase reactions is using catalyst supports. Effective factors on catalytic activity of solid catalysts are specic surface area, pore size, pore volume and active site concentration on the surface of catalyst. Supports can provide higher surface area through the existence of pores where metal particles can be anchored [94]. The use of catalyst supports, such as alumina [95,96], zinc oxide [97], silica [98] and zirconium oxide [99], could improve the mass transfer limitation of the three phase reaction. Furthermore, by anchoring metal oxides inside pores, catalyst supports could prevent active phases from sintering in the reaction medium [91]. In recent years, with the development of nano technology, nano technology is applied more and more in catalytic eld. Because nanocatalysts have high specic surface and high catalysis activities, they may provide a possible way to solve the above problems. Therefore, they have become the focus of recent research [100,101]. Most earlier studies have focused on the use of nanoparticlebased catalysts for the transesterication of the triglycerides into biodiesel. The very high activity and surface reactivity of nano catalysts were considered to be related to the high surface/volume ratio of nano-sized catalyst particles [102105]. Some researchers also tried to add magnetic substance in nano catalyst, in order to enhance separation efciency. This nano catalyst achieved favorable effects due to assembly of magnet and catalytic activity [106].

Recently, the CNTs (carbon nanotubes) showed various new performances in catalysis and nd more and more application as new kinds of high performance catalyst due to its high specic surface area and pore structure [107,108]. Sulfonated-multiwalled carbon nanotubes (s-MWCNTs) were used in the synthesis of biodiesel from methanol and oleic acid. The result showed that the solid acid catalyst, s-MWCNTs, has a high catalytic activity for biodiesel production from cheap raw feedstocks with high concentrations of FFAs [109]. Besides catalysts, studies on biodiesel synthesis have focused on development of process intensication technologies, for example ultrasonic and micro wave technology. Because oils and methanol are not completely miscible, the mixing efciency was stated as one of the most important factors affecting the yield of the transesterication [110]. Low frequency ultrasonic irradiation is widely used in industry for emulsication of immiscible liquids. Previously, productions of biodiesel from vegetable oils with shortchain alcohols (ethanol, propanol, and butanol) under ultrasonic irradiation were investigated. The results shown that low frequency ultrasound is an efcient, time saving and economically functional, offering a lot of advantages over the classical procedure. Ultrasounds can be a valuable tool for the transesterication, aiming to prepare the biodiesel fuel at industrial scale [111114]. The same to ultrasonic technology, microwave technology has also been developed for biodiesel synthesis. Because the mixture of vegetable oil, methanol, and alcohol contains both polar and ionic components, microwave irradiation can play an active role in heating reactants to the required temperature quickly and efciently. Breccia et al. [115] studied the transesterication of commercial seed oils with methanol under microwave irradiation. In the presence of a variety of catalysts, yields greater than 97% were achieved with reaction times of less than 2 min. Other studied shown that the preparation of biodiesel using microwave heating proved to be more energy efcient than the conventional synthesis as well [116118]. Apart from the aforementioned technologies, some other process intensication technologies have also been applied in transesterication, including static mixers [119], micro-channel [120,121], oscillatory ow [122] and cavitational [123]. These technologies can enhance reaction rate, reduce molar ratio of alcohol to oil and energy input by intensication of mass transfer and heat transfer, thus achieve continuous product in the reactor. Some of these technologies have already been commercialized successfully [124]. 3. Key drivers and challenges of biodiesel industry development 3.1. Security of energy supply Security of energy supply means that energy can be adequately, affordably and reliably supplied. For most countries, the primary reason for joining the biodiesel bandwagon is energy security [125]. In other words, one of the driving forces behind the development of biodiesel is to hope for a reduction in dependence on fossil-based oil. For the foreseeable future, fossil-based oil will continue to dominate world energy supply, but its production costs are rising, and supply is dominated by a few major producers, many of them in the volatile Middle East. Although fossil-based oil prices are currently relatively low, they are likely to be volatile in the short-term and to rise in the longer term [126128]. Dependence on imported fossil-based oil will pose serious threat to national security of energy supply. Hence, a number of national governments have used targeted policies to increase the production and use of a broadening range of biological resources for fuel. The US National Renewable Energy Laboratory (NREL) states that energy security is the number one driving force behind the US biofuels program and a White House Energy Security for the

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21st Century paper makes it clear that energy security is a major reason for promoting biodiesel. The EU commission president, Jose Manuel Barroso, speaking at a recent EU biofuels conference, stressed that properly managed biofuels have the potential to reinforce the EUs security of supply through diversication of energy sources [129]. Coupled with increased demand and strong growth in India and China, Asia will emerge as the epicenter for the global energy landscape. The International Energy Agencys (IEA) report projects that Asias energy demand will expand by 76% between 2007 and 2030 [130]. As home to 60% of the global population, Asias future energy needs are predicted to escalate in response primarily to increase in demand from the transport sector. At the same time, Asias energy security is considered one of the most fragile in the world because the region is heavily dependent upon imported oil to satisfy the demand of its transport sector. Therefore, the development of renewable energy technologies and policy, particularly those that promote the expansion of biofuels production, is believed to be one of the paths to achieving energy security. However, energy security improvements through biodiesel development must be based on differences in feedstock resources and energy consumption mix in different countries. Hence, it is important for the governments of different countries to implement policies aimed at incorporating biodiesel into their respective national energy mix. 3.2. Environmental effects The surge of interest in biodiesels has highlighted a number of environmental effects associated with its use. Biodiesel proponents argue that unlike fossil fuels which release carbon dioxide that has been stored for millions of years beneath the earths surface, biodiesel produced from biomass have the potential to be carbon neutral over their life cycles as their combustion only returns to the atmosphere the carbon dioxide absorbed from the air by feedstock crops through photosynthesis. It thus has the potential to replace fossil-based fuels and contribute to the mitigation of GHG emissions [131,132]. According to the EPAs Renewable Fuel Standards Program Regulatory Impact Analysis, released in February 2010, biodiesel from soy oil results, on average, in a 57% reduction in greenhouse gases compared to fossil diesel, and biodiesel produced from waste grease results in an 86% reduction [133]. Ensuring that biodiesel is a credible source of low-carbon energy that deliver greenhouse gas savings compared with fossil fuels is a key component of many countries efforts to set standards worldwide for lowering emissions in the future. Europes aim to cut GHG emission by one-fth by 2020, partly through demanding that one in 10 vehicles are fueled by biofuels, will spark a surge in demand for biodiesel. The president of USA, Barack Obama, announced that the Federal Government will reduce its GHG pollution by 28% by 2020. Meanwhile, the Chinese government announced the action to control greenhouse gas emissions targets, the decision by 2020 carbon dioxide emissions per unit of GDP than in 2005 dropped 4045%, and decided to help Africa countries to develop their clean energy projects. The Japanese government has a GHG emission reduction target of 6080% by 2050 from its current level [134]. India, Brazil, South Africa and other countries have also set their GHG reduction target and development program of substitute energy in the future. All of these provide biodiesel industry many unprecedented opportunities of development. However, the impact of biodiesel on environment widely varies, i.e., it may not necessarily be positive, or as positive as is often initially assumed. In other words, biodiesel is not always offering emissions reductions compared to fossil fuels. Consequently, we have to nd a way to address the GHG balance of using biodiesel for fuel. A useful tool for addressing GHG balance is the Life Cycle

Assessment (LCA), which has been applied to different biofuels, with varying results. LCA of GHG balance is complex, planting and harvesting of crops (including fertilizer and pesticide use, irrigation technology, and soil treatment); processing the feedstock into biodiesel; transporting the feedstock and nal fuel; storing, distributing, and retailing biodiesel can all have a considerable inuence on results [135137]. Apart from the aforementioned problems, the development of biodiesel industry may directly or indirectly cause other negative effects on environment. In order to grow the oil crops necessary to produce biodiesel, additional land must be brought into production. This has led to pristine rainforests being cleared for the sake of monoculture plantations. Rainforests are one of the worlds largest carbon sinks. The clearing of rainforest and peatland for oil crops results in a sudden release of large amounts of carbon dioxide. In addition, loss of biodiversity is also another issue that arises when rainforests are being cleared [138]. Moreover, the clearing of rainforest even cause climate change in some regions. For example, in recent months, Southeast Asia is suffering from drought. One possible cause is that many forests have been cleared and substituted for the energy crops in many Southeast Asia countries. Because forests can hold some of that excess water in rainy season and release it in the dry season. Right now, due to large-scale deforestation, the water storage and conservation capability of soil has been very much weakened. Meantime, we also should pay close attention to haze caused by the forest res in some developing countries, where farmers use re to clear land for agriculture uses. 3.3. Food security, land use changes and water source As populations grow over the next four decades, demand for food, and thus water, will continue to rise across the world. However, food prices have risen dramatically around the world, even triggering riots in West Africa. In the past there was no signicant correlation between biodiesel and food prices, but since 2002 the correlation has strengthened. Increases in producing biodiesel source material (such as soybean and rapeseed) costs by at least 50% over the past few years have harmed the comparative advantage and competitiveness of individual countries. While growth within the biodiesel sector can contribute to increases in the price of soybean oil and other biodiesel source material, the competitiveness of the sector can be adversely affected by these very same prices changes, as well as other economic factors. These emerging trends suggest that food and energy markets are likely to be more strongly linked in future such that spikes and uctuations in the prices of energy lead to corresponding changes in food prices. As a result, much of the literature on crop-based biodiesel production focuses on the potential impacts on food security as well as land use changes and water source. On the plus side, biodiesel production has helped some farmers and workers boost their incomes and increase employment in the agricultural sector, especially for developing countries. But, as with many other types of agriculture, other workers and farmers have experienced inadequate working conditions. In some countries, local communities have reportedly lost control ofor even been evicted fromtheir land to make way for biodiesel production. Farmers may switch from producing food crops to producing biodiesel crops to make more money, even if the new crops are not edible. The law of supply and demand predicts that if fewer farmers are producing food the price of food will rise. Such practices can reduce food availability and may consign food and feed production to less productive land, thus reducing yields and food security, and raising food prices. Meantime, higher commodity prices will have negative consequences for net food-importers. And for low income food decit countries, food

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import bills will rise, precipitously in some cases. In 2008, a FAO analysis found global expenditures on imported foodstuffs in 2007 rose by about 29% above the record of the previous year. The bulk of the increase was accounted for by rising prices of imported vegetable oils commodity groups that feature heavily in biodiesel production. Furthermore, boosting biodiesel production by growing more oil crops without considering the quality and availability of water by region could put a signicant strain on water resources in some parts of the world, especially in developing countries [139]. There is very high demand for access to water for irrigation, cooking, and drinking. Because the production of biodiesel is very water intensive, agricultural shifts to growing biodiesel crops could change the availability of clean water and greatly increase pressure on water resources in those areas. As a result, those areas will face serious challenges to meet the predicted increase in demand for food produce, let alone sustain any further growth prompted by expanding biodiesel production [140,141]. 4. Policy and government incentives In general, the energy policy may include international treaties, legislation on commercial energy activities (trading, transport, storage, etc.), incentives for investment, guidelines for energy production, conversion, and use (efciency and emission standards), taxation and other public techniques, energy-related research and development, energy economy, general international trade agreements and marketing energy diversity [142]. Current energy policies also address environmental issues including environmental friendly technologies to increase energy supplies and encourage cleaner, more efcient energy use, air pollution, greenhouse effect (mainly reducing carbon dioxide emissions), global warming and climate change [143146]. The energy policy will directly inuence the development of biodiesel industry. As a policymaker, government play an essential role in determining the course, and crucially, the scale, of biodiesel development, in particular by means of the proper incentives such as tax exemptions, price controls, targets and direct subsidies. A key question is the long-term economic, social and environmental sustainability of bio-energy policies. Therefore, comprehensive assessments will be required to improve their ability to identify the proper energy policies which are likely to avoid potential conicts with food production, land change, and provide most benets [18,147,148]. Now, there are many incentives that can be offered by a government to spur the development of biodiesel industry and maintain its sustainability, such as crop plantation in abandoned and fallowed agricultural lands, implementation of carbon tax, subsidizing the cultivation of non-food crops, and exemption from the oil tax [149,150]. Furthermore, some governments have mandated the use of biodiesel in recent years. For instance, the establishment of the directive on the promotion of the use of biofuels for transport in EU (Directive 2003/30/EC) mandates an increasing share of biofuels from 2% of total fuel supply in 2005 to 5.75% of total supply in 2010 (based on energy content). In other large countries, like USA and Canada, governments have also implemented similar directives, which triggered a huge demand for biodiesel [151,152]. Additionally, as of right now, general public awareness in biodiesel industry still remains low. Majority of the public is either ignorant or has limited knowledge on the biodiesel issues. Therefore, governments should enhance the promotion of biodiesel industry and increase public awareness on the biodiesel industry, which will help the governments biodiesel policies to garner sufcient public support [7].

Finally, while governments are focusing on the ways to improve biodiesel production and consumption, they have to give enough attention to unresolved issues like rainforest depletion, food prices increase. Worldwide, deforestation accounts for an estimated 20% of greenhouse gas emissions. And much of the forest now being cleared for palm oil is peatland, with marshy soils that are crucial holders of methane, a greenhouse gas even more potent than carbon dioxide. Without taking into account this, their policies might have detrimental effects on climate change. In this situation, governments should advocate biofule companies to use feedstocks from crops grown on degraded lands, waste products, plantations certied as sustainable, and clarify limits on fuels from sensitive areas like forests and partly drained peatlands. Meanwhile, agricultural subsidies should be paid to domestic farmers by their governments that guarantee them a xed income on traditional food crop. Furthermore, developed countries should pay poor ones to save forests. Through these ways, plantation can keep balance with forest. 5. Conclusions Biodiesel will form a small but very important part of global energy supply in the coming decades. Under the appropriate conditions, increasing biodiesels share of the energy mix can contribute to meet important global needs such as reducing GHG emissions, enhancing energy security and, particularly in developing countries, promoting sustainable rural development [5]. However, for biodiesel to establish and continue to mature in the market, various aspects must be examined and overcome. Even biodiesel industry itself faces strong competition from non-ester renewable diesel fuels and second generation bioethanol. Therefore, some of the key issues such as improving efciency of the production process, using low cost feedstock, developing cost effective catalyst, and managing agricultural land, have to be reviewed. As with any new technology or products, biodiesel will require continuous improvement especially in producing cleaner emissions and having less impact on the environment. Further development on the use of the by-product will enhance the economic viability of the overall biodiesel production process. Meanwhile, the incentives posed by the government resulting in promotion of the biodiesel production and usage will assist in establishing the biodiesel as a sustainable fuel. Finally, international society should establish a mechanism to encourage wider participation of the global community, such exible GHGs emissions reduction target, to cultivate a ground which will further promote the use of renewable fuels. Acknowledgements The nancial support from National Natural Science Foundation of China (30940058), National Science Foundation for Post-doctoral Scientists ofChina (20100471383), Jiangsu Planned Projects for Postdoctoral Research Funds (1001035B), Natural science foundation for colleges and universities in Jiangsu Province (09KJD4800001), Jiangsu key lab of mechanical clean energy and application foundation (QK09006), Jiangsu University research foundation for young Scholars (08JDG039) and Yancheng agricultural science and technology development program (YK2009081) are gratefully acknowledged. References
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