Bismuth-molybdate catalyst

2 Bismuth Molybdate Catalysts. The Raman spectra of the bismuth molybdates, with Bi/Mo stoichiometric ratios between 0.67 and 14, have been examined using the FLS approach (see Section 3.2). The bismuth molybdates fall into an unusual class of compounds, the ternary bismuth oxide systems Bi-M-0 (where M = Mo, W, V, Nb, and Ta) which exhibit a variety of interesting physical and chemical properties. Of commercial importance, the bismuth molybdates are heterogeneous catalysts for selective oxidations and ammoxidations (the Sohio process), for example, propylene ( 311 ) to acrolein (C3H4O) by oxidation or to acrylonitrile (C3H3N) by arrunoxidation.  

The observed Raman bands for the bismuth molybdate samples (0.67 Bi/Mo 14) have been tabulated and show that many of the compositions examined are multiphasic. As expected, the bismuth molybdate and bismuth oxide phases were also found to depend on the Bi/Mo ratio, with die following phases being identified by Raman spectroscopy a-Bi2Mo30j2, 6-Bi2Mo20g, y-Bi2MoO, (high-temperature 

In addition to the capability of Raman spectroscopy in determining the coordination numbers and bond lengths of molybdate species in bismuth molybdate phases, Raman spectroscopy can also be used as an in situ probe for the bismuth molybdates under reaction conditions. In situ Raman studies have been earned out, for example, on the 6-Bi2Mo209 phase under redox conditions, where insights into the surface mechanism of the 

Light hydrocarbons consisting of oxygen or other heteroatoms are important intermediates in the chemical industry. Selective hydrocarbon oxidation of alkenes progressed dramatically with the discovery of bismuth molybdate mixed-metal-oxide catalysts because of their high selectivity and activity ( 90%). These now form the basis of very important commercial multicomponent catalysts (which may contain mixed metal oxides) for the oxidation of propylene to acrolein and ammoxidation with ammonia to acrylonitrile and to propylene oxide. 

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In 1957 Standard Oil of Ohio (Sohio) discovered bismuth molybdate catalysts capable of producing high yields of acrolein at high propylene conversions (>90%) and at low pressures (12). Over the next 30 years much industrial and academic research and development was devoted to improving these catalysts, which are used in the production processes for acrolein, acryUc acid, and acrylonitrile. AH commercial acrolein manufacturing processes known today are based on propylene oxidation and use bismuth molybdate based catalysts. 

Fig. 2. Mechanism of selective ammoxidation and oxidation of propylene over bismuth molybdate catalysts. (31).

Selective oxidation and ammoxldatlon of propylene over bismuth molybdate catalysts occur by a redox mechanism whereby lattice oxygen (or Isoelectronlc NH) Is Inserted Into an allyllc Intermediate, formed via or-H abstraction from the olefin. The resulting anion vacancies are eventually filled by lattice oxygen which originates from gaseous oxygen dlssoclatlvely chemisorbed at surface sites which are spatially and structurally distinct from the sites of olefin oxidation. Mechanistic details about the... 

Using the pulse microreactor method( ), the general rate expression for reoxldatlon of bismuth molybdate catalysts was found to be ... 

The following data given in Tables 16.15, 16.16 and 16.17 on the oxidation of propylene over bismuth molybdate catalyst were obtained at three temperatures, 350,375, and 390°C (Watts, 1994). 

Figure 11.26 Plot of the position sensitivity of the degree of conversion for a set of 48 bismuth-molybdate catalysts (same batch) in propylene to acrolein conversion in a Stage II 48-fold-screening reactor (reaction conditions 2% hydrocarbon in air at GHSV of 3000 h-1, column no. 8 contains only inert carrier material).

Acrolein Production. Adams et al. [/. Catalysis, 3,379 (1964)] studied the catalytic oxidation of propylene on bismuth molybdate catalyst to form acrolein. With a feed of propylene and oxygen and reaction at 460°C, the following three reactions occur. 

Figure 2. Compositional diagram for the preparation of bismuth molybdate catalysts using the HI AD process configuration shown in Figure 1 at 900°C using air as make up gas. Plot is of concentrations of bismuth used in the reacting solution vs arc plasma analyzed concentrations of the finished catalysts directly fi-om HTAD reactor Circles Co-precipitation prepared materials. Triangles Up flow prepared aerosol materials. Squares. Down flow prepared aerosol materials.

Oxidation in the original Sohio process941,942 was carried out over a bismuth molybdate catalyst, which was later superseded by bismuth phosphomolybdate with various amounts of additional metal ions (Ce, Co, Ni), and multicomponent metal oxides based on Mo, Fe, and Bi supported on silica. 

Multicomponent Bismuth Molybdate Catalyst A Highly Functionalized Catalyst System for the Selective Oxidation of Olefin... 

Multicomponent bismuth molybdate catalyst. h Heteropoly compound. 

Fig. I. Mechanism of selective oxidation of propylene to acrolein over bismuth molybdate catalyst by Burrington et al. (19).

In spite of the accumulated mechanistic investigations, it still seems difficult to explain why multicomponent bismuth molybdate catalysts show much better performances in both the oxidation and the ammoxidation of propylene and isobutylene. The catalytic activity has been increased almost 100 times compared to the simple binary oxide catalysts to result in the lowering of the reaction temperatures 60 80°C. The selectivities to the partially oxidized products have been also improved remarkably, corresponding to the improvements of the catalyst composition and reaction conditions. The reaction mechanism shown in Figs. 1 and 2 have been partly examined on the multicomponent bismuth molybdate catalysts. However, there has been no evidence to suggest different mechanisms on the multicomponent bismuth molybdate catalysts. 

II. Characterization and Working Mechanism of Multicomponent Bismuth Molybdate Catalysts... 

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). 

The improvement of bismuth molybdate catalyst by the addition of various kinds of metal elements has been continued after the establishment of... 

Typical Reaction Conditions for the Oxidation and Ammoxidation of Propylene on the Simple and Multicomponent Bismuth Molybdate Catalyst°... 

One typical way to improve the catalyst system was directed at the multi-component bismuth molybdate catalyst having scheelite structure (85), where metal cations other than molybdenum and bismuth usually have ionic radii larger than 0.9 A. It is important that the a-phase of bismuth molybdate has a distorted scheelite structure. Thus, metal molybdates of third and fourth metal elements having scheelite structure easily form mixed-metal scheelite crystals or solid solution with the a-phase of bismuth molybdates. Thus, the catalyst structure of the scheelite-type multicomponent bismuth molybdate is rather simple and composed of a single phase or double phases including many lattice vacancies. On the other hand, another type of multi-component bismuth molybdate is composed mainly of the metal cation additives having ionic radii smaller than 0.8 A. Different from the scheelite-type multicomponent bismuth molybdates, the latter catalyst system is never composed of a simple phase but is made up of many kinds of different crys-... 

Multicomponent Bismuth Molybdate Catalysts with Scheelite Structure... 

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