Bismuth molybdates

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. 

Many key improvements and enhancements to the bismuth molybdate based propylene oxidation catalysts have occurred over the past thirty years. These are outlined in the following tabulation. 

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. 

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

The first catalysts used commercially to convert the propylene with high selectivity were mixed oxides of bismuth and molybdenum, referred to as bismuth molybdates. Improved catalysts consisting of a number of soHd phases have been developed, with each generation becoming more compHcated than its predecessor. Among the catalysts cited in a patent is the following Co gNi 2"Fe 3Bi (Mo0 22 Si02 with some P and K (88). Sihca is the... 

These enable temperature control with built-in exchangers between the beds or with pumparound exchangers. Converters for ammonia, 80.3, cumene, and other processes may employ as many as five or six beds in series. The Sohio process for vapor-phase oxidation of propylene to acrylic acid uses hvo beds of bismuth molybdate at 20 to 30 atm (294 to 441 psi) and 290 to 400°C (554 to 752°F). Oxidation of ethylene to ethylene oxide also is done in two stages with supported... 

Much work has been invested to reveal the mechanism by which propylene is catalytically oxidized to acrolein over the heterogeneous catalyst surface. Isotope labeling experiments by Sachtler and DeBoer revealed the presence of an allylic intermediate in the oxidation of propylene to acrolein over bismuth molybdate. In these experiments, propylene was tagged once at Ci, another time at C2 and the third time at C3. 

Another industrially important reaction of propylene, related to the one above, is its partial oxidation in the presence of ammonia, resulting in acrylonitrile, H2C=CHCN. This ammoxidation reaction is also catalyzed by mixed metal oxide catalysts, such as bismuth-molybdate or iron antimonate, to which a large number of promoters is added (Fig. 9.19). Being strongly exothermic, ammoxidation is carried out in a fluidized-bed reactor to enable sufficient heat transfer and temperature control (400-500 °C). 

In the case of selective oxidation catalysis, the use of spectroscopy has provided critical Information about surface and solid state mechanisms. As Is well known( ), some of the most effective catalysts for selective oxidation of olefins are those based on bismuth molybdates. The Industrial significance of these catalysts stems from their unique ability to oxidize propylene and ammonia to acrylonitrile at high selectivity. Several key features of the surface mechanism of this catalytic process have recently been descrlbed(3-A). However, an understanding of the solid state transformations which occur on the catalyst surface or within the catalyst bulk under reaction conditions can only be deduced Indirectly by traditional probe molecule approaches. Direct Insights Into catalyst dynamics require the use of techniques which can probe the solid directly, preferably under reaction conditions. We have, therefore, examined several catalytlcally Important surface and solid state processes of bismuth molybdate based catalysts using multiple spectroscopic techniques Including Raman and Infrared spectroscopies, x-ray and neutron diffraction, and photoelectron spectroscopy. 

Redox Processes and Solid State Transformations In Bismuth Molybdates... 

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 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. 

Analytical electron microscopy permits structural and chemical analyses of catalyst areas nearly 1000 times smaller than those studied by conventional bulk analysis techniques. Quantitative x-ray analyses of bismuth molybdates are shown from lOnm diameter regions to better than 5% relative accuracy for the elements 61 and Mo. Digital x-ray images show qualitative 2-dimensional distributions of elements with a lateral spatial resolution of lOnm in supported Pd catalysts and ZSM-5 zeolites. Fine structure in CuLj 2 edges from electron energy loss spectroscopy indicate d>ether the copper is in the form of Cu metal or Cu oxide. These techniques should prove to be of great utility for the analysis of active phases, promoters, and poisons. 

Several previous studies have demonstrated the power of AEH in various catalyst systems (1-11). Often AEM can provide reasons for variations in activity and selectivity during catalyst aging by providing information about the location of the elements involved in the active catalyst, promoter, or poison. In some cases, direct quantitative correlations of AEM analysis and catalyst performance can be made. This paper first reviews some of the techniques for AEM analysis of catalysts and then provides some descriptions of applications to bismuth molybdates, Pd on carbon, zeolites, and Cu/ZnO catalysts. 

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). 

Bismuth Molybdates. Bismuth molybdates are used as selective oxidation catalysts. Several phases containing Bi and/or Mo may be mixed together to obtain desired catalytic properties. While selected area electron diffraction patterns can identify individual crystalline particles, diffraction techniques usually require considerable time for developing film and analyzing patterns. X-ray emission spectroscopy in the AEM can identify individual phases containing two detectable elements within a few minutes while the operator is at the microscope. 

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).

Bismuth iron molybdate, 27 207-209 X-ray diffraction, TlilW Bismuth molybdate, 27 184-187, 189, 191-194, 196, 199--204, 30 124-125 active site, 27 210-213 alumina supported, 27 203, 204 ammoxidation, 30 159 P phase, 27 201 catalyst... 

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