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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Upstream and downstream strategies to economize biodiesel production

Meisam Hasheminejad a, Meisam Tabatabaei a,, Yaghoub Mansourpanah b, Mahdi Khatami far c, Azita Javani d
a Biodiesel Research Team (BRT), Microbial Biotechnology and Biosafety Department, Agricultural Biotechnology Research Institute of Iran (ABRII), Seed and Plant Improvement Institutes Campus, 31535-1897, Mahdasht Road, Karaj, Iran b Department of Chemistry, Faculty of Science, Lorestan University, Khorramabad, Iran c Iran Renewable Energy Organization (SUNA), 146861-1387, Tehran, Iran d Department of Applied Chemistry, Faculty of Chemistry, Islamic Azad University, North Tehran Branch, 191367-4711, Tehran, Iran

a r t i c l e

i n f o

a b s t r a c t
In recent years biodiesel has drawn considerable amount of attention as a clean and renewable fuel. Biodiesel is produced from renewable sources such as vegetable oils and animal fat mainly through catalytic or non-catalytic transesterication method as well as supercritical method. However, as a consequence of disadvantages of these methods, the production cost increases dramatically. This article summarizes different biodiesel production methods with a focus on their advantages and disadvantages. The downstream and upstream strategies such as using waste cooking oils, application of non-edible plant oils, plant genetic engineering, using membrane separation technology for biodiesel production, separation and purication, application of crude glycerin as an energy supplement for ruminants, glycerin ultrapurication and their consequent roles in economizing the production process are fully discussed in this article. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 15 May 2010 Received in revised form 3 September 2010 Accepted 3 September 2010 Available online 1 October 2010 Keywords: Biodiesel production Upstream Downstream Strategies Economize

1. Introduction Energy supply and its security issues have been the topic of interest lately. With growing environmental awareness about the negative implications brought by excessive usage of fossil fuels, the race for nding alternative energy as their substitutions is getting heated up (Lim and Teong, 2010). Recently, biodiesel has been receiving increasing attention not only as an alternative but also as a sustainable fuel (Rajendra et al., 2009). It is used for diesel engines (Haas, 2005) and is becoming well-known as an environmentally friendly fuel due to its non-toxic and biodegradable characteristics (Ellis et al., 2008). The many advantages of biodiesel include high cetane number (in the US at P47 while for diesel at P40), dissolved oxygen content (1012% by weight), sulphur-free, better combustion process and improved emission prole of exhaust gas (Lapuerta et al., 2009). The biodiesel production is increasing every year and in 2002, Wilson predicted that in the US alone, production will reach 1.3 billion liters annually by 2011 (Wilson, 2002), however this amount in the US and EU were about 1.5 and 5.7 million tonnes in 2007, respectively (Smith et al., 2010), which shows the rate of biodiesel production is far higher than predicted. In 2008, the production of biodiesel was increased by 180% compared to the year 2007 in the EU (Lozada et al., 2010).
Corresponding author. Tel.: +98 2612703536; fax: +98 2612704539.
E-mail address: meisam_tab@yahoo.com (M. Tabatabaei). 0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2010.09.094

Any types of feedstock which contains free fatty acids and/or triglycerides such as vegetable oils, waste cooking oil, animal fats, and waste greases can be converted into biodiesel (Janaun and Ellis, 2010). The most common way to produce biodiesel is by transesterication (Wang et al., 2009) which takes place between a vegetable oil and an alcohol (methanol or ethanol) in the presence a catalyst (homogeneous or heterogeneous) or without the application of catalysts as in supercritical uid method (SCM). Homogeneous catalysts i.e. basic (sodium hydroxide, potassium hydroxide and sodium methylate), and acidic catalysts (sulphuric acid) are necessary to boost the rate of the transesterication reaction. The type of homogenous used depends on the free fatty acids (FFA) content of the raw oil (Sharma et al., 2008). Heterogeneous catalysts such as metal oxides or carbonates, sulphonated amorphous carbon, heteropolyacid solid and biocatalysts (specically lipases) are commonly used as well. Various biodiesel production methods have disadvantages such as limitation for using unrened oils as in homogeneous catalyzed process, low rate reaction as in heterogeneous catalyzed process and high pressure and temperature required in SCM method. As a consequence of these disadvantages the production cost increases dramatically. Biocatalysts are also classied as a kind of heterogeneous catalyst used for biodiesel production through enzymatic transesterication, but the enzymes are expensive and unable to provide the degree of reaction completion required to meet the ASTM fuel specication (Gerpen, 2005). In addition, glycerin as a

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co-product has a serious negative effect on the enzyme (Soldi et al., 2009). The main drawback of using biodiesel is the high production cost relative to petroleum-derived fuels that is mainly driven by the cost of raw materials (vegetable oils, catalysts and alcohol) (Haas et al., 2006). So far, different upstream strategies such as recycled cooking oils and wastes from animal or vegetable oil (Phan and Phan, 2008), using biotechnological tools in the genetic improvement of non-edible potential sources of vegetable oil such as microalgae (Deng et al., 2009) and jatropha (Basha et al., 2009) have been taken into consideration in order to overcome the costly production controversy. The aim of this review is to highlight the different downstream and upstream strategies to economize the whole production process and the promotion of biodiesel worldwide. 2. Biodiesel production processes; catalytic and non-catalytic The catalysts used for transesterication are categorized into homogeneous and heterogeneous catalysts which the suitable selection of the catalyst is an important parameter to lower the biodiesel production cost (Sharma et al., 2008). Beside catalytic methods, SCM is a non-catalytic method for biodiesel production in which instead of using catalysts high pressure and temperature are used to carry out the transesterication reaction. 2.1. Catalytic biodiesel production 2.1.1. Homogeneous catalyzed biodiesel production Homogeneous catalysts are of two types; basic and acidic catalysts. The main disadvantage of the homogeneous acidic catalysts in comparison with the basic ones is their lower catalyzing speed in the transesterication reaction. In addition, acidic catalysts are corrosive and cause damages to the reactors. Acid-catalyzed transesterication also requires more extreme temperatures and pressure conditions (Freedman et al., 1984). Although using Lewis acids such as carboxylic salts (Peng et al., 1999) can help to shorten the long reaction time, but the reaction temperature should be too high and the conversion ratio would be relatively low (Wang et al., 2006). Therefore, the higher rate of the basic catalysts have made them more commercially acceptable relative to acidic catalysts. Sodium hydroxide and potassium hydroxide are usually used as basic homogeneous catalysts due to their low cost (Leung et al., 2010). Apart from the above-mentioned advantages for basic homogeneous catalysts, they have an illustrious advantage relative to the other methods which is the high conversion yield of more than 98% (Canakci and Sanli, 2008). In spite of all these attractive advantages, the main drawback of this method is the limitation to using the various oil sources. In fact, when an oil source with an amount of FFA over 0.10.5% is used, this method is not suitable due to the conversion of metals to metal soaps which introduces more difculties to the isolation and purication of the nal biodiesel. This also decreases the productivity of the reaction (Marchetti and Errazu, 2008). It is however, needless to stress that all these catalysts either basic or acidic have to be removed from the nal products (biodiesel and glycerin) after the methanolysis step (Bournay et al., 2005). Basic catalysts can be removed more difcultly, and two to three rounds of washing with hot distilled water are required (Sharma et al., 2008; Janaun and Ellis, 2010) which increases the production cost of biodiesel. The metal soaps are miscible in the glycerin and have to be removed. The conversion of metals to metal soaps takes place through the neutralization step which is carried out with a strong concentrated inorganic acids (i.e. sulphuric, hydrochloric and phosphoric) or an organic acid (i.e. acetic acid). Depending on the biodiesel production process, biodiesel has various qualities and

the purity of the glycerin produced could range between 55% and 90% as well (Gomes, 2010). Figs. 1a and 2 show the conventional industrial biodiesel processes using a homogeneous catalyst system (Bournay et al., 2005) and the glycerin upgrading from 5060% purity towards 7585% purity by means of glycerin splitting, respectively. 2.1.2. Heterogeneous catalyzed biodiesel production Although the production of biodiesel by homogeneous basic catalysts leads to an easy conversion at moderate temperatures (4065 C) (Marchetti and Errazu, 2008) but as mentioned earlier the FFA content of the oil source is a serious hinder. The cost of rened oils relative to waste oil is noticeably higher and pulls the biodiesel production process into the uneconomical zone. Hence, heterogeneous catalysts are known as good alternatives for using raw materials with high FFA content (>0.10.5%) (Leung et al., 2010). Similar to homogenous catalysts, heterogeneous catalysts are of two types too: basic and acidic catalysts. These include: zinc hydroxide nitrate, porous zirconia, titania and alumina micro-particulate, ion-exchange resin, strong acid zeolites. Recently, heterogeneous catalysts were examined for FFA conversion by Park et al. (2010). They used WO3/ZrO2 for FFA conversion to biodiesel and the yield of conversion was approximately 93%. Also Feng et al. (2010) investigated NKC-9, 001 7 and D61 resins and reported the yield of conversion of approximately 90% by NKC-9. Heterogeneous catalysts can also be reused for a new reaction cycle (Macario et al., 2010). Yan et al. (2009) used a series of heterogeneous zinc and lanthanum mixed oxides for biodiesel production of unrened or waste oils. In their study, the high yield of fatty acid methyl esters (FAME) was 96%. For biodiesel production from soybean oil, Xie and Li (2006) used Alumina-supported potassium iodide and the yield of conversion of 96% at 773 K in air was achieved. Moreover heterogeneous catalyzed biodiesel production does not face the obstacle of soap formation and consequent more complicated purication step as it is observed in homogenous catalyzed biodiesel production. Therefore, the purication of biodiesel and glycerin is easier and as a result the whole process is more economical comparatively (Nakagaki et al., 2008). A ow sheet of the new heterogeneous process namely Esterf-H is presented in Fig. 2b. (Bournay et al., 2005). These catalysts are not corrosive and are environmental friendly as well. In spite of the advantages mentioned for the heterogeneous catalysts, the yield of conversion is relatively lower and higher reaction temperature and pressure are required when compared to homogenous catalysts. However, the overall biodiesel production cost is more economical than that of the homogeneous catalyzed processes. This could be ascribed to much better selling price of the glycerol produced due to its purity and lowest capital investment cost due to the less amount of equipment involved in the process (Marchetti and Errazu, 2008). Table 1 compares the equipment costs of homogeneous and heterogeneous catalyzed biodiesel production processes (Marchetti and Errazu, 2008). 2.2. Non-catalytic biodiesel production; supercritical method Supercritical method (SCM) like heterogeneous catalysts can also be used for biodiesel production from vegetable oils containing high amount FFA. However, there is simply no catalyst involved. SCMs are of two types: one-step and two step processes (Kusdiana and Saka, 2004). Tan et al. (2009) managed to produce palm oil biodiesel through the one-step SCM. In their study, the optimal conditions for biodiesel production with a 70% yield were: temperature (239 C), pressure (8.1 MPa) and time reaction (20 min). Ilham and Saka (2010) studied biodiesel production from Jatropha curcas oil and dimethyl carbonate by the two steps SCM

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Fig. 1. (a) Biodiesel production process using a homogeneous catalyst system (Bournay et al., 2005); (b) Simplied ow sheet of the new heterogeneous process, Esterf-H (Bournay et al.,2005).

FFAs for biodiesel Crude glycerin (50-60%) + Acid wash water

Crude glycerin (80% pure)

K2SO4 Fertilizer
Fig. 2. Schematic picture of commonly used glycerin splitting at biodiesel factories.

and the optimal conditions for a yield of 97% were: temperature (300 C), pressure (9 MPa) and time reaction (15 min). Also the transestercation of triglycerides by supercritical methyl acetate (Tan et al., 2009) and methanol (Marchetti and Errazu, 2008) has proved to be the most promising process. Fig. 3 shows the SCM process (Marchetti and Errazu, 2008). As no catalyst is used in SCMs, therefore, no soap formation is encountered and the consequent necessity for soap removal step from glycerin is eliminated. Hence, high purity glycerin compared to catalyzed

processes is produced. In addition SCMs have high reaction rates and as a result the reactor volume can be reduced (Gilsic and Skala, 2009). Finally, the reaction time for high quality biodiesel production by SCMs is lower than those of homogeneous and heterogeneous processes. This method however based on the alcohol used requires very high temperature (239290 C) and reaction pressure (4.98.1 MPa) (Demirbas, 2005) which are considered as a serious drawback jeopardizing the economical aspects of the method strongly. Table 2 shows the comparison of homogeneous, heterogeneous and supercritical method for biodiesel production from Jatropha oil. 3. Strategies to economize biodiesel production As mentioned earlier, each of the methods currently used for biodiesel production has some disadvantages Such as limitation on oil source, long reaction time and high pressure and temperature. These consequently lead to high cost production processes. Thus it is required to nd strategies for economized biodiesel

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Table 1 Comparison of homogeneous and heterogeneous catalyzed biodiesel production in terms of equipment cost*. Equipment Pre-mixer of the catalyst Preesterication reactor 1st transesterication reactor 2nd transesterication rector Neutralizer reactor Sum of all decanters used in the process Distillation column to purier biodiesel Distillation column to separate the methanol Distillation column to separate the glycerol Case Ia ($) 50,000 349,000 350,000 350,000 13,500 116,000 60,000 40,000 77,500 Case IIa ($) 150,000 N/A 480,000 480,000 35,000 97,500 62,000 47,500 82,000 Case IIIa ($) N/A N/A 410,000 390,000 N/A 50,000 56,000 78,500 30,000

a Case I; homogeneous alkaline catalyst with acid preesterication, Case II; homogeneous acid catalyst, Case III; heterogeneous solid catalyst. * Marchetti and Errazu, 2008.

production. These strategies could be classied as upstream and downstream approaches. 3.1. Upstream approaches 3.1.1. Waste cooking oils and wastes from animal or vegetable oil Shortage of edible oil for human consumption in developing countries does not favor its use for biodiesel production (Divakara et al., 2010). Hence, non-edible oil such as waste cooking oils (WCO) and wastes from animal or vegetable oil is favored for biodiesel production. It is reported that approximately 70% (Meng et al., 2008) to 88% (Haas et al., 2006) of the total biodiesel production cost arises from the cost of raw material. Today increasing food consumption has increased the production of a large amount of waste cooking oils/fats. It was, for example, 4.511.3 billion liters a year in USA or 0.40.6 billion liters a year in Japan (Pugazhvadivu and Jeyachandran, 2005). Therefore, one prominent strategy for reduction of biodiesel production cost is using cheaper feedstock such as WCO. The price of WCO is 23 times cheaper than virgin vegetable oils (Glisic and Skala, 2009). Phan and Phan (2008) produced biodiesel from WCO. In their study, the reaction

conditions were: the methanol/oil ratios of 7:18:1, temperatures of 3050 C and 0.75 wt.% KOH and biodiesel yield of 8890% was obtained. Also biodiesel production from WCO via alkali catalyst was studied by Meng et al. (2008). The reaction conditions were methanol/oil molar ratio 9:1, with 1.0 wt.% sodium hydroxide, temperature of 50 C, 90 min and biodiesel yield of 89.8% was obtained. A main drawback for using WCO is the presence of water in the transesterication which causes the formation of diglycerides and FFA. Moreover, in the basic catalyzed reaction and in the presence of water, the FFA and bases form the soap which is not desirable in biodiesel production process. The result of the waters affect is low yield conversion biodiesel. For solving this drawback, hydrophobic solid acid catalysts, due to their preventing the hydration of OH groups are good alternatives instead of the basic catalysts. Shu et al. (2010) conducted a study using hydrophobic solid acid catalysts and improved the conversion of triglycerides derived from WCO to biodiesel (97.61 wt.%). In general, although in biodiesel production process from recycled cooking oils and wastes, the yield of conversion is lower than that of rened oils but due to theirs lower cost (23 times), using these raw materials is a good strategy to economize biodiesel production. 3.1.2. Application of non-edible plant oils Use of edible oils to produce biodiesel is not feasible in view of a big gap in demand and supply of such oils. Increased pressure to augment production of edible oil has also put limitation on the use of these oils for production of biodiesel (Azam et al., 2005). Instead, a large variety of plants that produce non-edible oils can be considered for biodiesel production (Rathore and Madras, 2007; Phan and Phan, 2008; Feng et al., 2010). Non-edible oils from sources such as neem, mahua, karanja, babassu, jatropha, microalgae, Camelina sativa, etc. are easily available in many parts of the world, and are very cheap compared to edible oils (Barnwal and Sharma, 2005). On the other side, for growing non-edible oil crops compared to edible oil crops, less fertilizer, herbicides and insecticides are required (Gui et al., 2008). In addition, non-edible oil plants have unique ecological requirements and botanical features that make them suitable to be cultivated in lands that are not suitable for food crops (Gui et al., 2008). Table 3 presents the oil yield (kg/ha and wt.%) and the price of various types of edible and

Methanol 2 Methanol Methanol Oil

Methanol 2

FAME

Supercritical Reactor 1 Glycerin1

Glycerin 2 Supercritical Reactor 2

Fig. 3. Case ow diagram of supercritical method (Marchetti and Errazu, 2008).

Table 2 The comparison of homogeneous, heterogeneous and SCM methods for biodiesel production from Jatropha. Method Homogeneous Heterogeneous SCM CA KOH KNO3/Al2O3 RT 64 70 320 RP A 8.4 AS 600 T 20 3600 4 C 1.3 6 MR 6:1 12:1 43:1 Y 98 84 100 Reference Lu et al. (2009) Vyas et al. (2009) Hawash et al. (2009)

CA, catalyst; RT, reaction temperature (C); RP, reaction pressure (MPa); A, Atmosphere; AS, agitation speed (rpm); T, reaction time; C, catalyst concentration; MR, mass ratio of MeOH/Oil; Y, yield.

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non-edible oil sources. It is obvious that higher oil yield always corresponds with lower cost. Some of the costs of the non-edible oils cannot be obtained as they are currently not traded in the open market (Chisti, 2007; Gui et al., 2008). 3.1.3. Plant Genetic Engineering Genetic engineering has always been considered as a powerful tool in order to improve plant and animal production such as increasing oil production in plants or manipulating the oil accumulation system to release the oil in the extra cellular space (Deng et al., 2009). These will also contribute to reducing the biodiesel production cost by decreasing the cost of raw material. Deng et al. (2009) conducted a study to regulate the activity of the enzyme that catalyzes the rate-limiting step in lipid production to increase photosynthetic efciency and biosynthesis of oil in microaglal. Recent interest in promotion of Jatropha curcas L. as a biodiesel crop demands genetic improvement of the crop for increased seed yield and oil content (Basha et al., 2009). Camelina is a low-cost oilseed crop that is not at present a major crop for food oil production; therefore it has great potential to become as a biotechnological platform for genetically engineered products (Downey, 1971). Vollmann et al. (2007) reported that variation in agronomic and seed quality characters of Camelina would clearly allow for an improvement of grain yield and oil content, whereas progress towards increased seed weight would be slow. Moreover, genetic engineering is to have the greatest impact on improving the economics of production of microalgal diesel (Chisti, 2007). Huang et al. (2010) investigated genetic engineering coupled with advanced cultivation and downstream technologies for the development of microalgae for biodiesel production. They reported that through genetic engineering, the oil content could reach 5660% of the total dry biomass and consequently contributes to decreasing the production cost. The high-oleic and high-stearic cottonseed oil initially developed for the health food industry might nd their ways into biodiesel use because of their enhanced cetane value and cold ow properties. 3.1.4. Membrane separation technology for biodiesel production Recently, membrane separation technology (MST) has been largely utilized in comparison with the conventional processes in the chemical industry. MST has many advantages including low consumption of energy, high rate of mass transfer, negligible pressure decrease and energy lost, higher efciency separation of very dilute solutions, cost effective compare to other processes based on the international gures, working at room temperature, and requires

less second chemical materials such as solvent, additive and etc. MST can be applied to economized biodiesel production in both of upstream and downstream strategies. In biodiesel production by using membrane reactors, MST can play an important role as an upstream strategy to economize the production cost. Process integration by combining reaction and membrane separation in a single unit promises numerous benets compared to conventional processes (Westermann and Melin, 2009). Membrane reactors can be used to carry out a reaction and a membrane-based separation simultaneously in the same physical enclosure (Cao et al., 2008). Dube et al. (2007) studied biodiesel production from canola oil/methanol/catalyst reaction mixture using a semi-batch two-phase carbon membrane reactor with pore sizes of 0.05 lm. During their research, the effect of temperature, catalyst concentration, ow rate, base catalyst, membrane material resistance to degradation were studied. They separated the FAME/glycerin in methanol from unreacted triglycerides to shift the reaction equilibrium in favor of the product; biodiesel. Unker et al. (2010) reported a biodiesel production using membrane reactor with 96% yield of conversion from WCO at slightly elevated temperatures of 4050 C, an overall feed of 1.2 L/min, a 6:1 M ratio of methanol to vegetable oil triglycerides, and a 11.3 wt.% potassium hydroxide catalyst loading. In a different study, Cao et al. (2008) applied the membrane reactor for recycling of methanol, glycerin and NaOH in a biodiesel production process at room temperature. The result of their investigation was the reduction of methanol:oil ratio and the reuse of NaOH in the biodiesel production which consequently reduced the production cost. Shi et al., 2010 reported biodiesel production using a heterogeneous catalytic membrane reactor by hybridizing metals sulfate (such as zirconium sulfate (Zr (SO4)2)) with sulfonated polymers (such as poly (vinyl alcohol) (SPVA)) and obtained the conversion yield of 94.5%. 3.2. Downstream approaches 3.2.1. Application of crude glycerin as an energy supplement for ruminants Biodiesel crude glycerin can potentially be used as an energy supplement for livestock (Chung et al., 2007). Roger et al. reported successful inclusion of biodiesel glycerin to animal feed at low concentrations (Roger et al., 1992). The main concern for using the crude glycerin as an energy supplement for ruminants when non-edible oils are used as feedstock for biodiesel production, is its potential toxicity. Nevertheless, this toxicity should not dampen the potential of using these oils as biodiesel feedstock, since the toxins can easily be removed from the extracted oil by using decantation prior to biodiesel production process (Kansedo et al., 2009). Moreover, rumen fermentation modies anti-nutritional factors to less toxic and so improves tolerance in ruminants species (Singh et al., 2006). Biodiesel glycerin is ingested by ruminants with phospholipids in the cell wall or lipids in the seeds and becomes a part of the lipidic fraction of the diet (Roger et al., 1992). Glycerin is then fermented to propionate by ruminal microbes or absorbed as glycerin escaping from rumen fermentation and has been used as an energy source for the prevention of ketosis in dairy cattle (Ferraro et al., 2009). Glycerin supplementation potentially improves rumen fermentation with increased propionate production and feed digestibility in the total digestive tract of beef cattle (Wang et al., 2009). Cows fed glycerin at 374 g/d lost less body weight (BW), and remained in more positive energy balance, than those fed 174 g/d glycerin (Fisher et al., 1973). Increased production of biodiesel and resulting glycerin when combined with an increased demand for corn in ethanol production may warrant use of glycerin as livestock feed (Julian et al., 1990). Therefore, animal feeding may be an alternative utilization for biodiesel crude

Table 3 Oil yield of major non-edible and edible oil sources*. Type of oil Non-edible oil Jatropha Oil yield (kg oil/ha) 1590 Oil yield (wt.%) Seed: 3540, kernel: 5060 4050 53 3040 54 70 30 20 20 3750 Prices (USD/ton) N/A

Rubber seed Castor Pongamia pinnata Sea mango Microalgae Microalgae Edible oil Soybean Palm Rapeseed
*

80120 1188 2252250 N/A 122,230 45,270 375 5000 1000

N/A N/A N/A N/A N/A N/A 684 478 683

(Chisti, 2007; Gui et al., 2008).

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glycerin to economize the whole biodiesel production process before a sufcient degree of purity could be achieved with less expensive rening systems (Casa et al., 2009). 3.2.2. Glycerin ultra-purication Glycerin is the co-product of biodiesel production. The ratio between glycerin and biodiesel produced through the transesterication process is about 1:10 (Sun and Chen, 2008). Production of biodiesel could be much more economical if such process scheme and technology gives the pharmaceutical grade of glycerin (>99.5 mass%) (Glisic and Skala, 2009). There are a few separation technologies that can be used for ultra purication of glycerin such as using distillation units, supercritical uid extraction followed by appropriate fractionation steps (Ashour and Aly, 1992) and MST (Sdrula, 2010). However, MST has proved to be the most efcient (Sdrula, 2010). Glycerin ultra-purication by using membrane separation technology could be very promising in reducing biodiesel production cost. Sdrula, (2010) conducted the ultra-purication biodiesel glycerin by applying MST (a combination of nanoltration, microltration, and electrodialysis) and achieved the purity of >99.5. The glycerin purication by using the conventional distillation method is shown in Fig. 4a. Sdrula (2010) proposed a technology for glycerin purication in which a combination of high efciency electrodialysis and nanoltration (HEEPM) was used for the separation of molecules and ions. He also used MF for the separation of triglycerids (Fig. 4b). This study highlighted the importance of membrane technologies which can rapidly extend, based on economical and operating advantages, in the domain of biodiesel industry (Fig. 4a and b). 3.2.3. Biodiesel separation and purication by using MST Biodiesel produced by catalyzed transesterication contains several impurities namely unreacted alcohol (methanol or ethanol), unreacted triglycerides (TG), mono (MG) and diglycerides (DG), residual catalyst, free fatty acid, free glycerin, water, and the other impurities. In fact, one of the main reasons leading to costly biodiesel production is the expenses involved in the biodiesel separation and purication stage. Biodiesel produced should be puried according to ASTM D6751 and EN 14214 standards. On the other hand, biodiesel should be separated and puried of these impurities because of their negative effect on the engine performance and natural environment. For instance, the burning of glycerin, one of the most important impurities, leads to the production the acrolein that is a toxic compound, in addition high free glycerol content can result in separation during storage, forming gum-like deposits around injector tips and valve heads, therefore causing

problems in the fuel system (Saleh et al., 2010). To overcome these problems, there are several different separation and purication techniques such as gravitational settling, distillation, evaporation, washing with water, acid, absorbent to produce a highly puried and quality biodiesel (Atadashi et al., 2010). Most of these conventional techniques are not economical compared to MST. Gomes et al. (2010) separated biodiesel and glycerin using ceramic membrane. In their study high glycerol retention of 99.6% was achieved. In a different study, Saleh et al. (2010) completely separated glycerin from biodiesel using modied polyacrylonitrile (PAN) as a polymeric membrane by ultraltration technology. In the conventional separation method, for each liter biodiesel, 10 l water is consumed for the washing step. In contrast, Saleh et al. (2010) used only 2.00 g water per liter biodiesel when applied MST.

4. Conclusion The growing global attention toward renewable energy sources including biodiesel and depletion of fusel fuels reserves are both strong driving forces to look for modern approaches to economize biofuels production. Biodiesel is currently of great importance among biofuels owing to its unique characteristics. Therefore, striving to reduce the biodiesel production costs using upstream and downstream approaches as previously discussed is a necessity. As mentioned earlier, the homogeneous and heterogeneous catalyzed systems as well as SCM are the main methods of biodiesel production. Comparatively, SCM is the least economical method. Although the yield of conversion by homogeneous process is high, the limitation on using various raw materials (rened oil) is considered as its main drawback. In fact, when high FFA content oils are used, a large amount of water in the washing step is required which increases the biodiesel production cost. So, it can be concluded that the heterogeneous process is the most desirable method due to the wide range of raw material used including high FFA content oils, less amount of equipment involved in the process and high purity of glycerin produced by this method. On the other hand, developing upstream and downstream strategies to economize biodiesel production is a necessity. Upstream strategies such as using WCO and wastes from animal or vegetable oil, using nonedible plant oils, genetic engineering of oil crops and using MSTequipped reactors for biodiesel production can be implemented to successfully lower the biodiesel production cost. In case of using WCO, the problem involved due to the presence of water and subsequent yield reduction could be overcome by using hydrophobic solid acid catalysts. Moreover, shifting toward non-edible plant oils

Crude Glycerin

Neutralization

Stripping

Filtration/ Centrifugation

Vacuum Distillation

USP Glycerin

Backwash Pretreatment Raw Feed M Filter HEEPMTM

Fig. 4. (a) Glycerol purication process by using the conventional methods (Sdrula, 2010); (b) Steps of glycerin purication by using a combination of high efciency electrodialysis and nanoltration (HEEPM) (Sdrula, S., 2010).

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and their genetic engineering are two other important strategies for reducing the cost imposed by the required raw materials. Downstream strategies such as ultra purication of the glycerin produced in biodiesel production processes, using crude biodiesel glycerin as an energy supplement for ruminants and applying MST for biodiesel separation and purication could be key factors to further economize biodiesel production. Ultimately, if optimum process efciency and economization are to be fully achieved, then future developments of the mentioned strategies are inevitable. These in combination can play an important role in the development of biodiesel production industry in future. Acknowledgements The authors would like to express their appreciation to Professor Sayed Siavash Madaeni for his valuable advice on preparing this review article. References
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