Vanadium pentoxide catalyst, oxidation

The relative proportions in which the products, chiefly benzaldehyde, benzoic acid, and anthraquinone, are obtained depends in a large measure on the temperatures to which the reaction mixture of toluene vapor and air is subjected. High temperatures, together with rapid rates of flow as well as high temperatures and mild catalysts, are conducive to bai-zaldehyde formation. With vanadium pentoxide catalysts oxidation of... 

Fumaric acid is conveniently prepared by the oxidation of the inexpensive furfural with sodium chlorate in the presence of a vanadium pentoxide catalyst ... 

Vapor-phase oxidation over a promoted vanadium pentoxide catalyst gives a 90% yield of maleic anhydride [108-31-6] (139). Liquid-phase oxidation with a supported palladium catalyst gives 55% of succinic acid [110-15-6] (140). 

Oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was first patented in 1921 (90), followed in 1933 by a patent for an iron oxide—molybdenum oxide catalyst (91), which is stiU the choice in the 1990s. Catalysts are improved by modification with small amounts of other metal oxides (92), support on inert carriers (93), and methods of preparation (94,95) and activation (96). In 1952, the first commercial plant using an iron—molybdenum oxide catalyst was put into operation (97). It is estimated that 70% of the new formaldehyde installed capacity is the metal oxide process (98). 

Oxidation. Benzene can be oxidized to a number of different products. Strong oxidizing agents such as permanganate or dichromate oxidize benzene to carbon dioxide and water under rigorous conditions. Benzene can be selectively oxidized in the vapor phase to maleic anhydride. The reaction occurs in the presence of air with a promoted vanadium pentoxide catalyst (11). Prior to 1986, this process provided most of the world s maleic anhydride [108-31 -6] C4H2O2. Currendy maleic anhydride is manufactured from the air oxidation of / -butane also employing a vanadium pentoxide catalyst. 

CAT-OX [Catalytic oxidation] An adaptation of the Contact process for making sulfuric acid, using the dilute sulfur dioxide in flue-gases. A conventional vanadium pentoxide catalyst is used. Developed by Monsanto Enviro-Chemical Systems, and operated in Pennsylvania and Illinois in the early 1970s. 

The process. A typical process for phthalic anhydride starts with mixing hor q-xylene vapor with excess preheated air in a ratio of 20 1 air to o-xylene by weight. The gaseous mixture is then fed to a reactor consisting of tubes packed with vanadium pentoxide catalyst on a silica gel. The reaction takes place at 800—1000°F. Like most oxidation reactions, this one is exothermic, and the heat of reaction must be removed from the tubes to maintain the reaction temperature. 

Vanadium pentoxide (V203)-based catalysts, for example, are extensively used in industry for a number of catalytic processes including the selective oxidation of aromatic hydrocarbons and transformation of SOj into SO3 [14,15]. The vanadium pentoxide catalysts are usually prepared in supported form on a proper... 

Sulphuric acid (98%) 400 000 tonnes Sulphur-burning process, followed by catalytic oxidation of S0-> (vanadium pentoxide catalyst). 

Deactivation of catalysts is a major problem in o-xylene oxidation [6,7]. For this reaction, deactivation has been mainly attributed to the irreversible anatase - rutile transformation [2,3]. In fact, anatase was found to be the best support for vanadium pentoxide catalysts leading the presence of rutile to lower activities and selectivities [8,9], The anatase-rutile transition can take place at temperatures above 973 K [10] but it is known that the presence of vanadia promotes such transformation [11-14] which, in these conditions, can start at 773 K [14], Such temperatures are easily attained in industrial reactors due to the high exothermicity of o-xylene oxidation that can lead to the formation of temperature profiles lengthwise with pronounced maxima (hot spot) [1]. 

Example 8.8 Entropy production in a homogeneous chemical system The oxidation of sulfur dioxide to trioxide over a vanadium pentoxide catalyst is... 

Under extreme conditions, the benzene ring can be oxidized to other products. Maleic anhydride is prepared industrially by passing a mixture of benzene and air over a vanadium pentoxide catalyst t 420 "C,... 

Other oxidizing agents have been used. Sodium chlorate with vanadium pentoxide catalyst attacks anthracene readily but is not powerful enough for the conversion of hydrocarbons of the naphthalene and phenanthrene series. An acetic acid solution of 30% hydrogen peroxide has also been used. °... 

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. 

P6 14b The production of maleic anhydride by the air oxidation of benzene was recently studied using a vanadium pentoxide catalyst [Chem. Eng. Set.. 43, 1051 (1988)]. The reactions that occur are ... 

Both the rate and tire equilibrium conversion of a chemical reaction depend on the tem-peraUire, pressure, and compositionof reactants. Consider,for example, the oxidation of sulfur dioxide to sulfur trioxide. A catalyst is required if a reasonable reaction rate is to be attained. Witli a vanadium pentoxide catalyst the rate becomes appreciable at about 573.15 K (300°C) and continues to mcrease at higher temperatures. On the basis of rate alone, one would operate tire reactorat the highest practical temperature. However, the equilibrium conversion to sulfur trioxide falls as temperature rises, decreasing from about 90% at 793.15 K (520°C) to 50% at about 953.15 K (680°C). These values represent maximum possible conversions regardless of catalyst or reaction rate. The evident conclusion is that both equilibrium and rate must be considered in the exploitation of chemical reactions for commercial purposes. Although reaction rates are not susceptible to thermodynamic treatment, equilibrium conversions are. Therefore, the purpose of this chapter is to detennine the effect of temperature, pressure, and initial composition on the equilibrium conversions of chemical reactions. 

The oxide V5O13 containing and is thought to play an important part in the action of vanadium pentoxide catalysts used in the oxidation of SO2 to SO3 and of naphthalene to phthalic anhydride. Its structure has been described in Chapter 5. 

At 600°C, the rate of reaction is some 30 to 50 times faster again, requiring an even smaller reactor for the same throughput, but the rate of dissociation of sulfur trioxide to sulfur dioxide becomes appreciable. The value of Kp drops to about 10, giving only about 60-65% of the sulfur as sulfur trioxide at this temperature, and the remainder as sulfur dioxide. For process purposes there is no point in considering the sulfur oxide equilibrium situation for any higher temperatures than this. With a promoted vanadium pentoxide catalyst bed at 600°C a 2-4 sec contact time is already sufficient to obtain essentially equilibrium concentrations at this temperature. 

Air is sufficient to oxidize the methyl groups of o-xylene, under the right conditions, like it is with p-, or w-xylene just described. However, here the similarity ends since commercial o-xylene oxidation is a vapor phase process [27]. ortf o-Xylene vapor, mixed with a large excess of air to ensure operation outside the explosive range, is fed to a reactor containing a supported vanadium pentoxide catalyst and heated to about 550°C. Using about a 0.1-second contact time under these conditions produces exit gases composed of phthalic anhydride, water, and carbon dioxide (Eq. 19.68). 

Important commercial reactions that are carried out in multistage adiabatic reactors include 1) the oxidation of SO2 to SO3 over a vanadium pentoxide catalyst, which is the key step in sulfuric acid manufacture, and 2) the silver-catalyzed oxidation of methanol to... 

The second method uses a metal oxide catalyst. All of the formaldehyde is produced from an exothermic reaction occurring at atmospheric pressure and 300-400 °C. The patent for formaldehyde production using a vanadium pentoxide catalyst was issued in 1921. Although the patent for an iron oxidemolybdenum oxide catalyst was issued in 1933, the first commercial facility did not begin operating until 1952 (Gerberich et al. 1980). 

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