ISOLATION OF CARDANOL FROM CASHEW NUT SHELL LIQUID USING THE VACUUM DISTILLATION METHOD 1)

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1 Isolation Indonesian of Journal cardanol of from Agriculture cashew nut 2(1), shell 2009: liquid ISOLATION OF CARDANOL FROM CASHEW NUT SHELL LIQUID USING THE VACUUM DISTILLATION METHOD 1) Risfaheri a), Tun Tedja Irawadi b), M. Anwar Nur b), and Illah Sailah b) a) Indonesian Center for Agricultural Postharvest Research and Development Jalan Tentara Pelajar No. 12 Bogor 16114, Phone: (0251) , , Facs.: (0251) , b) Bogor Agricultural University, Kampus IPB Darmaga, Bogor ABSTRACT Cashew nut shell liquid (CNSL) is a by-product from cashew nut processing that contains phenolic compounds, mainly cardanol. Cardanol is a monohydroxyl phenol with a long carbon chain in the metaposition. It has the potential as a substitute for phenol in resin phenolic-base chemical products. Research was done to find out the optimum condition for isolation of cardanol from the CNSL, to identify the characteristics of cardanol, and to estimate the feasibility of cardanol production at a commercial level. The study was carried out in five steps, i.e., (1) analyses of physicochemistry of the CNSL; (2) optimization of CNSL decarboxylation to convert anacardic acid into cardanol; (3) optimization of distillation temperature in cardanol isolation; (4) identification of CNSL distillate using the GC-MS, HPLC, and FTIR; and (5) estimation of feasibility of cardanol production. The optimum condition for the CNSL decarboxylation was heating at 140 C for 1 hour. Cardanol was obtained from a vacuum distillation process at 4-8 mmhg, and the optimum temperature was achieved at 280 C with 74.22% yield. Characteristics of CNSL distillate met specifications of the technical cardanol. The components of the CNSL distillate were cardanol (3-[8(Z),11(Z),14-pentadecatrienyl]phenol) 74.25%, resol (3-[8(Z),11(Z),14-pentadecadienyl]phenol) 10.94%, and cardol (3-[8(Z),11(Z),14-pentaecienyl]phenol) 14.81%. A cardanol production industry was feasible to be implemented with NPV Rp5,311,121,638, IRR 45.79%, net B/C 2.46, and PBP 2.22 years. [Keywords: Anacardium occidentale, cashew nut shell liquid, phenolic compounds] INTRODUCTION Potential for cashew nut (Anacardium occidentale) production in Indonesia is good. This is indicated by the annual increase in production of this commodity. In 1999, the cashew nut production reached 88,658 tons of unshelled nuts and by the year of 2002 it had increased to 1) Article in bahasa Indonesia has been published in Jurnal Penelitian Pascapanen Pertanian Vol. 1 No. 1, 2004, p ,439 tons (BPS 2002). This production will continue increasing, since the Directorate General of Estate Crops had implemented programs to enhance extensification and increase cashew nut production, particularly in eastern parts of Indonesia. Cashew plant has a superior characteristic, because it can grow well in areas with marginal agroecological conditions and dry climates. Therefore, this crop has been a priority commodity in eastern parts of Indonesia, such as South-East Sulawesi, West Nusa Tenggara, and East Nusa Tenggara. The main product of cashew plant is cashew nuts, while the secondary products are false fruits and cashew nut shell liquid (CNSL). Currently, both the false fruit and CNSL have not been exploited optimally, mostly just as wastes. The potential for CNSL exploitation in Indonesia is good enough. According to Muljohardjo (1990), the percentages of cashew nut shells (CNS) in unshelled nuts ranged from 45% to50% and the CNSL content in the CNS was about 18-23%. The production of unshelled cashew nuts in 2002 was 94,439 tons and about 42,498-47,220 tons of CNS were obtained, hence it contained about 7,650-10,861 tons of CNSL. The CNSL production in Indonesia was very low as compared to its potential, because most of the cashew nuts were exported in the form of unshelled nuts. Besides, industries that used CNSL as raw material have not been developed domestically. Based on export data of 2002, the volume of unshelled nuts export was 50,385 tons valued US$ 31,213, while that in the form of shelled nuts was 1,332 tons or a value of US$3,597 (BPS 2002). Exports of unshelled nuts reduce its additional values, both in the form of human resources and additional values of CNS. The main components of CNSL are anacardic acid, cardanol, and cardol. These are phenolic compounds that have double bonds in its branched chains. Cardanol compound has chemical structure similar to phenol, so it has the potential to be used as substitute for phenol compound. The difference with phenol is that cardanol has unsaturated branched chains (C 15 ) at the metaposition of the phenol core.

2 12 Risfaheri et al. CNSL and cardanol have a wide range of uses in chemical industry. A cardanol-based resin is commonly used in vehicle s brake lining as binder or friction powder and for surface coating, such as in anticorrosive paint, varnish, and lamination. In India, the lamination industry used tons of CNSL annually for cardanol production as material to produce laminating resin. Cardanol was also used as brick, concrete, steel, and plywood sealer. This compound has characteristics of humidity, acid, and alkaline resistances (Sanoor Cashew & Adarsh Industrial Chemicals 2003). Other cardanol product that has been used commercially are sulphonated ether cardanol, which is used as a wetting agent in textile industries, and amino cardanol ether, which is useful as a mineral oil additive to improve its viscosity, to inhibit sediment formation, and has an antioxidant activity. Waxes with high liquefaction temperatures can also be made from resin cardanol, through reaction of cardanol (3-pentadecyl phenol) with dichlorbutane. The waxes have liquefaction temperatures of o C, and their prices are cheap (Sanoor Cashew & Adarsh Industrial Chemicals 2003). The domestic need of phenol compounds in Indonesia is large enough. With a prediction of production of exterior type plywood about 10% of the total plywood production in Indonesia in 2002, the need of phenol reached 5,807 tons (Risfaheri et al. 2003). The large amount of phenol needs is not including that for other phenolic resin products, such as paint and varnish. Currently, paints, varnish, and glue industries that use phenol as the basic material, commonly use phenol from petrochemical products with a price of Rp 17,500/kg. Cardanol, the main component of CNSL, is expected cheaper than phenol, because it is produced from a waste product. Cardanol has a high potential to be used as substitute of phenol to supply the domestic needs. This study was done to find out an optimum condition to isolate cardanol from CNSL, to identify characteristics of the cardanol, and to estimate the feasibility of cardanol production. MATERIALS AND METHODS The research was conducted from 2002 to 2003, using the CNSL from PT Sekar Alam, Wonogiri, Central Java. A standard cardanol from Sigma was used as control. The apparatus used in the processing were stirrer (Karl Kolb D-6702, West Germany), a flat heater 1000 watts, a thermocontrol (Han Young Electronics Hy72D C), a vacuum distillation apparatus (with a 2 liter flasks and applicable capacity 500 ml, and height of cooler from the flask 10 cm), a jacket heater 1000 watts, and an Edwards model RV12 No.A vacuum pump. Other equipment used in analyses was a ph meter, a viscosimeter (Brookfield), a pycnometer, High Performance Liquid Chromatography (HPLC), Gas Chromatography-Mass Spectrum (GC-MS), and Fourier Transformed Infrared Spectroscopy (FTIR). The study was conducted in five steps as follows: 1. Physical and chemical analyses of CNSL, including water content, ash content, viscosity, specific gravity, ph, iodine value, saponification number, and hydroxyl number. 2. Optimization of time and heating temperature for CNSL decarboxylation. The decarboxylation process was aimed to convert anacardic acid into cardanol, which was indicated by ph changes from acidic to alkaline. The experiment was arranged in a factorial completely randomized design with three replications. The treatments were: (A) five heating temperatures (100, 120, 140, 160, and 200 C), and (B) five times of heating (0.5, 1, 2, 3, and 4 hours). Parameters observed were ph changes, changes of specific gravity during process, CNSL characteristics (ph, viscosity, specific gravity, iodine value, and hydroxyl value) at an optimum decarboxylation condition. 3. Optimization of distillation temperature of CNSL in cardanol isolation. The distillation was done under a vacuum condition (4-8 mmhg). The trial was designed in a factorial completely randomized design with three replications. The treatments were: (A) two different CNSL treatments prior to distillation (with and without decarboxylation), and (B) five distillation temperatures (240, 260, 280, 300, and 300 C). Parameters observed were distillate rendements and changes in distillate characteristics, including specific gravity, viscosity, iodine value, acid number, and hydroxyl value. 4. Identification of CNSL and its distillate using HPLC, GC-MS, and FTIR. The GC-MS specifications used in the identification of CNSL and its distillate were the BALAM method, GC [Hewlett Packard (HP) type 6890 Series], MSD (HP type 5973), Helium (He) carrier gas, Ultra 2 column (HP) 5% methyl siloxane 17 m x 0.20 mm x 0.11 mm, column pressure 11.8 psi. Constanta flow, starting temperature 100 o C, inlet 250 C, energy 70 ev. HPLC specifications used were: Waters-Automatic Gradient Controller, detector (Absorbance Model 440), water pump model 510, column C8 Bondapaq 5 µ (nonpolar type) Q = 3.9 x 150 mm, movement phase of methanol + acetonitril (gradient), temperature 23 C, inject volume 10 µl. The FTIR specification was Bio- Rad Merlin FTS Feasibility study on cardanol production for an industrial level. The criteria analyzed were NPV, IRR, net B/C, and PBP.

3 Isolation of cardanol from cashew nut shell liquid RESULTS AND DISCUSSION Analysis of Physical and Chemical Characteristics of CNSL Results of some physical and chemical characterizations of CNSL and comparison to the Indian and Brazilian standards are presented in Table 1. There were some differences in characteristics of the CNSL samples from Indonesia and those from India and Brazil, particularly in their specific gravity, viscosity, and iodine value. These differences were due to some factors, such as method of extraction, difference in cashew varieties tested, and agroclimatic conditions of the plant growth. The method of extraction had a major effect on the CNSL characteristics. The CNSL used in this study was obtained from a pressed material without heating. According to Khumar et al. (2002), the components obtained from the CNSL extraction using the solvent extraction method were anacardic acid (60-65%), cardol (15-20%), cardanol (10%), and a small amount of methyl cardol. The main CNSL components obtained from extraction using the roasting shell method consisted of cardanol (60-65%), cardol (15-20%), polymetric material (10%), and a small amount of methyl cardol. Tyman et al. (1989) mentioned that the difference in the components was because CNSL contained anacardic acid, which is thermolabile and decomposed into cardanol and carbon dioxide (CO 2 ) upon heating. Optimization of Heating Time and Temperature for CNSL Decarboxylation The CNSL used in this study was highly acidic (ph 4.3), indicating that the anacardic acid content in the liquid was very dominant. Heating CNSL decomposed the anacardic acid into cardanol and CO 2 (Figure 1). These changes were detected based on ph changes of the CNSL from acidic to alkaline (Figure 2). Based on the ph response curves, it was indicated that the higher the heating temperature and the longer the heating time, the higher the ph of the CNSL. Statistically, the heating temperature contributed 65% to the ph changes, while heating time contributed only 35%, and interaction between the two variables contributed 20.22%. Figure 2 also indicates that the lowest temperature to change of ph of the CNSL from acidic to alkaline (ph>7.0) was reached after 1 hour of heating at 140 C. The shortest time to change ph of the CNSL from acidic to alkaline was 0.5 hour at a heating temperature of 180 C. ph OH Figure Figure 2. COOH C 15 H OH + CO 2 + H 2 C 15 H Mechanism of convertion of the anacardic acid into cardanol. Temperature ( C) Heating time (h) Effect of temperatures and heating times on ph of CNSL. Table 1. Characteristics of Indonesian cashew nut shell liquid (CNSL) as compared to that of CNSL standards from Indian and Brazil Characteristics CNSL Indian Standard (IS840) 1) Brazilian Standard 2) Moisture content 4.11 Maximum 1.0 Maximum 1.0 Viscosity 343 Maximum 300 Maximum 600 (25 C) Specific gravity (30 C) (25 C) ph Minimum 6.0 Ash content 1.05 Maximum 1.0 Maximum 1.0 Iodine value Minimum 200 Saponification number Hydroxyl value Sources: 1) Bola Raghavendra Kanath and Sons (2003); 2) Amberwood Trading Ltd. (2003).

4 14 Risfaheri et al. Heating decreased specific gravity of the CNSL (Figure 3). The decrease in specific gravity was due to the release of CO 2 from anacardic acid to form cardanol, which has a smaller specific gravity than the anacardic acid, with the same structural space. According to Krisan Tradelink Private Ltd. (2002), the specific gravity of cardanol at 30 C ranged from 0.93 to 0.95, while the specific gravities of anacardic acid and cardol were and , respectively (Agarwal 1954 in Muljohardjo 1990). The decrease in specific gravity of CNSL after decarboxylation was influenced by the anacardic acid content in the CNSL and the amount of cardanol formed. The change in the CNSL specific gravity was very small at a heating temperature of 100 C. Based on data of ph changes, it was predicted that the amount of cardanol formed or the amount of decarboxylated anacardic acid was very small as indicated by the small increase in ph of the substrate. Data on characteristics of CNSL (Table 2) showed that heating also reduced the substrate viscosity, but increased both iodine and hydroxyl values. The increases in iodine and hydroxyl values were due to reduction in amount of CNSL masses and release of CO 2 and water during the decarboxylation. The decrease in viscosity was due to changes of anacardic acid into cardanol that has a lower viscosity. The cardanol viscosity ranged from 40 to 60 cp (Krisan Tradelink Private Ltd. 2002). The CNSL viscosity prior to the decarboxylation was influenced by the anacardic acid, which is the major component of CNSL. The anacardic acid has a carboxylic group (COOH) in its ortho position of the phenol core. According to Fessenden and Fessenden (1991), the type of a strong dipole-dipole interaction was particularly found between molecules that contained hydrogen atoms that were fixed by nitrogen, oxygen, or fluor. The hydrogen atoms that were partially positive from one molecule were linked into a separated electron pairs from atoms of other molecules, which were electronegative. Under a liquid condition, molecule of this compound has a strong attractant among each other. The effect of the hydrogen bond is a factor causing the high viscosity of the nondecarboxylated CNSL. The carboxylated CNSL had an averages of specific gravity and molecular weight lower than those of the original CNSL, so that the distributions of the molecule composer of CNSL were looser that cause the low energy among the molecules. The low intermolecular energy also had an impact on the decrease of CNSL viscosity. Specific gravity 1,02 1,01 1,00 0,99 0,98 0,97 0,96 Figure 3. Temperature ( C) , Heating time (h) Table 2. Characteristics Effect of temperatures and heating time on specific gravities of CNSL. Characteristics of the CNSL after decarboxylation. CNSL CNSL after decarboxylation 140 C, 1 hour 180 C, 0.5 hour ph Viscosity (30 C, cp) Specific gravity (30 C) Iodine value Hydroxil value Optimation of Distillation Temperature for Cardanol Isolation Rendements of the Distillate The decarboxylated CNSL produced more distillate rendements than the non-decarboxylated distillate (Figure 4). In early step of the distillation, the CNSL was first decarboxylated prior to the distillation process. Hence, this inhibited the process of vapor phase formation that cause the low amount of distillate rendements. Based on the statistical analysis, decarboxylation affected the amount of distillate rendements by 30.72%, while distillation temperature and heating time affected 27.29% and 40.81%, respectively. The highest content of distillate rendements (74.22%) was reached when the decarboxylated CNSL at 140 C for one hour was distillated at 280 C. The cardanol isolation was done based on differences in boiling temperatures of cardanol and cardol. Cardanol has one OH group, while cardol has two OH groups in their aromatic rings. The hydrogen bonds possessed by intermolecular cardanol, therefore, were less than those of cardol, hence the boiling temperature was also lower than cardol. A hydrogen bond connects hydrogen ions of a molecule with other electronegative molecules (intermolecular) or within the same molecule (intramolecular). This hydrogen

5 Isolation of cardanol from cashew nut shell liquid Rendement (%) Figure Distilation temperature ( C) Effect of decarboxylation and distillation temperatures on rendement of CNSL distillate. bond is an additional energy that becomes a characteristic of a molecule containing H atoms linked covalently to the highly electronegative atoms. An additional energy is needed to cut the hydrogen bonds if the respected molecules are to be changed from a liquid phase to a gas phase. Molecules that have more hydrogen bonds possessed higher boiling temperatures than those with less hydrogen bonds. The structure of a cardanol molecule is similar to that of phenol with additional C 15 chains at the meta position. On the other hand, the structure of cardol is similar to that of resorcinol with additional C 15 chains at the meta position. The boiling temperatures of phenol and resorcinol at 1 atmosphere pressure, were 182 and 281 o C, respectively, while the boiling temperature of cardanol was 195 o C at 1 mmhg pressure (Universite de Lousanne 2003). Based on the molecule structures and their analogy to phenol and resorcinol molecules, the boiling temperature of cardol is higher than that of cardanol. The CNSL distillation must be done as quickly as possible to get rid of CNSL to become more viscous due to the effect of heating. According to Steven (2001), some monomers can be polymerized by heating without the presence of additional initiators, when free radicals that initiate the reaction are produced in situ. The time needed to distillate 500 ml CNSL was minutes after the distillation temperature was reached. The distillation product of CNSL was cardanol compound, and the distillate residue was a viscous liquid and almost solid material called residol. Residol is rich of cardol and has a wide uses, such as in metal casting, paint, and surface coating industries (Sanoor Cashew & Adarsh Industrial Chemicals 2003). Characteristics of Distillate without decarboxylation heating 140 C, 1 hour heating 180 C, 0.5 hour (Figure 5). The distillation was done in a closed condition, therefore the CO 2 and H 2 O produced from the nondecarboxylated CNSL were not released into the environment, rather they were trapped in the distillate. On the contrary, distillation of CO 2 and H 2 O were not produced from the decarboxylated CNSL. The induction of CO 2 and H 2 O production weakened delivery power of the distillate (cardanol), which caused a lower viscosity of the distillate than that of the non-decarboxylated CNSL. The viscosity of the distillate also increased with the increasing distillation temperatures. It was as expected, because cardanol is a compound that has varied carbon chains (C 15 H ) in its phenol core. At higher distillation temperatures, the produced cardanol probably has more straight side chains than that resulted at lower temperatures. The difference in the form of side chains was influenced by the dipole-dipole interactions (pull and push away), which is known as the van der Waals potential. The continuous chain molecules can straighten their molecules according to the zig-zag chains that enable atoms from various molecules stay in proper positions with the van der Waals radius. The maximum van der Waals potential can occur between the long chain molecules, while the branched molecules cannot approach closer enough for all atoms to reach the van der Waals distance. Since more energy is needed to overcome the van der Waals potential, cardanol that has continuous (straight) chains posseses a higher boiling temperature than other compound that has branched chains of the same molecular weight (Fessenden and Fessenden 1986). The effect of van der Waals potential that caused production of distillate at high temperatures also caused viscosity of the distillate higher. Iodine values of the distillate were relatively the same in all the treatments, ranging from 214 to 235, and all of them met the cardanol specification (210). Acid values of the distillates were also relatively the same, from 1.10 to 4.03, all of them met acid value specification of the cardanol, Viscosity (cp) without decarboxylation heating 140 C, 1 hour heating 180 C, 0.5 hour Distilation temperature ( o C) Distillate from the decarboxylated CNSL had a higher viscosity than that from the non-decarboxylated CNSL Figure 5. Effect of decarboxylation and distillation temperatures on viscosity of CNSL distillate.

6 16 Risfaheri et al. at least 5 (Krisan Tradelink Private Ltd. 2002). The acid value indicates the number of free fatty acids in the distillate. According to Mahanwar and Kale (1996), CNSL that has an acid value >10 was not suitable for resin production, because it will produce a viscous liquid with very low resin content. The high acid value causes an acid-alkaline reaction with an alkaline catalyst, in the formation of resol from cardanol. The hydroxyl values of the CNSL distillate ranged from 185 to 216, and most of them met cardanol specification on the hydroxyl values ( ) (Natural Extracts 2001). A hydroxil value indicates the number of hydroxyl groups in the distillate. A high hydroxyl value indicates a good quality of the distillate. CNSL distillate were similar to the cardanol fragmentation of Khumar et al. (2002). The CNSL composed of a mixture of phenolic compounds of anacardic acid, cardanol, and cardol. Each compound is a mixture of saturated and unsaturated form of carbon chains that are bound on meta position of the phenol core. According to Kemp (1992), a phenolic compounds will experience fragmentation in its β position of the benzyl ring to form tropolium ions, which are more stable. This position will give a basic peak of the phenol compound at 108 m/z. The COOH group of the anacardic acid will experience fragmentation, because the identification was done at C. This condition had caused difficulties in identification of the phenolic compounds based on their mass spectrum. Identification of Chemical Components of CNSL Identification Using the GC-MS Based on results of identification using the GC-MS (Figure 6), it was known that the CNSL, the decarboxylated CNSL (heated 140 o C for 1 hour), and the CNSL distillates contained 76.91%, 86.61%, and 94.93% phenolic compounds, respectively. Results of fragmentation of the Identification Using the HPLC Results of identification of CNSL using the HPLC (Figure 7) indicated that the chromatogram profile of the distillate was similar to those of either the standard cardanol or that of Khumar et al. (2002). Using the peak enrichment technique and by referring to the chromatogram profile of cardanol from Paramashivappa et al. (2001) and Khumar et al. (2002), components that appear in each peak of the CNSL distillate were identified (Table 3). 108 a Abudance m/z E b Abundance 2.0E Figure 6. Profiles of GC-MS chromatograph: (a) fragmentation of CNSL distillate, and (b) fragmentation of cardanol from Khumar et al. (2002).

7 Isolation of cardanol from cashew nut shell liquid a b c S.P 800 Distillate Standard Khumar et al. (2002) S.P 800 Figure 7. Profiles of chromatograph from the HPLC of: (a) CNSL distillate; (b) standard cardanol, and (c) cardanol chromatograph of Khumar et al. (2002) Table 3. The chemical constituents of CNSL distillate. Sample No. Component Concentration (%) CNSL distillate (1) 3-[8(Z), 11(Z), 14-pentadecatrienyl] phenol (2) 3-[8(Z), 11(Z), 14-pentadecatrienyl] phenol (3) 3-[8(Z), 11(Z), 14-pentadecatrienyl] phenol Standard cardanol (1) 3-[8(Z), 11(Z), 14-pentadecatrienyl] phenol (2) 3-[8(Z), 11(Z), 14-pentadecatrienyl] phenol (3) 3-[8(Z), 11(Z), 14-pentadecatrienyl] phenol Based on the HPLC chromatogram profile, it is identified that cardanol composed of three components as indicated by the presence of three peaks on the HPLC chromatogram profile. According to Tyman (1973), cardanol is a mixture of saturated and unsaturated forms (n = 1, 2, and 3) of a long chain of side carbon bindings, where the chain is bound in the meta position. Cardanol that has unsaturated triene bonds is easily polymerized, while the unsaturated binding of monoene and diene are more stable. Cardanol used in this experiment composed of unsaturated bindings of 14.81% monoene, 10.94% diene, and 74.25% triene. The content of unsaturated triene of the tested cardanol was higher than that of the standard cardanol (46.19%), indicating that the carbon chains in the cardanol are easily polymerized. Identification Using the FITR Interpretation of infrared spectra was done by referring to a correlation map for identification of groups in the infrared spectra. Area between cm -1, the left side of the spectrum, is an area particularly useful for identification of functional groups. This area indicated absorptions that are caused by the extension modes. Areas to the right of 1400 cm -1 are commonly very complicated, because the extension mode or the bent up caused simultaneous absorptions in this area. In this area, usually correlation between a band and a specific functional group cannot be drawn accurately, although each organic compound has a unique absorption in the particular area (Fessenden and Fessenden 1991; Young 1996).

8 18 Risfaheri et al. The FTIR spectrum of cardanol (Figure 8) had absorption bands in cm -1 areas. The peak of absorption of OH group that indicated phenolic compounds appeared at a 3343 cm -1 frequency. The peaks that appear at frequencies of cm -1 indicated the presence of C-H branch chains of the phenolic compounds. Spectra appeared in the cm -1 area indicated C-O groups of the phenolic compounds. The C=C bonds in cardanol were found in the aromatic and branch rings, so that the absorption is strong. The absorption peaks that appeared in the 1595 cm -1 frequency indicated C=C bonds of the aromatic ring and branch chains of cardanol, while the peak that appeared in the 1458 cm -1 frequency indicated the C=C binding only from the aromatic chains. Feasibility Study of Cardanol Production A flowchart of cardanol production with a capacity of 25 tons of raw material per day, which was made with a consideration of the availability of a continuous supply of CNSL is shown in Figure 9. The raw material needs to be supplied by a cashew nut industry or by cashew nut producer that have a capacity of 50 tons of nuts per day or 15,000 tons/year. This designed cardanol factory will absorb 16% of the potential of total CNSL available. The rendement from the CNSL was 20%, while the cardanol rendement from the CNSL was 63%. Annually, the designed factory will produce 945 tons of cardanol as the main product, 405 tons of residol, and 6,000 tons of waste (dregs) as a side product that can be used as fuel source. The factory needs to be built at a site close to centers of cashew nut industries or cashew nut production areas, because the material of cashew nut shell is bulky. Feasibility analyses of investment on building a cardanol production factory was done using the following assumptions: 1. Number of working days per annum = 300 days. 2. Number of working hour per day = 8 hours per shift (two shifts per day). 3. Bank rate = 18%. 4. Costs (capital): obligation 60% and owned 40%. 5. Price of products: cardanol Rp4000/kg, residol Rp2000/ kg, and CNSL waste Rp50/kg. The market price of phenol for industry is Rp17,500/kg. This price is much higher than that of cardanol to be produced. Based on results of feasibility analyses in India, the price of cardanol was one third of the price of phenol (Sanoor Cashew & Adarsh Industrial Chemicals 2003). The parameters of value and component of investments analyzed in the feasibility study were done using the methods of Perry (1999) and Seider et al. (1999). The total investment (Table 4) was calculated using the equation (1). A constant of 1.05 was used as a correction factor in calculating the budget for machinery and equipment delivery to the factory site. The Lang factor (f L ) was used to calculate budgets for factory installation, instrument installation, building, land, service facilities, contractor fees, and contingency. The f L value is dependent on the type of factory; if the raw material is solid, the f L = 3.9, if it is solid/ liquid the f L = 4.1, and if it is liquid, the f L = 4.8 (Seider et al. 1999). % Transmittance OH =CH C-H C=C CH bending OH bending Wavenumber C-O C-C Figure 8. FTIR spectrum of the cardanol.

9 Isolation of cardanol from cashew nut shell liquid Silicon oil (0.25%) (Antifoam) CO 2, H 2 O Cashew nut shell (25 tons/day) Pressing Tank 1 CNSL Tank 2 Decarboxylated CNSL Dreg (20 tons/day) (5 tons/day) Decarboxylation (5 tons/day) (4.5 tons/day) NaOH Formalin (2.55 tons) (Formaldehide ton) Phenol (0.988 ton) (3.15 tons) Tank 3 Cardanol Tank 5 Cardanol-phenol formaldehide glue Mixing tank (3.15 tons/day) Vacuum destillation Tank 4 Residol (1.35 tons/day) Figure 9. Flowchart of a design process for cardanol production. Table 4. The investment cost of cardanol industry at the capacity of 25 tons of cashew shells per day. Equipment Total (unit) Value (Rp/unit) Total value (Rp) Press machine with a capacity of 500 kg/hour 5 125,000, ,000,000 Tank, capacity of 5,000 l 4 25,000, ,000,000 Decarboxylation equipment of l 1 75,000,000 75,000,000 Vacuum distillation of l 1 920,000, ,000,000 Cost of machines and equipments (Cp) 1,720,000,000 Total investment: C TPI = 1.05 f 1 S Cp 1 = 1.05 (4.8) Cp 1 8,668, C TPI correction = F ISF (C TPI ) = 0.42 C TPI 3,640, The total investment (C TPI ) = 1.05 f L å C Pi (1) å C Pi = total cost of machineries and major equipments Lang factor (f L ) = 4.8 Differences in cost of labors, labors efficiency, regulations, and other requisitions in a country, the value of total investment was corrected using the Typical Investment Site Factors (F ISF ). The value of F ISF is dependent on countries where the factory is built. Indonesia does not have F ISF value yet, therefore the Malaysian F ISF (0.42) was used (Perry 1999). Results of the analysis of investment feasibility showed that the values of NPV was Rp 5,311,121,638; IRR 45.79; net B/C 2.46, and PBP 2.22 years. The BEP was reached at a selling price of Rp914,160,770, consisted of cardanol Rp706,651,883.5 ( tons), residol Rp151,425,403.6 (75.71 tons), and CNSL waste Rp56,083, ( tons).

10 20 Risfaheri et al. CONCLUSION Decarboxylation of CNSL to convert anacardic acid into cardanol could be done by heating, with an optimum heating temperature of 140 C for 1 hour. Cardanol was isolated from the CNSL by vacuum distillation (4-8 mmhg) at high temperature, with an optimum temperature of 280 C, and the rendement 74.22%. Characteristics of the CNSL distillate met specifications of the technical cardanol and chromatogram profile of the standard cardanol. The distillate composed of 3- [8(Z),11(Z),14-pentadecatrienyl] phenol 74.25%, 3- [8(Z),11(Z),14-pentadecaienyl] phenol 10.94%, and 3- [8(Z),11(Z),14-pentadecienyl] phenol 14.81%. Construction of cardanol production industry was feasible with values of NPV Rp5,311,121,638; IRR 45.79%; net B/C 2.46; and PBP 2.22 years. The CNSL residues contained cardanol compounds and need to be studied further. The use of cardanol as phenol substitute in various resin products needs to be studied. ACKNOWLEDGMENTS The authors wish to thanks Mr. Lalu Sukarna of the Indonesian Center for Agricultural Posharvest Research and Development, Bogor, and Mr. Dedi Kustiwa of Indonesian Spices and Industrial Crops Research Institutes for their technical assistance in the study. REFERENCES Amberwood Trading Ltd Cashew Nut Shell Liquid. specifications/cnsl.htm. [24 February 2003]. BPS Statistik Perkebunan. Badan Pusat Statisik, Jakarta. Bola Raghavendra Kanath & Sons Cashew Nut Shell Liquid. cnsl.htm. [24 February 2003]. Fessenden, J.C. and J.S. Fessenden Organic Chemistry. Wadsworth, Massachusetts, USA. Kemp, W Organic Spectroscopy. 3 rd ed. MacMillan Education, Hong Kong. Krisan Tradelink Private Ltd Cardanol Specification. /business.cnsl.com/mitsan/card_ p.html. [16 May 2003]. Khumar. P.P., R. Paramashivappa, P.J. Vithayatil, P.V.S. Rao, and A.S. Rao Process of isolation of cardanol from technical cashew (Anacardium occidentale L.) nut shell liquid. J. Agric. Food Chem. 50: Mahanwar, P.A. and D.D. Kale Effect of cashew nut shell liquid (CNSL) on properties of phenolic resins. J. Appl. Polumer Sci. 61: Muljohardjo, M Jambu Mente dan Teknologi Pengolahannya. Liberty, Yogyakarta. Natural Extracts Cardanol. natural-extracts.htm. [22 January 2001] Paramashivappa, R., P.P. Kumar, P.J. Vithayatil, and A.S. Rao Novel method for isolation of major phenolic constituents from cashew (Anacardium occidentale L.) nut shell liquid. J. Agric. Food Chem. 49: Perry, R.H Perry s Chemical Engineer s Handbook. MacGraw-Hill, New York. Risfaheri, et al Perekat Kayu Lapis Berbasis Kardanol. Under patenting process (S ). Sanoor Cashew & Adarsh Industrial Chemicals Residol. / [9 March 2003]. Seider, W.D., J.D. Seider, and D.R. Lewin Process Design Principles. John Wiley & Sons, New York. Steven, M.P Polymer Chemistry: An introduction. Oxford Univ. Press, London. Tyman, J.H.P Long chain phenols. Part III. Identification of the components of a novel phenolic fraction in Anacardium occidentale (cashew nut shell liquid) and synthesis of the saturated member. J. Chem. Soc. Perkins Trans. 1: Tyman, J.H.P., R.A. Johnson, and R.R. Muir The extraction of natural cashew nut shell liquid from the cashew nut (Anacardium occidentale L.). J. Amer. Oil Chem. Soc. 68: Universite de Lausanne Chemexper. com. [21 October 2004]. Young, P.R Basic Infrared Spectroscopy. Organic Chemistry on Line. [1 November 2003].