Naphthalene partial oxidation process

The gas phase oxidation of naphthalene to phthalic anhydride over V2Os-based catalysts is one of the oldest successful partial oxidation processes and is still of industrial importance today. Common commercial catalysts are modified silica-supported V—K—S—O catalysts and catalysts similar to those used for benzene or o-xylene oxidation. Maximum phthalic anhydride yields of 80—85 mol. % (92—98 wt. %) at 350—400°C are reported. By-products are naphthoquinone (2—5%), maleic anhydride (2— 5%) and carbon oxides. 

Widespread successful process Very successful SOHIO ammoxidation process Oxychlorination of ethylene successful process Naphthalene partial oxidation supplanted by fixed-bed process... 

Approximately 45% of the world s phthaUc anhydride production is by partial oxidation of 0-xylene or naphthalene ia tubular fixed-bed reactors. Approximately 15,000 tubes of 25-mm dia would be used ia a 31,000 t/yr reactor. Nitrate salts at 375—410°C are circulated from steam generators to maintain reaction temperatures. The resultant steam can be used for gas compression and distillation as one step ia reduciag process energy requirements (100). 

Either naphthalene or ortho-xylene is an acceptable starting material for partial oxidation to phthalic anhydride, but current raw materials costs favor the former as a starting material. Both fixed and fluidized bed processes have been used on a commercial scale, but you are to focus your attention on the former. Figure 13.5 is a schematic flow diagram of the proposed process. Most research groups that have studied the catalytic oxidation of naphthalene over vanadium pentoxide agree that the principal reactions are... 

The oxidation of aromatic hydrocarbons originating from coal is one of the first organic gas phase oxidation processes carried out on an industrial scale. The development of these processes was initiated by the discovery that the V2Os catalyst used for the oxidation of sulphur dioxide was also applicable to the partial oxidation of benzene to maleic anhydride and naphthalene to phthalic anhydride. Remarkably, V2Os-based catalysts are still used in these processes today as they appear superior to any other type of catalyst. 

Maleic acid and anhydride are recovered as by-products of the oxidation of xylenes and naphthalenes to form phthalic acids, and are also made specifically by the partial oxidation of benzene over a vanadium pentoxide (V205) catalyst. This is a highly exothermic reaction, and several modifications of the basic process exist, including one using butylenes as the starting materials. 

There were 820 million pounds of phthalic anhydride produced in the United States in 1995. One of the end uses of phthalic anhydride is in the fiberglass of sailboat hulls. Phthalic anhydride can be produced by the partial oxidation of naphthalene in either a fixed or a fluidized catalytic bed. A flowsheet for die commercial process is shown in Figure P3-11. Here the reaction is carried out in a flxed-bed reactor with a vanadium pentoxide catalyst packed in 25 -mm-diameter tubes. A production rate of 31,000 tons pet year would require 15,000 tubes. 

Next to the Kawasaki Kasei process, which is used commercially and has a high naphthalene conversion rate, mention should be made especially of the Bayer pro-cess, which involves only partial conversion of the naphthalene through oxidation, and further reaction of the crude oxidation product with butadiene. 

Problem 8-4 (Level 3) A pilot plant is being operated to test a new catalyst for the partial oxidation of naphthalene to phthalic anhydride. The chemistry of this process can be approximated as two first-order reactions in series ... 

Pulping additives such as quinoid compounds increase the yield of the pulp mass up to 4% [128]. For commercial application the most promising additives are anthraquinone (AQ) or the more convenient soluble salt of tetrahydroan-thraquinone (THAQ). If AQ or THAQ could be obtained at a price below 2/kg it would find a substantial market as a pulping additive [129], Commercial production of THAQ is now based on the partial thermochemical oxidation of naphthalene. In recent years, however, the lure of the pulp market has promoted several attempts to develop a process for the electrosynthesis of THAQ based on the indirect electrooxidation of naphthalene to naphthaquinone (NQ) with Ce4+, according to the stoichiometry of the reactions 1, 2 and 3. 

Sumimoto introduced a new sebacic acid process including several catalytic hydrogenation reactions.342 The synthesis starts with naphthalene, which is first partially hydrogenated to tetralin over cobalt oxide or molybdenum oxide, then to decalin over ruthenium or iridium on carbon. The selectivity to cw-decalin is better than 90%. In a later phase of the synthesis 5-cyclododecen-l-one is hydrogenated over Raney nickel to obtain a mixture of cyclododecanone and cyclodode-canol in a combined yield of 90%. The selectivity of this step is not crucial since subsequent oxidation of either compound leads to the endproduct sebacic acid. 

Crude naphthalene obtained from coal tar may contain up to 5% benzo[6]thiophene which is only partially removed by selective sulfonation.43-45 Several improvements45-51 make this process more efficient. Other chemical methods of separation include oxidation with peracetic acid, which converts benzo[6]thiophene into its readily separated 1,1-dioxide,52 and treatment with ozone, which selectively... 

A process akin to the allylic oxidation in activation is aromatic side chain oxidation to produce acids or anhydrides. Phthalic anhydride, an important intermediate in production of polyesters, plasticizers, and fine chemicals synthesis, can be produced via selective oxidation of -xylenes using vanadium oxide catalysts (Eqn. 3). This process today accounts for over 85% of the phthalic anhydride produced worldwide, and has largely displaced the partially wasteful and more expensive naphthalene-based route (Eqn. 4), by which nearly all PA was produced in 1960 (Figure 4). Nearly all of the phthalic anhydride produced today is used for manufacturing vinyl plasticizers, with a much smaller application in the fine chemicals industry. 

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