Ferric molybdate catalysts

Formox [Formaldehyde by oxidation] A process for oxidizing methanol to formaldehyde, using a ferric molybdate catalyst. Based on the Adkins-Peterson reaction, developed by Reichold Chemicals, and licensed by that company and Perstorp, Sweden. Acquired by Dyno Industries in 1989. The process uses formaldehyde produced in this way to make formaldehyde-urea resin continuously. A plant using this process was to be built in Ghent by 1991, owned jointly by Dyno and AHB-Chemie. Licensed to 35 sites worldwide. Several other companies operate similar processes. 

The results from the infrared studies and from the GC analysis show that the reaction of methane with the ferric molybdate catalysts gives methanol, formaJdehyde, carbon dioxide, and carbon monoxide as final products. The IR spectra also indicate the formation of methoxy, surface dioxymethylene, surface formate species, and adsorbed formaldehyde. Based on these observations, a mechanism was proposed to account for all intermediates and final products and is shown in Figure 5. Since the surface structure of the catalysts is not known, the surface is represented by a straight line in the scheme. 

Figure 5. Proposed mechanism of catalytic conversion of methane over ferric molybdate catalysts.

Using in situ FT-IR spectroscopy, the gas phase products and the principal intermediates involved in the catalytic conversion of methane over ferric molybdate catalysts were identified and the reaction mechanism was proposed. In the absence of an oxidizing agent, methane reacts with the oxygen of the catalyst to produce methoxy species, which is an important intermediate for methanol formation. Further oxidation of the methoxy groups results in the formation of surface dioxymethylene, adsorbed formaldehyde, and surface formate species. The decomposition of surface dioxymethylene and surface formate species will give carbon oxides and hydrogen. 

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. 

A conmercial catalyst frcm Harshaw was used, a 3 1 mixture of molybdenum trioxide and ferric molybdate, as well as the two separate phases. Kinetic experiments were done previously in a differential reactor with external recycle using these same catalysts as well as several other preparations of molybdenun trioxide, including supported samples. Hie steady state kinetic experiments were done in the temperature range 180-300 C, and besides formaldehyde, the following products were observed, dimethylether, dimethoxymethane, methyl formate, and carbon-monoxide. Usually very little carbon dioxide was obtained, and under certain conditions, hydrogen and methane can be produced. 

Analytical electron microscopy of individual catalyst particles provides much more information than just particle size and shape. The scanning transmission electron microscope (STEM) with analytical facilities allows chemical analysis and electron diffraction patterns to be obtained from areas on the order of lOnm in diameter. In this paper, examples of high spatial resolution chemical analysis by x-ray emission spectroscopy are drawn from supported Pd, bismuth and ferric molybdates, and ZSM-5 zeolite. 

Figure 8. Temperature Programmed Desorption of methanol from the ferric molybdate (dashed line) and the manganese pyrophosphate (solid line) catalysts determined gravimetrically.

Figure 11. Mechanistic proposal for the aamoxidation of methanol to HCN over the ferric molybdate and the manganese pyrophosphate catalysts.

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-... 

Annenkova et al. (105) studied both the physicochemical and catalytic properties of the Bi-Fe-Mo oxide system. The X-ray diffraction, infrared spectroscopic, and thermographic measurements indicated that the catalysts were heterogeneous mixtures consisting principally of ferric molybdate, a-bismuth molybdate, and minor amounts of bismuth ferrite and molybdenum trioxide. The Bi-Fe-Mo oxide catalysts were more active in the oxidation of butene to butadiene and carbon dioxide than the bismuth molybdate catalysts. The addition of ferric oxide to bismuth molybdate was also found to increase the electrical conductivity of the catalyst. 

The most selective catalysts for the oxidation of methanol to formaldehyde are molybdates. In many commercial processes, a mixture of ferric molybdate and molybdenum trioxide is used. Ferric molybdate has often been reported to be the major catalytically active phase with the excess molybdenum trioxide added to improve the physical properties of the catalyst and to maintain an adequate molybdenum concentration under reactor conditions(l,2). In some cases, a synergistic effect is claimed, with maximum catalytic activity for a mixture with an Fe/Mo ratio of l.T( 3j. A defect solid solution was also proposed( ). Aging of a commercial catalyst has been studied using a variety of analytical techniques(4) and it was concluded that deactivation can largely be account for by loss of molybdenum from the catalyst surface. 

The IR spectra of methanol and methoxy groups adsorbed on M0O3, ferric molybdate, and other bulk molybdates and supported molybdena catalysts, have been reported. 

Although the stoichiometric ratio of molybdenum to iron in ferric molybdate is 1.5, the maximum activity is obtained at an atomic ratio of 1.7. However, the presence of free ferric oxide in the catalyst is known to reduce considerably the selectivity of the catalyst to the formation of formaldelyde. For this reason, excess molybdenum is usually added to the catalyst formulation to maximize the yield of the product. The optimum ratio is about 2.0. ... 

The catalyst is prepared by precipitation from solutions of ferric chloride and ammonium molybdate. The precipitate may not be homogeneous, with significant variations within a single batch. Hydrothermal aging of the precipitate may be necessary to provide a more uniform composition. Precipitation of the catalyst as a gel provides a more uniform ferric molybdate compositioa... 

The mechanism and rate of hydrogen peroxide decomposition depend on many factors, including temperature, pH, presence or absence of a catalyst (7—10), such as metal ions, oxides, and hydroxides etc. Some common metal ions that actively support homogeneous catalysis of the decomposition include ferrous, ferric, cuprous, cupric, chromate, dichromate, molybdate, tungstate, and vanadate. For combinations, such as iron and... 

In the preparation of a dyestuff from aniline, nitrobenzene (as oxidant), hydrochloric acid and sodium hydroxide, ferric chloride is often used as catalyst, but sodium molybdate was substituted as a more effective catalyst. The materials were charged into a 4.5 m3 reactor and heating was started after addition of nitrobenzene, but the temperature controller was mis-set, and overheating at a high rate ensued. The exotherm was much higher than normal because of the more effective catalyst, and partial failure of the cooling water led to an uncontrollable exotherm. 

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