PROCESS OF PURIFICATION OF CASHEW NUT SHELL LIQUID (CNSL) FOR ISOLATION OF CARDANOL

Jos Osvaldo B. CARIOCA1, Gala Freire Costa de VASCONCELOS1, Rosa Ferreira de Arajo ABREU1 and Carlos Thiago Fernandes MONTEIRO2 1Universidade Federal do Cear -Centro de Tecnologia-Departamento de Eng. Qumica. 60455-760 Fortaleza-Ce. 2. ADINOR-Padetec- Parque de Desenvolvimento Tecnolgico. Campus do Pici. 60455-760. Fortaleza- Ce.

Abstract. Cashew (Anacardium occidentale L.) nut shell liquid (CNSL) contains cardol, methyl-cardol and mainly cardanol (decarboxylated anacardic acid), a meta-substituted n-long chain (C15) unsaturated alkylphenol. With its polymerizable side chain and phenolic group, cardanol has been widely studied for its polymeric properties. Simple derivatives of cardanol were reported to process industrially important properties. Derivatives of cardanol find applications in the form of dyestuffs, plasticizers, and ionexchange resin. This paper describes the separation of cardanol from others constituents (cardol and methyl-cardol) through of different methods us which they base on the use of aminated compositions. The first method utilized consists on cardanol separation through from addition of methanol and ammonium hydroxide and extracted with hexane to obtain high pure cardanol. Another process it s similar to that described above but it s relation of CNSL with ammonium hydroxide and methanol is different. The method third of obtained pure cardanol based on Mannich reaction involves reacting the CNSL with formaldehyde and diethylenetriamine (DETA). Under these conditions, it has been found that while the dihydric phenol cardol forms a high molecular weight reaction product, to submit an extraction with methanol. The organic phase is added petroleum ether and saturated saline solution and the resulting organic layer was concentrated to get pure cardanol. An introduction of functional groups a chitosan is other method of separation which increase efficient adsorption or selectivity of the chitosan, generating a high pure cardanol.

Keywords: CNSL, cardanol and purification.

1. Introduction
Cashew (Anacarduim occidentale L.) nut shell liquid (CNSL) is a unique natural source for insaturated long- chain phenols (KUMAR et al., 2002). Obtained during the processing of cashew nuts, is used in the manufacture of industrially important products such as cement, specialty coatings, primers (MENON et al., 1985), paints and varnishe the main applications of are in the polymers industry. ( PARAMSHIVAPPA et al, 2001). Based resins posses outstanding resistance to the sulfining action of mineral oils and higt resistance to acids and alkalis (KNOP et al., 1979). Is classified into two types, solvents-extrated and technical based of the mode of extraction from cashew nut shell. Techinical contains mainly cardanol (60-65%), cardol (15-20%), polymeric material (10%), and traces of methyl- cardol. Solvent- extracted contains anacardic acid (60-65%), cardol (15-20%), cardanol (10%), and traces of methyl-cardol. (NEUMAN, 1985).

Cardanol
OH

a. R=8Z, 11Z, 14 Pentadecatrienyl b. R= 8Z, 11Z, Pentadecadienyl c. R=8Z pentadecenyl

R

d. R=Pentadecyl

Methyl-cardol

OH H3C HO R

e. R=8Z, 11Z, 14 Pentadecatrienyl f. R= 8Z, 11Z, Pentadecadienyl g. R=8Z pentadecenyl h. R=Pentadecyl

Cardol
OH

i. R=8Z, 11Z, 14 Pentadecatrienyl j. R= 8Z, 11Z, Pentadecadienyl

HO R

l. R=8Z pentadecenyl m. R=Pentadecyl

Fig. 1. Structures of Technical CNSL constituents.

Cardanol is a phenolic compound with a C15 aliphatic chain in the meta position, obtained from cashew nut shell liquid, that find many applications in form of phenol formaldehyde resins in vanishes, paints, and brakes linings (PRABHAKARAN et al., 2001). Derivatives of cardanol find applications in form of dyestaaffs, plasticizers, and ion-exchange resin. Chlorinated products of cardanol were found to have pesticidal action. Sulfonated derivatives of cardanol, tetrahydrocardanol, and their phenolic ethers are used as surface-active agents (KUMAR et al., 2002). It has been established that the dark colors formed during the polymerization of CNSL are attributable to the presence of polyhydric phenols, primarity cardol, the dihydric component, accounts for CNSL a vesicant activity and toxicity (WASSERMAN et al., 1948), However the application of CNSL in the surface-coating industry has been limited (TYMAN et al., 1981). In view of its biological and industrial applications it was considered necessary to development of an efficient method and industrially feasible process for the isolation of all the major phenolic constituents of CNSL (TYMAN et al., 1982). Various methods of purification CNSL are known. Technical CNSL can be distilled under high vacuum, column chromatography. However, this methods are expensives and time consuming and it is not suitable for use on an industrial scale. (TYMAN et al., 1982). This paper has as objective compares the efficiency of some methods of purification of CNSL, for obtaining of a possible more isolated cardanol, seeking your industrial application.

Cardanol presents chemical characteristics and peculiar phisical-chemistries. These characteristics become it one of natural composites of bigger functionality in organic chemistry. Thus, derived from cardanol they can widely be used in different industries with the advantage of being proceeding from one would materia cousin-regional

2. Materials and methods

2.1. Materiais. All organics solvents, chemical, and TLC plates were obtained from Vetec. Chitosan was supplied by Polymar Ind. Com. Imp. Ltd. GC-SM analysis was carried out using a Hewlett-Packard GC 5890 and a Hewlett-Packard 5971A mass selective detector, on an DB-5 column. Sample (1mg) was dissolved in dichloromethane.

2.2. Methods. 2.2.1. Method de purification the Technical CNSL-1. Technical CNSL (10g) was dissolved in methanol (32 mL), and ammonium hydroxide (20 mL) was added and stirred for 15 min. This solution was then extracted with hexane (4 x 20 mL). The organic layer was washed with 5% HCl (10 mL) followed by distilled water (100 mL). Activated charcoal (1 g) was added to the organic layer, stirred for 10 min, and filtered through Celite (1,5 g). The filtrate was dried over anhydrous sodium sulfate and concentrated to get pure cardanol (KUMAR et al., 2002). The purity of cardanol was confirmed by GC/MS (Figure 4).

2.2.2. Method de purification the Technical CNSL-2. Was the amount of used CNSL relative the half of the value of the reference, being followed the same methodology (Figure 5).

2.2.3. Method de purification the Technical CNSL-3. Technical CNSL (60g), 40% formaldehyde and diethylenetriamine were mixed in methanol (200m3). An exothermic reaction took place after mixing the reactants and after thirty minutes a phase separation occurred into an upper, slightly reddish, soluction and a lower phase wich solidified and was dark in colour. The upper phase was decanted and trested with water (40cm3) followed by petroleum ether. Methanol was recovered from the aqueous layer by distillation. The lower solidified phase wich was gel-like was readily removed from the frask (Figure 6). (TYMAN P.H 1985).

2.2.4. Method de purification the Technical CNSL-4. A column chromatography is used that has as phase movable hexane and phase fiza chitosan in a relationship chitosan and technical CNSL of 10:0.1 (Figure 7).

3. Results and discussion

In this methods 1 and 2, the technical CNSL was dissolved in a mixture of methanol and ammonium hydroxide. It was observed that the ratio of methanol and ammonium hydroxide was crucial. Depending on the departure material used the relationship among those two reagents it can vary. In the case of for solvent-

extracted CNSL, the methanol and ammonium hydroxide ratio was 4:5 (PARAMSHIVAPPA et al, 2001). In that first method it was maintained the same relationship of 8:5 exactly mentioned in the for technical CNSL. Already the second method the amount of CNSL used in the process it was reduced by the half. In the case of technical CNSL, due to presence of a higher cardanol percentage in relation to the cardol, the extraction was made through the hexano for obtaining of a pure cardanol. The percentage of hexane could be increased for better visualization of the separation between layers. The cardanol obtained in the two methods it should go by a chemical treatment to remove possible impurity. GC-MS analysis of sample de cardanol of the two methods is accomplished to confirm your degree of purity. (Figure 4 and 5). The chromatogram (Figure 4) regarding the method 1 exhibition the presence of cardanol picks in a percentage of 89.946%, besides cardol (6.602%) and methyl cardol (3.447%). Already the method 2 presented in the chromatogram (Figure 5) cardanol (93.230%) and methyl cardol (6.7%). That shows that those methods increased the cardanol percentage considerably after the separation if compared the percentages of present cardanol in the technical CNSL (NEUMAN, 1985). For the case of the method 03, the separation is based the interaction between dihydric phenols and amines. In the competition between cardanol e cardol, the former with its high first dissociation stage would
HO R HO RNH2 (B) R (1)

+
(A) OH

O-+NH3R

HO

R +NH3O RNH2

R (2)

+
O -+NH3R

O -+NH3R

R RNH2 (3)

+
OH (C)

(D) O -+NH R 3

Fig. 2. Competition between cardol and cardanol to combine with the amine

be expected to combine with the amine (see figure 2). At ambient temperature the equilibrium of (1) probably is well to the right and (2) may be a relatively minor reaction. The equilibrium of (3) would be expected to favor more of the free phenol and lie perhaps equally balanced between the phenol and the salt (TYMAN et al., 1982). The amine diethylenetriamine is effective due have a Kb value of greater than 7.6x10-6. The cardanol obtained was identity and confirmed by GC/MS. (Figure 6). The chromatogram (Figure 6) regarding the method 3 exhibition the presence of cardanol picks in a percentage of 96.164%, besides methyl cardol (3.846%), showing like this its efficiency in the obtaining of a cardanol of high purity. The last analyzed method bases on the use of the chitosan (obtained biopolmero of the reaction of desacetylation of the chitin, a macromolecule, extracted of the carapace of crustaceans) as phase fastens in a column cromatographic for the representatives of technical CNSL separation, since it is a polymeric one (figura 3) that presents in your structure grupamentos amina that you/they allow the cardol adsorption, liberating cardanol firstly for the hexano use as movable phase.

OH H O H NH2 O OH H

Fig.3. Monomer of molecule of chitosan

The first samples confirm the presence of pure cardanol confirmed by GC/MS. (Figure 7) Before the use of the cuitosan in column, the same was submitted the a standardization presenting characteristics several physical-chemistries (Table 1).

Table 1. Physico-chemical characteristics of chitosan

Teste Appearance Deacetykation degree Viscosity pH Scent

Resultado Satisfactory 73.788% 350cP 7,58 Satisfactory

The chromatogram of that method shows the presence of picks of cardanol 98% without lines of methyl cardol and cardol, confirming its efficiency for the obtaining of pure cardanol.

Fig. 4. Chromatogram method 1

Fig. 5. Chromatogram method 2

Fig. 6. Chromatogram method 3

Fig. 7. Chromatogram method 4

4. Conclusions
All the methods were shown efficient in the separation in the technical CNSL for cardanol obtaining in larger percentage. Inside all the four what presented better results that that used cuitosan as phase was it fastens in a column chromatography, since there were not cardol lines nor metilcardol.

References
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Wasserman, D.; Dawson, C. R. Cashew nut shell liquid. III. (1948) The cardol component of Indian cashew nut shell liquid with reference to the liquid s vesicant activity. J. Am. Chem. Soc., 70, 3675-3679.

Acknowledgments
We thank the CNPQ for the financial support and the ADINOR for the laboratorial structure.

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