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Potential application of Terminalia catappa L. and Carapa guianensis oils for biofuel production: Physical-chemical properties of neat vegetable oils, their methyl-esters and bio-oils (hydrocarbons)
Industrial Crops and Products 52 (2014) 95–98
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Industrial Crops and Products journal homepage: www.elsevier.com/locate/indcrop
Potential application of Terminalia catappa L. and Carapa guianensis oils for biofuel production: Physical-chemical properties of neat vegetable oils, their methyl-esters and bio-oils (hydrocarbons) Osvaldo K. Iha a , Flávio C.S.C. Alves a , Paulo A.Z. Suarez a,∗ , Cassia R.P. Silva b , Mario R. Meneghetti b , Simoni M.P. Meneghetti b,∗∗ a b
Laboratório de Materiais e Combustíveis, Instituto de Química, Universidade de Brasília, C.P. 4478, 70919-970 Brasília, DF, Brazil Grupo de Catálise e Reatividade Química, Instituto de Química e Biotecnologia, Universidade Federal de Alagoas, 57072-000 Maceió, AL, Brazil
a r t i c l e
i n f o
Article history: Received 16 June 2013 Received in revised form 30 September 2013 Accepted 3 October 2013 Keywords: Biodiesel Bio-oil Terminalia catappa L. Carapa guianensis Transesterification Thermal cracking
a b s t r a c t In this work, two different perennial tree species were studied as triacylglyceride sources for producing biofuels. These species grow wild in the Amazon and along the Brazilian coast and may be a good solution for oil production that does not rely on food sources or fossil fuels while encouraging preservation of the rain forest and seashore vegetation. Consequently, we studied the oils obtained from Terminalia catappa L. (TC) and Carapa guianensis (CG) to evaluate their characteristics and chemical composition. Furthermore, we produced biofuels from these oils and analyzed their physical-chemical properties. The physicalchemical properties of the TC and CG biodiesels make them acceptable for use in diesel engines showing a promising economic exploitation of these raw materials. The bio-oils obtained from TC and CG were not completely deoxygenated; however, their physical-chemical properties demonstrated the potential of these oils as acceptable renewable fuels for diesel engines. © 2013 Elsevier B.V. All rights reserved.
1. Introduction For environmental and economic reasons, Brazil and many other countries have decided to introduce biofuels to their energy matrix (Pousa et al., 2007; Suarez et al., 2006). It is important to note that these programs were designed to diversify not only the raw materials but also the technological approach to biofuel preparation. Indeed, the federal law introducing biodiesel to the Brazilian market defined it as any biofuel produced from a biological feedstock that could partially substitute fossil hydrocarbons in diesel engines (Pousa et al., 2007). Despite these initial objectives, the Brazilian National Petroleum, Natural Gas and Biofuels Regulatory Agency (ANP) has only allowed methyl and ethyl fatty acid esters to be commercially blended with fossil diesel (B5) after 8 years of program activity. The current biofuel industry in Brazil produces up to 2.4 billion liters of methyl fatty acid esters per year from soybean
∗ Corresponding author. ∗∗ Corresponding author. Tel.: ++55 82 3214 1703; fax: +55 82 3214 1384. E-mail addresses: [email protected] (P.A.Z. Suarez), [email protected] (S.M.P. Meneghetti). 0926-6690/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.indcrop.2013.10.001
(80%), beef tallow (15%) and cottonseed (5%) (ANP, 2013). Moreover, all biodiesel is produced via the alkaline transesterification of high grade fats and oils. For this reason, raw materials are currently responsible for up to 80% of biodiesel production costs (Suarez et al., 2009). Thus, more studies investigating alternative feedstocks, technological pathways, and renewable fuels are needed to diversify the biofuel industry and to avoid dependence on a few costly raw materials. Various approaches have already been proposed to identify alternative, less expensive sources of raw materials while also avoiding the dilemmas involving food, energy and the environment, such as using species of bushy-trees (Kumar and Sharma, 2008; de Oliveira et al., 2009), trees (Abreu et al., 2004; Santos et al., 2008; Sarin et al., 2010; Chakraborty and Baruah, 2012; Mangas et al., 2012) and palms (Abreu et al., 2004; Alves et al., 2010; Teixeira da Silva de La Salles et al., 2010). Furthermore, there are various reviews in the literature concerning the use of alternative feedstocks to biodiesel production (Kumar and Sharma, 2011; Pinzi and Pilar Dorado, 2012; Contran et al., 2013; Slade and Bauen, 2013). However, some of these fats and oils have a high acid content, which necessitates expensive purifying steps. Another possibility is to use alternative technological routes based on heterogeneous acid catalysts such as a combination of hydrolysis and esterification
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or esterification and transesterification (de Almeida et al., 2008; Dupont et al., 2009; Mendonc¸a et al., 2009; Alves et al., 2010; Brito et al., 2012). In addition, several studies have already been conducted by PETROBRAS and other research groups to obtain hydrocarbons and bio-oils via the thermal and catalytic cracking of fats and oils in the presence or absence of hydrogen (Suarez et al., 2009; Santos et al., 2010). In this approach, fats and oils are deoxygenated to produce a set of hydrocarbons, usually mixed with oxygenated compounds, that better resemble the chemistry of fossil diesel than the widely used fatty acid esters. It is well accepted in the literature that cracking fats and oils occurs in two steps. During the primary cracking, triacylglycerides decompose into two carboxylic acid molecules, cetene and acrolein. During the secondary cracking, these carboxylic acids are either decarboxylated to produce CO2 and a hydrocarbon or decarbonylated to produce water, CO and a hydrocarbon with a double bond. However, due to the high temperatures required, many side reactions involving the formed cetene, acrolein and hydrocarbons occur, thus forming a myriad of compounds (Santos et al., 2010). It is important to note that the physical-chemical properties of bio-oils (mainly hydrocarbons and oxygenated compounds) and biodiesel (methyl or ethyl fatty acid esters) obtained from the same raw material are quite different. Indeed, it was already published a comparison between the physical-chemical properties of biodiesel and bio-oil and their blends with diesel (Oliveira et al., 2006; Doll et al., 2008; Moser et al., 2009; Sharma et al., 2009). Indeed, a complete comparison between the heats of combustion, lubricity, density, kinematic viscosity, oxidation stability, low temperature properties and surface tensions of soybean biodiesel and bio-oil, as well as their blends with diesel, have been exhaustive studied and described. Concerning the energy content, it was shown that using the same raw-material bio-oil has more heat power than biodiesel (Oliveira et al., 2006), which is expected because of the lower oxygen content of the mixture of hydrocarbons than the mixture of methyl esters. In this context, investigating alternative triacylglyceride sources such as wild perennial tree species growing in the Brazilian rain forests or semiarid regions has become important for Brazilian researchers seeking biofuels that preserve natural vegetation. Terminalia catappa L. (TC), popularly known as “castanhola” in Brazil, and Carapa guianensis (CG), named “andiroba” in the Amazonia region, are considered examples of such species. The TC tree belongs to the Combretaceae family and has spread from its original region (Meridional Asia) to all tropical coastal environments (Cavalcante et al., 1986). This tree, which easily propagates from the seed, is tolerant of strong winds, salt sprays, and moderately high salinities in the root zone and grows with minimal maintenance along the entire Brazilian sea coast, where it is used for shade and ornamental purposes. Its fruits, which grow from November to March after 3 years of age, are ellipsoidal with coloration ranging from yellow to purple when ripe, and they contain a very hard kernel with an edible almond (Penna, 1946; Thomson and Evans, 2006). The CG tree belongs to the Meliaceae family and is native to the Amazonia and Central America (Lorenzi, 1992). This tree, which is propagated from seeds, grows wildly throughout the Brazilian rain forest. Its dry brown fruits, produced from January to May, feature a spherical capsule containing two to four seeds. The oil is extracted from these seeds for use in the cosmetics industry and by the local population as an insect repellent and for medicinal purposes. Therefore, we evaluated the characteristics and chemical composition of the oils obtained from TC and CG. Additionally, we produced biofuels from these oils and analyzed their physicalchemical properties.
2. Materials and methods 2.1. Materials CG oil was purchased in a popular market in the Brazilian Amazonian region (Ver o Peso market, Belem, PA, Brazil) and used as received. TC fruits were collected from trees growing on the Federal University of Alagoas Campus (Maceio, AL, Brazil). The isolated nuts were dried at 105 ◦ C for 24 h and then milled. The oil was extracted from the obtained flakes using n-hexane according to the official AOAC method 963.15 (A.O.A.C, 1976), and the oil content was also determined via this methodology. 2.2. Biodiesel preparation The TC and CG methyl esters were synthesized in a glass batch reactor equipped with a mechanical stirrer over two steps. First, the vegetable oil, methanol and sulfuric acid were gently refluxed for 2 h and then washed 3 times with 5% (mass%) sodium bicarbonate solution. Thus, the biodiesel/oil phase dissolved in the hexane, which was dried over magnesium sulfate for 2 h and filtered before removing the volatiles under vacuum. In the second step, the obtained biodiesel/oil phases were mixed with a solution of potassium hydroxide in methanol with magnetic stirring for 2 h at room temperature. The mixture was then allowed to stand until two phases were obtained (one containing fatty acid methyl esters and the other containing glycerin, potassium hydroxide and methanol). The excess methanol in the methyl ester phase was removed using a rotary evaporator at 70 ◦ C. The methyl ester was then washed once with phosphoric acid (5%, v/v) and thrice with brine, dissolved in hexane, dried over magnesium sulfate for 2 h, and filtered; then, the volatiles were removed under vacuum. The second step was repeated two more times until a methyl ester purity of greater than 98 mass% was detected by HPLC using the method described elsewhere (Carvalho et al., 2012). The methyl esters were stored in amber flasks in a freezer. 2.3. Bio-oil preparation The TC and CG oils (175 g) were pyrolyzed in a three-necked flask connected to a condenser. The oil was heated to 400 ◦ C (as measured using thermocouples throughout the reaction) when vapors formed and were condensed to obtain a two-phase system (an aqueous phase and a bio-oil). The bio-oil yields were approximately 60%. 2.4. Oil and biofuels characterization The vegetable oils were analyzed using the methods described by the Association of Official Analytical Chemists (AOAC, reapproved 1997). The biodiesel samples were analyzed via the standard methods indicated by the ANP for such biofuels (ANP, 2012). The bio-oils were analyzed according to the recommendations of the ANP for fossil diesel oil (ANP, 2010). The calorific values were evaluated using a Parr 1241 calorimetric bomb with an oxygen pressure of 3.0 Mega Pascals (Mpa). The fatty acid compositions of the oils were determined via gas chromatography (GC) using the official AOCS methods Ce 1-62 and Ce 2-26 (A.O.C.S., 1998). The bio-oil compositions were determined via gas chromatography (GC–MS) using a Shimadzu GC-17A chromatograph equipped with a mass spectrometer detector (Shimadzu GCMS-QP5050) and polydimethylsiloxane column (CBPI PONA-M50-042; 50 m, 0.15 mm i.d., and film thickness of 0.42 m) in the temperature range of 80–180 ◦ C, with a heating rate of 10 ◦ C/min. The peak identifications were made using a software library (Wiley Library CLASS-5000, 6th edition) and required over 95% similarity. The
O.K. Iha et al. / Industrial Crops and Products 52 (2014) 95–98 Table 1 Fatty acid composition of the TC and CG oils. Fatty acid
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Table 3 Physical-chemical properties of the bio-oils obtained from TC and CG oils. TC
CG
C14:0 (myristic acid) C16:0 (palmitic acid) C16:1 cis 9 (palmitoleic acid) C18:0 (estearic acid) C18:1 (oleic acid) C18:2 cis/cis 9,12 (linoleic acid) C18:3 cis/cis/cis 9,12,15 (linolenic acid)
0.1 28.3 0.9 4.9 30.0 32.8 1.7
0.5 25.3 – 10.5 57.8 5.9
Saturated chains (%) Mono-unsaturated chains (%) Poly-unsaturated chains (%)
34.2 30 34.5
36.3 57.8 5.9
Analysis 2
−1
Viscosity (mm s ) Flash point (◦ C) Acidity (mg KOH/g oil) Density at 20 ◦ C (g m−3 ) Cold filter plugging point (◦ C) Carbon Residue (%) Heat of combustion (MJ kg−1 ) Automatic distillation (◦ C) 10% 50% 90% Copper corrosion
TC
CG
Standard methoda
5.5 29 150.9 871 30 0.3 41
4.9 66 143.2 864 22 0.7 38
ASTM D445 ASTM D93 AOCS CD 3d-63 NBR 7148 ASTM 6371 ASTM D189 ASTM D240
218 329 326 1a
106 283 348 1a
ASTM D613
ASTM D130
a
Methods follow the specifications of the Brazilian National Petroleum Agency (ANP, 2010).
results of Table 1 are supported with literature data using additional column.
The transesterification of triglycerides using basic or acidic catalysts is well established in the literature. Basic catalysts are widely preferred because of their lower corrosivity and higher efficacy; however, such catalytic systems must be avoided for triglycerides containing high amounts of free fatty acids because soap formation consumes the alkaline catalyst, which generates an emulsion (Mittelbach and Tritthart, 1988). Because of their high acid value, two steps were used to obtain methyl esters from TC and CG: (i) an acid-catalyzed esterification, followed by (ii) a base-catalyzed transesterification, as proposed for acidic stocks over 50 years ago (Keim, 1945). Due to its higher acidity, the esterification of CG was performed twice to decrease the acidity to a suitable level for the alkaline transesterification, while only one esterification was required for TC. Three transesterification steps using potassium hydroxide were sequentially performed. As a result, biodiesels containing fatty acid methyl esters with over 99% purity were obtained. To the best of our knowledge, there are only a few reports on the use of TC and CG to produce biodiesel (Abreu et al., 2004; Santos et al., 2008). Table 2 summarizes the physical-chemical properties of the TC and CG biodiesels. With the exception of the oxidative stability of the TC biodiesel, the determined properties of both biofuels match the standard values usually obtained for biodiesels from raw materials with conventional fatty acid compositions, such as canola, linseed and sunflower oils (Lang et al., 2001).The notable difference in the oxidative stability of the TC and CG biodiesels is directly related to the difference in their degree of unsaturation. Soybean oil, which has a similar composition to TC, also exhibits a low oxidative stability and requires antioxidant additives to meet international specifications. According to the GC–MS analysis, the thermal cracking of both TC and CG oils leads to similar, complex mixtures of over 500 hydrocarbons and oxygenated compounds, mainly aliphatic olefins, paraffins and carboxylic acids with both short and long chains. As a result, similar physical-chemical properties were obtained for the two mixtures, as shown in Table 3. It is important to note that high acidities were observed, in agreement with the GC–MS
3. Results and discussion 3.1. Characteristics of TC and CG TC kernel oil content was found to be 50 mass%, which is higher than the value generally reported for soybean, cottonseed and other commercial oil sources and implies that processing this seed into oil would be economical. As described in the experimental section, the CG oil was directly acquired from a popular market, and the seed oil content was not determined in this work. However, the literature has found CG seeds to contain up to 45% oil, which is also generally higher than common sources (Cabral et al., 2013). The composition of the fatty acids from these oils is summarized in Table 1. As shown in Table 1, these oils have nearly the same saturated content (approximately 30%) and primarily have 16 carbons. Furthermore, CG contains almost entirely monounsaturated chains, while TC has a nearly even mix of mono- and di-unsaturated chains. The fatty acid compositions of the TC and CG oils studied in this work differ slightly from those published in the literature (Santos et al., 2008; Cabral et al., 2013), which is most likely due to variations in farming conditions such as weather, soil and seed variety. Table 2 summarizes the physical-chemical properties of the TC and CG oils and their derived biodiesels. A few of these oil properties were available in the literature (Santos et al., 2008; Cabral et al., 2013) and differ slightly from those found in this work because of small variations in the fatty acid content of the oils. The physical-chemical properties of these oils agreed with the values expected for materials with their fatty acid composition. High acid contents were observed for both CG (36.1 mg KOH g−1 ) and TC (10.5 mg KOH g−1 ), which may be related to their wild origin (differing degrees of maturation) and storage conditions. It is noteworthy that the oil content and acid values could be improved via plant breeding and proper farm system development. Table 2 Physical-chemical properties if the TC and CG oils and biodiesels. TC
CG
Analysis
Oil
Methylic biodiesel
Oil
Methylic biodiesel
Specificationsa
Standard methoda
Viscosity (mm2 s−1 ) Acidity (mg KOH/g oil) Density at 20 ◦ C (g m−3 ) Cold filter plugging point (◦ C) Heat of combustion (MJ kg−1 ) Oxidative stability (h) Copper corrosion
36.8 10.5 913 – 38.0
4.3 0.5 879 12 38.5 2.1 1a
38.4 36.1 915b – 37.6 2.8 1a
4.6 <0.5 875 0 39.1 6.7 1a
3.0–6.0 0.5 max 850–900 7 max – 6.0 min 1a
ASTM D445 AOCS CD 3d-63 NBR 7148 ASTM 6371 ASTM D240
a b
1a
Methods and specifications in accordance with specifications by the Brazilian National Petroleum Agency (ANP, 2012). Due to its low melting point, the density had to be determined at 25 ◦ C in order to guarantee the homogeneity of the sample.
ASTM D130
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results, indicating that the secondary cracking steps were inefficient at completely deoxygenating the carboxylic acids formed during the primary cracking. This problem may be solved by simply using a Lewis acid catalyst (Quirino et al., 2009) or hydrogen associated with a noble catalyst (Suarez et al., 2009). In contrast, the other physical-chemical properties demonstrate the high potential to obtain a suitable mixture of these bio-oils for use in diesel engines. A secondary cracking in the presence of a catalyst may be sufficient to improve their quality as renewable diesels. 4. Conclusions In summary, we studied two different perennial tree species as triacylglyceride sources for biofuel production. These two species grow wild in the Amazon and on the Brazilian coast, making them an elegant solution for producing oils while avoiding dilemmas related to food and fuel and helping preserve the rain forest and seashore vegetation. The high acid contents of the crude vegetable oils made the use of acid esterification steps imperative to avoid the formation of soaps and stable emulsions. Because of their fatty acid composition, TC may be classified as semi-drying, like soybean oil, and CG may be classified as non-drying, like canola oil (Bailey et al., 1979). The studied physical-chemical properties of the TC and CG biodiesels make them acceptable for use in diesel engines, which demonstrates the promising economic possibilities of these raw materials. The bio-oils of both TC and CG were incompletely deoxygenated; however, their physical-chemical properties showed potential for producing renewable fuels acceptable for diesel engines. Further studies are needed to achieve complete deoxygenation and improve the properties of these compounds. Acknowledgements Financial support from various Brazilian research funding agencies, such as the Research and Projects Financing (FINEP), National Counsel of Technological and Scientific Development (CNPq), Brazilian Federal Agency for the Support and Evaluation of Graduate Education (CAPES), Banco do Brasil Foundation (FBB), Federal District Research Support Foundation (FAPDF) and Alagoas Research Support Foundation (FAPEAL), are gratefully acknowledged. OKH, FCSCA, PAZS, MRM and SMPM thank CNPq for their research fellowships. CRPS thanks CAPES for a fellowship. The authors are indebted to CAPES for the PROCAD NF project (735/2010) that allowed the mobilization of researchers and students during this work. References Abreu, F.R., Lima, D.G., Hamú, E.H., Wolf, C.R., Suarez, P.A.Z., 2004. Utilization of metal complexes as catalysts in the transesterification of Brazilian vegetable oils with different alcohols. J. Mol. Catal. A Chem. 209, 29–33. Alves, M.B., Medeiros, F.C.M., Suarez, P.A.Z., 2010. Cadmium compounds as catalysts for biodiesel production. Ind. Eng. Chem. Res. 49, 7176–7182. ANP – National Agency of Petroleum, Natural Gas and Biofuel, Ministry of Mines and Energy, http://www.anp.gov.br/?id=472 (accessed 29.05.13). ANP – RESOLUC¸ÃO ANP N◦ 14, DE 11.5.2012 – DOU 18.5.2012. ANP – RESOLUC¸ÃO ANP N◦ 42, DE 16.12.2009 – DOU 17.12.2009 – RETIFICADA DOU 14.1.2010. Bailey, A.E., Swern, D., Formo, M.W., 1979. Bailey’s Industrial Oil and Fat Products, Volume 1, Edible Oil and Fat Products: Chemistry, Properties, and Health Effects, 6th ed. Wiley-Interscience, New York, USA. A.O.A.C., 1976. Association of Official Analytical Chemist: Method 963.15, Official Methods of Analysis, Washington, D.C.A.O.C.S., 1998. Official Methods and Recommended Practices of the AOCS, 5th edn. AOCS Press, Champaign.Brito, Y.C., Ferreira, D.A.C., Fragoso, D.M.A., Mendes, P.R., de Oliveira, C.M.J., Meneghetti, M.R., Meneghetti, S.M.P., 2012. Simultaneous conversion of triacylglycerides and fatty acids into fatty acid methyl esters using organometallic tin(IV) compounds as catalysts. Appl. Catal. A 443–444, 202–206. Cabral, E.C., da Cruz, G.F., Simas, R.C., Sanvido,.B., Gonc¸alves, L.V., Leal, R.V.P., da Silva, R.C.F., da Silva, J.C.T., Barata, L.E.S., da Cunha, V.S., de Franc¸a, L.F., Daroda, R.J., Sá, G.F., Eberlin, M.N., 2013. Typification and quality control of the Andiroba
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Industrial Crops and Products journal homepage: www.elsevier.com/locate/indcrop
Potential application of Terminalia catappa L. and Carapa guianensis oils for biofuel production: Physical-chemical properties of neat vegetable oils, their methyl-esters and bio-oils (hydrocarbons) Osvaldo K. Iha a , Flávio C.S.C. Alves a , Paulo A.Z. Suarez a,∗ , Cassia R.P. Silva b , Mario R. Meneghetti b , Simoni M.P. Meneghetti b,∗∗ a b
Laboratório de Materiais e Combustíveis, Instituto de Química, Universidade de Brasília, C.P. 4478, 70919-970 Brasília, DF, Brazil Grupo de Catálise e Reatividade Química, Instituto de Química e Biotecnologia, Universidade Federal de Alagoas, 57072-000 Maceió, AL, Brazil
a r t i c l e
i n f o
Article history: Received 16 June 2013 Received in revised form 30 September 2013 Accepted 3 October 2013 Keywords: Biodiesel Bio-oil Terminalia catappa L. Carapa guianensis Transesterification Thermal cracking
a b s t r a c t In this work, two different perennial tree species were studied as triacylglyceride sources for producing biofuels. These species grow wild in the Amazon and along the Brazilian coast and may be a good solution for oil production that does not rely on food sources or fossil fuels while encouraging preservation of the rain forest and seashore vegetation. Consequently, we studied the oils obtained from Terminalia catappa L. (TC) and Carapa guianensis (CG) to evaluate their characteristics and chemical composition. Furthermore, we produced biofuels from these oils and analyzed their physical-chemical properties. The physicalchemical properties of the TC and CG biodiesels make them acceptable for use in diesel engines showing a promising economic exploitation of these raw materials. The bio-oils obtained from TC and CG were not completely deoxygenated; however, their physical-chemical properties demonstrated the potential of these oils as acceptable renewable fuels for diesel engines. © 2013 Elsevier B.V. All rights reserved.
1. Introduction For environmental and economic reasons, Brazil and many other countries have decided to introduce biofuels to their energy matrix (Pousa et al., 2007; Suarez et al., 2006). It is important to note that these programs were designed to diversify not only the raw materials but also the technological approach to biofuel preparation. Indeed, the federal law introducing biodiesel to the Brazilian market defined it as any biofuel produced from a biological feedstock that could partially substitute fossil hydrocarbons in diesel engines (Pousa et al., 2007). Despite these initial objectives, the Brazilian National Petroleum, Natural Gas and Biofuels Regulatory Agency (ANP) has only allowed methyl and ethyl fatty acid esters to be commercially blended with fossil diesel (B5) after 8 years of program activity. The current biofuel industry in Brazil produces up to 2.4 billion liters of methyl fatty acid esters per year from soybean
∗ Corresponding author. ∗∗ Corresponding author. Tel.: ++55 82 3214 1703; fax: +55 82 3214 1384. E-mail addresses: [email protected] (P.A.Z. Suarez), [email protected] (S.M.P. Meneghetti). 0926-6690/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.indcrop.2013.10.001
(80%), beef tallow (15%) and cottonseed (5%) (ANP, 2013). Moreover, all biodiesel is produced via the alkaline transesterification of high grade fats and oils. For this reason, raw materials are currently responsible for up to 80% of biodiesel production costs (Suarez et al., 2009). Thus, more studies investigating alternative feedstocks, technological pathways, and renewable fuels are needed to diversify the biofuel industry and to avoid dependence on a few costly raw materials. Various approaches have already been proposed to identify alternative, less expensive sources of raw materials while also avoiding the dilemmas involving food, energy and the environment, such as using species of bushy-trees (Kumar and Sharma, 2008; de Oliveira et al., 2009), trees (Abreu et al., 2004; Santos et al., 2008; Sarin et al., 2010; Chakraborty and Baruah, 2012; Mangas et al., 2012) and palms (Abreu et al., 2004; Alves et al., 2010; Teixeira da Silva de La Salles et al., 2010). Furthermore, there are various reviews in the literature concerning the use of alternative feedstocks to biodiesel production (Kumar and Sharma, 2011; Pinzi and Pilar Dorado, 2012; Contran et al., 2013; Slade and Bauen, 2013). However, some of these fats and oils have a high acid content, which necessitates expensive purifying steps. Another possibility is to use alternative technological routes based on heterogeneous acid catalysts such as a combination of hydrolysis and esterification
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or esterification and transesterification (de Almeida et al., 2008; Dupont et al., 2009; Mendonc¸a et al., 2009; Alves et al., 2010; Brito et al., 2012). In addition, several studies have already been conducted by PETROBRAS and other research groups to obtain hydrocarbons and bio-oils via the thermal and catalytic cracking of fats and oils in the presence or absence of hydrogen (Suarez et al., 2009; Santos et al., 2010). In this approach, fats and oils are deoxygenated to produce a set of hydrocarbons, usually mixed with oxygenated compounds, that better resemble the chemistry of fossil diesel than the widely used fatty acid esters. It is well accepted in the literature that cracking fats and oils occurs in two steps. During the primary cracking, triacylglycerides decompose into two carboxylic acid molecules, cetene and acrolein. During the secondary cracking, these carboxylic acids are either decarboxylated to produce CO2 and a hydrocarbon or decarbonylated to produce water, CO and a hydrocarbon with a double bond. However, due to the high temperatures required, many side reactions involving the formed cetene, acrolein and hydrocarbons occur, thus forming a myriad of compounds (Santos et al., 2010). It is important to note that the physical-chemical properties of bio-oils (mainly hydrocarbons and oxygenated compounds) and biodiesel (methyl or ethyl fatty acid esters) obtained from the same raw material are quite different. Indeed, it was already published a comparison between the physical-chemical properties of biodiesel and bio-oil and their blends with diesel (Oliveira et al., 2006; Doll et al., 2008; Moser et al., 2009; Sharma et al., 2009). Indeed, a complete comparison between the heats of combustion, lubricity, density, kinematic viscosity, oxidation stability, low temperature properties and surface tensions of soybean biodiesel and bio-oil, as well as their blends with diesel, have been exhaustive studied and described. Concerning the energy content, it was shown that using the same raw-material bio-oil has more heat power than biodiesel (Oliveira et al., 2006), which is expected because of the lower oxygen content of the mixture of hydrocarbons than the mixture of methyl esters. In this context, investigating alternative triacylglyceride sources such as wild perennial tree species growing in the Brazilian rain forests or semiarid regions has become important for Brazilian researchers seeking biofuels that preserve natural vegetation. Terminalia catappa L. (TC), popularly known as “castanhola” in Brazil, and Carapa guianensis (CG), named “andiroba” in the Amazonia region, are considered examples of such species. The TC tree belongs to the Combretaceae family and has spread from its original region (Meridional Asia) to all tropical coastal environments (Cavalcante et al., 1986). This tree, which easily propagates from the seed, is tolerant of strong winds, salt sprays, and moderately high salinities in the root zone and grows with minimal maintenance along the entire Brazilian sea coast, where it is used for shade and ornamental purposes. Its fruits, which grow from November to March after 3 years of age, are ellipsoidal with coloration ranging from yellow to purple when ripe, and they contain a very hard kernel with an edible almond (Penna, 1946; Thomson and Evans, 2006). The CG tree belongs to the Meliaceae family and is native to the Amazonia and Central America (Lorenzi, 1992). This tree, which is propagated from seeds, grows wildly throughout the Brazilian rain forest. Its dry brown fruits, produced from January to May, feature a spherical capsule containing two to four seeds. The oil is extracted from these seeds for use in the cosmetics industry and by the local population as an insect repellent and for medicinal purposes. Therefore, we evaluated the characteristics and chemical composition of the oils obtained from TC and CG. Additionally, we produced biofuels from these oils and analyzed their physicalchemical properties.
2. Materials and methods 2.1. Materials CG oil was purchased in a popular market in the Brazilian Amazonian region (Ver o Peso market, Belem, PA, Brazil) and used as received. TC fruits were collected from trees growing on the Federal University of Alagoas Campus (Maceio, AL, Brazil). The isolated nuts were dried at 105 ◦ C for 24 h and then milled. The oil was extracted from the obtained flakes using n-hexane according to the official AOAC method 963.15 (A.O.A.C, 1976), and the oil content was also determined via this methodology. 2.2. Biodiesel preparation The TC and CG methyl esters were synthesized in a glass batch reactor equipped with a mechanical stirrer over two steps. First, the vegetable oil, methanol and sulfuric acid were gently refluxed for 2 h and then washed 3 times with 5% (mass%) sodium bicarbonate solution. Thus, the biodiesel/oil phase dissolved in the hexane, which was dried over magnesium sulfate for 2 h and filtered before removing the volatiles under vacuum. In the second step, the obtained biodiesel/oil phases were mixed with a solution of potassium hydroxide in methanol with magnetic stirring for 2 h at room temperature. The mixture was then allowed to stand until two phases were obtained (one containing fatty acid methyl esters and the other containing glycerin, potassium hydroxide and methanol). The excess methanol in the methyl ester phase was removed using a rotary evaporator at 70 ◦ C. The methyl ester was then washed once with phosphoric acid (5%, v/v) and thrice with brine, dissolved in hexane, dried over magnesium sulfate for 2 h, and filtered; then, the volatiles were removed under vacuum. The second step was repeated two more times until a methyl ester purity of greater than 98 mass% was detected by HPLC using the method described elsewhere (Carvalho et al., 2012). The methyl esters were stored in amber flasks in a freezer. 2.3. Bio-oil preparation The TC and CG oils (175 g) were pyrolyzed in a three-necked flask connected to a condenser. The oil was heated to 400 ◦ C (as measured using thermocouples throughout the reaction) when vapors formed and were condensed to obtain a two-phase system (an aqueous phase and a bio-oil). The bio-oil yields were approximately 60%. 2.4. Oil and biofuels characterization The vegetable oils were analyzed using the methods described by the Association of Official Analytical Chemists (AOAC, reapproved 1997). The biodiesel samples were analyzed via the standard methods indicated by the ANP for such biofuels (ANP, 2012). The bio-oils were analyzed according to the recommendations of the ANP for fossil diesel oil (ANP, 2010). The calorific values were evaluated using a Parr 1241 calorimetric bomb with an oxygen pressure of 3.0 Mega Pascals (Mpa). The fatty acid compositions of the oils were determined via gas chromatography (GC) using the official AOCS methods Ce 1-62 and Ce 2-26 (A.O.C.S., 1998). The bio-oil compositions were determined via gas chromatography (GC–MS) using a Shimadzu GC-17A chromatograph equipped with a mass spectrometer detector (Shimadzu GCMS-QP5050) and polydimethylsiloxane column (CBPI PONA-M50-042; 50 m, 0.15 mm i.d., and film thickness of 0.42 m) in the temperature range of 80–180 ◦ C, with a heating rate of 10 ◦ C/min. The peak identifications were made using a software library (Wiley Library CLASS-5000, 6th edition) and required over 95% similarity. The
O.K. Iha et al. / Industrial Crops and Products 52 (2014) 95–98 Table 1 Fatty acid composition of the TC and CG oils. Fatty acid
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Table 3 Physical-chemical properties of the bio-oils obtained from TC and CG oils. TC
CG
C14:0 (myristic acid) C16:0 (palmitic acid) C16:1 cis 9 (palmitoleic acid) C18:0 (estearic acid) C18:1 (oleic acid) C18:2 cis/cis 9,12 (linoleic acid) C18:3 cis/cis/cis 9,12,15 (linolenic acid)
0.1 28.3 0.9 4.9 30.0 32.8 1.7
0.5 25.3 – 10.5 57.8 5.9
Saturated chains (%) Mono-unsaturated chains (%) Poly-unsaturated chains (%)
34.2 30 34.5
36.3 57.8 5.9
Analysis 2
−1
Viscosity (mm s ) Flash point (◦ C) Acidity (mg KOH/g oil) Density at 20 ◦ C (g m−3 ) Cold filter plugging point (◦ C) Carbon Residue (%) Heat of combustion (MJ kg−1 ) Automatic distillation (◦ C) 10% 50% 90% Copper corrosion
TC
CG
Standard methoda
5.5 29 150.9 871 30 0.3 41
4.9 66 143.2 864 22 0.7 38
ASTM D445 ASTM D93 AOCS CD 3d-63 NBR 7148 ASTM 6371 ASTM D189 ASTM D240
218 329 326 1a
106 283 348 1a
ASTM D613
ASTM D130
a
Methods follow the specifications of the Brazilian National Petroleum Agency (ANP, 2010).
results of Table 1 are supported with literature data using additional column.
The transesterification of triglycerides using basic or acidic catalysts is well established in the literature. Basic catalysts are widely preferred because of their lower corrosivity and higher efficacy; however, such catalytic systems must be avoided for triglycerides containing high amounts of free fatty acids because soap formation consumes the alkaline catalyst, which generates an emulsion (Mittelbach and Tritthart, 1988). Because of their high acid value, two steps were used to obtain methyl esters from TC and CG: (i) an acid-catalyzed esterification, followed by (ii) a base-catalyzed transesterification, as proposed for acidic stocks over 50 years ago (Keim, 1945). Due to its higher acidity, the esterification of CG was performed twice to decrease the acidity to a suitable level for the alkaline transesterification, while only one esterification was required for TC. Three transesterification steps using potassium hydroxide were sequentially performed. As a result, biodiesels containing fatty acid methyl esters with over 99% purity were obtained. To the best of our knowledge, there are only a few reports on the use of TC and CG to produce biodiesel (Abreu et al., 2004; Santos et al., 2008). Table 2 summarizes the physical-chemical properties of the TC and CG biodiesels. With the exception of the oxidative stability of the TC biodiesel, the determined properties of both biofuels match the standard values usually obtained for biodiesels from raw materials with conventional fatty acid compositions, such as canola, linseed and sunflower oils (Lang et al., 2001).The notable difference in the oxidative stability of the TC and CG biodiesels is directly related to the difference in their degree of unsaturation. Soybean oil, which has a similar composition to TC, also exhibits a low oxidative stability and requires antioxidant additives to meet international specifications. According to the GC–MS analysis, the thermal cracking of both TC and CG oils leads to similar, complex mixtures of over 500 hydrocarbons and oxygenated compounds, mainly aliphatic olefins, paraffins and carboxylic acids with both short and long chains. As a result, similar physical-chemical properties were obtained for the two mixtures, as shown in Table 3. It is important to note that high acidities were observed, in agreement with the GC–MS
3. Results and discussion 3.1. Characteristics of TC and CG TC kernel oil content was found to be 50 mass%, which is higher than the value generally reported for soybean, cottonseed and other commercial oil sources and implies that processing this seed into oil would be economical. As described in the experimental section, the CG oil was directly acquired from a popular market, and the seed oil content was not determined in this work. However, the literature has found CG seeds to contain up to 45% oil, which is also generally higher than common sources (Cabral et al., 2013). The composition of the fatty acids from these oils is summarized in Table 1. As shown in Table 1, these oils have nearly the same saturated content (approximately 30%) and primarily have 16 carbons. Furthermore, CG contains almost entirely monounsaturated chains, while TC has a nearly even mix of mono- and di-unsaturated chains. The fatty acid compositions of the TC and CG oils studied in this work differ slightly from those published in the literature (Santos et al., 2008; Cabral et al., 2013), which is most likely due to variations in farming conditions such as weather, soil and seed variety. Table 2 summarizes the physical-chemical properties of the TC and CG oils and their derived biodiesels. A few of these oil properties were available in the literature (Santos et al., 2008; Cabral et al., 2013) and differ slightly from those found in this work because of small variations in the fatty acid content of the oils. The physical-chemical properties of these oils agreed with the values expected for materials with their fatty acid composition. High acid contents were observed for both CG (36.1 mg KOH g−1 ) and TC (10.5 mg KOH g−1 ), which may be related to their wild origin (differing degrees of maturation) and storage conditions. It is noteworthy that the oil content and acid values could be improved via plant breeding and proper farm system development. Table 2 Physical-chemical properties if the TC and CG oils and biodiesels. TC
CG
Analysis
Oil
Methylic biodiesel
Oil
Methylic biodiesel
Specificationsa
Standard methoda
Viscosity (mm2 s−1 ) Acidity (mg KOH/g oil) Density at 20 ◦ C (g m−3 ) Cold filter plugging point (◦ C) Heat of combustion (MJ kg−1 ) Oxidative stability (h) Copper corrosion
36.8 10.5 913 – 38.0
4.3 0.5 879 12 38.5 2.1 1a
38.4 36.1 915b – 37.6 2.8 1a
4.6 <0.5 875 0 39.1 6.7 1a
3.0–6.0 0.5 max 850–900 7 max – 6.0 min 1a
ASTM D445 AOCS CD 3d-63 NBR 7148 ASTM 6371 ASTM D240
a b
1a
Methods and specifications in accordance with specifications by the Brazilian National Petroleum Agency (ANP, 2012). Due to its low melting point, the density had to be determined at 25 ◦ C in order to guarantee the homogeneity of the sample.
ASTM D130
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results, indicating that the secondary cracking steps were inefficient at completely deoxygenating the carboxylic acids formed during the primary cracking. This problem may be solved by simply using a Lewis acid catalyst (Quirino et al., 2009) or hydrogen associated with a noble catalyst (Suarez et al., 2009). In contrast, the other physical-chemical properties demonstrate the high potential to obtain a suitable mixture of these bio-oils for use in diesel engines. A secondary cracking in the presence of a catalyst may be sufficient to improve their quality as renewable diesels. 4. Conclusions In summary, we studied two different perennial tree species as triacylglyceride sources for biofuel production. These two species grow wild in the Amazon and on the Brazilian coast, making them an elegant solution for producing oils while avoiding dilemmas related to food and fuel and helping preserve the rain forest and seashore vegetation. The high acid contents of the crude vegetable oils made the use of acid esterification steps imperative to avoid the formation of soaps and stable emulsions. Because of their fatty acid composition, TC may be classified as semi-drying, like soybean oil, and CG may be classified as non-drying, like canola oil (Bailey et al., 1979). The studied physical-chemical properties of the TC and CG biodiesels make them acceptable for use in diesel engines, which demonstrates the promising economic possibilities of these raw materials. The bio-oils of both TC and CG were incompletely deoxygenated; however, their physical-chemical properties showed potential for producing renewable fuels acceptable for diesel engines. Further studies are needed to achieve complete deoxygenation and improve the properties of these compounds. Acknowledgements Financial support from various Brazilian research funding agencies, such as the Research and Projects Financing (FINEP), National Counsel of Technological and Scientific Development (CNPq), Brazilian Federal Agency for the Support and Evaluation of Graduate Education (CAPES), Banco do Brasil Foundation (FBB), Federal District Research Support Foundation (FAPDF) and Alagoas Research Support Foundation (FAPEAL), are gratefully acknowledged. OKH, FCSCA, PAZS, MRM and SMPM thank CNPq for their research fellowships. CRPS thanks CAPES for a fellowship. The authors are indebted to CAPES for the PROCAD NF project (735/2010) that allowed the mobilization of researchers and students during this work. References Abreu, F.R., Lima, D.G., Hamú, E.H., Wolf, C.R., Suarez, P.A.Z., 2004. Utilization of metal complexes as catalysts in the transesterification of Brazilian vegetable oils with different alcohols. J. Mol. Catal. A Chem. 209, 29–33. Alves, M.B., Medeiros, F.C.M., Suarez, P.A.Z., 2010. Cadmium compounds as catalysts for biodiesel production. Ind. Eng. Chem. Res. 49, 7176–7182. ANP – National Agency of Petroleum, Natural Gas and Biofuel, Ministry of Mines and Energy, http://www.anp.gov.br/?id=472 (accessed 29.05.13). ANP – RESOLUC¸ÃO ANP N◦ 14, DE 11.5.2012 – DOU 18.5.2012. ANP – RESOLUC¸ÃO ANP N◦ 42, DE 16.12.2009 – DOU 17.12.2009 – RETIFICADA DOU 14.1.2010. Bailey, A.E., Swern, D., Formo, M.W., 1979. Bailey’s Industrial Oil and Fat Products, Volume 1, Edible Oil and Fat Products: Chemistry, Properties, and Health Effects, 6th ed. Wiley-Interscience, New York, USA. A.O.A.C., 1976. Association of Official Analytical Chemist: Method 963.15, Official Methods of Analysis, Washington, D.C.A.O.C.S., 1998. Official Methods and Recommended Practices of the AOCS, 5th edn. AOCS Press, Champaign.Brito, Y.C., Ferreira, D.A.C., Fragoso, D.M.A., Mendes, P.R., de Oliveira, C.M.J., Meneghetti, M.R., Meneghetti, S.M.P., 2012. Simultaneous conversion of triacylglycerides and fatty acids into fatty acid methyl esters using organometallic tin(IV) compounds as catalysts. Appl. Catal. A 443–444, 202–206. Cabral, E.C., da Cruz, G.F., Simas, R.C., Sanvido,.B., Gonc¸alves, L.V., Leal, R.V.P., da Silva, R.C.F., da Silva, J.C.T., Barata, L.E.S., da Cunha, V.S., de Franc¸a, L.F., Daroda, R.J., Sá, G.F., Eberlin, M.N., 2013. Typification and quality control of the Andiroba
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