Vapor phase oxidation

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). 

The catalytic vapor-phase oxidation of propylene is generally carried out in a fixed-bed multitube reactor at near atmospheric pressures and elevated temperatures (ca 350°C) molten salt is used for temperature control. Air is commonly used as the oxygen source and steam is added to suppress the formation of flammable gas mixtures. Operation can be single pass or a recycle stream may be employed. Recent interest has focused on improving process efficiency and minimizing process wastes by defining process improvements that use recycle of process gas streams and/or use of new reaction diluents (20-24). 

Liquid-Phase Oxidation of Acrolein. As discussed before, the most attractive process for the manufacture of acrylates is based on the two-stage, vapor-phase oxidation of propylene. The second stage involves the oxidation of acrolein. Considerable art on the Hquid-phase oxidation of acrolein (17) is available, but this route caimot compete with the vapor-phase technology. 

Above about 250°C, the vapor-phase oxidation (VPO) of many organic substances becomes self-sustaining. Such oxidations are characterized by a lengthy induction period. During this period, peroxides accumulate until they can provide a source of new radicals to sustain a chain reaction. Once a critical threshold peroxide concentration is reached, the reaction accelerates very rapidly. 

Reactions of /l-Butane. The most important industrial reactions of / -butane are vapor-phase oxidation to form maleic anhydride (qv), thermal cracking to produce ethylene (qv), Hquid-phase oxidation to produce acetic acid (qv) and oxygenated by-products, and isomerization to form isobutane. 

Process Technology Evolution. Maleic anhydride was first commercially produced in the early 1930s by the vapor-phase oxidation of benzene [71-43-2]. The use of benzene as a feedstock for the production of maleic anhydride was dominant in the world market well into the 1980s. Several processes have been used for the production of maleic anhydride from benzene with the most common one from Scientific Design. Small amounts of maleic acid are produced as a by-product in production of phthaHc anhydride [85-44-9]. This can be converted to either maleic anhydride or fumaric acid. Benzene, although easily oxidized to maleic anhydride with high selectivity, is an inherently inefficient feedstock since two excess carbon atoms are present in the raw material. Various compounds have been evaluated as raw material substitutes for benzene in production of maleic anhydride. Fixed- and fluid-bed processes for production of maleic anhydride from the butenes present in mixed streams have been practiced commercially. None of these... 

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. 

Phthalic Anhydride Recovery and Purification. The accepted method of recovering phthalic anhydride from vapor-phase oxidation... 

Vapor-phase catalytic oxidation of dutene is a mote direct route to the dianhydtide. Hbls in Europe apparently uses this route, which eliminates the need for a separate dehydration step and for handling of any oxidants or solvents. Continuous operation is faciHtated, corrosion is minimized, and product recovery is simplified. The vapor-phase oxidation of dutene is similar to that of o-xylene to phthaHc anhydtide, and phthaHc anhydtide units can be... 

Propanol has been manufactured by hydroformylation of ethylene (qv) (see Oxo process) followed by hydrogenation of propionaldehyde or propanal and as a by-product of vapor-phase oxidation of propane (see Hydrocarbon oxidation). Celanese operated the only commercial vapor-phase oxidation faciUty at Bishop, Texas. Since this faciUty was shut down ia 1973 (5,6), hydroformylation or 0x0 technology has been the principal process for commercial manufacture of 1-propanol ia the United States and Europe. Sasol ia South Africa makes 1-propanol by Fischer-Tropsch chemistry (7). Some attempts have been made to hydrate propylene ia an anti-Markovnikoff fashion to produce 1-propanol (8—10). However, these attempts have not been commercially successful. 

Conversion per pass is reported to be low, 10—20%, with equally low yields, 30—50% (5). The vapor-phase oxidation of toluene was the dominant toluene oxidation process ia the 1950s and early 1960s, but is no longer of iadustrial importance. The Hquid-phase process now dominates. 

Vapor-phase oxidation of toluene to produce benzoic acid and benzaldehyde has been tried utilizing several different catalysts, but yields are low and the process cannot compete with the Hquid-phase process (see Benzaldehyde). Other processes for the production of benzoic acid are presendy of htde commercial importance. 

The vapor-phase oxidation (VPO) of butadiene with air at 200—500°C produces maleic anhydride [108-31-6]. Catalysts used are based on vanadium and molybdenum oxides (89,90). Alternatively, when using a catalyst containing Al, Mo, and Ti, butadiene undergoes a complex series of condensations and oxidations to form anthraquinone at 250°C (91). 

Vapor-phase oxidation of cyclohexane is commercially feasible, but the preferred route is Hquid-phase cyclohexane oxidation (2). In the latter... 

Other large-volume esters are vinyl acetate [108-05-4] (VAM, 1.15 x 10 t/yr), methyl methacrylate [80-62-6] (MMA, 0.54 x 10 t/yr), and dioctyl phthalate [117-81-7] (DOP, 0.14 x 10 t/yr). VAM (see Vinyl polymers) is produced for the most part by the vapor-phase oxidative acetoxylation of ethylene. MMA (see Methacrylic polymers) and DOP (see Phthalic acids) are produced by direct esterification techniques involving methacryHc acid and phthaHc anhydride, respectively. 

Viayl acetate [108-05-4] is obtained by vapor-phase oxidation of ethylene with acetic acid. Acetic acid is obtained by oxidation of acetaldehyde. 

The per pass ethylene conversion in the primary reactors is maintained at 20—30% in order to ensure catalyst selectivities of 70—80%. Vapor-phase oxidation inhibitors such as ethylene dichloride or vinyl chloride or other halogenated compounds are added to the inlet of the reactors in ppm concentrations to retard carbon dioxide formation (107,120,121). The process stream exiting the reactor may contain 1—3 mol % ethylene oxide. This hot effluent gas is then cooled ia a shell-and-tube heat exchanger to around 35—40°C by usiag the cold recycle reactor feed stream gas from the primary absorber. The cooled cmde product gas is then compressed ia a centrifugal blower before entering the primary absorber. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

These enable temperature control with built-in exchangers between the beds or with pumparound exchangers. Converters for ammonia, 80.3, cumene, and other processes may employ as many as five or six beds in series. The Sohio process for vapor-phase oxidation of propylene to acrylic acid uses hvo beds of bismuth molybdate at 20 to 30 atm (294 to 441 psi) and 290 to 400°C (554 to 752°F). Oxidation of ethylene to ethylene oxide also is done in two stages with supported... 

Currently, phthalic anhydride is mainly produced through catalyzed oxidation of o-xylene. A variety of metal oxides are used as catalysts. A typical one is V2O5 -1- Ti02/Sb203. Approximate conditions for the vapor-phase oxidation are 375-435°C and 0.7 atmosphere. The yield of phthalic anhydride is about 85% ... 

For the manufacturing of sulfosuccinic acid esters, which belong to a special class of surfactants, maleic acid anhydride is needed. Maleic acid anhydride is an important intermediate chemical of the chemical industry. Its worldwide output amounts to about 800,000 tons (1990) [64]. Maleic acid is produced by catalytic vapor phase oxidation process of benzene or n-C4 hydrocarbons in fixed bed or fluidized bed reactors according the following reaction equations. The heat of reaction of the exothermic oxidation processes is very high. 

There are four principal processes that may be used to manufacture the glass body that is drawn into today s optical fiber. "Outside" processes—outside vapor-phase oxidation and vertical axial deposition— produce layered deposits, of doped silica by varying the concentration of SiCl4 and dopants passing through a torch. The resulting "soot" of doped silica is deposited and partially sintered to form a porous silica boule. Next, the boule is sintered to a pore-free glass rod of exquisite purity and transparency. 

Very little information exists in the literature on the transformation and degradation of methyl parathion in air. An early study indicated that direct photolysis of methyl parathion may occur however, the products of this photolysis were not determined (Baker and Applegate 1974). A later study found a transformation product of methyl parathion, methyl paraoxon, in air samples taken from areas where methyl parathion had been applied. Formation of methyl paraoxon was attributed to the vapor phase oxidation of methyl parathion (Seiber et al. 1989). Recent monitoring studies in California have also found both methyl parathion and methyl paraoxon (Baker et al. 1996). 

Pyruvic acid is the simplest homologue of the a-keto acid, whose established procedures for synthesis are the dehydrative decarboxylation of tartaric acid and the hydrolysis of acetyl cyanide. On the other hand, vapor-phase contact oxidation of alkyl lactates to corresponding alkyl pyruvates using V2C - and MoOa-baseds mixed oxide catalysts has also been known [1-4]. Recently we found that pyruvic acid is obtained directly from a vapor-phase oxidative-dehydrogenation of lactic acid over iron phosphate catalysts with a P/Fe atomic ratio of 1.2 at a temperature around 230°C [5]. 

For the complete vapor-phase oxidation of methane over a palladium alumina catalyst, conversion-space-time data were taken at 350°C and 1 atm total pressure the fractional factorial design of Table X (Hll) specified the settings of the feed partial pressures of the reacting species. 

Bhattakarya, S. K., N. K.. Nag and N. D. Ganguly. 1971. Kinetics of vapor phase oxidation of methanol on reduced silver catalyst. J. Catai 23 158-167 Burggraaf, A. J. and K. Keizer. 1991. Synthesis of Inorganic Membranes. In Inorganic Membranes Synthesis Characteristics and Applications, Eds R. Bhave, van Nostrand Reinhold, New York (Chapter 2). 

There are several other routes to acetone of minor importance air oxidation of IPA reaction between IPAand acrolein for the production of allyl alcohol, with acetone as the by-product vapor phase oxidation of butane coproduction when IPA is oxidized yielding acetone and H2O2, hydrogen peroxide, the principal ingredient of bleach and by-product production from the manufacture of methyl ethyl ketone. 

The newest and most commercially successful process involves vapor phase oxidation of propylene to AA followed by esterification to the acrylate of your choice. Chemical grade propylene (90—95% purity) is premixed with steam and oxygen and then reacted at 650—700°F and 60—70 psi over a molybdate-cobait or nickel metal oxide catalyst on a silica support to give acrolein (CH2=CH-CHO), an intermediate oxidation product on the way to AA. Other catalysts based on cobalt-molybdenum vanadium oxides are sometimes used for the acrolein oxidation step. 

Acetaldehyde may be made (1) from ethylene by direct oxidation, with the Wacker-catalyst containing copper(II) and palladium(II) salts (2) from ethanol by vapor-phase oxidation or dehydrogenation or (3) from butane by vapor-phase oxidation. The direct oxidation of ethylene is the most commonly used process, accounting for 80% of acetaldehyde production. 

Maleic anhydride is made by the vapor-phase oxidation of -butane. See Chapter 10, Section 10. 

Maleic anhydride (2,5-furandione) is obtained as a by-product in the production of phthalic anhydride and by the vapor phase oxidation of butylene or crotonaldehyde. It is also obtained by the dehydration of maleic acid and by the oxidation of benzene. Maleic anhydride is used for the production of unsaturated polyester resin. This reactant, like most reactants, is fairly toxic and should be treated as such. 

Titanium dioxide is mined from natural deposits. It also is produced from other titanium minerals or prepared in the laboratory. Pigment-grade dioxide is produced from tbe minerals, rutile and dmenite. Rutile is converted to pigment grade rutile by chlorination to give titanium tetrachloride, TiCU. Anhydrous tetrachloride is converted back to purified rutile form by vapor phase oxidation. 

Pd and Cu ion containing zeolites catalyze the vapor phase oxidation of methylpyridines [129]. Thus, on PdCuNa-mordenite, 2-methylpyridine was oxidized to 2-pyridinecarbaldehyde with 40% yield. The reduced reactivity ratio of 2,6-dimethylpyridines to monomethylpyridines on zeolite catalysts compared to oxide catalysts, demonstrates the presence of steric control in these reactions. 

The vapor-phase oxidation of lactic acid with air was executed using an iron phosphate catalyst with a P/Fe atomic ratio of 1.2. It was found that lactic acid is selectively converted to form pyruvic acid by oxidative dehydrogenation. The one-pass yield reached 50 mol% however, acetaldehyde, acetic acid, and CO2 was still formed, and the pyruvic acid produced decomposes over time to give acetic acid and C02. ... 

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