Catalyst bismuth oxide

Saturated hydrocarbons may also be oxidized by bismuth oxide catalysts. For example, methane is converted to CO2 and a mixture of higher hydrocarbons over bismuth oxide catalysts that also contain sodium, calcium, cesium, and/or halide... 

Cho YG, Park DK, Park DW, Woo HC and Chung JS (2002) Selective Oxidation of hydrogen sulfide to ammonium thiosulfate and sulfur over vanadium-bismuth oxide catalysts. Res Chem Intermediates 28(5) 419-431. 

The reactors were thick-waked stainless steel towers packed with a catalyst containing copper and bismuth oxides on a skiceous carrier. This was activated by formaldehyde and acetylene to give the copper acetyUde complex that functioned as the tme catalyst. Acetylene and an aqueous solution of formaldehyde were passed together through one or more reactors at about 90—100°C and an acetylene partial pressure of about 500—600 kPa (5—6 atm) with recycling as required. Yields of butynediol were over 90%, in addition to 4—5% propargyl alcohol. 

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. 

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

In the vapor phase, acetone vapor is passed over a catalyst bed of magnesium aluminate (206), 2iac oxide—bismuth oxide (207), calcium oxide (208), lithium or 2iac-doped mixed magnesia—alumina (209), calcium on alumina (210), or basic mixed-metal oxide catalysts (211—214). Temperatures ranging... 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

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. 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

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). 

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... 

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). 

Invented and developed independently in the late 1950s by D.G. Stewart in the Distillers Company, and R. Grasselli in Standard Oil of Ohio. The former used a tin/antimony oxide catalyst the latter bismuth phosphomolybdate on silica. Today, a proprietary catalyst containing depleted uranium is used. See also Erdolchemie, OSW, Sohio. 

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. 

For this reaction, our aim was to improve the known catalytic action of iron oxides to an extent that the high activity of the generally used platinum catalyst would be equalled. Together with Ch. Beck, the author finally found iron oxide-bismuth oxide combinations, and iron oxide-manganese oxide-bismuth oxide combinations which were outstanding catalysts. An iron oxide-lead oxide catalyst proved to be less satisfactory (44). 

One of the simplest examples for such effects is the oxidation of ammonia with iron oxide-bismuth oxide as a catalyst. Here, the addition of bismuth oxide results in the formation of nitrous oxides as the main product whereas an iron oxide catalyst without bismuth oxide yields nitrogen almost exlcusively. Selectively guiding catalysts become increasingly important in the synthesis of organic compounds, e.g., in the hydrogenation of carbon monoxide where the type of obtainable product can be varied, within wide limits, by the kinds of catalysts and promoters which are employed. 

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. 

Although this report describes the preparation of a wide variety of oxidation catalysts, only the iron modified bismuth molybdates will be described in detail. Other preparations are described in this section through an indication of the starting soluble salts and their synthesis temperatures which are the key process parameters. Other aspects of their HTAD preparations are similar to that described for the iron bismuth molybdates which follows. 

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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