Maleic anhydride, oxidation butane

The catalyst used in the production of maleic anhydride from butane is vanadium—phosphoms—oxide (VPO). Several routes may be used to prepare the catalyst (123), but the route favored by industry involves the reaction of vanadium(V) oxide [1314-62-1] and phosphoric acid [7664-38-2] to form vanadyl hydrogen phosphate, VOHPO O.5H2O. This material is then heated to eliminate water from the stmcture and irreversibly form vanadyl pyrophosphate, (V(123,124). Vanadyl pyrophosphate is befleved to be the catalyticaHy active phase required for the conversion of butane to maleic anhydride (125,126). 

Phosphorus-Vanadium Oxide Catalysts for Butane to Maleic Anhydride Oxidation... 

BP Chemicals, Inc. Maleic anhydride n-Butane Fluid-bed catalytic oxidation process with an aqueous-based recovery and purification 3 1994... 

Catalysts which can selectively activate the normally un-reactive paraffins have been developed in recent years. The production of maleic anhydride from butane over vanadium-phosphorous-oxide catalysts has received much attention (Eqn. 5), and is beginning to replace the more wasteful production of maleic anhydride from benzene (Eqn. 6) which is still the major feedstock. Maleic anhydride production from butene or butadiene is also possible (Eqn. 7), but cannot compete with the cheaper butane feed. Maleic anhydride is mainly used in the manufacture of unsaturated polyester resins, fumaric acid manufacture, insecticides, and fungicides (Figure 5). ... 

A fluidized bed process has recently been developed for producing maleic anhydride from butane and is distinguished by better heat dissipation, lower maintenance costs and reduced investment it can also be applied to butene. Figure 5.41 shows the diagram for butane oxidation. 

Igarashi, H., Tsuji, K., Okuhara, T., et al. (1993). Effects of Consecutive Oxidation on the Production of Maleic Anhydride in Butane Oxidation over Four Kinds of Well-characterized Vanadyl Pyrophosphates, J. Phys. Chem., 97, pp. 7065-7071. 

Centi G., Fornasari G. and Trifirh F. (1984). On the mechanism of n-butane oxidation to maleic anhydride Oxidation in oxygen-stoichiometry-controlled conditions, J. Catal., 89, pp. 44-51. 

It can be argued that some mixed metal oxides can also be technically considered as supported metal oxide catalysts because the surface is discernibly different from the underlying mixed metal oxide in terms of composition and molecular structure. For example, the vanadium phosphorus oxide (VPO) catalyst is used in the commercial production of maleic anhydride from butane [12]. The most active crystal phase is the vanadium pyrophosphate (VO)2P207, and the surface structure proposed to be the active phase is a nanometer-thick amorphous VPO layer enriched in phosphorus [12,15]. As another example, Wachs and coworkers [16]... 

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. 

Production of maleic anhydride by oxidation of / -butane represents one of butane s largest markets. Butane and LPG are also used as feedstocks for ethylene production by thermal cracking. A relatively new use for butane of growing importance is isomerization to isobutane, followed by dehydrogenation to isobutylene for use in MTBE synthesis. Smaller chemical uses include production of acetic acid and by-products. Methyl ethyl ketone (MEK) is the principal by-product, though small amounts of formic, propionic, and butyric acid are also produced. / -Butane is also used as a solvent in Hquid—Hquid extraction of heavy oils in a deasphalting process. 

The bulk stmcture of the catalyticaHy active phase is not completely known and is under debate in the Hterature (125,131—133). The central point of controversy is whether (Valone or in combination with other phases is the most catalyticaHy active for the conversion of butane to maleic anhydride. The heart of this issue concerns the role of stmctural disorder in the bulk and how it arises in the catalyst (125,134,135). Most researchers agree that the catalysts with the highest activity and selectivity ate composed mainly of (Vthat exhibits a clustered or distorted platelet morphology (125). It is also generaHy acknowledged that during operation of the catalyst, the bulk oxidation state of the vanadium in the catalyst remains very close to the +4 valence state (125). 

Benzene-Based Catalyst Technology. The catalyst used for the conversion of ben2ene to maleic anhydride consists of supported vanadium oxide [11099-11-9]. The support is an inert oxide such as kieselguhr, alumina [1344-28-17, or sUica, and is of low surface area (142). Supports with higher surface area adversely affect conversion of benzene to maleic anhydride. The conversion of benzene to maleic anhydride is a less complex oxidation than the conversion of butane, so higher catalyst selectivities are obtained. The vanadium oxide on the surface of the support is often modified with molybdenum oxides. There is approximately 70% vanadium oxide and 30% molybdenum oxide [11098-99-0] in the active phase for these fixed-bed catalysts (143). The molybdenum oxide is thought to form either a soUd solution or compound oxide with the vanadium oxide and result in a more active catalyst (142). 

Butane-Based Fixed-Bed Process Technology. Maleic anhydride is produced by reaction of butane with oxygen using the vanadium phosphoms oxide heterogeneous catalyst discussed earlier. The butane oxidation reaction to produce maleic anhydride is very exothermic. The main reaction by-products are carbon monoxide and carbon dioxide. Stoichiometries and heats of reaction for the three principal reactions are as follows ... 

Butane-Based Transport-Bed Process Technology. Du Pont aimounced the commercialization of a moving-bed recycle-based technology for the oxidation of butane to maleic anhydride (109,149). Athough maleic anhydride is produced in the reaction section of the process and could be recovered, it is not a direct product of the process. Maleic anhydride is recovered as aqueous maleic acid for hydrogenation to tetrahydrofuran [109-99-9] (THF). 

Fresh butane mixed with recycled gas encounters freshly oxidized catalyst at the bottom of the transport-bed reactor and is oxidized to maleic anhydride and CO during its passage up the reactor. Catalyst densities (80 160 kg/m ) in the transport-bed reactor are substantially lower than the catalyst density in a typical fluidized-bed reactor (480 640 kg/m ) (109). The gas flow pattern in the riser is nearly plug flow which avoids the negative effect of backmixing on reaction selectivity. Reduced catalyst is separated from the reaction products by cyclones and is further stripped of products and reactants in a separate stripping vessel. The reduced catalyst is reoxidized in a separate fluidized-bed oxidizer where the exothermic heat of reaction is removed by steam cods. The rate of reoxidation of the VPO catalyst is slower than the rate of oxidation of butane, and consequently residence times are longer in the oxidizer than in the transport-bed reactor. 

An important future use for maleic anhydride is beUeved to be the production of products in the 1,4-butanediol—y-butyrolactone—tetrahydrofuran family. Davy Process Technology has commercialized a process (93) for producing 1,4-butanediol from maleic anhydride. This technology can be used to produce the product mix of the three molecules as needed by the producer. Another significant effort in this area is the tetrahydrofuran plant under constmction in Spain by Du Pont in which butane is oxidized and recovered as maleic acid and the maleic acid is then reduced to tetrahydrofuran (109). 

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. 

Prior to 1975, benzene was catalytically oxidized to produce maleic anhydride, an intermediate in synthesis of polyester resins, lubricant additives, and agricultural chemicals. By 1986 all commercial maleic anhydride was derived from oxidation of / -butane. It is expected that / -butane will remain the feedstock of choice for both economic and environmental reasons. 

Mixed Metal Oxides and Propylene Ammoxidation. The best catalysts for partial oxidation are metal oxides, usually mixed metal oxides. For example, phosphoms—vanadium oxides are used commercially for oxidation of / -butane to give maleic anhydride, and oxides of bismuth and molybdenum with other components are used commercially for oxidation of propylene to give acrolein or acrylonitrile. 

Manufacturing. Almost all the THE in the United States is currendy produced by the acid-catalyzed dehydration of 1,4-butanediol [10-63-4]. Only one plant in the United States still makes THE by the hydrogenation of furfural (29). Du Pont recendy claimed a new low cost process for producing THE from / -butane that they plan to commercialize in 1995 (30—32). The new process transport-bed oxidizes / -butane to cmde maleic anhydride, then follows with a hydrogen reduction of aqueous maleic acid to THE (30). 

Like propane, n-hutane is mainly obtained from natural gas liquids. It is also a hy-product from different refinery operations. Currently, the major use of n-hutane is to control the vapor pressure of product gasoline. Due to new regulations restricting the vapor pressure of gasolines, this use is expected to he substantially reduced. Surplus n-butane could be isomerized to isobutane, which is currently in high demand for producing isobutene. Isobutene is a precursor for methyl and ethyl tertiary butyl ethers, which are important octane number boosters. Another alternative outlet for surplus n-butane is its oxidation to maleic anhydride. Almost all new maleic anhydride processes are based on butane oxidation. 

Other catalyst systems such as iron V2O5-P2O5 over silica alumina are used for the oxidation. In the Monsanto process (Figure 6-4), n-butane and air are fed to a multitube fixed-bed reactor, which is cooled with molten salt. The catalyst used is a proprietary modified vanadium oxide. The exit gas stream is cooled, and crude maleic anhydride is absorbed then recovered from the solvent in the stripper. Maleic anhydride is further purified using a proprietary solvent purification system. ... 

A new process for the partial oxidation of n-butane to maleic anhydride was developed by DuPont. The important feature of this process is the use of a circulating fluidized bed-reactor. Solids flux in the rizer-reactor is high and the superficial gas velocities are also high, which encounters short residence times usually in seconds. The developed catalyst for this process is based on vanadium phosphorous oxides... 

For many years the catalytic air oxidation of benzene was the main source of maleic anhydride. Obviously, two carbons from each ring are wasted as carbon dioxide in this process. Although some is still made that way, most modem maleic anhydride plants are based on butane oxidation. Because butane is forecast to be plentiful and low-cost, new routes to four-carbon chemicals from maleic anhydride are under active development. 

Pyrophosphate, Catalyst for the Selective Oxidation of M-Butane to Maleic Anhydride... 

The reactivity of vanadyl pyrophosphate (VO)2P207, catalyst for n-butane oxidation to maleic anhydride, was investigated under steady and unsteady conditions, in order to obtain iirformation on the status of the active surface in reaction conditions. Specific treatments of hydrolysis and oxidation were applied in order to modify the characteristics of the surface layer of the catalyst, and then the unsteady catalytic performance was followed along with the reaction time, until the steady original behavior was restored. It was found that the transformations occurring on the vanadyl pyrophosphate surface depend on the catalyst characteristics (i.e., on the PfV atomic ratio) and on the reaction conditions. 

The industrial catalyst for n-butane oxidation to maleic anhydride (MA) is a vanadium/phosphoras mixed oxide, in which bulk vanadyl pyrophosphate (VPP) (VO)2P207 is the main component. The nature of the active surface in VPP has been studied by several authors, often with the use of in situ techniques (1-3). While in all cases bulk VPP is assumed to constitute the core of the active phase, the different hypotheses concern the nature of the first atomic layers that are in direct contact with the gas phase. Either the development of surface amorphous layers, which play a direct role in the reaction, is invoked (4), or the participation of specific planes contributing to the reaction pattern is assumed (2,5), the redox process occurring reversibly between VPP and VOPO4. 

ALMA [Alusuisse maleic anhydride] A process for making maleic anhydride by oxidizing -butane, using a fluid bed reactor and a special organic solvent recovery system. The catalyst contains vanadium and phosphoms on iron oxide. Developed jointly by Alusuisse Italia and ABB Lummus Crest. First licensed to Shin-Daikowa Petrochemical Company, Yokkaichi, Japan, in 1988. The world s largest plant plant was built for Lonza in Ravenna, Italy, in 1994. 

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