IBP1987_12 OIL OKRA: ALTERNATIVE SOURCE FOR BIODIESEL PRODUCTION OF HIGH OXIDATIVE STABILITY Clediana D. Calixto 1, Rebeca T.

Aguiar2, Sarah S. Damasceno 3, Andréa S. G. C. Pontes4, Manoel B. Dantas5, Marco A. R. de Melo 6, Marcos A. G. Pequeno 7, Ieda M. G. Santos8, Antonia Lúcia de Souza9, Antonio G. de Souza10.

Copyright 2012, Instituto Brasileiro de Petróleo, Gás e Biocombustíveis - IBP Este Trabalho Técnico foi preparado para apresentação na Rio Oil & Gas Expo and Conference 2012, realizado no período de 17 a 20 de setembro de 2012, no Rio de Janeiro. Este Trabalho Técnico foi selecionado para apresentação pelo Comitê Técnico do evento, seguindo as informações contidas no trabalho completo submetido pelo(s) autor(es). Os organizadores não irão traduzir ou corr igir os textos recebidos. O material conforme, apresentado, não necessariamente reflete as opiniões do Instituto Brasileiro de Petróleo, Gás e Biocombustíveis, Sócios e Representantes. É de conhecimento e aprovação do(s) autor(es) que este Trabalho Técnico seja publicado nos Anais da Rio Oil & Gas Expo and Conference 2012.

Resumo
O biodiesel foi implantado em escala comercial no Brasil em 2005 e atualmente vem sendo utilizado como aditivo no diesel, na proporção de 5%, se consolidando firmemente na matriz energética brasileira. No entanto, sua utilização ainda enfrenta sérios problemas inerentes a serem superados. Um aspecto envolve a questão da matéria-prima utilizada para a produção deste biocombustível, pois apesar do país ser um celeiro no cultivo de oleaginosas, a soja constitui-se ainda como a principal fonte produtora. Outro obstáculo é a alta susceptibilidade à oxidação de determinados tipos de biodiesel, que torna necessário o uso de aditivos antioxidantes para aumentar o tempo de vida útil dos mesmos. Neste trabalho foram avaliadas as qualidades técnicas combustíveis do biodiesel produzido a partir do óleo de quiabo, oleaginosa não convencional. Os resultados apontaram um perfil de ésteres de ácidos graxos do biodiesel de quiabo, com uma composição elevada de ésteres insaturados (65,42%) principalmente linoleato de etila, mas com uma quantidade expressiva de palmitato (30,44%). As propriedades de fluxo do biodiesel mostraram valores concordantes com o estabelecido pelas normas da ANP para comercialização. A estabilidade oxidativa realizada de acordo com a norma EN 14112 indicou um período de indução de 7,54 h, atendendo a especificação (6h). Essa elevada estabilidade ainda pôde ser evidenciada pela técnica PDSC e através do PetroOxy.

Abstract
Biodiesel was employed in Brazilian commercial scale in 2005 and nowadays it has been used with 5% in diesel as additive which consolidates it in energy matrix of Brazil. However its application confronts inherent problems to be overcome. One of these problematic points is the feedstock to produce it because the main oleaginous to produce biodiesel in Brazil is soybean despite the other ones that could be cultivated in this country. Another obstacle is its oxidation susceptibility that may be reduced with the use of antioxidants. Owing to produce biodiesel from non conventional seedoils, this paper aims to evaluate fuel technical qualities of biodiesel from okra oil. Its esters profile contains high concentration of unsaturated esters (65.4%), mainly ethyl linoleate, but with an expressive content of palmitate (30.4%). Biodiesel flow properties show values that were concordant with those established by ANP resolution. Oxidative stability according EN 14112 was 7.5 h what is greater than ANP specification (6h). This high stability could be corroborated by PDSC and PetroOXY techniques.

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Master, Chemistry – LACOM – DQ – CCEN – UFPB Industrial Chemisty – LACOM – DQ – CCEN – UFPB 3 Master, Chemistry – LACOM – DQ – CCEN – UFPB 4 Master, Chemistry – LACOM – DQ – CCEN – UFPB 5 Doctor, IFPB – SOUSA 6 Master, Chemistry – LACOM – DQ – CCEN – UFPB 7 Master, Chemistry – LACOM – DQ – CCEN – UFPB 8 Doctor, LACOM – DQ – CCEN – UFPB 9 Doctor, LACOM – DQ – CCEN – UFPB 10 Doctor, LACOM – DQ – CCEN – UFPB

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1. Introduction
Brazil has appropriated climate and soil conditions for oleaginous cultivation whereby it widen feedstock options to biodiesel production whose range varies from conventional crops (as soybean, palm, cottonseed, castor and sunflower oils) to native species and non conventional ones, such as babassu and jatropha oils (ANP, 2011). Brazilian government introduced biodiesel in its energetic matrix through National Program of Biodiesel Production and Uses (PNPB, in portuguese) in 2005. It aimed not only use biodiesel as a clean energy, but also to implant a social program for straitening familiar farming and incoming generation through oleaginous cultivation that favors the climate of each Brazilian region. Considering PNPB fundaments, it appears that some goals have not been achieved yet since the main feedstock to biodiesel production has been soybean, whose cultivation is less available for family farming, it concurs with food industry and its oxidative properties do not attend to Petroleum, Natural Gas and Biofuels National Agency (ANP, in Portuguese) specifications (Pousa et. al., 2007). The oxidation susceptibility is the main obstacle for biodiesel production and use because its instability may origin sediments, gums and darkening of this biofuel. Operational problems associated to these factors are deposits formation in the combustion chamber and clogging in injector beaks and fuel filters. Moreover, during oxidative process are originated wide compounds such as alcohols, aldehydes, organic acids which are responsible for increasing of the acidity in fuels and corrosion of metallic parts (Jain and Sharma, 2010). In this sense, okra (Albemoschus esculentus) is presented as a promising non conventional feedstock for biodiesel production due to low impact in food industry and it is a consolidated culture in Brazil because of the it has good climate and cultivation conditions (Mota et. al., 2000). This plant exhibits desirable characteristics as a fast cycle, economical production cost and high levels of oils in seeds (Jarret et. al., 2011). Furthermore, researchers show Brazilian okra production was 116,990 ton in 2006 and from this just 15,021 ton were employed for food and a little portion located for other proposes such as animal food and vegetable processing and beneficiation. It is noteworthy that part of the harvest seeds are intended for seeding and regeneration and then they are discarded and classified as unfit for seeding (Adelakun et. al., 2009). In this context this paper aims evaluate biodiesel from okra oil whose specifications are based on ANP regulations.

2. Materials and Methods
Okra seeds were purchased in João Pessoa – PB – Brazil. They were dried at 50 °C, soaked in a knife mill to facilitate solvent penetration. Oil extraction was performed using a Soxhlet extractor at a temperature around 67 °C with n-hexane for 6 h (Moretto and Fett, 1998). Thereafter the oil was neutralized and subjected to the transesterification process with ethanol proportion of 1:7 (oil:alcohol), via homogenous catalysis with 1% (w/w) KOH (Anwar et. al., 2010). Okra biodiesel was analyzed based on physical, chemical and flow properties such as acid value (ASTM D664), iodine value (EN 14112), kinematic viscosity at 40 °C (ASTM D445), cold filter plugging point (ASTM D6371), cloud and pour point (ASTM D5772). Esters identification and quantification of okra biodiesel were performed by a gas chromatography coupled with mass spectrometer Shimadzu CG-MS QP 2010 equipped with split injector and automatic sample. Capillary column was DB-23 (30 m; 0.25 mm; 0.25 µm) and helium was carrier gas with 96 mL.min -1 flow. 1 µL of the sample was injected with injector temperature of 230 °C. Oxidative stability determination was carried out in a PetroOXY from Petrotest whereby oxygen is consumed by the sample when it is heated at 110 °C under an initial pressure of 700 kPa. The final analysis is recorded by the time the sample requires to absorb 10% of the initial oxygen pressure. P-DSC analysis was obtained by non isotherm and isotherm conditions, the first to select the isotherm temperature for the second that indicates high pressure oxidation induction time – HPOIT. These curves came from differential scanning calorimeter coupled with pressure cell from TA Instruments DSC 2920. The pan was platinum with 10 mg of sample under oxygen pressure of 1400 kPa. Heating flow of 10 °C.min -1 in temperature range of 25-600 °C and for the non isotherm condition is at 100 °C for isotherm one. HPOIT values were determined by the difference between onset time and initial time (ASTM, 2011). Oxidation stability was also evaluated by EN 14112 method with Rancimat from Metrohm. 3g of the sample are aged at 110 °C under 10 L.h -1 of air. Oxidation products are volatized and carried to a vessel containing deionized water whose conductivity is measured constantly.

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3. Results and Discussions
The oil yield in okra seeds was 18% (w/w) and it can be considered satisfactory because this value is equivalent to the main biodiesel feedstock in Brazil such as soybean and cottonseed oils, whose seeds show oil yield around 18-20% (Anwar et. al., 2010). However, the okra oil had acid value of 6.0 mg KOH.g -1 due to the chemical extraction process that runs at 60 °C, so it was necessary to neutralize it. After the treatment, the acid value of this oil reached 0.8 mg KOH.g-1 which was able for transesterification process. Table 1 presents the physical and chemical properties of ethyl okra biodiesel (EOB) that is in accordance to ANP specifications.

Table 1. Characterizations of ethyl okra biodiesel

Parameters Acid value (mg KOH.g-1) Iodine value (mg I2/100g) Kinematic viscosity (mm².s-1) Cloud point (°C) Cold filter plugging point (°C) Pour point (°C)

Okra Biodiesel 0.4 138 4.7 20 12 8

ANP Limits 0.5 3.0-6.0 19 -

Table 2 shows the ethyl esters of okra biodiesel that reveals the low kinematic viscosity is directly related with the high content of unsaturated fatty chains (oleic and linolenic). According with Pontes (2010), the presence of unsaturated compounds alters the hydrocarbons conformations which render intermolecular interactions less effective due to steric disadvantages. This effect makes the molecule packing more difficult and consequently it reduces its viscosity.

Table 1. Chemical composition of the okra biodiesel
Ethyl Fatty Acid C16:0 (palmitate) C18:0 (estearate) C18:1 (oleate) C18:2 (linoleate) C20:0 (eicosanoate) Percentage (%) 30.4 3.5 24.6 40.7 0.4

Ethyl oleates (even with a cis unsaturation configuration) origins high intermolecular interactions between π electrons in its double bonds which provide a packing among the molecules and consequently it increases the viscosity of the fatty acid. Polyunsaturated esters show, due to the spatial geometry of its chains, interactions between π orbitals very low with weak Van der Waals intermolecular forces which results in a hard packing and consequently the decreasing of the compound viscosity. The values of cloud, pour and cold filter plugging points of the okra biodiesel present high temperatures when it is compared to another biodiesels with similar fatty acids such as cottonseed biodiesel (Rashid et. al., 2009). These properties are influenced by the saturated fatty acids that may be correlated with the high amount of ethyl palmitate (30.4%) because these ethyl esters, due to the facility of its chain interactions, are more prone to nucleation and subsequent crystallization at low temperatures. It restricts fuel circulation through the filters and feed system during the motor ignition (Knothe, 2005). The oxidative stability of okra biodiesel was determined using the accelerated oxidation methods such as Rancimat, PetroOXY and P-DSC. The results show a high oxidative stability, considering the okra fatty acids with 65.4% of unsaturated esters. In Rancimat technique, the induction period of okra biodiesel was 7.5 h (Figure 1) which is higher than those that have similar fatty constitution as soybean with 2.3 h (Dantas et. al., 2011) and sunflower biodiesels with 1.2 h (Ferrari and Souza, 2009). It is worth highlighting that this Rancimat value qualifies okra biodiesel in relation to the stability parameter once it exceeds the minimum of 6h specified by ANP legislation.

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Figure 1. Rancimat curve of the ethyl okra biodiesel The PetroOXY curve (Figure 2) shows that the induction period for ethyl okra biodiesel was 1.5 h. This index evaluate the propagation step of the auto-oxidation mechanism due to it is related to oxygen consumption through its reaction with the free radicals presented in the biodiesel during the hydroperoxide formation.

Figure 2. Pressure in function of time in PetroOXY method. In the P-DSC curves (Figure 3), it is observed that the OT was 156.1 °C (Figure 3a) and HPOIT at 100 °C was 284.6 min (Figure 3b). This value is considered as high when it is compared with other oleaginous. It is important to study this technique because it presents the main point of the detection of any oxidative process, independently of the volatile products formed, once P-DSC measures the exothermic effects of the auto-oxidation process. So through P-DSC method was possible to evaluate the oxidative stability of okra biodiesel.

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Figure 3. P-DSC curves of EOB. (a) non isotherm mode (b) isotherm mode at 100 °C.

PetroOXY (Figure 2) and P-DSC (Figura 3b) showed high induction period and oxidation induction time, respectively, but they was below than Racimat method because the conditions are more critic in those assays and they differ in relation to the oxidative step of the auto-oxidation reaction. This high oxidation stability may be understood by the prominent presence of ethyl palmitate and oleate in EOB that may contribute to increase the oxidative stability due to its lower propensity to oxidation. However, in terms of fatty composition, one of the main factors to improve the oxidative stability is the absence of linolenate esters, since they are more reactive than oleate and linoleate ones. It is because the hydrogen abstraction in bis-allylic positions are preferred due to the lower dissociation energy of these bonds when they are compared to allylic ones with values of 65 and 77 kcal.mol-1, respectively (Shahidi, 2004). Knothe (2006) referenced the relative rates of oxidation to oleates (1), linoleates (41) and linolenates (98) that corroborates with the dissociation energy once the linolenic fatty acid has two bis-allylic positions and consequently more prone to oxidation. Another factor that possibly interferes in oxidation stability of EOB is the presence of high content of polyphenols (Shui and Peng, 2004; Huang et. al., 2007; Arapitsas, 2008) and α-tocopherol (Karakoltsidis and Constantinidis, 1975). Anwar and collaborators (2011) quantified the tocopherols levels in okra oil and they verified that it has a significant content in okra oil, mainly α-tocopherol that was quantified around 653-696 mg.kg-1. This value was greater than the found to soybean (99.5 mg.kg-1), corn (282 mg.kg-1), cottonseed (338 mg.kg-1) and palm (89 mg.kg-1) oils. Shui and Peng (2004) identified some flavanoids in okra such as epigallocatechin, quercetin and its derivates. They verified that quercetin was responsible for 70% of total antioxidant of okra. This composition is also cited by Huang et al. (2007). Whereupon these composts, in small quantities, may be present in EOB and it can confer the oxidative stability of okra biodiesel in agreement with the ANP specifications without the use of antioxidants additives.

4. Conclusion
Analysing of ethyl okra biodiesel, it was observed that it attends the parameters established by ANP resolution to biodiesel commercialization and uses for the quality control of this biofuel with the needing of adding antioxidants to correct its oxidative stability and flow properties. These results qualify okra oil as an alternative feedstock for the biodiesel production, since in all evaluated methods, okra biodiesel presented satisfactory answers with better properties than the conventional oleaginous, such soybean biodiesel.

5. Acknowledgments
The authors thank MCT/CGTS by provided support, FINEP to available sources through Covenant nº. 01.06.1021.00; Employment Project from Rede ARMAZIBIOD; CNPq and CAPES for the financial support.

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6. References
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