Decomposition of 2-Isopropylnaphthalene Hydroperoxide into 2

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Decomposition of 2-Isopropylnaphthalene Hydroperoxide into 2-Naphthol and Acetone in the Presence of Acetic Acid and H2O2 Fatma Gu 1 l Boyacı, Serpil Takaç ,* and Tunç er H. O 2 zdamar Department of Chemical Engineering, Ankara University, Tandogˇ an, Ankara, 06100 Turkey

Process conditions for the acid-catalyzed decomposition of 2-isopropylnaphthalene hydroperoxide (2-IPNHP) into 2-naphthol and acetone were investigated in the presence of acetic acid and H2O2 as the solvent and oxidizing reagent, respectively. 2-Naphthol and acetone are produced from 2-IPNHP by the ionic decomposition mechanism; however, reaction conditions that lead to the formation of radicals mainly favor the byproducts dimethyl-2-naphthylcarbinol (DMNC) and acetonaphthone (AN). The effects of the catalyst type and concentration on the 2-naphthol yield and on the product distribution were investigated by HClO4, H2SO4, H3PO4, and HCl. The catalytic activities of the acids in the decomposition of 2-IPNHP to produce 2-naphthol decreased in the order HClO4 > H2SO4 > HCl > H3PO4 depending on their acid strengths in acetic acid. The higher the catalyst concentration employed, the higher the 2-naphthol yield obtained. The high concentrations of 2-IPNHP did not lead to the hydroperoxide-induced decomposition reactions; instead they increased the ionic decomposition rate due to the polar character of 2-IPNHP. The increase in the DMNC concentration in the decomposition medium slightly decreased the 2-naphthol production rate and yield. The increase in temperature in the range of 22-40 °C increased the 2-naphthol production. The process conditions such as low acid strength, low catalyst concentration, and high temperature that lead to radical reactions increased the production of AN. The other byproduct DMNC was also oxidized to 2-IPNHP with H2O2 in the reactor. A 61% yield of 2-naphthol was obtained under the batch reactor conditions of 0.114 mol dm-3 HClO4 and 1.036 mol dm-3 initial 2-IPNHP concentrations at 22 °C. Introduction The chemical pathway of the novel 2-naphthol and acetone process (Talukder and Kates, 1995) that is designed as an alternative (O ¨ zdamar et al., 1989) to the highly energy-intensive conventional fusion process (Talukder and Kates, 1995) starts by the alkylation of naphthalene with propene to give 2-isopropylnaphthalene (2-IPN) (Ç alık and O ¨ zdamar, 1990; Ç alık and O ¨ zdamar, 1994), continues by the oxidation of 2-IPN to 2-isopropylnaphthalene hydroperoxide (2-IPNHP) (Takaç and O ¨ zdamar, 1993; Boyacı et al., 1997; Boyacı et al., 1998; Takaç et al., 1998), and in the end produces 2-naphthol and acetone by the decomposition of 2-IPNHP (Boyacı et al., 1999). In this paper we report on the decomposition process of 2-IPNHP by acid catalysts in the presence of acetic acid (AcOH) and H2O2 as the solvent and oxidizing reagent, respectively. 2-IPNHP decomposes into different products through either radical or ionic reactions depending on the process conditions such as catalyst type and concentration, solvent type, reactant concentration, and temperature. 2-Naphthol, which is of industrial importance as an intermediate in the dye, pigment, rubber, and pharmaceutical industries and in manufacturing of perfuming agents, is produced from 2-IPNHP by the ionic decomposition mechanism that involves nucleophilic elimination, rearrangement, and nucleophilic addition reactions (Boyacı et al., 1999). On the other hand, reaction conditions that lead to the formation of radicals mainly favor dimethyl2-naphthylcarbinol (DMNC) and acetonaphthone (AN) * To whom correspondence should be addressed. Phone: 0090-312-212-67-20/1310.Fax:00-90-312-223-23-95.E-mail: takac@ science.ankara.edu.tr.

(Boyacı, 1998). Therefore, employment of the appropriate process conditions in the 2-IPNHP decomposition process is necessary to be able to produce the desired products with a high conversion and yield. Ionic decomposition of alkyl hydroperoxides occurs by the catalytic effect of acids. However, the strength of the acid catalyst can change the decomposition route, divert the mechanism from ionic to radical, and alter the product distribution. The effects of the catalyst type and concentration on the yield and product distribution in the decomposition reaction of 2-IPNHP are not available in the literature. However, the decomposition ofsthe key intermediate of the analogous reaction pathwayscumene hydroperoxide (CHP) into phenol and acetone has been extensively studied in the presence of H2SO4 (Armstrong, 1950; Kharasch et al., 1950; Topchiev et al., 1964; Pujado et al., 1976; Hatch and Matar, 1978; Wallace, 1996), and this catalyst is currently used in several industrial phenol production plants (Pujado, 1990; Shelpakova et al., 1991; Jordan et al., 1991; Weissermel and Arpe, 1993; Wallace, 1996). The catalytic activities of HClO4 and HCl in the CHP decomposition process are also reported (Kharasch et al., 1950; Tobolsky and Mesrobian, 1954; Kislina et al., 1988; Kislina et al., 1990; Vinnik et al., 1990). In addition, the solid catalysts such as KU-2, zeolite (SH-500), sulfonated poly(styrene-divinylbenzene), VIONIT CS1, and silica-based sulfocationites are used in several alkyl hydroperoxide decomposition processes (Iditoiu et al., 1978; Vodnar, 1991; Shelpakova et al., 1991). Identically, Topchiev et al. (1964) and Talukder and Kates (1995) asserted that 2-IPNHP can be decomposed into 2-naphthol and acetone by using H2SO4, activated fuller clay, or ion-exchange resins. Besides, Shelpakova

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et al. (1991) reported the advantages of solid catalysts over liquid catalysts as making it possible to eliminate the stages of neutralization and removal of salts from the reaction medium, and to eliminate irreversible loss of the catalyst. However, the disadvantages of the solid catalysts were mentioned such as the low activity, low intergeneration range, diffusional complications, swelling of polymer, low heat stability, and proneness to oxidative breakdown. In our earlier experimental works, we observed that organopolymeric catalysts (Amberlite IR-120 P and Amberlite IR-122) had low activity in the decomposition of 2-IPNHP, and they were deformed and catalytically deactivated throughout the reaction (Boyacı, 1994). Therefore, we used liquid acid catalysts (HClO4, H2SO4, and HCl) in our further studies and investigated the effects of the catalyst-solvent interactions on the 2-IPNHP decomposition mechanism, rate, and product distribution (Boyacı et al., 1999). The polarity, dipole moment, acid strength, capacity for hydrogen bonding of the solvent, and the intermolecular forces between the solvent, catalyst, and reactant were found to affect the decomposition yield. Among eight different solvents classified into four groups, AcOH yielded the highest 2-naphthol by the decomposition of 2-IPNHP in the presence of H2O2 (Boyacı et al., 1999). The increase in the peroxide concentration increases the radical decomposition rate rather than the ionic decomposition due to the hydroperoxide-induced decomposition effect (Stannett and Mesrobian, 1950; Kharasch et al., 1950; Hattori et al., 1970; Scott, 1965; Scott, 1993; Sanchez and Myers, 1996). Thomas (1955) reported that the decomposition rate of tetralin hydroperoxide increased with increasing initial reactant concentration in the presence of medicinal white oil as the solvent. Ivanov and Karshalykov (1979) obtained results for CHP decomposition similar to those found for tetralin hydroperoxide by Thomas (1955). Scott (1965) reported that the hydroperoxide-induced decomposition occurred through the formation of hydrogen bonds between hydroperoxide molecules whose strengths depend on the hydroperoxide concentration and type as well as the solvent type. The hydroperoxide decomposition medium may contain impurities of byproducts of the previous oxidation stage, and these impurities affect the yield and product distribution of the decomposition process. The effects of dimethylphenylcarbinol (DMPC) and acetophenone (AP) on the decomposition of CHP in the presence of silica-based sulfocationies and benzene were also investigated by Shelpakova et al. (1991). DMPC had a considerable influence on the decomposition of CHP; when the reactant mixture contained a small amount of DMPC, decomposition practically ceased. The presence of AP, however, had no effect on the decomposition process of CHP in a wide range of concentrations. On the other hand, the rate of the decomposition in the phenol-acetone medium was so high that no influence of the byproducts on the CHP decomposition was observed. Kharasch et al. (1950) reported that the formation of phenol from CHP decreased evidently in the presence of a trace of bases such as alcohols or was inhibited completely by high concentrations of DMPC. Beltrame et al. (1988) found that DMPC converted to R-methylstyrene and its dimers in the presence of phenol, acetone, and H2SO4. Since the presence of carbinol in the decomposition medium decreases the decomposition rate, H2O2 can be introduced into the

reactor to oxidize the carbinol to the alkyl hydroperoxide by the catalytic effect of acids (Kharasch et al., 1950; Davies et al., 1953; Swern, 1970; Ito et al., 1986; Corma et al., 1996). Decker et al. (1992) investigated the stepwise oxidation of 2-IPN by oxygen and H2O2, and submitted the results related to the oxidation of DMNC to 2-IPNHP by H2O2 in the presence of H2SO4 catalyst. In the present study, we used the 2-IPN oxidation mixture, which contains DMNC and AN in addition to 2-IPNHP, as the initial reactant mixture without subjecting it to any separation processes. Therefore, we introduced H2O2 as an oxidant that is also a nucleophile reagent into the decomposition reactor for decreasing DMNC concentration by oxidizing it to 2-IPNHP. Organic peroxides are thermally sensitive compounds because of the facile cleavage of the weak oxygenoxygen bond. They decompose into radicals and molecular products such as alcohols, aldehydes, ketones, and acids at high temperatures; moreover, the product distribution changes with temperature. Milas and Surgenor (1946) reported that tert-butyl hydroperoxide decomposed to give tert-butyl alcohol, acetone, methane, methanol, formaldehyde, carbon monoxide, and water at 250 °C; however, it produced tert-butyl alcohol and oxygen at the temperature range of 95-100 °C. Since the rate of radical decomposition reaction increases with increasing temperature (Stannett and Mesrobian, 1950; Kharasch et al., 1951; Bailey and Godin, 1956; Topchiev et al., 1964; Scott, 1965; Emanuel et al., 1967), high temperature is not favorable for any product formed through the ionic decomposition mechanism such as 2-naphthol from 2-IPNHP. The major objective of the present study is to find the best process conditions for the production of 2-naphthol and acetone from 2-IPNHP with high conversion and yield. We performed the decomposition reactions of 2-IPNHP by four different liquid acid catalysts, which are HClO4, H2SO4, HCl, and H3PO4, and investigated the effects of the catalyst and reactant concentrations, the impurity DMNC concentration, and temperature on the concentrations of 2-IPNHP, 2-naphthol, and radical byproducts DMNC and AN. The reactions were carried out in the presence of AcOH, which was previously found to be the most favorable solvent when H2O2 is present in the medium (Boyacı et al., 1999). The results were discussed in combination with the general features of alkyl hydroperoxides and with the ionic and radical decomposition reactions of hydroperoxides. Experimental Section The experimental runs were carried out in a mechanically agitated, temperature-controlled, batch, multiphase reactor system consisting of a Pyrex reactor equipped with thermometer and condenser at 1000 rpm agitation rate. The isothermal temperature of 22 °C was employed unless otherwise noted. The reactant mixture consisting of 2-IPNHP, DMNC, and AN was produced by the oxidation of 2-IPN as described previously (Boyacı et al., 1998). The decomposition of 2-IPNHP was performed in the presence of the protogenic solvent AcOH. H2O2 was also introduced into the reactor to oxidize DMNC to 2-IPNHP. The effects of the catalyst type and concentration were investigated by HClO4, H2SO4, HCl, and H3PO4. The initial concentrations of 2-IPNHP, DMNC, AN, and H2O2 were 1.078, 0.222, and 8.680 × 10-3 and 0.255 mol dm-3, respectively, in the decomposition reactions carried out by HClO4, H2SO4,

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and HCl catalysts. The reactant mixture consisting of 0.993 mol dm-3 2-IPNHP, 0.285 mol dm-3 DMNC, 0.010 mol dm-3 AN, and 0.321 mol dm-3 H2O2 was used in the reactions by H3PO4. The effects of impurities on the decomposition process were studied by using reactant mixtures of differing DMNC concentrations that were produced under different 2-IPN oxidation conditions (Takaç et al., 1998). The concentrations of 2-IPNHP and total peroxide were followed by iodometric titration (Wagner et al., 1947; Dickey et al., 1949). 2-Naphthol, DMNC, and AN were analyzed with an FTIR spectrophotometer (MIDAC) using ZnCe disks at 3311, 3680, and 1682 cm-1 wavenumbers, respectively (Boyacı, 1998). Samples were also analyzed with gas chromatography (HP 5890) using a methylsilicone fused-silica capillary column to follow decomposition products (Boyacı, 1998). Results Catalytic Activities of HClO4, H2SO4, and HCl. We reported the catalytic activities of HClO4, H2SO4, and HCl in the 2-IPNHP decomposition process in the presence of eight different solvents, and explained the solvent-catalyst interactions through the ionic decomposition mechanism in our previous paper (Boyacı et al., 1999). According to the results of that research, the characters of the catalyst and solvent, and more significantly the interactions between them and other reaction components, affect the decomposition mechanism and product yield. The strength and ionization degrees of the acid catalyst in the solvent as well as the polarity of the solvent are the most important properties to be taken into account for the high yield and conversion. The protogenic solvent AcOH gives the highest 2-naphthol yield; however, the catalytic activity of the acids changes depending on their acid strengths in AcOH. Since the acid strength of HClO4 is higher than those of H2SO4 and HCl in AcOH (Jander and Lafrenz, 1970), the higher yield of 2-naphthol was obtained by HClO4 catalyst under the most favorable reaction conditions. As the catalyst concentration is among the parameters that influence the progress of the reaction according to the ionic decomposition mechanism, in the present study we investigated the effect of HClO4, H2SO4, HCl, and H3PO4 concentrations on the 2-IPNHP decomposition process in the presence of AcOH and H2O2 as the solvent and oxidizing reagent, respectively. Effect of HClO4 Concentration. HClO4, which is an oxyacid of one proton, is the most favorable catalyst for 2-naphthol production from 2-IPNHP in the presence of AcOH (Boyacı et al., 1999). The effect of HClO4 concentration on the 2-IPNHP decomposition reaction was investigated at 0.029, 0.057, and 0.114 mol dm-3 HClO4 values. The decomposition rate of 2-IPNHP as well as the production rate and concentration of 2-naphthol increased with increasing HClO4 concentration (Figure 1). The DMNC concentration decreased with residence time for all the acid concentrations, and the DMNC consumption rate increased with increasing HClO4 concentration (Figure 2). DMNC, which was initially present in the decomposition medium, can be produced from 2-IPNHP and be oxidized to AN through radical reactions, or can be oxidized to 2-IPNHP by H2O2 depending on the reaction conditions. The variations in the DMNC concentration with reaction parameters indicate that DMNC converted to either AN or 2-IPNHP in the decomposition reactor. On the other hand, the AN concentration increased with residence time, indi-

Figure 1. Effect of HClO4 concentration on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 1.078 mol dm-3, CDMNC,o ) 0.222 mol dm-3, CAN,o ) 8.680 × 10-3 mol dm-3, CH2O2 ) 0.255 mol dm-3, T ) 22 °C, N ) 1000 rpm. HClO4 concentration for 2-IPNHP, mol dm-3: (O) 0.029; (4) 0.057; (0) 0.114. HClO4 concentration for 2-naphthol, mol dm-3: (b) 0.029; (2) 0.057; (9) 0.114.

Figure 2. Effect of HClO4 concentration on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 1.078 mol dm-3, CDMNC,o ) 0.222 mol dm-3, CAN,o ) 8.680 × 10-3 mol dm-3, CH2O2 ) 0.255 mol dm-3, T ) 22 °C, N ) 1000 rpm. HClO4 concentration for DMNC, mol dm-3: (O) 0.029; (4) 0.057; (0) 0.114. HClO4 concentration for AN, mol dm-3: (b) 0.029; (2) 0.057; (9) 0.114.

cating that it is a byproduct of the 2-IPNHP decomposition process (Figure 2). As the increase in acid concentration prevents the radical decomposition of 2-IPNHP, the AN concentration decreased with increasing HClO4 concentration. These results show that the ionic decomposition of 2-IPNHP for 2-naphthol production can be achieved at high acid concentrations. A concentration of 0.114 mol dm-3 HClO4 is the favorable one for 2-naphthol production with a yield of 61%. Effect of H2SO4 Concentration. H2SO4, which is an oxyacid of two protons, is the second favorable catalyst for 2-naphthol production from 2-IPNHP (Boyacı et al., 1999); however, it is not as strong an acid as HClO4 in AcOH. The effect of H2SO4 concentration on the 2-IPNHP decomposition process was investigated at 0.029, 0.057, and 0.114 mol dm-3 H2SO4 values. The initial rates of 2-IPNHP decomposition and 2-naphthol production increased with catalyst concentration (Figure 3), whereupon the concentration of 2-naphthol increased with increasing H2SO4 concentration. The reaction rates were lower than those obtained by HClO4. The variation


Figure 3. Effect of H2SO4 concentration on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 1.078 mol dm-3, CDMNC,o ) 0.222 mol dm-3, CAN,o ) 8.680 × 10-3 mol dm-3, CH2O2 ) 0.255 mol dm-3, T ) 22 °C, N ) 1000 rpm. H2SO4 concentration for 2-IPNHP, mol dm-3: (O) 0.029; (4) 0.057; (0) 0.114. H2SO4 concentration for 2-naphthol, mol dm-3: (b) 0.029; (2) 0.057; (9) 0.114.

Figure 5. Effect of HCl concentration on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 1.078 mol dm-3, CDMNC,o ) 0.222 mol dm-3, CAN,o ) 8.680 × 10-3 mol dm-3, CH2O2 ) 0.255 mol dm-3, T ) 22 °C, N ) 1000 rpm. HCl concentration for 2-IPNHP, mol dm-3: (O) 0.057; (4) 0.114; (0) 0.343; (]) 0.688; (+) 1.375. HCl concentration for 2-naphthol, mol dm-3: (b) 0.057; (2) 0.114; (9) 0.343; ([) 0.688; (*) 1.375.

Figure 4. Effect of H2SO4 concentration on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 1.078 mol dm-3, CDMNC,o ) 0.222 mol dm-3, CAN,o ) 8.680 × 10-3 mol dm-3, CH2O2 ) 0.255 mol dm-3, T ) 22 °C, N ) 1000 rpm. H2SO4 concentration for DMNC, mol dm-3: (O) 0.029; (4) 0.057; (0) 0.114. H2SO4 concentration for AN, mol dm-3: (b) 0.029; (2) 0.057; (9) 0.114.

Figure 6. Effect of HCl concentration on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 1.078 mol dm-3, CDMNC,o ) 0.222 mol dm-3, CAN,o ) 8.680 × 10-3 mol dm-3, CH2O2 ) 0.255 mol dm-3, T ) 22 °C, N ) 1000 rpm. HCl concentration for DMNC, mol dm-3: (O) 0.057; (4) 0.114; (0) 0.343; (]) 0.688; (+) 1.375 HCl concentration for AN, mol dm-3: (b) 0.057; (2) 0.114; (9) 0.343; ([) 0.688; (*) 1.375.

in the DMNC concentration with residence time in the presence of H2SO4 differed from that of HClO4 at the same acid catalyst concentrations. At the lowest catalyst concentration, the DMNC concentration first increased and then decreased with residence time. However, at the medium concentration of H2SO4, DMNC concentration decreased after a short period of time. Further, at the highest acid concentration DMNC started to be consumed at the beginning of the decomposition reaction (Figure 4). This variation in the DMNC concentration shows that DMNC is produced from 2-IPNHP through radical reactions at low acid concentration. However, with the increase in acid concentration, the oxidation rate of DMNC by H2O2 superimposes upon radical reactions and DMNC starts to be consumed. The formation of AN was also observed in the presence of H2SO4 (Figure 4). Contrary to the results obtained by HClO4, the concentration of AN increased with H2SO4 concentration. Since H2SO4 is a less strong acid than HClO4, the increase in the H2SO4 concentration increased the homolytic fission of the hydroperoxide molecule more

than the ionic reactions in the concentration range studied. The best H2SO4 concentration that gives a 54% yield of 2-naphthol is 0.114 mol dm-3. Effect of HCl Concentration. The decomposition of 2-IPNHP in the presence of HCl, which is a hydroacid of one proton and weaker than HClO4 and H2SO4 in AcOH, was carried out at 0.057, 0.114, 0.343, 0.688, and 1.375 mol dm-3 HCl concentrations. The initial decomposition rate of 2-IPNHP increased with the increase in catalyst concentration between 0.057 and 0.343 mol dm-3 HCl; however, further increase in acid concentration did not change the decomposition rate (Figure 5). The production rate of 2-naphthol increased with HCl concentration as seen in Figure 5. The DMNC concentration decreased with residence time at all the catalyst concentrations except for 0.057 mol dm-3 HCl, which indicates the formation of DMNC from 2-IPNHP at low acid concentration and its consumption by H2O2 at high acid concentrations (Figure 6). At higher concentrations of HCl than 0.343 mol dm-3 the consumption rate of

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Figure 7. Effect of H3PO4 concentration on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 0.993 mol dm-3, CDMNC,o ) 0.285 mol dm-3, CAN,o ) 0.010 mol dm-3, CH2O2 ) 0.321 mol dm-3, T ) 22 °C, N ) 1000 rpm. H3PO4 concentration for 2-IPNHP, mol dm-3: (O) 0.072; (4) 0.143. H3PO4 concentration for 2-naphthol, mol dm-3: (b) 0.072; (2) 0.143.

DMNC did not change. The concentration and production rate of AN first increased and then decreased with increasing HCl concentration. At the low concentrations of HCl, radical reactions preferably occur; however, with increasing the acid catalyst concentration, the decomposition route diverts to ionic reactions and consequently the AN production decreases. These results show that the decomposition of 2-IPNHP for 2-naphthol is better obtained at high HCl concentrations. A 52% yield of 2-naphthol was obtained at 1.375 mol dm-3 HCl concentration. Effect of H3PO4 Concentration. H3PO4 is an oxyacid of three protons and is weaker than HClO4, H2SO4, and HCl. The effect of H3PO4 concentration on the decomposition of 2-IPNHP was investigated at 0.072 and 0.143 mol dm-3 H3PO4 concentrations. The decomposition rate of 2-IPNHP and the production rate of 2-naphthol increased with increasing H3PO4 concentration (Figure 7). The concentration of DMNC first increased and then decreased insignificantly with residence time; however, it did not change considerably with catalyst concentration (Figure 8). The concentration of AN increased slightly with residence time independently of the catalyst concentration (Figure 8). Although the 2-naphthol yield increased with catalyst concentration, it was low and the residence time for the high yield was longer. Therefore, H3PO4 is not a good catalyst for the decomposition process of 2-IPNHP into 2-naphthol and acetone. A 12% yield of 2-naphthol was obtained at 0.143 mol dm-3 H3PO4 concentration. Effect of Initial 2-IPNHP Concentration. The effect of the initial reactant concentration on the decomposition process was investigated at 0.959, 0.993, and 1.036 mol dm-3 2-IPNHP concentrations in the presence of HClO4 as the catalyst, where CDMNC/CHClO4, CAN/CHClO4, and CH2O2/CHClO4 ratios were 1.99, 0.07, and 2.24, respectively. The initial decomposition rate and final concentration of 2-IPNHP did not change considerably with increasing initial 2-IPNHP concentration; however, the concentration and the production rate of 2-naphthol increased (Figure 9). The DMNC concentration decreased with residence time independently of the initial reactant concentration (Figure 10). The concentration of AN increased with residence time at 0.959 and 0.993 mol dm-3 initial 2-IPNHP concentrations,

Figure 8. Effect of H3PO4 concentration on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 0.993 mol dm-3, CDMNC,o ) 0.285 mol dm-3, CAN,o ) 0.010 mol dm-3, CH2O2 ) 0.321 mol dm-3, T ) 22 °C, N ) 1000 rpm. H3PO4 concentration for DMNC, mol dm-3: (O) 0.072; (4) 0.143. H3PO4 concentration for AN, mol dm-3: (b) 0.072; (2) 0.143.

Figure 9. Effect of initial 2-IPNHP concentration on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. CDMNC,o/CHClO4 ) 1.99, CAN,o/ CHClO4 ) 0.07, CH2O2/CHClO4 ) 2.24, T ) 22 °C, N ) 1000 rpm. Initial 2-IPNHP concentration for 2-IPNHP, mol dm-3: (O) 0.959; (4) 0.993; (0) 1.036. Initial 2-IPNHP concentration for 2-naphthol, mol dm-3: (b) 0.959; (2) 0.993; (9) 1.036.

whereas AN kept its initial concentration value at 1.036 mol dm-3 initial 2-IPNHP concentration (Figure 10). Although a decrease was expected in the 2-naphthol production at high initial 2-IPNHP concentrations related to the hydroperoxide-induced decomposition effect, higher yields of 2-naphthol were obtained at higher 2-IPNHP concentrations. At 0.959, 0.993, and 1.036 mol dm-3 initial 2-IPNHP concentrations, yields of 44, 45, and 61% for 2-naphthol were obtained, respectively. Effect of Impurities. The effect of impurities existing in the reactant mixture on the decomposition process of 2-IPNHP to produce 2-naphthol and acetone was investigated at two different initial DMNC concentrations, 0.222 and 0.285 mol dm-3. The initial reactant mixture used in the experiments contained 0.993 mol dm-3 2-IPNHP, 0.010 mol dm-3 AN, and 0.321 mol dm-3 H2O2. The 2-IPNHP decomposition rate did not change with initial DMNC concentration where the concentration and production rate of 2-naphthol decreased with increasing initial DMNC concentration (Figure 11). The DMNC concentration decreased with residence time and did not change with initial DMNC concentration (Figure


Figure 10. Effect of initial 2-IPNHP concentration on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. CDMNC,o/CHClO4 ) 1.99, CAN,o/CHClO4 ) 0.07, CH2O2/CHClO4 ) 2.24, T ) 22 °C, N ) 1000 rpm. Initial 2-IPNHP concentration for DMNC, mol dm-3: (O) 0.959; (4) 0.993; (0) 1.036. Initial 2-IPNHP concentration for AN, mol dm-3: (b) 0.959; (2) 0.993; (9) 1.036.

Figure 12. Effect of initial DMNC concentration on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 0.993 mol dm-3, CAN,o ) 0.010 mol dm-3, CH2O2 ) 0.321 mol dm-3, CHClO4 ) 0.143 mol dm-3, T ) 22 °C, N ) 1000 rpm. Initial DMNC concentration for DMNC, mol dm-3: (O) 0.222; (4) 0.285. Initial DMNC concentration for AN, mol dm-3: (b) 0.222; (2) 0.285.

Figure 11. Effect of initial DMNC concentration on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 0.993 mol dm-3, CAN,o ) 0.010 mol dm-3, CH2O2 ) 0.321 mol dm-3, CHClO4 ) 0.143 mol dm-3, T ) 22 °C, N ) 1000 rpm. Initial DMNC concentration for 2-IPNHP, mol dm-3: (O) 0.222; (4) 0.285. Initial DMNC concentration for 2-naphthol, mol dm-3: (b) 0.222; (2) 0.285

Figure 13. Effect of temperature on the 2-IPNHP and 2-naphthol concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 0.993 mol dm-3, CDMNC,o ) 0.285 mol dm-3, CAN,o ) 0.010 mol dm-3, CH2O2 ) 0.321 mol dm-3, CHClO4 ) 0.143 mol dm-3, N ) 1000 rpm. Temperature for 2-IPNHP, °C: (O) 22 °C; (4) 30 °C; (0) 40 °C. Temperature for 2-naphthol, °C: (b) 22 °C; (2) 30 °C; (9) 40 °C.

12). The AN concentration increased with the increase both in residence time and in initial DMNC concentration (Figure 12). Although a decrease in the 2-naphthol yield was obtained with increasing DMNC concentration as expected, this decrease is not a considerable value for the DMNC concentration range studied. Effect of Temperature. The thermal decomposition of hydroperoxides gives free radicals and leads to radical-induced reactions; however, 2-naphthol is produced only through the ions. We investigated the effect of temperature on the 2-IPNHP decomposition reaction at a low-temperature range to minimize the formation of the racidal products. The reactions were carried out at 22, 30, and 40 °C temperatures in the presence of 0.143 mol dm-3 HClO4 catalyst. The rates of 2-IPNHP decomposition and 2-naphthol production increased with the increase in temperature (Figure 13). The concentration of DMNC decreased rapidly with residence time independently of temperature (Figure 14). The production rate of AN, which forms mainly through radical reactions, increased with temperature as expected (Figure 14). By using initial rates, the activation energies from the Arrhenius plots of the 2-IPNHP

Figure 14. Effect of temperature on the DMNC and AN concentrations in the decomposition of 2-IPNHP in the presence of AcOH and H2O2. C2-IPNHP,o ) 0.993 mol dm-3, CDMNC,o ) 0.285 mol dm-3, CAN,o ) 0.010 mol dm-3, CH2O2 ) 0.321 mol dm-3, CHClO4 ) 0.143 mol dm-3, N ) 1000 rpm. Temperature for DMNC, °C: (O) 22 °C; (4) 30 °C; (0) 40 °C. Temperature for AN, °C: (b) 22 °C; (2) 30 °C; (9) 40 °C.

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decomposition and 2-naphthol production reactions were calculated as 11.872 and 9.525 kcal/mol, respectively. Discussion and Conclusions Decomposition of organic peroxides into molecular products proceeds through either radical or ionic reactions depending on the reaction conditions. The acidcatalyzed decomposition of 2-IPNHP for 2-naphthol and acetone production occurs by the ionic reaction mechanism. This mechanism involves the formation of the protonated hydroperoxide by the acid catalyst, and the conversion of this unstable cation into 2-naphthol and acetone in sequence by water elimination, aromatic group migration, and water addition reactions (Boyacı et al., 1999). The strength of the acid catalyst and the interactions between the acid, reactant, and solvent affect the course of the reactions. In the first step of this reaction sequence, a proton is formed by the ionization of the acid in the solvent, and this proton is then attached to the 2-IPNHP molecule, which contains an electronegative oxygen atom to give the protonated peroxide. This step is relatively fast; however, the concentration of the proton is dependent on the strength of the acid catalyst. Since AcOH was previously found to be the convenient solvent for 2-naphthol and acetone production from 2-IPNHP (Boyacı et al., 1999), we used AcOH throughout the experiments. We investigated the effect of catalyst concentration with three oxyacids, i.e., HClO4, H2SO4, and H3PO4, and a hydroacid, i.e., HCl, whose ionization degrees and strengths in AcOH are different and showed that the acid-reactant interaction depends on the strength of the acid used in the reactor. The strength of the acids in AcOH decreases in the order HClO4 (pK ) 4.87) > H2SO4 (pK ) 7.24) > HCl (pK ) 8.55) (Bruckenstein and Kolthoff, 1956). Consistent with this pattern, we observed that the catalytic activities of acids for the decomposition of 2-IPNHP and production of 2-naphthol decreased in the order HClO4 > H2SO4 > HCl > H3PO4. Since the concentration of acid proton decreases when the acid catalyst does not completely ionize in the reaction medium, the production of the protonated peroxide cation that is obtained in the first step of the ionic decomposition mechanism decreases. In addition, the residence time for the same 2-naphthol yield decreases by increasing the catalyst concentration. DMNC, which is initially present in the decomposition medium, can also be formed from 2-IPNHP through the radical reactions as one of the byproducts of the decomposition reaction. DMNC can convert to alkenes (eqs 1 and 2) and ethers (eqs 1 and 3, or eqs 1 and 4) in the decomposition reactor or be oxidized to 2-IPNHP by H2O2 (eqs 1 and 5) as follows:

C10H7(CH3)2COH + H+ f C10H7(CH3)2COH2+ f C10H7(CH3)2C+ + H2O (1) C10H7(CH3)2C+ f C10H7C(CH3)dCH2 + H+

(2)

C10H7(CH3)2C+ + C10H7(CH3)2COH f C10H7(CH3)2COC(CH3)2C10H7 + H+ (3) C10H7(CH3)2C+ + C10H7OH f C10H7(CH3)2COC10H7 + H+ (4) C10H7(CH3)2C+ + H2O2 f C10H7(CH3)2COOH + H+ (5)

On the other hand, DMNC is able to combine the catalyst proton more easily than 2-IPNHP as it is more basic than the hydroperoxide; however, the following water elimination reaction from the cation of DMNC is more difficult because of the strong C-O bond in the molecule. DMNC can also produce the other byproduct AN, which is alternatively formed through the radical decomposition reactions of 2-IPNHP (Takaç and O ¨ zdamar, 1993; Takaç et al., 1998). The production rates and concentrations of these byproducts depend on the medium properties and the decomposition mechanism of 2-IPNHP. Because of the different reactions of DMNC in the decomposition medium, a systematic variation in the DMNC concentration with reaction parameters was not observed. DMNC is not produced in the presence of a strong acid, i.e., HClO4; instead, it is consumed to produce 2-IPNHP or AN. However, with the decrease in acid strength the higher concentrations of catalyst are required to prevent DMNC production. The formation of the other byproduct, i.e., AN, is through the radical reactions; therefore, the decrease in both acid concentration and strength increased the AN concentration in the decomposition reactor. The concentration of organic peroxides in the reaction medium is an important process parameter since both the hydroperoxide-induced and radical-induced decomposition reactions increase with increasing hydroperoxide concentration (Kharasch et al., 1950; Topchiev et al., 1964; Scott, 1965, Scott, 1993; Sanchez and Myers, 1996). As a result of the induced decomposition reactions, we expected a decrease in the yield and selectivity of 2-naphthol at high initial 2-IPNHP concentrations. However, the 2-naphthol production rate and concentration increased with initial 2-IPNHP concentration. According to the ionic decomposition mechanism, 2-IPNHP, which has a nucleophile character, can attach to the carbocation instead of water in the nucleophilic addition reaction (Boyacı et al., 1999). This is because hydroperoxides are stronger nucleophiles than water (Swern, 1971). In addition, the rate of the nucleophilic elimination reaction, that is, the water elimination reaction, increases with increasing 2-IPNHP concentration due to the slightly polar character of 2-IPNHP. As a result of these properties of 2-IPNHP, we did not observe the induced peroxide effect for the initial 2-IPNHP concentration range studied. The reactant composition is another parameter for the decomposition reactions of the peroxides. Hydroperoxide, which is the first product of the hydrocarbon oxidation, can be used in the decomposition processes without purification. However, byproducts of the oxidation can give further reactions either with the decomposition products or with each other in the presence of the acid catalysts, leading to new byproducts (Kharasch et al., 1951; Beltrame et al., 1988; Shelpakova et al., 1991). Our studies carried out for the purification of 2-IPNHP resulted in obtaining highly pure 2-IPNHP; however, the loss of 2-IPNHP up to 20% is indeed important for the process (Boyacı, 1994). Consequently, we used the oxidation reaction mixture that contains low concentrations of DMNC and AN without any downstream processing in the 2-IPNHP decomposition experiments. The reactions of DMNC (eqs 1-5) are particularly important as they change the resulting 2-naphthol yield and selectivity. The effect of impurities was investigated with different oxidation mixtures possessing different DMNC concentrations. The decom-


position rate and conversion of 2-IPNHP did not change with initial DMNC concentration. However, the production rate and yield of 2-naphthol decreased with increasing DMNC concentration. These results are consistent with the literature (Kharasch et al., 1950; Beltrame et al., 1988; Shelpakova et al., 1991). By increasing the DMNC concentration, the formation rate and concentration of AN also increased. These results indicate that the formation of AN occurs via DMNC. Since the decomposition reactions were carried out in the presence of H2O2 that oxidized DMNC to 2-IPNHP in the 2-IPNHP decomposition reactor, the effect of initial DMNC concentration on the DMNC consumption was not observed clearly in this study. Since peroxides are heat-sensitive compounds and decompose into radicals and unstable products at high temperatures, we performed the decomposition reactions of 2-IPNHP at 22, 30, and 40 °C, and observed that the increase in temperature increased the 2-naphthol production rate and yield. Since DMNC can give several reactions in the decomposition medium, the effect of temperature on the DMNC production is not observed clearly in the experiments. The concentration of AN increased with temperature as a result of the radical decomposition of 2-IPNHP at high temperatures. Under the best conditions developed for the high 2-naphthol yield and selectivity in the presence of AcOH and H2O2, which are the HClO4 concentration of 0.114 mol dm-3 and initial 2-IPNHP concentration of 1.036 mol dm-3 at 22 °C, 2-naphthol production was achieved with 61% yield. In this research, we carried out the decomposition of 2-IPNHP in the presence of H2O2, which was introduced into the reactor to oxidize DMNC to 2-IPNHP to prevent its retarding effect on the ionic decomposition reactions. The increase in the DMNC consumption rate with both acid strength and acid concentration (Figures 2, 4, and 6) led us to conclude that H2O2 converted DMNC to 2-IPNHP under acidic conditions. To evaluate the effect of H2O2 on the process, the decomposition reaction of 2-IPNHP was carried out at different H2O2 concentrations and obtained 59, 67, 61, 47, and 47% 2-naphthol yields at 0, 0.164, 0,225, 0.321, and 0.619 mol dm-3 H2O2 concentrations, respectively (Boyacı, 1998). The increase in the 2-naphthol yield with increasing H2O2 concentration from 0 to 0.167 mol dm-3 shows the increased conversion of DMNC to 2-IPNHP, which in turn decomposes to give 2-naphthol and acetone. However, H2O2 is a nucleophile reagent and can also contribute to the ionic reaction sequence through nucleophilic reactions. The decrease in the 2-naphthol yield after 0.167 mol dm-3 H2O2 concentration is due to the nucleophile character of H2O2. The process conditions in the absence of H2O2, and the effect of H2O2 as a nucleophile reagent on the ionic decomposition mechanism, will be presented in the papers that are under preparation. The separation yield of 2-naphthol is also an industrially important parameter; therefore, we performed some separation experiments to find the best procedure to recover 2-naphthol. We separated 2-naphthol produced under the best process conditions from the reaction mixture that consisted of the solvent AcOH, coproduct acetone, byproduct AN, and inorganic compounds (acid, water, and H2O2). The mixture was first neutralized with NaHCO3/Na2CO3 to separate AcOH and then with NaOH to precipitate 2-naphthol. The following acid treatment of sodium naphthoxide recovered pure 2-naph-

thol. Since the differences between the boiling points of the remaining compounds in the organic phase are large (56 and 301 °C for acetone and AN, respectively (Weast 1984)), their separation was performed by distillation easily. We achieved ca. 95% recovery of the produced 2-naphthol after this separation procedure. Acknowledgment We are grateful to the Scientific and Technical Research Council of Turkey (TU ¨ BI˙ TAK) that encouraged us to start the research on the 2-naphthol and acetone process by the project Contract No. MAG-623 (1984-1988), and to the Industrial Biotechnology Department of Ankara University Biotechnology Research Center for their collaboration. F.G.B. was awarded a Ph.D. scholarship by TU ¨ BI˙ TAK (BAYG). Nomenclature AcOH ) acetic acid AN ) 2-acetonaphthone, C10H7(CH3)CO AP ) acetophenone C ) concentration, mol dm-3 CHP ) cumene hydroperoxide DMNC ) dimethyl-2-naphthylcarbinol, C10H7(CH3)2COH DMPC ) dimethylphenylcarbinol IPN ) isopropylnaphthalene, C10H7(CH3)2CH 2-IPNHP ) 2-isopropylnaphthalene hydroperoxide, C10H7(CH3)2COOH N ) agitation rate, rpm pK ) dissociation constant t ) residence time, h T ) temperature, °C

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Received for review March 15, 1999 Revised manuscript received June 18, 1999 Accepted July 7, 1999 IE9901877

Decomposition of 2-Isopropylnaphthalene Hydroperoxide into 2

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