Oxidation reactions molybdenum

Oxidation Catalysis. The multiple oxidation states available in molybdenum oxide species make these exceUent catalysts in oxidation reactions. The oxidation of methanol (qv) to formaldehyde (qv) is generally carried out commercially on mixed ferric molybdate—molybdenum trioxide catalysts. The oxidation of propylene (qv) to acrolein (77) and the ammoxidation of propylene to acrylonitrile (qv) (78) are each carried out over bismuth—molybdenum oxide catalyst systems. The latter (Sohio) process produces in excess of 3.6 x 10 t/yr of acrylonitrile, which finds use in the production of fibers (qv), elastomers (qv), and water-soluble polymers. 

Propylene oxide is also produced in Hquid-phase homogeneous oxidation reactions using various molybdenum-containing catalysts (209,210), cuprous oxide (211), rhenium compounds (212), or an organomonovalent gold(I) complex (213). Whereas gas-phase oxidation of propylene on silver catalysts results primarily in propylene oxide, water, and carbon dioxide as products, the Hquid-phase oxidation of propylene results in an array of oxidation products, such as propylene oxide, acrolein, propylene glycol, acetone, acetaldehyde, and others. 

Much like the oxidation of propylene, which produces acrolein and acrylic acid, the direct oxidation of isobutylene produces methacrolein and methacrylic acid. The catalyzed oxidation reaction occurs in two steps due to the different oxidation characteristics of isobutylene (an olefin) and methacrolein (an unsaturated aldehyde). In the first step, isobutylene is oxidized to methacrolein over a molybdenum oxide-based catalyst in a temperature range of 350-400°C. Pressures are a little above atmospheric ... 

The cations in transition metal oxides often occur in more than one oxidation state. Molybdenum oxide is a good example, as the Mo cation may be in the 6-r, 5-r, and 4+ oxidation states. Oxide surfaces with the cation in the lower oxidation state are usually more reactive than those in the highest oxidation state. Such ions can engage in reactions that involve changes in valence state. 

Figure 6. Reaction of n-butyllithium with titanium disulfide, vanadium pent oxide, and molybdenum trioxide (reprinted with permission from ref 77, copyright 1977 The Electrochemical Society).

The oxidation of ethanol to acetic acid was among the first heterogeneous catalyzed reactions to be reported, but it has not attracted continued interest. During the 1990ies, however, 100% conversion of ethanol coupled with 100% selectivity to acetic acid was reported in a gas-phase reaction using molybdenum oxide catalytic systems on various supports, at temperatures below 250 Similarly, a tin oxide and molybdenum oxide catalyst was... 

In this paper selectivity in partial oxidation reactions is related to the manner in which hydrocarbon intermediates (R) are bound to surface metal centers on oxides. When the bonding is through oxygen atoms (M-O-R) selective oxidation products are favored, and when the bonding is directly between metal and hydrocarbon (M-R), total oxidation is preferred. Results are presented for two redox systems ethane oxidation on supported vanadium oxide and propylene oxidation on supported molybdenum oxide. The catalysts and adsorbates are stuped by laser Raman spectroscopy, reaction kinetics, and temperature-programmed reaction. Thermochemical calculations confirm that the M-R intermediates are more stable than the M-O-R intermediates. The longer surface residence time of the M-R complexes, coupled to their lack of ready decomposition pathways, is responsible for their total oxidation. 

In the investigation of hydrocarbon partial oxidation reactions the study of the factors that determine selectivity has been of paramount importance. In the past thirty years considerable work relevant to this topic has been carried out. However, there is yet no unified hypothesis to address this problem. In this paper we suggest that the primary reaction pathway in redox type reactions on oxides is determined by the structure of the adsorbed intermediate. When the hydrocarbon intermediate (R) is bonded through a metal oxygen bond (M-O-R) partial oxidation products are likely, but when the intermediate is bonded through a direct metal-carbon bond (M-R) total oxidation products are favored. Results on two redox systems are presented ethane oxidation on vanadium oxide and propylene oxidation on molybdenum oxide. 

Temperature Programmed Reaction. Examination of another redox system, propylene oxidation on M0O3, provides further insight. It is well accepted that propylene oxidation on molybdenum-based catalysts proceeds through formation of allylic intermediates. From isotopic studies it has been demonstrated that formation of the allylic intermediate is rate-determining (H/D effect), and that a symmetric allylic species is formed ( C labelling). 

Sumimoto introduced a new sebacic acid process including several catalytic hydrogenation reactions.342 The synthesis starts with naphthalene, which is first partially hydrogenated to tetralin over cobalt oxide or molybdenum oxide, then to decalin over ruthenium or iridium on carbon. The selectivity to cw-decalin is better than 90%. In a later phase of the synthesis 5-cyclododecen-l-one is hydrogenated over Raney nickel to obtain a mixture of cyclododecanone and cyclodode-canol in a combined yield of 90%. The selectivity of this step is not crucial since subsequent oxidation of either compound leads to the endproduct sebacic acid. 

Catalytic oxidation of propylene to acrolein was first discovered by the Shell group in 1948 on Cu20 catalyst (/). Both oxidation and ammoxidation were industrialized by the epoch-making discovery of bismuth molybdate catalyst by SOHIO (2-4). The bismuth molybdate catalyst was first reported in the form of a heteropoly compound supported on Si02, Bi P,Mo,2052/Si02 having Keggin structure but it was not the sole active species for the reactions. Several kinds of binary oxides between molybdenum trioxide and bismuth oxide have been known, as shown in the phase... 

In the 1960s, a number of binary oxides, including molybdenum, tellurium, and antimony, were found to be active for the reactions and some of them were actually used in commercial reactors. Typical commercial catalysts are Fe-Sb-O by Nitto Chemical Ind. Co. (62 -64) and U-Sb-O by SOHIO (65-67), and the former is still industrially used for the ammoxidation of propylene after repeated improvements. Several investigations were reported for the iron-antimony (68-72) and antimony-uranium oxide catalysts (73-75), but more investigations were directed at the bismuth molybdate catalysts. The accumulated investigations for these simple binary oxide catalysts are summarized in the preceding reviews (5-8). 

Tribochemical reaction The formation of an iron sulfide tribofilm may be displaced by other surface active elements such as oxygen, where the oxide of the iron heat of formation AHf = -2.82 eV is thermodynamically more stable than the sulfide AHf = -1.04 eV. Using the data from Table 5.11, compare the heat of formation of molybdenum oxide and molybdenum sulfide. 

Figure 4.2 shows the SIMS spectrum of a promoted iron-antimony oxide catalyst used in selective oxidation reactions. Note the simultaneous occurrence of single ions (Si+, Fe+, Cu+, etc.) and molecular ions (SiO+, SiOH+, FeO+, SbO+, SbOSi+). Also clearly visible are the isotope patterns of copper (two isotopes at 63 and 65 amu), molybdenum (seven isotopes between 92 and 100 amu), and antimony (121 and 123 amu). Isotopic ratios play an important role in the identification of peaks, because all peak intensities must agree with natural abundances. Figure 4.2 also illustrates the differences in SIMS yields of the different elements although iron and antimony are present in comparable quantities in the catalyst, the iron intensity in the spectrum is about 25 times as high as that of antimony ... 

Molybdenum oxide trichloride has been prepared by heating molybdenum(VI) oxide or molybdenum dioxide dichloride with molybdenum(V) chloride. Molybdenum(VI) oxide tetrachloride is a by-product of the latter reaction.1 It was also prepared by the sealed-tube reaction of liquid sulfur dioxide with molybdenum (Y) chloride2 and by the thermal decomposition of molybdenum oxide tetrachloride in a stream of nitrogen. In the following procedure, it is prepared by reducing molybdenum oxide tetrachloride with refluxing chlorobenzene.4... 

Since the reaction involves irreversible oxidation of molybdenum, it would not be expected to be catalytic. 

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