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Maleic anhydride catalyst developments

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... [Pg.176]

Survey of the patent Hterature reveals companies with processes for 1,4-butanediol from maleic anhydride include BASF (94), British Petroleum (95,96), Davy McKee (93,97), Hoechst (98), Huels (99), and Tonen (100,101). Processes for the production of y-butyrolactone have been described for operation in both the gas (102—104) and Hquid (105—108) phases. In the gas phase, direct hydrogenation of maleic anhydride in hydrogen at 245°C and 1.03 MPa gives an 88% yield of y-butyrolactone (104). Du Pont has developed a process for the production of tetrahydrofuran back-integrated to a butane feedstock (109). Slurry reactor catalysts containing palladium and rhenium are used to hydrogenate aqueous maleic acid to tetrahydrofuran (110,111). [Pg.453]

Polyester resins can also be rapidly formed by the reaction of propylene oxide (5) with phthaUc and maleic anhydride. The reaction is initiated with a small fraction of glycol initiator containing a basic catalyst such as lithium carbonate. Molecular weight development is controlled by the concentration of initiator, and the highly exothermic reaction proceeds without the evolution of any condensate water. Although this technique provides many process benefits, the low extent of maleate isomerization achieved during the rapid formation of the polymer limits the reactivity and ultimate performance of these resins. [Pg.314]

Maleic anhydride is made by oxidation of benzene with air above 350°C (662°F) with V-Mo catalyst in a mnltitiibiilar reactor with 2-cm tubes. The heat-transfer medium is a eutectic of molten salt at 375°C (707°F). Even with small tubes, the heat transfer is so hmited that a peak temperature 100°C (212°F) above the shell side is developed and moves along the tubes. [Pg.2104]

The discovery that Lewis acids can promote Diels-Alder reactions has become a powerful tool in synthetic organic chemistry. Yates and Eaton [4] first reported the remarkable acceleration of the reactions of anthracene with maleic anhydride, 1,4-benzoquinone and dimethyl fumarate catalyzed by aluminum chloride. The presence of the Lewis-acid catalyst allows the cycloadditions to be carried out under mild conditions, reactions with low reactive dienes and dienophiles are made possible, and the stereoselectivity, regioselectivity and site selectivity of the cycloaddition reaction can be modified [5]. Consequently, increasing attention has been given to these catalysts in order to develop new regio- and stereoselective synthetic routes based on the Diels-Alder reaction. [Pg.99]

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. [Pg.485]

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. [Pg.18]

Styrene-divinylbenzene resins, 23 353 Styrene-DVB copolymers, 14 388 Styrene ionomers, 14 466, 481 properties of, 14 470-473 Styrene liquid, 23 347 Styrene-maleic anhydride (SMA) copolymers, 23 391 copolymer, 10 207 Styrene manufacture, 24 259 Styrene manufacturing, 23 326, 334-345 development of high selectivity catalyst for, 23 339... [Pg.894]

EP-4 developed by ERDL is a very flexible polyester based on polyethylene glycol with molecular weight-200 (PEG-200), isophthalic acid (IPA) and maleic anhydride (MAn). Before its use, it is blended with styrene monomer (1 1) and cured at room temperature using cobalt naphthenate (as an accelerator) and methyl ethyl ketone (MEK) peroxide (as a catalyst). This meets the requirements of the main inhibitor and is used for inhibition of DB and CMDB propellants after the application of a barrier coat (generally a rigid polyester such as PR-3). However, it is observed during manufacture of EP-4 that there is a lot of batch-to-batch variation in properties in spite of the strict quality control measures adopted during its manufacture. [Pg.299]

The present chapter will primarily focus on oxidation reactions over supported vanadia catalysts because of the widespread applications of these interesting catalytic materials.5 6,22 24 Although this article is limited to well-defined supported vanadia catalysts, the supported vanadia catalysts are model catalyst systems that are also representative of other supported metal oxide catalysts employed in oxidation reactions (e.g., Mo, Cr, Re, etc.).25 26 The key chemical probe reaction to be employed in this chapter will be methanol oxidation to formaldehyde, but other oxidation reactions will also be discussed (methane oxidation to formaldehyde, propane oxidation to propylene, butane oxidation to maleic anhydride, CO oxidation to C02, S02 oxidation to S03 and the selective catalytic reduction of NOx with NH3 to N2 and H20). This chapter will combine the molecular structural and reactivity information of well-defined supported vanadia catalysts in order to develop the molecular structure-reactivity relationships for these oxidation catalysts. The molecular structure-reactivity relationships represent the molecular ingredients required for the molecular engineering of supported metal oxide catalysts. [Pg.38]

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. [Pg.196]

The creation of selective catalysts for such complex reactions seems to be an especially difficult problem. Nevertheless, surprisingly, selective catalysts have been developed for complex reactions, which can be exemplified by the oxidation and ammoxidation of propylene, oxidation of butene and even butane to maleic anhydride (which requires seven oxygen atoms). Such reactions are usually performed over V and Mo oxide systems [4, 6, 8-10]. High selectivity of these systems is presumably provided by a special structure of the catalyst surface that allows control... [Pg.217]

The cycle approach for oxidation has been adopted at an industrial level for the Wacker-Chemie process for acetaldehyde production, in which ethylene is first put in contact with the oxidized catalyst solution, containing palladium chloride, and in the second step the solution containing the reduced catalyst is sent to a regeneration reactor containing cupric chloride and inside which also air is fed. The regenerated catalyst solution is returned to the first oxidation stage. Another industrial application is the Lummus process for the anaerobic ammoxidation of o-xylene to o-phthaloni-trile [68]. Du Pont has developed the oxidation of n-butane to maleic anhydride catalyzed by V/P/O, in a CFBR reactor, and built a demonstration unit in Spain [69] however, a few years ago the plant was shut down, due to the bad economics. [Pg.308]

The oxidation of butane (or butylene or mixtures thereof) to maleic anhydride is a successful example of the replacement of a feedstock (in this case benzene) by a more economical one (Table 1, entry 5). Process conditions are similar to the conventional process starting from aromatics or butylene. Catalysts are based on vanadium and phosphorus oxides [11]. The reaction can be performed in multitubular fixed bed or in fluidized bed reactors. To achieve high selectivity the conversion is limited to <20 % in the fixed bed reactor and the concentration of C4 is limited to values below the explosion limit of approx. 2 mol% in the feed of fixed bed reactors. The fluidized-bed reactor can be operated above the explosion limits but the selectivity is lower than for a fixed bed process. The synthesis of maleic anhydride is also an example of the intensive process development that has occurred in recent decades. In the 1990s DuPont developed and introduced a so called cataloreactant concept on a technical scale. In this process hydrocarbons are oxidized by a catalyst in a high oxidation state and the catalyst is reduced in this first reaction step. In a second reaction step the catalyst is reoxidized separately. DuPont s circulating reactor-regenerator principle thus limits total oxidation of feed and products by the absence of gas phase oxygen in the reaction step of hydrocarbon oxidation [12]. [Pg.16]

The C,-fraction of naphtha crackers is used as a feedstock in the Mitsubishi fluid bed process for the production of maleic anhydride. This process was commercialized in 1970. Many data related to this process including the catalyst screening, laboratory experiments, pilot plant design, reactor behaviour and the development of higher selectivity catalysts may be found in the patent literature (12-17).The patents thus give a nearly complete picture of the scale-up process. The data have been used in the present investigation to test the fluid bed reactor model. [Pg.125]

Much more work has involved N-protected 1,2-dihydropyridines thus, DielsAlder reactions between dihydropyridine 533 and many acrylic acid esters or dimethyl maleate have been described, though variable yields of endo 543 and exo 544 2-azabicyclo[2.2.2]octene products are obtained. The reaction with maleic anhydride yielded only the endo product 545 <2003T7555>. Chiral catalysts have been developed to allow the enantioselective DielsAlder reactions of 1,2-dihydropyridines <2002T8299>. [Pg.324]

The introduction of rhodium has allowed the development of processes which operate under much milder conditions and lower pressures, are highly selective, and avoid loss of alkene by hydrogenation. Although the catalyst is active at moderate temperature, plants are usually operated at 120°C to give a high n/iso (linear/ branched) ratio. The key to selectivity is the use of triphenylphosphine in large excess which leads to >95% straight chain anti-Markovnikov product. The process is used for the hydroformylation of propene to n-butyraldehyde, allyl alcohol to butanediol, and maleic anhydride to 1,4-butanediol, tetrahydrofuran, and y-butyrolactone. [Pg.1254]

The first reports of successful water cleavage followed the development of RUO2 as a catalyst for O2 production from [Ru(bipy)j] . Simply mixing colloidal RUO2 and colloidal platinum protected by styrene-maleic anhydride copolymer with [Ru(bipy)j] and leads to H2... [Pg.524]

In the case of tetramethylbutatriene, Ni(0) catalyzes not only the cyclodimerization (formation of [4]radialene 94), but also the cyclotrimerization, leading to [6]radialene 95 and its isomer 96 (see also Section ILD). The product pattern depends to some extent on the nature of the catalyst, but the choice of solvent seems to be more crucial. This is illustrated impressively by the Ni(cod)2-catalyzed reaction of 93, which leads exclusively to the [4]radialene in toluene solution, but to the [6]radialene in DMF. Interestingly, the stoichiometric reaction between 93 and (2,2Tbipyridyl)-(l,5-cyclooctadiene)nickel yields the nickel complex 97, which has been isolated and characterized by X-ray diffraction. On treatment of 97 with two equivalents of maleic anhydride, reductive elimination of nickel takes place and octamethyl[4]radialene (94) is formed in good yield. This reaction sequence sheds light on the mechanism of the Ni-catalyzed reactions mentioned above further ideas on the mechanism of the cyclodimerization and cyclotrimerization reactions have been developed by lyoda and coworkers. ... [Pg.951]


See other pages where Maleic anhydride catalyst developments is mentioned: [Pg.453]    [Pg.316]    [Pg.202]    [Pg.812]    [Pg.825]    [Pg.23]    [Pg.74]    [Pg.100]    [Pg.157]    [Pg.951]    [Pg.174]    [Pg.522]    [Pg.316]    [Pg.524]    [Pg.860]    [Pg.17]    [Pg.3]    [Pg.502]    [Pg.221]    [Pg.42]    [Pg.157]    [Pg.6]    [Pg.345]    [Pg.216]    [Pg.813]    [Pg.46]   


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