Bismuth molybdates composition

Catalytic Studies using Bismuth Molybdate Compositions... 

Patents claiming specific catalysts and processes for thek use in each of the two reactions have been assigned to Japan Catalytic (45,47—49), Sohio (50), Toyo Soda (51), Rohm and Haas (52), Sumitomo (53), BASF (54), Mitsubishi Petrochemical (56,57), Celanese (55), and others. The catalysts used for these reactions remain based on bismuth molybdate for the first stage and molybdenum vanadium oxides for the second stage, but improvements in minor component composition and catalyst preparation have resulted in yields that can reach the 85—90% range and lifetimes of several years under optimum conditions. Since plants operate under more productive conditions than those optimum for yield and life, the economically most attractive yields and productive lifetimes maybe somewhat lower. 

The structure of the single phase bismuth-iron molybdate compound of composition Bl3FeMo20.2 related to the scheellte structure of Bi2Mo30-2( ). It is reported(, ) that the catalytic activity and selectivity of bismuth-iron molybdate for propylene oxidation and ammoxidatlon is not greater than that of bismuth molybdate. 

Three well known examples of processes employing fluidised-bed operations are the oxidations of naphthalene and xylene to phthalic anhydride using a supported V2O5 catalyst and ammoxidation of propylene utilising a mixed oxide composition containing bismuth molybdate. Typically, this latter reaction is executed by passing a mixture of ammonia, air and propylene to a fluidised bed operating at about 0.2 MPa pressure, 400—500°C and a few seconds contact time between gas and fluidised catalyst peirticles. 

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.

Finally, Arrhenius treatments of the catalytic data were examined for the HTAD synthesized substitutional series, Bi(2-2x) 2x 030i2, and the binary bismuth molybdate series where Bi/Mo ratios were varied fi-om pure Mo oxide to pure Bi oxide. The noteworthy aspect of the oxidation results is that in the most reactive regime of x = 0-5% atom fi-action Fe, before separate phase Fe3Mo30j2 begins to dominate the catalyst composition in the iron series, the apparent activation energies were all in the range of 19-20 kcal/mol. Furthermore, the activation energies for the pure Bi-Mo series were between 19-20 kcal/mol while the activities were considerable different. Thus, the chief difference in the reactivities in both series is in the preexponential factor, i.e. the number of active sites. 

Crystal structures of the bismuth molybdate and of the mixed iron and cobalt solid solution molybdate samples were controlled by X-ray diffraction (10). The chemical compositions of the samples were determined by atomic absorption and their surface areas measured by nitrogen adsorption using the BET method. 

During the history of a half century from the first discovery of the reaction (/) and 35 years after the industrialization (2-4), these catalytic reactions, so-called allylic oxidations of lower olefins (Table I), have been improved year by year. Drastic changes have been introduced to the catalyst composition and preparation as well as to the reaction process. As a result, the total yield of acrylic acid from propylene reaches more than 90% under industrial conditions and the single pass yield of acrylonitrile also exceeds 80% in the commercial plants. The practical catalysts employed in the commercial plants consist of complicated multicomponent metal oxide systems including bismuth molybdate or iron antimonate as the main component. These modern catalyst systems show much higher activity and selectivity... 

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. 

Fig. 5. Composition of multicomponent bismuth molybdate catalyst having multiphase structure.

Choosing divalent and trivalent cations and determining the composition is the most important in designing the multicomponent bismuth molybdate catalyst system. Catalytic activities of typical tri- and tetracomponent bismuth molybdate catalysts having multiphase structure were reported for the oxidation of propylene to form acrolein (35, 36, 40-43, 97, 98). A typical example of the activity test is shown in Fig. 6. Summarizing the results shown in Fig. 6 and reported previously (30, 43, 44), the following trends are generally found. 

Surface analyses were investigated mainly by using XPS (Fig. 7). It was clearly indicated that many composite oxides found by XRD are located un-homogeneously in the catalyst particle. Molybdenum and bismuth are undoubtedly concentrated in the surface layer of the catalyst particle and divalent and trivalent metal cations are found in the bulk of the catalyst. As a result, it is clear that bismuth molybdates, especially its a-phase, is located on the surface of each particle, and metal molybdates of divalent and trivalent cations are situated in the bulk of the catalyst. 

Villa et al. [340] have shown that the bismuth tungstates are comparable with bismuth molybdates with respect to dehydrogenation catalysis, although activities and selectivities are somewhat lower. Although the phase structures are different, interesting catalysts are formed in a similar composition range Bi/W = 2/3 to 2/1. (Note that, in case of propene (amm)oxidation, tungstates are definitely inferior to molybdates.)... 

Bismuth molybdate and other binary compositions (Fe—Mo, Sn—Sb and others) were tested by Germain and Perez [128] using a pulsed reactor. The authors demonstrate that a qualitative analogy may exist between ammonia and propene oxidation but if activities are compared, different sequences of catalytic efficiency arise. It must be noted, however, that these conclusions are based only on pulse experiments. These can be quite different from results in flow reactors, depending mainly on the nature of the steady state. 

As a catalyst for propylene oxidation, Bi203 itself has fairly low activity and yields primarily the products of complete oxidation. Pure molybdenum trioxide has an even lower activity, but is fairly selective. In combination, however, remarkable activity and selectivity for propylene oxidation is obtained. Although industrial catalysts contain silica and phosphate as well as Bi203 and Mo03, many fundamental studies have employed catalysts containing only bismuth and molybdenum oxides in an attempt to determine the structure of the catalytically active phase. As a result of such studies, it is now known that bismuth molybdate catalysts display their superior properties only if the catalyst composition lies within the composition range of Bi/Mo = f to f (atomic ratio). 

The establishment of the structures and thermal transformations of the catalytically active phases of bismuth molybdate resulted in research directed toward investigating the stability of the structure under reducing conditions. Fattore et al. (38) investigated an unsupported bismuth molybdate catalyst with composition Bi2032.66M0O3 during propylene... 

Silica supported bismuth molybdate catalysts were examined by Dalin et al. (85) during extended steady-state ammoxidation of propylene. X-Ray diffraction measurements indicated that a significant alteration in the phase composition of supported catalysts occurred during operation. The a and /3 phases of bismuth molybdate, which were originally present, transformed into the y phase of bismuth molybdate as described by the equation... 

Daniel and Keulks (104) investigated Bi-Fe-Mo oxide catalysts prepared by reacting the a-bismuth molybdate with ferric hydroxide. Comparison of these catalysts with bismuth molybdate and ferric oxide indicated that mechanistically the Bi-Fe-Mo oxide catalysts resembled bismuth molybdate in their ability to form an allyl species. Under the same reaction conditions, the composition with Bi-Fe-Mo atomic ratio equal to 6 9 10 exhibited higher conversion than and the same selectivity as the bismuth molybdate catalysts. In contrast to bismuth molybdate, the Bi-Fe-Mo oxide catalysts were found to maintain their activity and se-... 

Matsuura and Wolfs (110) examined the surface composition of the a, f3, and y phases of bismuth molybdate utilizing ESCA. The authors observed the presence of both Mo6+ and Bi3+ in the surface layers of the three bismuth molybdate phases. The relative intensity of the bismuth signal increased while the molybdenum signal remained constant with an increasing concentration of bulk-phase bismuth in the catalysts. 

One possible conclusion is that under reducing conditions, metal cation movement occurs. Another possible conclusion is that despite the similar surface layer composition of bismuth and molybdenum for the three phases of bismuth molybdate, the three bismuth molybdate phases possess different catalytic activities, catalytic selectivities, adsorption properties, surface oxomolybdenum species, and reducibilities because the surface properties of the active bismuth molybdates are dependent upon the foundation upon which they exist, i.e., upon the bulk structure and its chemical and electronic properties. 

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... 

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