Ethylene ammoxidation

Chromium zeolites are recognised to possess, at least at the laboratory scale, notable catalytic properties like in ethylene polymerization, oxidation of hydrocarbons, cracking of cumene, disproportionation of n-heptane, and thermolysis of H20 [ 1 ]. Several factors may have an effect on the catalytic activity of the chromium catalysts, such as the oxidation state, the structure (amorphous or crystalline, mono/di-chromate or polychromates, oxides, etc.) and the interaction of the chromium species with the support which depends essentially on the catalysts preparation method. They are ruled principally by several parameters such as the metal loading, the support characteristics, and the nature of the post-treatment (calcination, reduction, etc.). The nature of metal precursor is a parameter which can affect the predominance of chromium species in zeolite. In the case of solid-state exchange, the exchange process initially takes place at the solid- solid interface between the precursor salt and zeolite grains, and the success of the exchange depends on the type of interactions developed [2]. The aim of this work is to study the effect of the chromium precursor on the physicochemical properties of chromium loaded ZSM-5 catalysts and their catalytic performance in ethylene ammoxidation to acetonitrile. 

Catalytic performances in ethylene ammoxidation as function of reaction temperature of the different catalysts are compiled in Table 2. Data were collected under stationary conditions after a transition period of one hour. All catalysts are active and selective toward acetonitrile. Wherein, Cr-Cl catalyst exhibits the higher ethylene conversion and the higher acetonitrile selectivity. Chromium with highly oxidation state (VI) seems to play a key role in the ammoxidation reaction as confirmed by TPR and DRS spectroscopy results. This idea is strongly supported by the difference between catalytic behaviour of Cr03 and Cr203 supported on ZSM-5. Nevertheless, Cr(III) oxide seems to... 

Reactions of the Methyl Groups. These reactions include oxidation, polycondensation, and ammoxidation. PX can be oxidized to both terephthahc acid and dimethyl terephthalate, which ate then condensed with ethylene glycol to form polyesters. Oxidation of OX yields phthaUc anhydride, which is used in the production of esters. These ate used as plasticizers for synthetic polymers. MX is oxidized to isophthaUc acid, which is also converted to esters and eventually used in plasticizers and resins (see Phthalic acids and otherbenzenepolycarboxylic acids). 

Processes rendered obsolete by the propylene ammoxidation process (51) include the ethylene cyanohydrin process (52—54) practiced commercially by American Cyanamid and Union Carbide in the United States and by I. G. Farben in Germany. The process involved the production of ethylene cyanohydrin by the base-cataly2ed addition of HCN to ethylene oxide in the liquid phase at about 60°C. A typical base catalyst used in this step was diethylamine. This was followed by liquid-phase or vapor-phase dehydration of the cyanohydrin. The Hquid-phase dehydration was performed at about 200°C using alkah metal or alkaline earth metal salts of organic acids, primarily formates and magnesium carbonate. Vapor-phase dehydration was accomphshed over alumina at about 250°C. 

Vinyl chloride is an important monomer for polyvinyl chloride (PVC). The main route for obtaining this monomer, however, is via ethylene (Chapter 7). A new approach to utilize ethane as an inexpensive chemical intermediate is to ammoxidize it to acetonitrile. The reaction takes place in presence of a cobalt-B-zeolite. 

Telescope the Process by Combining Stages. This has been done successfully in the conversion of propylene to acrylonitrile by direct ammoxidation rather than oxidation to acrolein followed by reaction with ammonia in a separate stage, as was described in the earlier patent literature. The oxychlorination of ethylene and HC1 directly to vinyl chloride monomer is another good example of the telescoping of stages to yield an economic process. 

Cr-ZSM-5 catalysts prepared by solid-state reaction from different chromium precursors (acetate, chloride, nitrate, sulphate and ammonium dichromate) were studied in the selective ammoxidation of ethylene to acetonitrile. Cr-ZSM-5 catalysts were characterized by chemical analysis, X-ray powder diffraction, FTIR (1500-400 cm 1), N2 physisorption (BET), 27A1 MAS NMR, UV-Visible spectroscopy, NH3-TPD and H2-TPR. For all samples, UV-Visible spectroscopy and H2-TPR results confirmed that both Cr(VI) ions and Cr(III) oxide coexist. TPD of ammonia showed that from the chromium incorporation, it results strong Lewis acid sites formation at the detriment of the initial Bronsted acid sites. The catalyst issued from chromium chloride showed higher activity and selectivity toward acetonitrile. This activity can be assigned to the nature of chromium species formed using this precursor. In general, C r6+ species seem to play a key role in the ammoxidation reaction but Cr203 oxide enhances the deep oxidation. 

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. 

Other catalytic reactions carried out in fluidized-bed reactors are the oxidation of naphthalene to phthalic anhydride [2, 6, 80] the ammoxidation of isobutane to mcthacrylonitrilc [2] the synthesis of maleic anhydride from the naphtha cracker C4 fraction (Mitsubishi process [81, 82]) or from n-butane (ALMA process [83], [84]) the reaction of acetylene with acetic acid to vinyl acetate [2] the oxychlorination of ethylene to 1,2-di-chloroethane [2, 6, 85, 86] the chlorination of methane [2], the reaction of phenol with methanol to cresol and 2,6-xylenol [2, 87] the reaction of methanol to gasoline... 

The initial drive for acrylonitrile (AN) production (6.2 Mt/a in 2004 worldwide) was the discovery, in the late 1930s, of the synthetic rubber Buna N. Today nitrile rubbers represent only a minor outlet for AN which is utilized primarily for polymerization to give textile fibres (50%) and ABS resins (24%), and for dimerization to adiponitrile (10%). Early industrial processes depended on the addition of hydrogen cyanide to acetylene or to ethylene oxide, followed by the dehydration of intermediate ethylene cyanohydrin. Both processes are obsolete and are now supplanted by the ammoxidation of propylene (Equation 34) introduced in 1960 by Standard Oil of Indiana (Sohio). The reason for the success stems from the effectiveness of the catalyst and because propylene,... 

Active and selective in propane oxidation to acrylic acid propane ammoxid. to acrylonitrile ethane oxidation to ethylene/acetic acid... 

A different type of catalyst is conshtuted by Co ion-exchanged zeolites and mesoporous materials (MCM-49). Co-ZSM-5 was found to be selective in ethane ammoxidation [135]. A good correlahon between the acidity and the catalytic activity was observed. The strength of ammonia bonding to the catalyst appears to have a crucial effect on the activity of Co-ZSM-5. Li and Armor [136] reported that dealuminated zeolite was achve for the ammoxidation of ethane to acetonitrile. Pan and coworkers [137] instead studied ion-exchanged Co-Na-MCM-49 and Co-H-MCM-49 materials for the same reaction, reporting that the presence of ammonia in the feed considerably improved the selectivity and total yield of ethylene and acetonitrile. 

Examples of synergistic effects are now very numerous in catalysis. We shall restrict ourselves to metallic oxide-type catalysts for selective (amm)oxidation and oxidative dehydrogenation of hydrocarbons, and to supported metals, in the case of the three-way catalysts for abatement of automotive pollutants. A complementary example can be found with Ziegler-Natta polymerization of ethylene on transition metal chlorides [1]. To our opinion, an actual synergistic effect can be claimed only when the following conditions are filled (i), when the catalytic system is, thermodynamically speaking, biphasic (or multiphasic), (ii), when the catalytic properties are drastically enhanced for a particular composition, while they are (comparatively) poor for each single component. Therefore, neither promotors in solid solution in the main phase nor solid solutions themselves are directly concerned. Multicomponent catalysts, as the well known multimetallic molybdates used in ammoxidation of propene to acrylonitrile [2, 3], and supported oxide-type catalysts [4-10], provide the most numerous cases to be considered. Supported monolayer catalysts now widely used in selective oxidation can be considered as the limit of a two-phase system. 

Supported metal oxides are currently being used in a large number of industrial applications. The oxidation of alkanes is a very interesting field, however, only until recently very little attention has been paid to the oxidation of ethane, the second most abundant paraffin (1). The production of ethylene or acetaldehyde from this feed stock is a challenging option. Vanadium oxide is an important element in the formulation of catalysts for selective cataljdic reactions (e. g. oxidation of o-xylene, 1-3, butadiene, methanol, CO, ammoxidation of hydrocarbons, selective catalytic reduction of NO and the partial oxidation of methane) (2-4). Many of the reactions involving vanadium oxide focus on the selective oxidation of hydrocarbons, and some studies have also examined the oxidation of ethane over vanadium oxide based catalysts (5-7) or reviewed the activity of vanadium oxide for the oxidation of lower alkanes (1). Our work focuses on determining the relevance of the specific oxide support and of the surface vanadia coverage on the nature and activity of the supported vanadia species for the oxidation of ethane. 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

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