Oxidation naphthalene

Although BASF are said to have produced phthalic anhydride by oxidizing naphthalene as early as 1916, the first serious investigations were described by H. D. Gibbs and his associates at the US Bureau of Chemistry. Gibbs and Condover were granted a large number of patents from 1917 for the production of phthalic anhydride from naphthalene.  

Up to about 1945 the typical naphthalene oxidation catalyst was fused vanadium pentoxide, sometimes combined with molybdenum trioxide, on an inert support. At that time US production of phthalic anhydride was probably less than 60,000 tonnes year and catalyst quality was not very important. 

Over a period of time, the introduction of alkah sulfates to moderate the reaction led to some improvements in selectivity. The developments may have 

---

Fixed-Bed Vapor-Phase Oxidation of Naphthalene. A sihca gel or sihcon carbide support is used for catalyst involved in the oxidation of naphthalene. The typical naphthalene oxidation catalyst is a mixture of vanadium oxide and alkali metal sulfate on the siUca support. Some changes, such as the introduction of feed vaporizers, are needed to handle a naphthalene feed (14), but otherwise the equipment is the same. 

An alternative route to phthalic anhydride is the partial oxidation of naphthalene. The heat of reaction is — 430 kcal/mol. This reaction can be performed using a promoted V2O5 catalyst on silica, much like that considered in Example 9.1. Suppose In(fik) = 31.6800—19,100/T for the naphthalene oxidation reaction and that the subsequent, complete oxidation of phthalic anhydride follows the kinetics of Problem 9.3. Suppose it is desired to use the same reactor as in Example 9.1 but with a,>, = 53g/ m. Determine values for and T aii that maximize the output of phthalic anhydride from naphthalene. 

Dunn NW, IC Gunsalus (1973) Transmissible plasmid coding early enzymes of naphthalene oxidation in Pseudomonas putida. J Bacteriol 114 974-979. 

Ensley BD, BJ Ratzken, TD Osslund, Ml Simon, LP Wackett, DT Gibson (1983) Expression of naphthalene oxidation genes in Escherichia coli results in the biosynthesis of indigo. Science 222 167-169. 

Oxidations of polyaromatics over Ti02 have been studied, for example, naphthalene oxidation to various oxygenated species [235] and phenanthrene to obtain coumarin derivatives as important compounds in the production of pharmaceuticals and dyes [236]. 

A process, which considered the bio-oxidation of naphthalene compounds using naphthalenes-oxidizing bacteria, was applied for the treatment of gas oil. The quality of the product not only exhibited a sulfur content closed to specifications but also a high lubricity. Description on the used microbial strain was not provided [432],... 

For fitting such a set of existing data, a much more reasonable approach has been used (P2). For the naphthalene oxidation system, major reactants and products are symbolized in Table III. In this table, letters in bold type represent species for which data were used in estimating the frequency factors and activation energies contained in the body of the table. Note that the rate equations have been reparameterized (Section III,B) to allow a better estimation of the two parameters. For the first entry of the table, then, a model involving only the first-order decomposition of naphthalene to phthalic anhydride and naphthoquinone was assumed. The parameter estimates obtained by a nonlinear-least-squares fit of these data, are seen to be relatively precise when compared to the standard errors of these estimates, s0. The residual mean square, using these best parameter estimates, is contained in the last column of the table. This quantity should estimate the variance of the experimental error if the model adequately fits the data (Section IV). The remainder of Table III, then, presents similar results for increasingly complex models, each of which entails several first-order decompositions. 

Summary of Nonlinear Fitting of Naphthalene Oxidation Data... 

Riley, H. L. Trans. Inst. Chem. Eng. 37 (1959) 305. Design of fluidised reactors for naphthalene oxidation a review of patent literature. 

Wilson and Madsen [152] used the metabolic pathway for bacterial naphthalene oxidation as a guide for selecting l,2-dihydroxy-l,2-dihydronaphthalene as a unique transient intermediary metabolite whose presence in samples from a contaminated field site would indicate active in situ naphthalene biodegradation (Fig. 26). Naphthalene is a component of a variety of pollutant mixtures. It is the major constituent of coal tar [345], the pure compound was commonly used as a moth repellant and insecticide [345], and it is a predominant constituent of the fraction of crude oil used to produce diesel and jet fuels [346]. Prior studies at a coal tar-contaminated field site have focused upon contaminant transport [10,347], the presence of naphthalene catabolic genes [348, 349], and non-metabolite-based in situ contaminant biodegradation [343]. 

Kanekal S, Plopper C, Morin D, Buckpitt A (1991) Metabolism and cytotoxicity of naphthalene oxide in the isolated perfused mouse lung. J Pharmacol Exp Ther 256 391—401. 

Figure 8. Response of first order biotransformation rate constants for naphthalene oxidation to naphthalene perturbation frequency in a continuous activated sludge biotreatinent reactor.

Kinetics of naphthalene and substituted naphthalenes oxidation by stoich. RuOy CCl to phthalic acids suggest an initial second-order reaction giving a complex with a naphthalene-0-Ru(Vl) bond, followed by a slower decomposition of this intermediate involving C-H bond cleavage [371]. 

Narro, M. L., Cerniglia, C. E., Van Baalen, C. Gibson, D.T. (1992a). Evidence of NIH shift in naphthalene oxidation by the marine cyanobacterium, Oscillatoria species strain JCM. Applied and Environmental Microbiology, 58,1360-3-... 

Naphthalene oxidation is very similar to benzene oxidation except for the much greater importance of naphthoquinone, compared with benzo-quinone, as a reaction intermediate. Roughly equal amounts of phthalic anhydride and naphthoquinone are initially formed from naphthalene. A suitable simplified reaction scheme is... 

The kinetics of the naphthalene oxidation obviously depend on the properties of the catalyst used, but some general statements can be made for the majority of V205-based catalysts. 

Acenaphthene. (CAS 83-32-9]. Acenaphthene is a hydrocarbon, C12H10, present in high temperature coal tar. Acenaphthene may be halogenated. sulfonated. and nitrated in a manner similar to naphthalene. Oxidation first yields acenaphthenequmone, followed by 1.8-naphthalenedicarboxyhc acid anhydride and pesticides. 

Comparison of the reactivities of benzene oxides, naphthalene oxides, phenanthrene oxides, and arene oxides derived from benzo [a] pyrene and 7,12-dimethylbenz[a] anthracene with hepatic glutathione S-epoxide transferase showed that benzene oxides without electron-withdrawing groups are poor substrates as also are polycyclic arene oxides. Only naphthalene oxide was a good substrate. 

Expression of Naphthalene Oxidation Genes in Escherichia coli Results in the Biosynthesis of Indigo , Science 1983, 222, 167-169. 

Foster et al.90 studied the role of alkali metal additives on Si02 supported catalysts and observed decreasing activity and surface area together with increasing selectivity with increasing atomic number of the alkali metal. No explanation in simple terms could be given for these effects. Westerman et al.91 observed that a sharply defined level of S03 in the reaction mixture is1 needed to obtain optimum activity in naphthalene oxidation and that the selectivity was not influenced by the S03 level. 

The intermediacy of arene oxides in these systems has been firmly established by subsequent mechanistic studies.658"668 Nonenzymatic rearrangement of 3,4-toluene-4-2H oxide gave 4-hydroxytoluene with the same amount of deuterium retention (in the 3-position) as that observed in the enzymatic hydroxyla-tion of toluene-4-2H by liver microsomes 658 1,2-Naphthalene oxide could actually be isolated as the initial product of the enzymatic hydroxylation of naphthalene.659... 

---