Fuel 89 (2010) 35793589

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How much of the target for biofuels can be met by biodiesel generated from residues in Ireland?
T. Thamsiriroj, J.D. Murphy *
Department of Civil and Environmental Engineering, University College Cork, Cork, Ireland

a r t i c l e

i n f o

a b s t r a c t
This study focuses on biodiesel production from residues in particular tallow and used cooking oil (UCO). Ireland has 8% of the EU cattle herd with less than 1% of the EU population. Thus a signicant quantity of slaughter residues is available for energy production. The total energy potential associated with slaughter wastes and UCO is estimated to be 7.07 PJ/a; 61% of which is suitable for biodiesel production. The potential quantity of biodiesel is equivalent to 2.1% of predicted transport fuel use in 2010; three quarters of the 2010 biofuels target. Biodiesel production from these two residue streams may be expressed as equivalent to 22% of arable land in Ireland under oilseed rape. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 10 February 2009 Received in revised form 11 January 2010 Accepted 3 June 2010 Available online 17 June 2010 Keywords: Biodiesel Tallow Used cooking oil

1. Introduction Ireland has set national targets to substitute conventional fuels with biofuels in the transport sector. These targets included 5.75% substitution by 2010 and 10% by 2020, to comply with the governments White Paper Delivering a Sustainable Energy Future for Ireland, published in March 2007 [1]. An obligation of 5% biofuels in retailed petrol and diesel was scheduled to be introduced to the transportation market by 2009. However, in September 2008 the Irish government revised the 5.75% target, and lowered it to 3% by 2010. The target of 10% by 2020 still remains as a commitment to achieving the EU targets [2]. The main reasons for this revision are the increase in global food prices, which is linked to the transfer of land from food to energy crops and also doubts as to whether biofuels are as environmentally friendly as originally thought [2]. The Republics biofuels sector produces only 0.6% of all fuel, with a greater quantity being imported to meet the biofuels target of 2.2% by 2008 [3,4]. A paper written by the authors [5] shows that 1% of total agricultural land is required to satisfy 1% substitution of transport fuels with rapeseed biodiesel. To achieve 5.75% substitution according to the previous target would thus require 5.75% of all agricultural land under oilseed rape, which is equivalent to 63% of arable land in Ireland. Food crops are grown on arable land and hence this raises the conict of land for food versus land for fuel. The EU Renewable Energy Directive [6] states that biofuels to be used in 2020 will only be classied as biofuels if they contribute
* Corresponding author. Tel.: +353 21 490 2286; fax: +353 21 427 6648. E-mail address: jerry.murphy@ucc.ie (J.D. Murphy). 0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2010.06.009

greenhouse-gas (GHG) emissions savings of at least 60% compared to conventional fuels. Using a life cycle analysis approach without allocation to co-products or by-products, Thamsiriroj and Murphy [5] calculated a GHG emissions reduction of 28.8% for biodiesel produced from Irish-grown rapeseed. The energy used in agriculture (e.g. ploughing, fertilizing) is the major energy-consuming process in rapeseed biodiesel production, releasing a signicant amount of GHG emissions in the biodiesel life cycle [5]. Recently, interest has been focused on transport fuels produced from residues, wastes, and by-products. These feedstocks do not have the associated GHG emissions from crop production; for example agriculture is responsible for 14% of the parasitic energy demand in rapeseed biodiesel and 79% of the GHG emissions in the life cycle analysis. Biofuels produced from wastes, residues, and by-products have a signicantly better energy balance with less GHG emissions than biofuels produced from energy crops. Tallow and used cooking oil (UCO) are considered to be renewable and sustainable feedstocks for biodiesel production. Their relatively low costs contribute to a low biodiesel price and allow biodiesel to compete economically with diesel. In the USA, one of the largest fats and oils trading countries, inedible tallow and recycled greases have remained the lowest priced among the various types of oil and fat, since records began in 1990 [7,8]. The produced quantity of tallow and greases is predicted to increase every year [9] as a result of increasing population, rising food consumption and an increased demand for industrial products. It is estimated that the potential of UCO collectable in the EU is between 700,000 and 1,000,000 t/a [10], which could account for up to 20% of biodiesel produced in the EU (based on 4,890,000 t/a biodiesel production in 2006 [11]).

3580

T. Thamsiriroj, J.D. Murphy / Fuel 89 (2010) 35793589 Table 1 SFA and FFA contents in some oils and fats. Oils and fats Soybean Palm Rapeseed Jatropha Animal fats % Saturated fatty acids 14.3 [22], 15.5 [23] 43.4 [23], 47.0 [24] 4.1 [24], 5.1 [25] 21.1 [23], 22.9 [26] Lard 39.3 [19], chicken fat 32.0 [16], beef tallow 45.6 [19], mutton tallow 61.1 [16] 11.8 [27], 13.6 [22], 90.9 [28] % Free fatty acids 0.1% [22] 0.4% [29] 0.02% [30] 0.1% [26] Inedible tallow: 11.2 20% [31] 1.8 [28], 5.6% [32]

The 1st generation feedstocks for biofuels produced from energy crops have resulted in concerns over change in land use and food price increase. The next generation feedstocks need to be truly benecial in a more sustainable manner; food supply should not be adversely affected and net environmental benets should result. Biodiesel production from tallow and used cooking oil has been developed to a commercial scale in Ireland, and a facility with a production capacity of 30,000 t/a has been operational since mid2008 [12]. Biofuels produced from residues (such as tallow and used cooking oil) are allowed a double count towards the biofuels targets according to the Renewable Energy Directive [6]. 2. Methodology and objectives Initially this paper reviews the available processes for generating biodiesel in the form of fatty acid methyl ester (FAME) from residues such as used cooking oil (UCO) and tallow, which are high in either free fatty acids (FFA) or saturated fatty acids (SFA) as compared to pure plant oil (PPO). An analysis is undertaken to estimate the quantity of residues, which are readily available in Ireland and to estimate the potential production of biodiesel from such sources. Of particular interest is the quantity of land that would need to be under rapeseed to produce a similar quantity of biodiesel; previous work by the authors [5] showed that 1355 L of biodiesel is the average production of rapeseed biodiesel per hectare per annum in Ireland. This is especially important as only 9% of land in Ireland is arable and thus there is extreme competition between food and fuel. A sensitivity analysis is carried out by examining the readily available feedstock. Thus the paper has a number of objectives:  quantify animal by-products and used cooking oil in Ireland;  estimate the proportion of the national biofuels target that can be met by biodiesel from residues;  calculate the land under oilseed rape required to produce the same quantity of biodiesel. 3. Biodiesel produced from animal fats and used cooking oil 3.1. Terminology The term fats may be briey dened either as animal tissue distended with greasy or oily matter, or as glyceride compounds of fatty acids [13]. The former denition, which is mostly used in this paper, species that fats are animal products. In the latter definition, the entire range of fats and oils from vegetables and animals is included. Greases generally refer to solid or thick oil. Greases can be classied as yellow and brown greases. Yellow grease is UCO collected from commercial or industrial cooking businesses, and brown grease is the grease recovered from grease traps and interceptors [14]. Finally, tallow is the term used for animal fats obtained by either the melting process or rendering process [15]. Inedible tallow, generally produced from the rendering process, is a competitive feedstock in biodiesel production due to its low cost [14,1618]. 3.2. Saturated fatty acid (SFA) content Fats and oils are made up of 1 mol of glycerol and 3 mol of fatty acids, and are commonly referred to as triglycerides. There are also minor quantities of monoglycerides and diglycerides in fats and oils [1921]. Primarily, there are two types of fatty acids, saturated and unsaturated fatty acids. SFA content in animal fats is typically higher than in most type of vegetable oils. However, in UCO it can

Used cooking oil

vary by a wide range, depending on the usage and properties of the original oil. Table 1 shows the SFA content of some fats and oils. A large variation can be seen in UCO (1190% SFA). High SFA content causes the oil to solidify at room temperature. 3.3. Free fatty acid (FFA) content The FFA content of oil feedstocks is a key parameter in determining the viability of the transesterication process. For fats and oils with an FFA content of less than 23%, feedstock pretreatment is not required and alkaline-catalyzed transesterication can be simply performed. The higher the acidity of the oil, which is associated with higher FFA content, the lower the conversion efciency of biodiesel through alkaline catalysis [14,33]. Rendered tallow and UCO normally contain a signicant quantity of FFA (see Table 1). The upper value is between 15% and 20% FFA for rendered tallow [15,34]. For UCO, the FFA content is typically less than 15% [14]. With these high FFA content feedstocks, alternative transesterication methods to the simple one-step, alkali-catalyzed process should be considered in order to achieve a high yield of biodiesel. 3.4. Transesterication methods Transesterication is a chemical reaction which involves the mixing of a fat or oil with an alcohol in the presence of a catalyst to produce fatty acid esters (biodiesel) and glycerol. It transforms the large, branched molecular structure of the bio-oils into smaller, straight-chain molecules, with fuel characteristics similar to those of regular diesel. Methanol is the most commonly used alcohol because of its low price compared to other alcohols [14,17,19,3537]. The transesterication reaction of a triglyceride and methanol is outlined by the chemical reaction in Fig. 1. 3.5. Reduced yield from alkaline-catalyzed transesterication of high FFA feedstock Alkalines, e.g. KOH and NaOH, are the most common catalysts used in the one-step process. The reaction is faster for alkaline- than for acid-catalyzed processes (only 30 min compared to 18 h for the acid catalysis) [21,25]. However, the yield of methyl ester will substantially decrease if high FFA content feedO CH2 O C R1 O CH O C R2 O CH2 O C R3 Triglyceride Methanol + 3 CH3OH
(Catalyst)

O CH3 O C R1 O CH3 O C R2 O CH3 O C R3 Methyl ester CH2 OH Glycerol + CH OH CH2 OH

Fig. 1. Transesterication reaction.

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(Fig. 3b), thus resulting in additional soap products. The presence of water causes further saponication (Fig. 3c), which also produces more soap [21]. Hence, one-step, alkaline-catalyzed transesterication is not an appropriate process for high FFA content feedstocks. 3.6. Acid-catalysed processes for feedstock with high FFA A one-step transesterication process may be applied to high FFA content feedstocks using an acid as a catalyst. Sulfuric acid (H2SO4) is a commonly chosen catalyst. The reaction of the onestep, acid-catalyzed transesterication process is also based on Fig. 1. Although the reaction can produce a high yield of biodiesel, the reaction is relatively slow and a reactor is required to withstand an acidic environment [39]. Alkaline-catalyzed transesterication is much more effective in terms of reaction rate. This advantage of alkaline catalysts can be applied to high FFA content feedstocks through a two-step transesterication process. In the rst step, pretreatment known as esterication (Fig. 4a) uses an acid catalyst to convert FFA into biodiesel; the remainder of the triglycerides are subsequently transesteried to biodiesel in the second step using an alkaline catalyst [21,38]. 3.7. Alternative transesterication methods for feedstock with high FFA
+ CH3OH Methanol

Fig. 2. Yield of methyl esters related to %FFA [14].

(a)
O

Dehydrolysis reaction O + KOH K + -O C R Potassium soap + H2 O Water

HO C R

Free fatty acid Potassium Hydroxide

(b)

Hydrolysis reaction O O + H2O Water HO C R Free fatty acid

CH3 O C R Methyl ester

(c)

Saponification reaction O O K + -O C R O + 3 KOH K+ -O C R + CH OH O K + -O C R Potassium Hydroxide Potassium soap CH2 OH Glycerol CH2 OH

CH2 O C R1 O CH O C R2 O CH2 O C R3 Triglyceride

Fig. 3. (a) Dehydrolysis reaction, (b) hydrolysis reaction and (c) saponication reaction.

stocks are used. An example of the reduced yield in the one-step, alkaline-catalyzed transesterication is outlined in Fig. 2. When adding an alkaline catalyst, FFA reacts with the catalyst to form soap and water in a dehydrolysis reaction (Fig. 3a) [38]. Water can further react with methyl esters to produce more FFA

The supercritical methanol method is an alternative to the transesterication of oil feedstocks with high FFA content. A catalyst is not required in the process; as a result, the wastewater containing acid or alkaline can be avoided in the washing process. The reaction rate is relatively high; a residence time of between 12.5 and 50 min is required. However, the reaction has a high energy demand as high temperatures and pressures are required (at least 250 C and 10 MPa) [35,40]. Enzymatic catalysts like lipases are also used in transesterication. Triglycerides and FFA can be enzymatically transesteried to biodiesel in a one-step process because lipases catalyze both transesterication and esterication reactions (Fig. 4b) [41]. Hence, FFA contained in oil feedstocks can be completely converted to biodiesel, and the difculty of recovering glycerol is also overcome as no soap is produced in the process. On the other hand, the production cost of lipase catalysts is higher than that for alkaline catalysts [33,42]. Renewable diesel may also be generated using hydrogenation; the end product is not FAME but synthetic diesel. It is very attractive to petroleum rening companies but is not discussed further in this paper. Table 2 outlines some studies dealing with high FFA content tallow and UCO. Most of the processes are viable for these oil feed-

(a)
O

Esterification reaction O + CH3OH Methanol

(H2SO4)

HO C R Free fatty acid

CH3 O C R Methyl ester

H2O Water

(b)

Combined esterification and transesterification reactions

O CH2OH O O (3n+m) CH3OCRn + n CHOH + m H2O (Lipase) CH2OH

CH2OCR1 O n CHOCR2 + m HOCR4 + (3n+m) CH3OH O CH2OCR3

Triglyceride Free fatty acid Methanol

Methyl ester

Glycerol Water

Fig. 4. (a) Esterication reaction and (b) combined esterication and transesterication reactions.

3582 Table 2 Processing conditions and biodiesel yield. Alkaline catalysis (onestep) [31] Feedstocks %FFA in feedstock Process temperature (C) Process pressure (MPa) Catalyst used Residence time Biodiesel yield (%)
a

T. Thamsiriroj, J.D. Murphy / Fuel 89 (2010) 35793589

Acid catalysis (onestep) [43] UCO 5.6 65

Acid, alkaline catalysis (twostep) [44] Tallow 9 60

Supercritical methanol [43] UCO 5.6 350

Lipase catalysis [45] UCO 8.5 50

Tallow 20 55

0.1 KOH 1h 34.5

0.1 H2SO4 48 h 97.8

0.1 H2SO4, NaOCH3 1 h, 1 h, 8 h 90.2

a

43 No 4 min 96.9

0.1 Immobilized lipase PS-30 18 h 94

Two stages of pretreatment by acid-catalyzed esterication with residence time of 1 h each, and 8 h for alkaline-catalyzed transesterication.

Table 3 Fuel properties of biodiesel. Properties Density (kg/L) Viscosity (mm2/s) Cetane number Cold lter plugging point (C) Pour point (C) Cloud point (C) Acid value (mg KOH/g) Iodine value Tallow 0.877 [47] 5.0 [48] 58.0 [47] 8 [48] 9 [48] 11 [48] 0.44 [48] 53.6 [48] UCO 0.882 [32] 4.68 [32] 54.5 [32] 1 [49] 3 [32] 1 [32] 0.5 [32] 85.83 [32] Rape seed oil 0.882 [50] 4.58 [50] 52.9 [50] 10 [51] 15 [52] 0 [52] 0.16 [51] 97.4 [50] EU biodiesel standard 0.860.90 3.55.0 >51.0 <0.5 <120

stocks, except the one-step, alkaline-catalyzed transesterication process. The yield of biodiesel is unacceptably low and this process is not therefore feasible for commercial production. 3.8. Fuel quality Biodiesel is required to comply with the EN 14214 standard [46]. The fuel properties of biodiesel produced from tallow and UCO can be different from those of biodiesel from virgin oils because of the higher FFA and SFA contents of recycled oils. FFA and SFA affect many important fuel parameters including cetane number (CN), cold ow properties, acid value, and iodine value. Some fuel properties are presented in Table 3 and discussed below: Cetane number indicates the ignition properties of the fuel. It is generally dependent on the composition of the fuel and can impact the engines startibility, noise level, and exhaust emissions. The higher the cetane number, the more efcient the ignition [53,54]. Biodiesel from high SFA content feedstocks has a higher cetane number, which has a positive impact on the diesel engine [55]. Iodine value is a measure of total unsaturation within a mixture of fatty acids. It is expressed in grams of iodine which reacts with double bonds in a 100 g oil sample. The limitation of unsaturated fatty acid is necessary due to the fact that heating the unsaturated fatty acids results in polymerization of glycerides. This can lead to the formation of deposits or deterioration of the lubrication. The iodine value is also important in measuring the oxidation stability of fuels. The oxidation stability decreases with the increasing content of polyunsaturated methyl esters [32,51]. Biodiesel from high SFA content feedstocks has a lower iodine value, which also has a positive impact on the diesel engine. Acid value is a measure of the number of acidic functional groups in a sample, and is measured in terms of the quantity of potassium hydroxide required to neutralize the sample [14]. The presence of acid affects fuel aging. High acid value in fuel may be caused by either high FFA content in oil feedstocks or by the amount of acid added in the transesterication process [21,33]. A case of high acid value caused by the amount of added acid was studied by Rice and Frohlich [31]; a two-stage transesterication

process was selected in the study, in reverse order to the typical process, i.e. alkaline-catalyzed transesterication in the rst step, followed by acid-catalyzed esterication in the second step. The biodiesel product had an acid value as high as 1.5 mg KOH/g (limited to less than 0.5 mg KOH/g in the EN 14214 standard). Biodiesel from high FFA content feedstocks has a higher acid value, which has a negative impact on the diesel engine. Cold ow properties are characterized by three temperature measures including cloud point (CP), pour point (PP), and cold lter plugging point (CFPP). CP is the temperature at which the fuel shows a haze from the formation of crystals; PP is the lowest temperature at which the liquid will ow; and nally, CFPP is the temperature at which the crystals formed will cause the plugging of the lters [56]. Among these fuel properties, cold ow properties and acid value are the most critical and require control measures (Table 3). Additives may be used to reduce cold-starting problems [57]. Blending biodiesel with conventional diesel will also improve the cold ow properties [56]. For biodiesel produced from tallow, PP is reduced to 11.1 C and CP to 9.9 C when neat biodiesel is displaced by B20 biodiesel [48]. The high acid value can be reduced with a two-step process, consisting of acid-catalyzed esterication followed by alkaline-catalyzed transesterication. Most of the acid residues are neutralized in the second step. However, the use of an additional alkaline catalyst for neutralization increases the cost of biodiesel [58]. 3.9. Emissions from biodiesel fuel Biodiesel produced from high SFA content feedstocks such as tallow results in a higher combustion efciency due to its increased cetane number, and thus in a reduction in the emissions of CO, HC, and white smoke [33]. Studies of engine tests [48,59,60] show that a higher degree of unsaturation in biodiesel results in an increase in NOx emission levels. NOx emissions from tallow B20 were found to be as low as emissions from diesel fuel, while from soybean B20, NOx emissions were 6.2% above diesel fuel [48]. Methyl esters high in saturated fat produce a high ame

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temperature. This could lead to an increase in combustion temperature and NOx emission levels [61]. However, a model simulation by Yuan et al. [59] shows that the increased NOx emissions are also inuenced by earlier start of injection and shorter ignition delay. These factors result in higher NOx emission levels for methyl esters high in unsaturated fat than for methyl esters high in saturated fat [59]. Biodiesel from high SFA content feedstocks therefore has a positive impact on NOx emission levels. Particulate matter (PM) emissions relate to the oxygen content of fuels. There is no signicant difference in PM emissions between highly saturated and unsaturated methyl esters; blending diesel with biodiesel helps to reduce PM emissions because of the increased oxygen content [60]. 3.10. Technology at commercial scale It is found that most of the commercial biodiesel processing plants are currently based on the homogenous, alkaline-catalyzed process. Sodium and potassium hydroxides are traditional catalysts, but potassium hydroxide is preferable as potassium soap is softer than sodium soap and, unlike sodium soap, does not block the bottom of the separation funnel. Another advantage of potassium hydroxide is the potential to recover potash fertilizer, which creates an added value. The use of sodium or potassium methoxides is also increasing. They have an advantage over the sodium and potassium hydroxides in that they reduce side reactions, such as saponication, resulting in an improved biodiesel yield [14,62]. The acid-catalyzed transesterication process has been proven to be technically feasible for high FFA content oils. It is less complex than the alkaline-catalyzed transesterication process and is therefore a competitive alternative to commercial biodiesel production using the alkaline-catalyzed process [63]. However, because of the slow reaction rate, acid catalysts are only used in the esterication reaction in the pretreatment stage of the twostep process. In commercial biodiesel production, the two-step process commonly uses sulfuric acid to esterify oil feedstocks prior to the alkaline-catalyzed transesterication. This process offers a large potential to process high FFA content oils. Some examples of industrial technology using the two-step process include BDI, CMB, DSB, and Energea [62]. Heterogeneous catalyzed transesterication through solid alkaline or solid acid catalysts has also been developed to the production stage at commercial scale. The technology known as EsterpH process was developed by Institut Franais du Ptrole (IFP) and commercialized by Axens. The main advantages of the process are the production of high quality glycerol with over 98% purity and the fact that the disposal of salts resulting from catalyst usage is not required. The biodiesel yield is close to 100%. However, it is only economically feasible at a scale above 100,000 t/a, and only virgin vegetable oils with a maximum FFA content of 0.25% are suitable for the process [62,64]. 4. Tallow, and used cooking oil (UCO) 4.1. The rendering process Rendering is the recycling of raw material tissue from animals used for food and waste cooking fats and oils from all types of eating establishments into a variety of value-added products. During the rendering process, heat, separation technology, and ltering are applied to the material using various processes. Heat is used in the cooking process. The temperature and duration of the cooking process are critical and so are the primary determinants of the quality of the nished products [65,66]. The diagram in Fig. 5 illustrates the rendering process. The principle rendering process used

Raw materials

Sizing

Heat processing (Time x Temperature)

Protein

Press

Grinding Fat clean-up Storage/Load out

Fig. 5. Rendering process [67].

in the EU is pressure-cooking. According to the EU Regulation EC 1774/2002 [68], animal by-products that are not intended for human consumption must be cooked using one of ve different options. The most applicable option is cooking at 133 C and 3 bar for 20 min, with the particle size of starting material 650 mm [68]. 4.2. Tallow, and meat and bone meal (MBM) All rendering system technologies include the collection and sanitary transport of raw material to a facility, where it is processed into a consistent particle size and conveyed to a cooking vessel, which can be either continuous-ow or of batch conguration. Fat is separated from the cooked material via a screw press within a closed vessel. The fat known as tallow is stored and transported in tanks. After the cooking and fat separation stages, the crackling (which includes protein, minerals, and some residual fat) is further processed by moisture removal and grinding to produce meat and bone meal (MBM) [65,69]. MBM is currently used as a substitute for fossil fuel. It is often co-incinerated in power generating plants or used in cement manufacturing [34]. The ban on the feeding of MBM to farmed animals in the EU has been in place since its introduction in 2000 [70]. 4.3. Animal by-products Three categories of animal by-products are dened in the EU Regulation EC 1774/2002 [68]. Category 1 materials are animal by-products that are regarded as a high-risk of TSE (Transmissible spongiform encephalopathies). All category 1 materials must be either incinerated; rendered and subsequently incinerated; co-incinerated; or buried under strict conditions. Category 2 materials are animal by-products that still possess a risk (but not a TSE risk). This category covers materials not included in category 1 or 3. There are more options for the disposal of category 2 materials than for category 1. Category 3 materials are animal by-products that possess a low risk. These by-products are derived from animals considered t but not chosen for human consumption. This category includes by-products from the slaughter process: degreased bones; former foodstuffs of animal origin devoid of an infectious risk to humans and animals; fresh sh by-products; and catering waste other than that of international transport origin. Materials in this third category can be used for pet-food production, animal feed for nonfood-producing animals, or technical products after appropriate processing in an approved category 3 processing plant [69].

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T. Thamsiriroj, J.D. Murphy / Fuel 89 (2010) 35793589 Table 4 Carcass weight of animals slaughtered in Ireland [78]. (000 t) Cattle Pig Sheep Poultry Total 2000 577 230 83 123 1013 2001 579 240 78 123 1020 2002 540 230 67 122 959 2003 568 219 63 123 973 2004 564 204 72 128 968 2005 546 205 73 129 953 2006 572 209 70 123 974 Average 563.7 219.6 72.3 124.4 980

4.4. Use of tallow from animal by-products as a source of biodiesel Tallow produced from all three categories is permitted to be used for biodiesel production according to the EU Regulation EC 92/2005 [71]. Scientic studies in recent years have conrmed that crude, unltered tallow produced by a rendering procedure is safe from infectivity, even if the starting materials contain a high concentration of pathogenic prions and the 133 C/3 bar/20 min condition is not achieved. The downstream biodiesel is considered safe [72,73]. 4.5. Cleaning process for used cooking oil (UCO) UCO can be used as a raw material for many applications including biodiesel and a variety of oleochemical products such as surfactants, plasticizers, cosmetics and lubricants [74]. It can be used directly as fuel in a modied diesel engine. In animal feed production, the use of UCO as a raw material has been banned in the EU since 2004 [31]. Most of the UCO collected from restaurants and fried food processing lines is currently delivered to biofuel and oleochemical industries. The quality of this UCO may be expected to vary depending on the original oil types, cooking practices, waste oil storage methods, and collection systems [75]. After collection, the oil is transferred to large holding tanks where it is blended with other waste oils; however, the quality is very inconsistent. The impurities present in UCO consist primarily of FFA, polymers, chlorides, and phospholipids [76]. A cleaning process separates the water and solid portion from the oil, but the impurities in the oil require further processing (e.g. transesterication and separation steps) to make it suitable for industrial applications. The cleaning process includes steam injection (heating the oil), coarse screening, and centrifugation to eliminate the ne portion and water [31]. The water-soluble impurities which dissolve in water can be removed by washing the oil with water or water vapour. The oil may also be neutralized by adding alkali but this must be in a small quantity in order to avoid the production of a lot of soap. More detail on oil cleaning techniques can be found in Ref. [77]. 5. Potential energy associated with selected residues in Ireland 5.1. Tallow and MBM The total number of livestock (i.e. cattle, pigs, and sheep) slaughtered in Ireland is estimated to be about 9 million annually (Fig. 6). This is twice the population of the country (4.42 million
12000 No. of animals slaughtered (thousand heads)

people [78]). About 90% of beef produced in Ireland is exported, mainly to EU countries. More than 85% of Irish cattle outputs are slaughtered in Ireland; the remainder are exported live [79]. More than 50% of the total carcass weight of livestock and poultry animals slaughtered in Ireland is from the slaughtering of cattle (see Table 4). There are currently nine licensed rendering plants in Ireland. These plants are classied as follows: ve category 1 and four category 3. There are no category 2 plants currently licensed in the country [80]. In 2006, 558,000 t/a of animal by-products were used to produce 151,000 t/a of MBM and 88,000 t/a of tallow in Ireland [81]. Based on these gures, approximately 16% of the by-product quantity can be converted to tallow and 27% to MBM, while 57% is lost in the process [34]. The percentage of losses in the rendering process is high, because the major component of animal by-products is water. Animal carcasses can contain up to 68% water [82]. Rendering plants accept animal carcasses, such as heads, feet, offal, excess fat, excess meat, hides, skin, feathers, and bones. In Germany, on average 35% of the live weight of all animal species is transported to inedible rendering plants [82]. If this gure is treated as the quantity of animal by-products available to the rendering process, the tallow and MBM potentially available in Ireland are calculated as 92,600 and 156,300 t/a respectively (Table 5). This compares favourably with the 2006 production gures (88,000 and 151,000 t/a). 5.2. Biogas from paunch content If we consider slaughter waste, it is important to also consider the element of slaughter waste which is suitable for digestion and conversion to biogas/biomethane. Belly grass, which is digestive tract content (stomach content) obtained from cattle, is normally removed in slaughterhouses in the form of discharged slurry. Belly grass is classied as a category 2 material under the
Cattle Pig Sheep Total

10000

8000

6000

4000

2000

0 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 Year
Fig. 6. Number of livestock slaughtered in Ireland [78].

T. Thamsiriroj, J.D. Murphy / Fuel 89 (2010) 35793589 Table 5 Potential of animal by-products in Ireland. (Data 20002006) Average carcass wt (000 t/a) Carcass wt as % of live wt (%)b Average live wt (000 t/a) 35% live wt as by-products (000 t/a) 16% by-products as tallow (000 t/a) 27% by-products as MBM (000 t/a)
a b a

3585

Cattle 563.7 54 1043.9

Pig 219.6 77 285.2

Sheep 72.3 49 147.6

Poultry 124.4 70 177.7

Total 980 1654.4 579 92.6 156.3

From Table 4. Average values in Europe modied from [82].

EU Regulation EC 1774/2002. Land-spreading of this material is permissible in Ireland under the same regulations as manure [83]. It can be used in pet-food production [82] and also possesses the potential to produce biogas through anaerobic digestion. About 92 kg of stomach content may be expected per bovine, 7 kg per pig and 5 kg per sheep [84,85]. The dry solids (DS) content of the material from the various animals is very similar, i.e. 11% DS for cattle and sheep, and 10% DS for pigs stomach content. For all animals, the gures of 80% and 85% are used for volatile dry solids (VS) content and volatile dry solids destroyed (VSdest) respectively [84]. The biogas potential from the stomach content of these farmed animals in Ireland is esti3 mated to be 15.21 million mn /a of biogas @55.5% CH4 (8.45 mil3 lion mn CH4/a) (Box 1). This is equivalent to 0.32 PJ/a. Box 1. Biogas potential from animals stomach content. Cattle Average No. of cattle slaughtered (20002006): 1,814,000 cattle/a Stomach content @92 kg/cattle @11%DS @80%VS @85%VSdest: 6.88 kg VSdest/cattle Destruction of 1 kg VS = 1 mn3 biogas @55.5% CH4 Biogas produced from stomach content: 12.48 million mn3/a (6.93 million mn3 CH4/a) Sheep Average No. of sheep slaughtered (20002006): 3,593,000 sheep/a Stomach content @5 kg/sheep @11%DS @80%VS @85%VSdest: 0.37 kg VSdest/sheep Biogas produced from stomach content: 1.34 million mn3/ a (0.75 million mn3 CH4/a) Pig Average No. of pigs slaughtered (20002006): 2,918,000 pig/a Stomach content @7 kg/pig @10%DS @80%VS @85%VSdest: 0.48 kg VSdest/pig Biogas produced from stomach content: 1.39 million mn3/ a (0.77 million mn3 CH4/a) Total biogas potential: 15.21 million mn3/a (8.45 million mn3 CH4/a) 5.3. Used cooking oil (UCO) A study done by the Irish Universities Nutrition Alliance [86] investigating the habitual food consumption of Irish people from 1997 to 1999 showed that on average Irish people had a daily fat intake of 87.1 g/day (31.79 kg/a). About 82% of this fat intake (26.07 kg/a) is considered to be from vegetable oils and animal fats, which are used in a variety of food categories including meats, spreads, cake and biscuits, confectionery, breads, potato products, and others. The remaining 18% of fat intake is fats from milk and

yogurt, cheeses, and vegetables. Records from the FAO (Fig. 7) indicate that the average quantity of oils and fats used in Ireland for food consumption activities (both direct and indirect), between the same period (19971999) was 32.93 kg/capita/a. Of this quantity, 16.16 kg/capita/a was from vegetable oils and 16.77 kg/capita/ a was from animal fats [87]. The estimation of recoverable cooking oil is outlined in Table 6 to be 6.86 kg/capita/a, accounting for 20.8% of the total quantity for food consumption activities. The calculated gure (20.8%) will be further used to estimate a more updated quantity of recoverable cooking oil in the following paragraph. Fig. 7, which outlines the quantity of vegetable oils and animal fats consumed per person from 1990 to 2003, indicates a signicant drop in animal fat consumption after 1998. This is due to a change in peoples habitual consumption. The decrease in animal fat consumption has been associated with an increase in vegetable oil consumption. The historical data show that the total oil and fat consumption has never dropped below 25 kg/capita/a. Hence, this gure may be used as the bottom line to calculate the potential recoverable quantity. Most oils and fats associated with food residues collected from households are disposed to landll sites, composting plants, and wastewater treatment systems. As a result, not all of the total quantity produced is collectable. Only around twothirds are believed to be realistically collectable in Ireland [88]. The potential collectable UCO in Ireland is thus estimated to be 15,300 t/a (see Box 2), compared to the reported collected quantity of 9381 t in 2006 [89]. Hence, a further 5919 t/a could be collected with a better collection network and a more economically viable usage. Box 2. Potential of UCO in Ireland. Oils/fats used for food activities: 25 kg/capita/a Recoverable quantity @20.8%: 5.2 kg/capita/a Collectable quantity @66.67%: 3.46 kg/capita/a Population of Ireland 2008: 4,422,100 people Potential collectable UCO in Ireland: 15.3 thousand t/a

5.4. Total energy produced from animal by-products and UCO Three different biofuels can be produced from animal by-products including inedible tallow, MBM, and biogas from animals stomach content. Tallow can be used as a direct fuel in boilers (except tallow produced from category 1 material under the EU regulation EC 1774/2002 which strictly requires incineration or coincineration) and for biodiesel production, while MBM is a good biomass energy source [82]. Biogas can be upgraded to biomethane and consequently to bio-CNG which is used as a transport fuel. It is also a source of energy for heat production and combined heat and power (CHP) production systems [9094]. The lower heating value (LHV) of tallow is reported to be 39.8 GJ/t; the gure may also be

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T. Thamsiriroj, J.D. Murphy / Fuel 89 (2010) 35793589

35 Oils and fats quantities/capita/a (kg) 30 25 20 15 10 5 0 1990

Total oils and fats Vegetable oils Animal fats

1991

1992

1993

1994

1995

1996 1997 Year

1998

1999

2000

2001

2002

2003

Fig. 7. Quantity of oils and fats used for food in Ireland [87].

Table 6 Recoverable quantity of cooking oil. Period 19971999 (kg/capita/a) Fat eaten Fat eaten sourced from oils/fats @82% Quantity used for food activities Recoverable quantity Total 31.79 26.07 32.93 6.86 16.16 (49.1%) 3.37a 16.77 (50.9%) 3.49a Vegetable oils Animal fats

% average recoverable oils/fats = 20.8% (i.e. 6.86/32.93) Assuming a direct relationship between the quantity used for food activities and the recoverable quantity.
a

assumed for UCO. For MBM, the LHV is about 15.7 GJ/t [82], while the energy content of biogas (@55.5% CH4) is approximately 21 MJ/ mn3 [84]. The total energy potential is estimated to be 6.46 PJ/a from animal by-products and 7.07 PJ/a if UCO is included (Box 3). Box 3. Total energy potential. Tallow @92,600 t/a @39.8 GJ/t: 3.69 PJ/a MBM @156,300 t/a @15.7 GJ/t: 2.45 PJ/a Biogas @15.21 million mn3/a @21 MJ/ mn3: 0.32 PJ/a Total energy from animal by-products: 6.46 PJ/a UCO @15,300 t/a @39.8 GJ/t: 0.61 PJ/a Total energy from animal by-products and UCO: 7.07 PJ/a

target of 3% biofuel substitution by 2010, this equates to 5.64 PJ/a in Ireland. If the target was to be met solely by biodiesel, 164.5 million L/a would be required (based on the biodiesel energy content of 34.32 MJ/L). The existing production of tallow and UCO is about 88,000 and 9400 t/a, respectively (Table 7). About 95% of the potential quantity of tallow is met by the existing production of tallow, while only 61% is met by the existing collection of UCO. Based on the conversion efciency of 95% from oils/fats to biodiesel, 102,505 t/a of biodiesel could be potentially produced from the feedstocks (scenario 1, Table 8). Such biodiesel quantity could substitute 2.1% of transport fuels in 2010, which would account for about three quarters of the target (3% substitution). This is also equivalent to 85,970 ha of arable land (21.5% of the countrys arable land) under oilseed rape if used for biodiesel production in Ireland.

5.6. Sensitivity analysis Three scenarios are examined in relation to the quantities of tallow and UCO used for biodiesel production. Existing collection of oils and fats. The most up to date data are the collected tallow and UCO (Table 7). This is available from two national reports; the 2007 EPA national waste report [89] and the 2003 SEI report on UCO and animal fats [88]. These gures are considered the mean case for production (not all produced fat is collected) and are included as scenario 2 in the middle column of Table 8. Potential production of oils and fats. The collected quantity of UCO according to the EPA report [89] is 9381 t/a. The SEI report [88] states that only two-thirds of the produced UCO is collected; this would yield a potential production gure of about 14,000 t/a. Our analysis generates (Section 5.3) a theoretical gure for recoverable UCO of 15,300 t/a, which indicates that our analysis is close to the expected value. The collection network may improve if a viable UCO biodiesel market exists. Our analysis on tallow indicates that production exceeds collection by 5%

Of this energy potential, 60.8% (4.3 PJ/a) is associated with tallow and UCO. Therefore, tallow and UCO are the most signicant products among the residues to produce biofuels in Ireland. Paunch content is considered to be an excellent and plentiful feedstock for biomethane production through anaerobic digestion [84,9094]. However, it may produce up to only 4.5% (0.32 PJ/a) of the total energy potential explored here. MBM accounts for 34.7% (2.45 PJ/a) of the total energy potential, which is signicant. However it has found favour as a displacement for conventional fuels for thermal energy production in industries such as cement manufacturing. 5.5. Substitution of biodiesel based on potential production Final energy consumption in the road transport sector in Ireland is predicted to be 188.15 PJ/a in 2010 [95]. With the new national

Table 7 Feedstock potential for biodiesel production. (000 t/a) Potential quantity Existing productiona
a

Tallow 92.6 88

UCO 15.3 9.4

Total 107.9 97.4

Based on the gures in 2006.

T. Thamsiriroj, J.D. Murphy / Fuel 89 (2010) 35793589 Table 8 Potential contribution of tallow and UCO to biodiesel based on three scenarios. Scenario 1: potential production of oils and fats Total oils/fats quantity (t/a) Total biodiesel produced @95% (t/a) Biodiesel energy value (GJ/t) Biodiesel gross energy (PJ/a) Transport fuel required in 2010 (PJ/a) Biodiesel substitution in 2010 (%)a Equivalent arable land required under oilseed rape (kha/a)b Equivalent percent arable land (%)c Equivalent percent agricultural land (%)d
a b c d

3587

Scenario 2: existing collection of oils and fats 97,400 92,530 39 3.61 188.15 1.9 77.61 19.4 1.7

Scenario 3: oils and fats presently exported 49,486 47,010 39 1.83 188.15 1.0 39.43 9.9 0.9

107,900 102,505 39 4.0 188.15 2.1 85.97 21.5 1.9

Based Based Based Based

on on on on

188.15 PJ of the transport energy (petrol and diesel) required in 2010 [95]. gross energy of biodiesel produced from rape seed at 46.5 GJ/ha/a [5]. the total 400 kha of arable land in Ireland [90]. the total 4.45 million ha of agricultural land in Ireland [90].

(Table 7); this is not unlikely. These values are included as scenario 1 in Table 8. Oils and fats presently exported. Tallow may be used in animal feed, soap manufacture, biodiesel production and oleochemical industries. In Ireland in 2003, 54% of collected tallow was used as a substitute for mineral oil in the rendering industry while the remainder was exported [96]. Thus, conservatively 44,800 t/a of tallow should be readily available for biodiesel production. In 2006, 50% of UCO (4686 t) was exported. This should also be readily available for biodiesel production. Range of values. With respect to Table 8 it may be noted that the biodiesel may substitute between 1% and 2.1% of transport fuel with scenarios ranging from present export levels to collection of total produced oils.

Acknowledgement The research is funded by the Higher Education Authority (HEA) under the HEA PRTLI Cycle 4 programme.

References
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6. Conclusions This paper focuses on the use of residues to produce biodiesel. Tallow and used cooking oil (UCO) are examined as sources of biodiesel which may substitute for oilseed rape. Rapeseed biodiesel requires extensive quantities of land to meet biofuel targets. Ireland has a signicant quantity of livestock in comparison to its population. The slaughter industry is a very important industry; for example beef exports account for 90% of beef production. Thus Ireland has a rich source of biodiesel in the form of slaughter wastes. Tallow and meat and bone meal (MBM) can be produced from animal by-products through the rendering process. Biogas can also be produced from the paunch content removed in the slaughterhouse as a raw material. It is estimated in this study that 92,600 t/a of tallow and 156,300 t/a of MBM are potentially available in Ireland. There is also potential for biogas from 205,000 t/a of paunch content. Of the energy potential in these residues, 60.8% is associated with tallow and UCO and is suitable for biodiesel production. Biomethane from the paunch content is limited to 4.5% of the total energy potential explored. MBM accounts for 34.7% of the total energy potential, which is signicant. However MBM has found favour as a displacement for conventional fuels for thermal energy production in industries such as cement manufacturing. The potential quantity of tallow and UCO produced in Ireland could be used to produce 116.5 million L/a of biodiesel and effect a substitution of 2.1% of transport fuels (based on the predicted 2010 energy demands). This is equivalent to 85,970 ha of arable land under oilseed rape, if it was grown to produce biodiesel in Ireland. Thus energy content in tallow and UCO may be expressed as equivalent to 21.5% of all arable land in Ireland.

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