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Modified Diesohol Using Distilled Cashew Nut Shell Liquid and Biodiesel Thapanee Bangjang, Amaraporn Kaewchada, and Attasak Jaree Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b01188 • Publication Date (Web): 29 Aug 2016 Downloaded from http://pubs.acs.org on September 4, 2016

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Modified Diesohol Using Distilled Cashew Nut Shell Liquid and Biodiesel Thapanee Bangjanga, Amaraporn Kaewchadab, Attasak Jareea,* a

Chemical Engineering Department Department of Chemical Engineering, Kasetsart University, Bangkok, 10900 Thailand b

Department of Agro-Industrial, Food and Environmental Technology King Mongkut’s University of Technology North Bangkok Pracharat 1 Road, Wongsawang, Bangsue, Bangkok, 10800, Thailand

Abstract Emulsifier is generally required to stabilize the EtOH-Diesel mixture due to the difference in polarity of the compounds. This research applied distilled cashew nut shell liquid (DT-CNSL) and biodiesel as additives for modified diesohol. Different proportions of DTCNSL, diesel, and ethanol were prepared in order to study the physical and chemical properties together with the action of emulsifier. The effect of CNSL composition variation on the fuel properties was studied for DE20, DE30, DE50 and DE70. The viscosity and heating value of fuel blend were related to the proportion of biodiesel and ethanol in the blend. Biodiesel was used as an eumulsifier in this work due to the dark color of the blends. The cetane index of DE20 with the content of 1-3% DT-CNSL and 6-20% of biodiesel was in the range of 42-52%. With the fuel properties comparable to that of diesel fuel, the proposed blending formulae offers a potential use of DT-CNSL and biodiesel for the modification of diesohol.

Keywords Distilled Cashew nut shell (DT-CNSL), Diesohol, Biodiesel, Cetane index

__________________________________ * Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Chatuchak, Bangkok, 10900, Thailand. E-mail: [email protected]

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1. Introduction Although the worldwide population is increasingly concerned about the depletion of fossil fuel and the greenhouse effect, the consumption of diesel fuel will still dominate the energy demand for many years. The world’s energy consumption for fossil fuel continues to increase by 37% from 2013 to 2035 due to the population growth.1 In Thailand, alternative energy, such as ethanol, biodiesel, solar energy, and biogas, is an ongoing intense research in order to reduce the amount of imported oil to strive for energy independence. Diesohol (diesel and ethanol blend) is the one of the promising alternative fuels. To reduce the use of fossile fuel and pollutant emissions in many parts of the world such as Europe, Australia, and the US, dieshol has been used for public transport.2 One of the major effects of diesohol is a significant reduction in visible smoke, particulate emission, and carbon emission.3,4 Generally, ethanol is immiscible in diesel because of the polarity difference. SPAN80 (a trade name of sorbitan mono-leate) and isopropanol have been used as emulsifying agent to resolve the issue of in compatibility between diesel and ethanol.5,6 Biodiesel was studied by previous work as emulsifier for diesel/ethanol mixture because of the similar structure of both diesel and ethanol.7 Park S. et. al. studied the use of biodiesel as emulsifier in diesel/ethanol blend, and found that 10% of biodiesel created the homogeneous mixture of diesel/ethanol (80/20) with phase stability exceeding 96 hours.8 According to Kwanchareon et al.9, diesel/biodiesel/ethanol (80:15:5) provided similar properties to diesel. The stability issue of diesohol blend arisen from the use of biodiesel as emulsifier because O2 can react with unsaturated fatty acids.10 Products from the oxidation reaction are acids or polymer which can blocked the engine injectors.11,12 To resolve this issue, an antioxidant generating labile hydrogen is commonly added in order to inhibit the oxidation reaction of the fuel.13 One of natural antioxidant extractable from cashew nut industry is cardanol.14 It can be obtained via chemical conversion of anacardic acid, the main constituent of the oil trapped inside the cashew nut shells (cashew nut shell liquid, CNSL).15 Upon heating, anacardic acid is decarboxylated to produce distilled technical CNSL (DT-CNSL), which contains cardanol as the main component, as shown in figure 1.16 Kubo et al.17 found that, when cardanol was added to linoleic acid, the occurrence of free radicals was reduced by 30. Moreover, the molecular structure of cardanol has both non-polar (lipophilic) and polar (hydrophilic) ends; typical characteristics for emulsifying agent. Therefore, it is plausible that cardanol can be used to blend with diesel, ethanol, and biodiesel, while keeping the unwanted oxidation during storage subdued. Although there has been research in using CNSL as emulsifier18, this work is the first investigation on the utilization of DT-CNSL for diesohol blends. We studied the stability of fuel blend and explored the fuel properties of modified diesohol by using DT-CNSL and biodiesel. Measurements of physical and chemical properties will be compared with the standard of diesel in Thailand and previous work.


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2. Material and Method 2.1 Material The cashew nut shells, palm oil and diesel were obtained from Methee Phuket Company, Morakot Industies Public Company Limited and Bangchak Petoleum Plublic Company, respectively. The analytical grade ethanol with a purity of 99.9% was used in this work. The KOH and MeOH was purchased from MERCK. 2.2 Extraction of DT-CNSL DT-CNSL was extracted from cashew nut shell liquid. The comminuted cashew nut shell via a cross-beater mill was dissolved in ethanol (150g of cahew nut shell : 1 liter EtOH) for 1 hour. The DT-CNSL was separated from ethanol using a rotary vacuum evaporator (180ºC for 2 hrs.). 2.3 Biodiesel synthesis 1 wt% of KOH was added into the reaction mixture of palm oil and methanol (1 mol/6mol). The mixture was refluxed at 65°C in a water bath with constant magnetic stirring for 3 h. After the tranesterification, the mixture was cooled. The glycerol and biodiesel phases were separated by a separating funnel. Biodiesel was further purified by washing with excessive quantities of deionized water (80°C) to remove methanol followed by drying at 107°C for 30 min. 2.4 The blending of DT-CNSL and diesohol Diesel, Ethanol DT-CNSL and biodiesel were defined by D, E, DT-C and B respectively. For illustration, DE20 indicates the content of 80%vol. of Diesel and 20%vol. of ethanol. DT-C1 means 1%vol. of DT-CNSL of the volume of mixture. First, all chemical components including diesel, ethanol, and biodiesel were mixed with certain amount of DT-CNSL by a vortex mixer for 3 min at room temperature. The blending was repeated 3 times/sample. 2.5 Properties of the fuel blends 2.5.1 Acid value and Viscosity The acid value of the mixture was determined by the standard titration method. The viscosity of fuel blend was measured by Ostwald viscometer based on ISO 3104. More details on the procedure for the determination of acid value and viscosity can be found in Banjang et al.18 2.5.2 Heating value The samples were tested for the heating value by using a bomb calorimeter (PARR 1261).


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2.5.3 Analysis from FT-IR The Bruker Alpha FT-IR spectroscopy was used to record the IR-Spectrum of samples, with the frequency in the range of 600-4100 cm-1. Sample (1 g) was cast on KBr plates and ran in FT-IR mechine with the resolution of 4 cm-1. 2.5.4 GC-MS (Gas chromatrography-massspectrometer) Anaylytical GC-MS was performed on Agilent GC-6890N, on Agilent 5975 mass selective detector, on a column of HP-5MS (30 m x 0.25 mmID x 0.25), helium carrier gas. The 1 mg of sample was dissolved in dichlorometane (10ml). 1µL of this sample was tested in GCMS, the temperature rising from 50ºC to 250ºC in the rate of 10 oC/min. 2.5.5 Cetane Index The cetane index (ASTM D976) was estimated from density and mid-boiling point of fuel blend which was measured by using the psycnometer and distillation. 2.5.6 Oxidation Stability of fuel blend Oxidation stability of fuel blend was studied according to the Rancimat method. Rancimat method (EN 14112) is not suitable for samples containing volatile compounds such as diesel so that the modified Ranciamat (EN15751) method was developed to determine oxidation stability of hydrocarbon fuel (Diesel) with high content of volatile matter.19-21 Hence, the modified method was employed in this work. 3 g of sample was kept at a constant temperature of 110oC, and the air passed through the sample at a rate of 10 l/h. The products of oxidation are transferred into the water by the flow of air. The conductivity of water was measured by a conductivity electrode. The inductive period (IP) was obtained from the intonation of graph between conductivity and time. The IP was registered when the conductivity increased rapidly.23 2.5.7 Color Color of fuel blends was measured according to ASTM D1500. 50 ml of sample was transferred into the cuvette. The rage of color for standard diesel is from 0.5 to 8.0, which was used to compare with the color of sample. Determine the colored glass disk comparator that matches the color of sample. 2.5.8 Analysis of droplets size The droplets size of fuel blend was determined by dynamic light scattering using a Zetasiser ZS. Measurement (1ml of sample) was carried out at 25oC with a fixed angle 90o. Measurement rage id 0.3 nmto 10microns (diameter).


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3. Result and discussion The individual constituent used for blending fuel was subject to various testing in order to obtain basic fuel properties. Prior to the preparation of different formulas for fuel blend, the DTCNSL was analyzed for the chemical bonding. After that the physical properties of the blends with different proportions were studied. Finally, additional fuel testing was carried out for the selected fuel blend.

3.1 Physical and Chemical properties of fuel components Four types of fuel including diesel, ethanol, DT-CNSL, and biodiesel were separately tested for physical properties including color, density, viscosity, acid value, and calorific value. The physical properties are summarized in Table 1. Note that the color of DT-CNSL is dark brown and its viscosity is quite high compared to that of diesel. In this work, however, we applied small amount of DT-CNSL in the fuel blend. Ethanol, on the other hand, has low viscosity and is colorless. This could, in fact, counteract the effect of DT-CNSL to a certain extent. Similarly, the effect of high acid value for DT-CNSL would be tempered by other components in the blend. 3.2 Functional group analysis of DT-CNSL Prepared samples of DT-CNSL and CNSL were analyzed by FT-IR in order to verify the decarboxylation of the extracted CNSL. Figure 2 and Table 2 show frequency range and functional group of CNSL and DT-CNSL from FT-IR analysis. The peak of absorption of CNSL and DT-CNSL that appeared at 1580-1650 cm-1 indicate the C=C stretching of aromatic compounds. The peak at 2900 cm-1 refers to the C-H stretching of long aliphatic chain of CNSL and DT-CNSL. The absorption range of 2545-2800 cm-1 represents the stretching of carboxylic group in the aromatic ring designating the decarboxylation of anacardic acid. DT-CNSL has characteristically strong absorption bands arising from hydroxyl (O-H) around 3600-3300 cm-1 in contrast with that of CNSL. Identification of DT-CNSL from GC-MS analysis is shown in Table 3. The chemical contituents of DT-CNSL included cardanol (89.14%), cardol (10.84%) and phenol (0.667%). Risfaheri et al. obtained distillate CNSL via thermal treatment method for the decarboxylation of CNSL. The reported composition of DT-CNSL was 74.22% of cardanol, 14.22% of cardol and 10.94 of other phenol.24 Although the same method was applied to convert CNSL into DTCNSL, our decarboxylation temperature and period were 180°C and 2 hr (as compared to 140°C and 1 hr used by Risfaheri et al.). Consequently, we obtained higher composition of cardanol in our DT-CNSL. 3.3 Stability of diesohol blend


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The homogeneity testing was carried out for the mixtures of diesel, DT-CNSL and ethanol. Stability of fuel blend was tested for DE70, DE50, DE30 and DE20 as shown in figure 3. Black squares represent the threshold limits that the mixtures (i.e. DE70, DE50, and DE30 at 1% of DT-CNSL) separated within 3 minutes after vigorous agitation. White squares indicate the homogenous blends where the mixtures were stable at least 3 weeks (no phase separation). The stability of diesohol blend depended on the concentration of DT-CNSL. When DT-CNSL was increased from 1% to 3%, DE50 and DE30, the homogeneous mixtures lasted for approximately 5 minutes. For long term stability (3 weeks), DE50 and DE30 required at least 6% of DT-CNSL, while DE20 was stable with 1% (or more) of DT-CNSL. This is because DT-CNSL can act as emulsifier. The hydrophilic-lipophilic balance (HLB) can be associated with properties of emulsifier. Here, we obtained the HLB of DT-CNSL by water-solubility method.25,26 It was found that DT-CNSL poorly dispersed in water as shown in figure 4, indicating the HLB of DTCNSL in the range of 3-6. An emulsifier with a 4-6 HLB number is suitable for water in oil emulsion25, therefore, DT-CNSL can be an emulsifying agent for diesohol. This mixture consisted of ethanol droplets dispersed in a continuous oil phase. The polar heads of DT-CNSL were attracted to ethanol (water phase) and the non-polar tails formed chemical bond with the diesel (oil phase).11 The effect of DT-CNSL as emulsifier was investigated by analyzing the droplets size. Figure 5 shows a profile of droplet size of dieshol with different emulsifiers. It is apparent that the fuel blend of biodiesel and DT-CNSL as emulsifier exhibited unimodal distribution, giving a average diameter of 32.67 and 11.7 nm respectively. The average droplet size of modified diesohol using DT-CNSL was smaller than that using biodiesel. This was due to the difference of viscosity between biodiesel and DT-CNSL.27 The droplets size of emulsion decreases when the emulsion viscosity increased28 relating to the high interfacial force between dispersed phase and emulsifier to form small droplets. However, due to the dark color of the fuel blend with DT-CNSL as emulsifier, biodiesel was appended in order to tone down the color of the blend. 3.3 The properties of modified diesohol According to previous studies11-12 biodiesel was used as an effective emulsifier for diesohol blending. Biodiesel has high cetane number and heating value similar to that of diesel.14 Therefore, in this work, biodiesel was used in the range of 8-20% of the combined volume of diesel and ethanol. The color of modified diesohol with different formulations is shown in figure 6. The color index of DE20:DT-C1:B20 and DE20:DTC3:B20 were 3.5 and 6.5 (on the ASTM D1500 color scale) which were compatible with the commercial (Maximum of 4) and industrial diesel (in the rage of 4.5-7.5), respectively. When increased the content of DT-CNSL, the color of fuel blend turned dark. The color index of DE20:DT-C6:B20 and DE20:DT-C8:B20 exceeded 8 for the standard of diesel fuel. Therefore, the proportion of 1% and 3%DT-CNSL was subsequently studied for fuel properties of modified diesohol.

3.4.1 Acid value Acid value is an index used to indicate how much acid is in the sample. High amount of acid in diesohol could lead to corrosion of automotive parts for longtime usage. According to the


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standard diesel in Thailand, the acid value must be less than 0.8. Figure 7 shows the variation in acid value of the fuel blends for DE70, DE50, DE30 and DE20 with 1 and 3% of DT-CNSL and 8-20% of biodiesel. The dash line indicates the maximum threshold of acid value. The acid value of 1% and 3% of DT-CNSL in diesohol was 0.22 mgKOH/g (ASTM D664, minimum 0.5 mgKOH/g). This is because the major constituent of DT-CNSL is cardanol, which is noncarboxylic. Note that all formulas of fuel blend were stored for 6 months in order to assure no phase separation. 3.4.2 Viscosity It is important that fuel viscosity be measured because it significantly affects the atomization and injection flow. Inferior fuel injection and combustion performance may result from high viscosity fuel. In contrast, insufficient lubrication may be caused by low viscosity.29 The viscosity of DE70 to DE20 with 1 and 3% of DT-CNSL and 8-20% of biodiesel is shown in Figure 8. In each graph (Figure 8), the molar composition of both ethanol and biodiesel composition changed markedly while the composition of diesel was approximately constant. For instance, in the case of DE70 at 1% of DT-CNSL, the viscosity of diesohol increased due to the increase of mole fraction of biodiesel from 0.018 (8% of biodiesel ) to 0.045 (20% of biodiesel) and the decrease of mole fraction of ethanol from 0.872 (8% biodiesel) to 0.849 (20% of bioidiesel). For the same reason, 1% of DT-CNSL resulted in lower viscosity of the blend compared to the case of 3% of DT-CNSL. The same explanation holds for the cases of DE50, DE30 and DE20 with 1% and 3% of DT-CNSL. The entire data series for viscosity of DE70 fell below the threshold limit for high speed diesel fuel. This is due to the high proportion of ethanol in the blends (see Table 2). The viscosity of DE50 was lower than the standard rage of viscosity of diesel in Thailand. On the other hand, the viscosity of DE30 and DE20 was well within the standard range while no data points exceeded the maximum threshold limit of 4.1 cSt. Hence, DE70 will not be a studied for other properties. These 3 types (DE50, DE30, and DE20) of fuel blend will undergo further testing. 3.4.3 Calorific value The calorific value indicates how much energy is released from fuel combustion. Fig. 9 shows the calorific value of the fuel blends for DE50, DE30, and DE20 with 1 and 3% of DTCNSL and 8-20% of biodiesel. Among the 4 fuel components, ethanol has the lowest calorific value of 30.00 Mg/kg. It is conceivable that the fuel blend will not meet the minimum calorific value specification if too much proportion of ethanol was used in the blend. According to the standard of diesel, the dash line exemplifies the minimum standard calorific value. DE50 with 1% of DT-CNSL has the lowest calorific value of 34.92 MJ/kg because the highest portion of ethanol compared to other fuel formulas. With more diesel content, DE30 and DE20 provided higher calorific value than DE50. On the whole, the increased calorific value was affected by the increase of the amount of DT-CNSL and/or biodiesel content. It can be observed that DE30 and DE20 yielded the calorific values were higher than the standard of diesel value (minimum 36.42 MJ/kg) for 1 and 3% of DT-CNSL and biodiesel content throughout the range studied. Similar formulations of diesohol were studied by Satge et. al.30 and found that with 1% of 1-octylamino3-octyloxy-2-propanol and 1% of N-octyl nitramine as emulsifier in fuel blend (Diesel + 20% of


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ethanol), the heating value of this blend was 39.59 MJ/kg, comparable to the calorific value of the DE20 in this work. This was mainly due to the similar content of ethanol. Kwanchareon, et al.9 also reported that the content of ethanol was inversely proportional to the calorific value of diesohol.

3.4.4 Cetane index The engine start up, combustion control, and engine performance are related to the cetane index.31 Figure 10 shows cetane index of DE20 and DE30 with the content of DT-CNSL of 1-3% and biodiesel content of 8-20%. Increasing biodiesel content contributed to the increase of cetane index of the fuel blend because of the relatively high cetane index of biodiesel compared to other fuel components.11 The results showed that cetane index of DE20:DT-C1 and DE20:DT-C3 were in the range of 49-52 exceeding the standard of diesel. On the contrary, cetane index of DE30:DT-C1 and DE30:DT-C3 were below the threshold limit for diesel fuel because of the great amount of ethanol. Note that high cetane index indicates better fuel combustion and engine motor efficiency.32 3.5 Oxidation stability using Rancimat method. The molecular structures of unsaturated fatty acids in biodiesel have an effect on to oxidation stability during storage.20 The IP for biodiesel and fuel blends with DT-CNSL, diesel, and ethanol are summarized in Table 4 and figure 11. For the case of biodiesel, the conductivity of the measuring cell increased to 173.3 µS/cm after 17 hr due to the products of oxidation reaction between biodiesel and oxygen (in air). The IP of biodiesel was 13.69 hr (±0.24), while the conductivity of the measuring cell for the cases of DE20:DT-C1:B20 and DE20DT-C3:B20 increased to 11.6 and 10.6 3 µS/cm, respectively, after 24 hr. The IP of fuel blend exceeded 24 hours suggesting that the fuel can resist oxidation reaction in the presence of DT-CNSL. This was due to the compound structure of DT-CNSL (chain breaking antioxidant, AH) containing labile hydrogen which can rapidly interact with peroxyl radical (ROO. ) generated from the initiation step of the oxidation reaction as shown in equation (3).21,33 Initial radicals (I . ) react with RH (fatty acid in the fuel blend) which initial radicals are formed by thermal dissociation, metal catalysed decomposition and light.21 Carbon-based fatty acid radicals (R. ) react with O2 to produce fatty acid peroxide radicals (ROO. ) as shown in equation (4,5).12 These radicals remove hydrogen from carbon atoms of biodiesel (RH). In the termination step, R. meets another radical to produce a stable product. DT-CNSL is an antioxidant which produces antioxidant free radicals (A. ). These radicals can be stable or further react to form stable molecules.12 Initial step RH + I . → R. + IH . (3) Propagation step R. + O → ROO. (4) . . ROO + RH → ROOH + R (5) Termination step R. + R. → R − R (6) ROO. + ROO. → Stable products (7) . . . Antioxidant ROO + AH → ROOH + A (8)


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Therefore, the oxidation of the blends was suppressed. The minimum induction period of 20 hours (EN 590) was satisfied for all blends with DT-CNSL. 3.6 Properties of fuel blend Table 5 summarizes the basic fuel properties of DE20 with 1% of DT-CNSL and 20% of biodiesel. The density and viscosity of this blend is 0.85 g/cm3 and 2.41 cSt. Mole fraction of diesel, ethanol, DT-CNSL and biodiesel is 0.510, 0.445, 0.012 and 0.033 respectively. Consequently, ethanol and diesel were the major constituents affecting the viscosity of fuel blend. Due to the simplicity and the availability of the instruments, cetane index was used to estimate the cetane number of fuel.34,35 Flash point was not measured because earlier works about flash point of diesohol reported in the rage of 12-17°C.10,36 Despite the proportion of ethanol, the flashpoint of diesohol does not meet the standard of pure diesel.36 Therefore, the storage, handling and transportation of diesohol must be managed in a special and proper way.10,37 A comparison of fuel properties of fuel blend in this work and from previous literature is shown in Table 7. Apanee et al.10 and Y. Reyes et. al.38 studied properties of diesohol using biodiesel and SPAN 80 as emulsifier. The density of fuel blend in this work was similar to previous work. The viscosity and the heating value of this work are lower than diesohol that using biodiesel and SPAN80 due to the higher ethanol content. Therefore, DT-CNSL and biodiesel can be applied together as emulsifying agent for diesel/ethanol. 4. Conclusion DT-CNSL was applied as emulsifying agent to stabilize a mixture between diesel fuel and ethanol. The phase stability of fuel was observed for more than 1 month. As the results of the color of the fuel blend, biodiesel was added by volume of CNSL. The effect of viscosity was from the amount of ethanol and diesel. The fraction of ethanol was limited to below 50 because of the criteria of calorific value. Finally, DE20:DT-C1 was selected to investigate all basic fuel properties, which were compatible with the standard according to diesel standard in Thailand and previous work. These newly proposed blending formulae can promote the use of bioethanol and biodiesel to partially substitute fossil diesel fuel. It will also be an alternative for dealing with cashew nut from the cashew manufacturing. Acknowledgments The authors acknowledge the financial support from the Thailand Research Fund through the Royal Golden Jubilee Ph.D. Program (Grant No. PHD/0243/2553).

5. Reference (1)

BP p.l.c. BP Energy Outlook 2035. BP Statistical review of world: London, England, 2015.


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10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(2)

Purcell, F. The Environment Protection Agency 2008, 2008; pp.1-60.

(3)

Ayhan D. Energ. Convers. Manage. 2008, 49, 2106-2116.

(4)

Premkartikkumar, SR.; Annamalai, K.; Pradeepkumar, A R. JCPS. 2015, 212-214.

(5)

Cheenkachorn, K.; Monpilai, H. N.; Pupakornnopparut, J. As. J. Energy Env. 2006, 7, 267-276.

(6)

Can, O.; Celikten, I.; Usta, N. Energ. Convers. Manage. 2004, 45, 2429-2440.

(7)

Ferreira, V. P.; Martins, J.; Torres, E.A.; Pepe, I.M.; João R. De Souza, M. S. Energ. Sustain. Dev. 2013, 14, 649-657.

(8)

Park, S.; Kim, S.; Lee, C. Energy Fues 2009, 23, 5228-5235.

(9) Kwanchareon, P.; Luengnaruemitchai, A.; Jai-in, S. Fuel 2007, 86, 1053-1061.

(10) Agarwal, A.K. ; Khurana, D. Fuel. Process. Technol. 2013, 106, 447-452.

(11) Shahabuddin, M.; Kalam, MA.; Masjuki, HH.; Bhuiya, MMK.; Mofijur, M. Energy 2012, 44, 616-622.

(12) Pullen, J.; Saeed, K. Renew. Energ. Rev. 2012, 16, 5924-5950.

(13) D. E. G., S.; Rafie El, S.; Hawash, S. Int. J.Environ. Sci. Tech. 2009, 6, 369-378.

(14) Rios Façanha, M. A.; Mazzetto, S.E.; Beserra Carioca, J. O.; de Barros, G. G. Fuel 2007, 86, 2416-2421. (15) Velmurugan, A.; Loganathan, M.; James Dunasekaran, E. Fuel 2014, 236-245.


Page 11 of 27

Energy & Fuels

11 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(16) Smith Jr, R.L.; Malaluan, R.M.; Setianto, W.B.; Inomata, H.; Arai, K. Bioresource. Technol. 2003, 88, 1-7.

(17)

Kubo, I.; Masuoka, N.; Ha, T.J.; Tsujimoto, K. Acids. Food. Chem. 2006, 99,555-562.

(18)

Bangjang, T.; Saisangtong, R.; Kaewchada, A.; Jaree, A. Energ. Tech. 2014, 825-831.

(19) Karavalakis, G.; Hilari, D.; Givalou, L.; Karonis, D.; Stournas, S. Energy 2011, 36, 369374. (20) Karavalakis, G.; Stournas, S.; Karonis, D. Fuel 2010, 89, 2483-2489.

(21)

Siddharth, J.; Sharma, M.P. Renew. Sust. Energ. Rev. 2010, 14, 667-678.

(22)

Jain, S. Int. J. Energy Environ. 2011, 2, 533-542.

(23)

Das, P.; Sreelatha, T., Ganesh, A. Biomass. Bioenerg. 2004, 27,265-275.

(24)

Risfaheri, T.T.; Irawadi, M.A.; Nur and I. Sailah. Indones. J. Agric. Sci. 2009, 2, 20.

(25)

Griffin, W. C. J. Soc. Cosmet. Chem. 1949, 1, 311-326.

(26)

Stanga, M. Sanitation: Cleaning and Disinfection in the Food Industry; Wiley-VCH, 2010; pp.163.

11-

(27) Yuan, Y.; Gao, Y.; Zhao, J.; Mao, L. Food Res. Int. 2008, 41, 61-68.

(28) Bouchemal, K.; Briancom, S.; Perrir, E.; Fessi, H. Int. J. Pharm. 2004, 280, 241-251.

(29) Velmurugan, A.; Loganathan, M. World Acad. Sci. Eng. Technol. 2011, 58, 889.

(30) Satge´ de Caro, P.; Mouloungui, Z.; Vaitilingom, G.; Berge, J.Ch. Fuel 2001, 80, 565-574.


Energy & Fuels

Page 12 of 27

12 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(31) K. Cheenkachorn, M. H. Narasingha and J. Pupakornnopparut. Am. J. Env. Eng. 2006, 7, 267-276.

(32) Candeia, R.A.; Silvab, M.C.D.; Carvalho Filhoa, J.R.; Brasilinoa, M.G.A.; Bicudoa, T.C.; Santosa, I.M.G.; Souzaa, A.G.; Fuel 2009, 88, 738-743.

(33)

Jain, S.; M. P. Sharma. Fuel 2014, 116, 14-18.

(34) Bezaire, N.; Wadumesthrige, K.; Simon Ng, K.Y.; Salley, Steven O. Fuel 2010, 89, 38073813 (35) Lin, C.Y.; Li, R.J. Fuel. Process. Technol. 2009, 90, 130-136.

(36) Shahir, S.A.; Masjuki, H.H.; Kalam, M.A.; Imran, A.; Rizwanul Fattah, I.M.; Sanjid,A. Renew. Sust. Energ. Rev. 2014, 32, 379-395.

(37) Barabás, I.; Todoruţ, A.; Băldean, D.; Fuel 2010, 89, 3827-3832.

(38) Reyes, Y.; Aranda, D. A. G.; Santander, L. A. M.; Cavado, A.; Belchior C. R. P. Energ. Fuel 2009, 23, 2731- 2735.

Figure legend Figure 1 Carboxylation of Anarcardic acid Figure 2 FT-IR spectra of DT-CNSL and CNSL Figure 3 Phase diagram of Diesel ethanol and DT-CNSL Figure 4 Dispersibility of DT-CNSL in water Figure 5 Droplet size of Diesel/ethanol/biodiesel and Diesel/ethanol/DT-CNSL Figure 6 The mixtures of modified diesohol with different amounts of DT-CNSL Figure 7 Acid value of the fuel blend Figure 8 Viscosities of the DE70, DE50, DE30 and DE20 fuel blended with 1, 3, 6, and 8% of DT-CNSL and 8-20% of biodiesel.


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13 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 9 Heating value of the DE70, DE50, DE30 and DE20 fuel blended with 1, 3, 6, and 8% of DT-CNSL and 8-20% of biodiesel. Figure 10 Cetane index of DE30 and DE20 fuel blended with 1, 3, 6, and 8% of DT-CNSL and 8-20% of biodiesel. Figure 11 Oxidation stability of fuel blend(a) and pure biodiesel(b)

Table 1 Physical and Chemical properties of fuels. Properties Color Density (g/cm3) @ 15 °C Viscosity (cSt) @ 40 °C Acid value (mg KOH/g) Calorific value (MJ/kg)

Diesel Yellow

Ethanol Colorless

DT-CNSL Dark brown

Biodiesel* Light yellow

Method -

0.835

0.789

0.935a

0.882

ASTM D1298

3.04

1.19

148.6

4.17

ASTM D 445

0.11

0.11

5

0.22

ASTM D 664

45.53

30.00

39.42

39.55

ASTM D 240

Note * % FAME of Biodiesel is 97.43 a Temperature @ 30 oC


Energy & Fuels

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Table 2 Frequency range and functional group associated with FT-IR spectra.23 Frequency range (cm-1) Group 3600 - 3300 O-H (O-H stretching) 3100 - 3000 C-H (C-H stretching) 3050 - 2800 C-H (C-H stretching) C=O (C=O 1750 - 1650 stretching) C=C (C=C 1650 - 1580 stretching) 1470 - 1350 C-H (C-blending) 1300 - 950 C-O (C-O stretching) 915 - 615 O-H (O-H bending)

Class of compound Polymeric O-H, water impurities Aromatic Alkanes Ketones, Aldehydes, Carboxylic acids Alkenes Alkanes Primary, Secondary and Tertiary Alcohol Phenol, Ester, Ether, Aromatic compounds

Table 3 Quantification of DT-CNSL from analytical GC-MS. Retention time 43.149-43.605 46.393 47.373-47.481

Correction area 79198763 129678 9056071

% of total 89.14 0.667 10.84


Compound Cardanol Phenol Cardol

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Table 4 Effect of DT-CNSL on oxidation stability of modified diesohol Component B100 DE20:DT-C1:B20 DE20:DT-C3:B20

Inductive period (hr) 13.69 >24 >24

Table 5 Properties of the fuel blend. The mixing fuel DE20: DTC1:B20% by volume

Kwanchareon, P. et. al. 11**

Reyes, Y. et.al.38***

Standard diesel

Method

0.85

0.8375

0.8563

0.81 - 0.87

ASTM 1298

2.42

na*

4.62

1.8 - 4.1

ASTM D 445

38.92

43.32

40.92

36 min.

ASTM D 240

Color

3.5

-

-

4 max

Cetane index

52

43.3

51.5

45 min

0.11

-

-

0.8 max.

-2

-

-

10 max.

8

-

-

-

-3

-

-

-

Properties

Density @ 15°C (g/cm3) Viscosity @ 40°C (cSt) Calorific value (MJ/kg)

Acid value (mgKOH/g) Pour point (°C) Cloud point (°C) Freezing point (°C)


ASTM D1500 ASTM D 976 ASTM D 664 ASTM D 97 ASTM D 2500 -

Energy & Fuels

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Note * Not available ** Diesel 80%, Ethanol 5% and 15% of biodiesel ***Diesel, 8% of ethanol, 2%biodiesel, 0.5% of SPAN8038


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Energy & Fuels

Fig. 1. Carboxylation of Anarcardic acid Fig. 1. 33x14mm (600 x 600 DPI)


Energy & Fuels

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Fig. 2. FT-IR spectra of DT-CNSL and CNSL Fig. 2. 50x32mm (600 x 600 DPI)


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Energy & Fuels

Fig. 3. Phase diagram of Diesel ethanol and DT-CNSL 63x38mm (300 x 300 DPI)


Energy & Fuels

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Fig. 4. Dispersibility of DT-CNSL in water 48x31mm (300 x 300 DPI)


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Fig. 5. Droplet size of Diesel/ethanol/biodiesel and Diesel/ethanol/DT-CNSL 26x16mm (600 x 600 DPI)


Energy & Fuels

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Fig. 6. The mixtures of modified diesohol with different amounts of DT-CNSL 48x29mm (600 x 600 DPI)


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Energy & Fuels

Fig. 7. Acid value of the fuel blend 17x5mm (600 x 600 DPI)


Energy & Fuels

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Fig. 8. Viscosities of the DE70, DE50, DE30 and DE20 fuel blended with 1, 3, 6, and 8% of DT-CNSL and 8-20% of biodiesel. 34x22mm (600 x 600 DPI)


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Fig. 9. Heating value of the DE70, DE50, DE30 and DE20 fuel blended with 1, 3, 6, and 8% of DT-CNSL and 8-20% of biodiesel. 30x17mm (600 x 600 DPI)


Energy & Fuels

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Fig. 10. Cetane index of DE30 and DE20 fuel blended with 1, 3, 6, and 8% of DT-CNSL and 8-20% of biodiesel. 28x25mm (600 x 600 DPI)


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Fig. 11. Oxidation stability of fuel blend(a) and pure biodiesel(b) 29x8mm (300 x 300 DPI)


Modified Diesohol Using Distilled Cashew Nut ... - ACS Publications

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