Renewable and Sustainable Energy Reviews

Renewable and Sustainable Energy Reviews 42 (2015) 234 –239

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Renewable and Sustainable Energy Reviews journal homepage: www.elsevier.c www.elsevier.com/locate/rser om/locate/rser

Potential of tilapia oil and waste in biodiesel production n

Gislaine Iastiaque Martins, Deonir Secco, Luciene Kazue Tokura , Reinaldo Aparecido Bariccatti, Bruna Dresch Dolci, Reginaldo Ferreira Santos College of Agriculture Engineering, Post-Graduation Program of Energy in Agriculture, Western Paraná State University, UNIOESTE, Cascavel, PR, Brazil

a r t i c l e

i n f o

 Article history: Received 24 January 2014 Received in revised form 8 August 2014 Accepted 5 October 2014 Available online 28 October 2014 Keywords: Acid number Oil content Energy source

a b s t r a c t

Fish oil shows up as an alternative for the recovery of waste from processing of tilapia as a way of adding value to this raw material for biodiesel production. Thus, this study aimed to evaluate the yield and acid number of tilapia oil according to the type of waste used as well as to estimate its potential for biodiesel production as a function of the oil obtained. The waste consisted of   � sh viscera,  � ns, heads, skin, scales and mix of all residues mentioned. Such residues were provided provided by COPACOL  COPACOL ’s (Consolata Agro industrial Cooperative) � sh refrigerator and kept refrigerated for 24 h. Then oil was obtained by means of cooking and waste pressing. It was not possible to obtain oil from the scales and skin of tilapia by the method used. Fish viscera presented oil content of 22% and the mix of residues had a content of 6.12%. The oil obtained from the viscera showed unsuitable acidity for the production of biodiesel by transesteri �cation, requiring a process of neutralization in order to be processed into biodiesel. The remaining residues, except waste mix, were suitable for the acid transesteri �cation and biodiesel production. Fish oil has potential pote ntial for biod biodiese iesell produ productio ction n from tilapia processing processing wast waste. e. The oil obtained from the viscera presented the highest potential to produce biodiesel per ton of waste processed (217 l), followed by the oil obtained from  � sh heads (91 l) and mixed waste (60 l), showing that it is possible to convert waste into biodiesel, which can totally or partially replace the use of diesel. &  2014 Elsevier Ltd. All rights reserved.

Contents

1. In Intr trod oduc ucti tion. on. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Ma Mate teri rial al and and met metho hods. ds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Re Resu sult ltss and dis discu cuss ssio ions. ns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. Co Conc nclu lusi sion on . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Refe Re fere renc nces es . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Intro Introducti duction on

The production and use of biodiesel in Brazil favor the development of a sustainable energy source under the environmental, economi econ omicc and soci social al aspe aspects, cts, and also bring the perspecti perspective ve of  reducing diesel imports [1] [1].. The biodiese biodiesell whe when n use used d in die diesel sel engi en gine ness re redu duce cess in 50 50% % pa part rtic icula ulate te an and d sul sulfur fur in 98 98%, %, wh when en compare comp ared d wit with h pet petrol roleum eum die diesel sel.. In add additi ition, on, the bio biodies diesel el is

n

Corresponding author Corresponding author.. Tel.:  þ 55 45 3220 3155. E-mail addresses:   [email protected]  (D. Secco), [email protected]  (L. Kazue Tokura). http://dx.doi.org/10.1016/j.rser.2014.10.020 1364-0321/&  2014 Elsevier Ltd. All rights reserved.

234 235 23 5 236 23 6 238 238 238 23 8

biodegradable and nontoxic. It can also be used pure or in blend with conventional engines [2] engines  [2].. The production of this biodiesel in Brazil, in general, will not compete with food for resources during their production and the prices or during marketing, as will be produced from �sh waste. Thus, Thu s, the dev develop elopmen mentt of alt alter ernat native ive fue fuels ls fro from m ren renew ewable able sources, has received considerable attention and an alternative is the use of industrial waste generated in the tilapia ’s processing, for biodiesel production [3] production  [3].. In countries such as Hondura Honduras, s, approximately approximately 8000 t of wastes tilapia per year is converted in 1.4 million liters of biodiesel from recove rec overed red oil oil,, in oth other er wor words, ds, 0. 0.1 18 l of biod biodies iesel el pr produc oduced ed per kilogram of  � sh waste [4] waste  [4]..

G. Iastiaque Martins et al. / Renewable and Sustainable Energy Reviews 42 (2015) 234 – 239

The production of tilapia (Oreochromis niloticus) in 2009 represented 39% of the �sh production from continental �shfarming [5]. According to Ref.  [3], such species is one of the most indicated for intensive  � sh-farming for presenting typical requirements of the consumer market favorite �sh, such as white meat with �rm texture, delicate �avor and absence of interspersed �shbone, as well as productive features, as high growth rate and adaptability in several climatic conditions and also great national and international consumer market acceptance  [6]. The state of Paraná is the  � fth largest  � sh producer in Brazil. Its west region concentrates the highest production and is responsible for more than 50% of the total volume of  �sh production in the state. Tilapia represents approximately 75% of the total �sh production in Paraná, which is also one of the pioneers in the production of tilapia �llet. The Copacol tilapia slaughterhouse is the largest of Brazil with current production capacity of 20 t per day, but it can reach capacity of 50 t per day  [7]. The processes of commercialization and industrialization of  �sh for human nourishment in the world utilize 25% to 70% of the feedstock as edible products. Unusable parts reach up to millions of tons and there is also a considerable amount of  � sh that is not used for human consumption [6]. According to Ref. [8], the production of waste from �sh processing factories, mainly from the tilapia �lleting industry represents from 62.5% to 66.5% of feedstock, what requires the processing of such residues in order to reduce environmental impact. According to Ref. [9], 68% of these residues were forwarded to the feed industries, 23% to the municipal land�ll and 9% discharged directly into rivers, thus constituting a serious environmental impact. In this scenario were sought value-added alternative enabling the management of tilapia waste for the biodiesel production. The term waste refers to residues and sub-products from the processing of foods that have relatively low value [10]. Fish heads, �ns, skin, scales and viscera are characterized as waste  [11,12]. The expansion of the  � shing activity resulted in the production of large quantities of  �sh waste, especially viscera, which represent 7.5% to 15% of  � sh weight and 35% to 45% of the production of  oil that can be used in biodiesel production [3], what makes the use of residues an economical and environmental alternative for the sector. Proper disposal of residues provides additional income to processing units with the insertion of new products in the market, avoiding losses and environmental impact. Thus, it is necessary to search for viable alternatives that utilize the residues generated both in large and small scales. In that sense, �sh oil arises as an alternative for biodiesel production [10]. Fish waste oil presents large potential for being used as a substratum in biodiesel production, not only due to its lipid composition, which is rich in long-chain fatty acids [13–16,12,17], but also for being an abundant feedstock in Brazil. The percentage of tilapia oil obtained after the processing of  residues depends on several factors, such as  � sh size and production system, which are the ones that in �uence the most in the  � nal results [18]. Another parameter that might in �uence in the  � nal product is the �sh oil quality, mainly because of acidity increase. Acid number is a very important analysis for oil or biodiesel production, given that high acidity complicates the transesteri �cation reaction and an acid biodiesel may cause engine corrosion or biofuel deterioration. Thus, it becomes important to analyze physicchemically the acidity of oil for biodiesel production and compare the results with the parameters pre-set by National Agency of Oil, Gas and Biofuels (ANP). In Brazil, biodiesel production is regulated by ANP. The physic-chemical characteristics is made in accordance

235

with national standards of Brazilian Standard (NBR), by Brazilian Association of Technical Standards (ABNT), by international standards of the American Society for Testing and Materials (ASTM), by International Organization for Standardization (ISO), and the Comité Européen de Normalisation (CEN). Transesteri�cation consists of a process in which the triglycerides react with an alcohol forming esters and glycerin  [19–21]. In order to be properly used, the oil must present a maximum acid number of 0.50 mg KOH/g according to Resolution 07 of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) [22]. In that sense, the aim of this work was to assess the oil yield and acid number of tilapia oil according to the type of  �sh waste and estimate its potential for biodiesel production.

2. Material and methods

The experiment was conducted at the Biofuel Laboratory of  UNIOESTE (State University of West Paraná), Cascavel campus. The material used was acquired from COPACOL (Consolata Agro industrial Cooperative)  � sh slaughterhouse, located in the Nova Aurora County, in the west region of Paraná state. Tilapia waste (heads, �ns, skin, scales, viscera and mix of all residues) was provided by COPACOL, in samples with an average of  5 kg of each residue in clean recipients, which were processed in the factory on the day the �sh were slaughtered and kept refrigerated until the beginning of the experiment, what happened on the following morning. Residue samples were assessed individually, as shown in Fig. 1. An amount of 1 kg of residue was used for oil production. It was cooked in a pressure cooker, at high temperature (110 7 10 C) for an average time of 1 h and 30 min. After cooking, the material was pressed (Fig. 2) provided with a screw or auger that crushes the material, releasing the oil. From the pressed material was obtained oil and press cake, which was discarded according to the methodology proposed by Ref. [23]. According to Ref. [24], the cooking residue is essential for the release of water and oil material while pressing its purpose is to remove the liquid portion of the material, which is subjected to centrifugation followed by  � ltration, giving rise to liquid and solid portion. The liquid portion, known as the press liquor is composed of water-soluble solids and crude oil. The solid portion, known as press cake is composed of wet solid and can be used as feedstock for the production of feed for cats. After the obtainment of oil the material was taken to a greenhouse at 60 7 10 C for 24 h for water excess removal. All analyses were performed in quadruplicate. The  � sh oil was assessed in what concerns to residue oil yield and content of free fatty acids (acid number). The yield of tilapia oil extracted after drying in the greenhouse and separation by centrifugation was calculated based on the relation between oil mass (m ) and residue mass (m ). It was expressed in percentage, as shown in Eq.  (1). 1

1

o

R ¼

r 

mo  100 % mr 

ð1Þ

in which R ¼ oil residue yield, in %, m ¼ oil mass, g, m ¼ residue mass, g. Average values obtained for  � sh residue oil yield were used to describe the potential for oil and biodiesel production from wastes generated from tilapia processing. The acid number assessment was performed according to the analytic norms of Ref.   [25]. In the analytical procedure, the samples were homogeneous and completely liquid. An amount of 2 g of sample were weighed into Erlenmeyer �ask. Was added 25 ml of ether-alcohol (2:1) neutral. Was added two drops of  o

r 

G. Iastiaque Martins et al. / Renewable and Sustainable Energy Reviews 42 (2015) 234 – 239

236

Fig. 1.  Fish residues: (A) heads, (B)  � ns, (C) skin, (D) scales and (E) viscera.

via base catalysis and followed the recommendation of Resolution No. 07 of the National Agency of Petroleum, Natural Gas and Biofuels [22], which determines the standards national the quality and recommends that the acid must have a limit of 0.50 mg KOH/g, to be turned into biodiesel. The statistical design used in the experiment was completely random with six treatments (heads, �ns, skin, scales, viscera and mix of all residues) and four replications for each treatment. Means were subjected to analysis of variance (ANOVA) and compared by Tukey’s test, at 5% of signi�cance.

3. Results and discussions

Fig. 2.  Pressing of cooked residues for oil extraction.

phenolphthalein indicator. Was titrated with a solution of 0.1 M sodium hydroxide, until the appearance of pink color, which persisted for 30 seconds. For the calculation of the acid number (IA), was used Eq. (2). IA

mg KOH g

¼ V   M   F  

56 11 m ;

ð2Þ

where IA ¼ acid number,  V ¼ volume (ml) of 0.1 M NaOH spent in the sample titration, M ¼ molarity of 0.1 M NaOH, F ¼ correction factor solution of sodium hydroxide 0.1 M, m ¼ mass (g) of the sample (oil). The methodology for the extraction of biodiesel from waste tilapia was performed according to the transesteri �cation process

Table 1 presents the mean values of tilapia oil content according to the type of residue processed. According to the results obtained the type of residue interfered in the oil content. Viscera presented the highest oil content (22.02%), differing statistically from the means of other treatments. Oil contents obtained from heads (9.23%) and mix of  residues (6.12%) did not differ statistically from each other. The lowest oil content was found in  � ns (4.33%). It was not possible to obtain oil after cooking and pressing scales (0.00%) and skin (0.00%). Based on these results one can observe that the mix of residues –   with oil yield of 6.12% –  presented a slightly inferior result to those of other studies found in the literature, what may be explained by the composition of the sampled mix, which must have presented a higher amount of skin, scales and �ns, which showed low oil yield. Authors such as Ref.   [23]   applied the technique of cooking and pressing for tilapia oil extraction (mix of residues) and obtained yield of 15%. While Ref.  [26] obtained a 11% extraction yield of oil from the �sh waste. Ref. [27] evaluating the oil viscera curimbata ( Prochilodus spp.), rainbow trout ( Oncorhynchus mykiss) and pacu (Piaractus mesopotamicus) obtained a yield of 13.75%, 27.58% and 42.53% oil, respectively in the processing of the �sh viscera. Ref.  [28] evaluated the oil from  Pangasius hypophthalmus and Pangasius bocourti   (Tra and Basa cat �sh) for the production of  biodiesel by transesteri�cation reaction by ultrasound. According to the authors, the  � sh oil present levels of unsaturated fatty acid of 57.97% and 64.17%, respectively for   Pangasius hypophthalmus and Pangasius bocourti and there was an increase in the conversion ef �ciency of 91.66% when the molar ratio methane/oil was 12/1. Still based on the results obtained,  � sh viscera are amenable to enzymatic activity, what favors the hydrolysis of triacylglycerol,

G. Iastiaque Martins et al. / Renewable and Sustainable Energy Reviews 42 (2015) 234 – 239  Table 1

Oil content according to the type of residue. Residues

Oil content (%)

C.V. (%)

M.S.D.

Viscera Heads Mix Fins Skin Scales

22.02 a 9.23 b 6.12 b 4.33 c 0.00 c 0.00 c

13.52 1.04 55.17 24.09 0.00 0.00

2.05 0.06 2.49 0.73 0.00 0.00

* Treatment means followed by the same letter do not differ from each other signi�cantly by Tukey’s test at 5% of signi �cance. C.V.: Coef �cient of Variation; M.S.D.: Minimum Signi �cant Difference.

 Table 2

Acidity of tilapia oil obtained from different residues. Residues

Acidity (mg KOH/g)

C.V. (%)

M.S.D.

Fins Heads Mix Viscera

0.10 a 0.10 a 0.86 b 2.67 c

15.12 10.87 45.68 5.25

0.010 0.008 0.276 0.107

*Treatment means followed by the same letter do not differ from each other signi�cantly by Tukey’s test at 5% of signi �cance. C.V.: Coef �cient of Variation; M.S.D.: Minimum Signi �cant Difference.

which releases fatty acids and elevates oil acidity   [12]. Thus, an alternative for the treatment of this oil would be a preliminary stage of sterilization in order to inactivate the endogenous enzymes present in the animal ’s stomach. The process normally occurs at room temperature with the homogenization of the material   [29,10,12]. It is applied for the obtainment of oils with lower acid values. One of the concerns related to the production of biodiesel from �sh waste is related to the quality of the oil produced, especially with regard to low-lubrication, higher viscosity, �ash point   [17], water content and high acidity  [30,12]. Table 2 presents mean values for the tilapia residue oil acidity. One can observe that there was no signi�cant difference in the acid number of oils obtained from  � ns (0.10 mg KOH/g) and heads (0.10 mg KOH/g), which differed signi�cantly from the acidity index of the mix of residues (0.86 mg KOH/g) and viscera (2.67 mg KOH/g), which presented signi�cant difference from each other. As the transesteri �cation reaction is directly in �uenced by oil quality and the maximum acidity established by Resolution 07 of  the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) [22] is 0.50 mg KOH/g, the oil extracted from heads and  � ns by transesteri �cation can be recommended with no need for neutralization, once the values found in this study are within these limits. However, oils obtained from tilapia viscera and mix of  residues presented high acid values, what required a neutralization process for the oil to go through transesteri �cation. Some authors found acidity values superior to those observed in this study, as those observed by Ref. [31], who veri �ed acidity of  5.8 mg KOH/g for tilapia oil under the process of cooking and pressing extraction. Other authors, such as Ref. [32] found results lower than the work, when studied marine  � sh species. Regarding oil extraction temperature, Ref.   [33]   veri �ed that crude tilapia oil presented higher acid values when extracted at high temperatures in comparison to oil extracted at low temperatures, obtained by means of pressing, which was 1.23 mg KOH/g, what indicates that the extraction at higher temperatures interferes in lipid fraction quality, due to the fact that �sh oils may easily suffer from oxidative deterioration, mainly when heated [34].

237

Biodiesel production from vegetal oil or animal fat may occur by transesteri�cation or acid esteri�cation. What process to apply will depend on how the oil is going to be used. Transesteri �cation is a process in which the triglycerides react with alcohol and form esters and glycerin [21]. Thus, one can observe that the extraction of oil contained in �sh residues, except for scales and skins –  which did not produce oil –  constitutes an alternative for biodiesel production once these residues are mostly discarded, what may contaminate soil, air and groundwater. It also represents an income complement for  � shermen and boosts the biofuel industry due to the low cost of  � sh oil. However, the remaining waste of scales and skin, after the extraction of tilapia oil can still be used as feedstock in the extraction of the collagen for the pharmaceutical and food industry [35],  and other by-products production chain of aquaculture, such as leather tanning for the furniture industry, clothing and crafts; composting;  � sh meal and silage [23]. Another important parameter related to biodiesel quality is the speci�c mass at 20 C, which is determined by the ratio between mass and volume of a substance at speci�c temperature and pressure, also called density. The aim of such parameter is to restrict the use of some feedstocks in biodiesel production because these characteristics have great in �uence on processes such as fuel injection and preparation for automatic ignition. So in order to estimate the extraction potential of tilapia oil it was necessary to take into account a research performed by Ref.  [36], in which the authors found speci�c mass of 914 kg m  3 for tilapia oil and the oil contents for each residue analyzed in this experiment. The transesteri �cation reaction by base catalysis of oils with high acidity was considered for estimating biodiesel production potential (Table 3). In this work, was found that per liter of tilapia waste oil from viscera was produced 0.9 l of biodiesel, as shown in Table 3. In Iran, [26]   working with extraction of oil from �sh waste for the production of biodiesel by transesteri�cation process, obtained similar values. A large amount of the �sh production ends up becoming industrial waste. The survival of the �sh industry is related to the ability of treating or �nding new functions for wastes. This search for new  � nalities not only meets the needs of consumption, but also new attitudes of consumption [32]. In that sense, one can observe that with the improvement in residue selection, extraction and processing it is possible to obtain quality oil that may be used as human or animal nourishment. Also, by neutralizing its acidity it can be used as feedstock in the production of biofuels, such as biodiesel. Checking the ef �ciency the biodiesel of tilapia in diesel engines, Ref.   [37]   compared the performance of an engine generator set with power of 7.36 kW (10 hp) coupled to a generator 5.0 kWe using biodiesel tilapia in the proportions of 100% biodiesel (B100), 20% biodiesel blended with petroleum diesel (B20) and pure mineral diesel (B0) and found that using 100% biodiesel tilapia (B100) engine generator showed higher performance when 1

 Table 3

Tilapia oil extraction potential and estimate biodiesel production according to each type of residue. Residues

Production capacity (l oil.ton residue  1)

Production capacity (l biodiesel.ton residue  1)

Viscera Heads Mix Fins

220.2 92.3 61.2 43.3

198.3 83.3 54.8 35.0

The estimate of the biodiesel production capacity (l oil.ton residue  1) was obtained by the proportion of oil content into each residue, showed in  Table 1.

G. Iastiaque Martins et al. / Renewable and Sustainable Energy Reviews 42 (2015) 234 – 239

238  Table 4

Total costs per liter of biodiesel for each feedstock. Products

U$ l  1 of biodiesela

Authors

Biodiesel of tallow Biodiesel of chicken Biodiesel of soybean Biodiesel of sun�ower

0.89 0.97 1.43 1.48

[36]

a

 

US$ 1 ¼ R$ 2.26.

compared to pure diesel (B0) and B20, reaching an ef �ciency of  21.6% at a loading of 2.6 kW, while the ef �ciency of B0 and B20 to the same load was 18%. According to the authors, lower speci�c fuel consumption (SFC) was obtained for B20 and B100 blend compared to pure diesel (B0). The B20 mixture (473.6 g kW  1) showed a reduction of 1.5% of SFC, when compared to B0 (480.9 g kW h  1). For B100 (457 g kW h  1) the reduction was 5%, when compared to B0. Ref.   [38]   evaluated the reuse of beef tallow for biodiesel production through methylic and ethylic routes and observed that the biodiesel samples when subjected to analyzes of density, viscosity, �ash point, acid number, water content, power heat and gas chromatography, showed results within the limits established by the ANP. The authors also comment that the ethyl biodiesel showed the greater potential for work generation in engines, increased security by presenting high  � ash point. Furthermore, biodiesel methyl demonstrated to be more resistant to oxidation and methyl route showed higher yield of biodiesel. Considering the relevance of the production costs of biodiesel compared to diesel, Ref.   [39]   assessed the cost of producing biodiesel from soybean, sun�ower, chicken and beef tallow relative to commercial diesel and found that overall the best value (variable costs þ �xed costs) per liter of biodiesel produced was obtained for biodiesel from tallow, followed by chicken, soybean and sun�ower, respectively (Table 4). According to the authors, the methodology showed that the costs go beyond the because of  production expenses, and procurement, because the consumption of each fuel is distinct, as has happened with gasoline and ethanol. 4. Conclusion

Higher oil yields were obtained with the use of tilapia viscera, which presented the highest biodiesel production potential among the residues studied. However, its acidity was not adequate for biodiesel production by means of transesteri �cation, the process neutralization is necessary improve for quality of acidity, whereas the other residues except the mix of residues showed adequate acid values. The oils extracted from the mix of residues, �ns and heads meet the requirements of the National Agency of Petroleum, Natural Gas and Biofuels (ANP), regarding oil acidity for biodiesel production. Higher capacity of producing biodiesel per ton of processed residues was obtained with the oil from viscera (217 l), followed by �sh heads (91 l) and mix of residues (60 l). References [1]   Conceição MM, Candeia RA, Dantas HJ, Soledade LEB, Fernandes Jr VJ, Souza AG. Rheological behavior of castor oil biodiesel. Energy Fuels 2005;19:2185 –8. [2]   Aranda DAG, Rosa LP, Oliveira LB, Costa AO, Pimenteira CAP, Mattos LBR, Henriques RM, Moreira JR. Geração de energia a partir de resíduos do lixo e óleos vegetais: Fontes Renováveis de Energia no Brasil. Rio de Janeiro: Interciência; 2003. [3]  Santos FFP, Malveira JQ, Cruz MGA, Fernandez FAN. Production of biodiesel by ultrasound assisted esteri�cation of   Oreochromis niloticus   oil. Fuel 2010;89 (2):275 –9.

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