Molybdenum molybdate

Molybdenum Molybdate, molybdenum blue, the blue oxide of molybdenum, has already been described (see p. 131). 

Molybdate. See Molybdenum Molybdate, calciuia See Calcium molybdate Molybdate orange Molybdate red. S Pigment red 104 Molybdenite. See Molybdenum disulfide... 

Molybdenum is also recovered as a by-product of copper and tungsten mining operations. The metal is prepared from the powder made by the hydrogen reduction of purified molybdic trioxide or ammonium molybdate. 

Description of Method. The FIA determination of phosphate is an adaptation of a standard spectrophotometric analysis for phosphate. In the presence of add, phosphate reacts with molybdate to form a yellow-colored complex in which molybdenum is present as Mo(VI). 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

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. 

Molybdenum. The commonly used molybdenum materials are sodium molybdate [7631-95-0] ammonium molybdate [12027-67-7] molybdenum trioxide [1313-27-5] molybdenum sulfate [51016-80-9] and frits. Molybdenum is used in smaller amounts than any of the other micronutrients, ranging from a few grams to 3 kg/hm of Mo. 

Molybdenum Oxides. Molybdenum was one of the first elements used to retard the flames of ceUulosics (2). Mote recently it has been used to impart flame resistance and smoke suppression to plastics (26). Molybdic oxide, ammonium octamolybdate, and zinc molybdate ate the most widely used molybdenum flame retardants. Properties ate given in Table 5. These materials ate recommended almost exclusively for poly(vinyl chloride), its alloys, and unsaturated polyesters (qv). 

Molybdenum trioxide is a condensed-phase flame retardant (26). Its decomposition products ate nonvolatile and tend to increase chat yields. Two parts of molybdic oxide added to flexible poly(vinyl chloride) that contains 30 parts of plasticizer have been shown to increase the chat yield from 9.9 to 23.5%. Ninety percent of the molybdenum was recovered from the chat after the sample was burned. A reaction between the flame retardant and the chlorine to form M0O2 012 H20, a nonvolatile compound, was assumed. This compound was assumed to promote chat formation (26,27). 

Molybdenum is also a smoke suppressant for poly(vinyl chloride). It promotes the formation of cis- rather than the trans-polymeric decomposition products which ate the precursors for smoke. The sources for molybdates ate Climax Performance Material Cotp. and Sherwin WiUiams. 

Molybdenite concentrate contains about 90% M0S2. The remainder is primarily siUca, with lesser amounts of Fe, Al, and Cu. The concentrate is roasted to convert the sulfide to technical molybdic oxide. Molybdenum is added to steel in the form of this oxide. In modem molybdenum conversion plants, the oxidized sulfur formed by roasting M0S2 is converted to sulfuric acid. 

Technical molybdic oxide can be reduced by reaction of ferrosiUcon in a thermite-type reaction. The resulting product contains about 60% molybdenum and 40% iron. Foundries generally use ferromolybdenum for adding molybdenum to cast iron and steel, and steel mills may prefer ferromolybdenum to technical molybdic oxide for some types of steels. 

Chemical products are produced from technical-grade oxide in two very different ways. Molybdenum trioxide can be purified by a sublimation process because molybdenum trioxide has an appreciable vapor pressure above 650°C, a temperature at which most impurities have very low volatiUty. The alternative process uses wet chemical methods in which the molybdenum oxide is dissolved in ammonium hydroxide, leaving the gangue impurities behind. An ammonium molybdate is crystallized from the resulting solution. The ammonium molybdate can be used either directly or thermally decomposed to produce the pure oxide, MoO. ... 

Analytical Methods. Molybdenum contents in ore concentrates and technical oxide are most accurately deterrnined gravimetricaHy by precipitating lead molybdate. Molybdenum content is usually not determined on pure compounds or metal. Instead, spectrographic methods are used to measure impurity elements that must be controlled. Carbon and oxygen in metal products are measured by standard gas analysis methods. 

Manufacturing Processes. Ammonium molybdate or molybdenum trioxide is reduced to molybdenum metal powder by hydrogen in a two-stage process. In the first stage, MoO or ammonium molybdate is reduced to molybdenum dioxide, M0O2, at temperatures around 600°C in the... 

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

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. 

In addition to these principal commercial uses of molybdenum catalysts, there is great research interest in molybdenum oxides, often supported on siHca, ie, MoO —Si02, as partial oxidation catalysts for such processes as methane-to-methanol or methane-to-formaldehyde (80). Both O2 and N2O have been used as oxidants, and photochemical activation of the MoO catalyst has been reported (81). The research is driven by the increased use of natural gas as a feedstock for Hquid fuels and chemicals (82). Various heteropolymolybdates (83), MoO.-containing ultrastable Y-zeoHtes (84), and certain mixed metal molybdates, eg, MnMoO Ee2(MoO)2, photoactivated CuMoO, and ZnMoO, have also been studied as partial oxidation catalysts for methane conversion to methanol or formaldehyde (80) and for the oxidation of C-4-hydrocarbons to maleic anhydride (85). Heteropolymolybdates have also been shown to effect ethylene (qv) conversion to acetaldehyde (qv) in a possible replacement for the Wacker process. 

Coatings, Paints, and Pigments. Various slightly soluble molybdates, such as those of zinc, calcium, and strontium, provide long-term corrosion control as undercoatings on ferrous metals (90—92). The mechanism of action presumably involves the slow release of molybdate ion, which forms an insoluble ferric molybdate protective layer. This layer is insoluble in neutral or basic solution. A primary impetus for the use of molybdenum, generally in place of chromium, is the lower toxicity of the molybdenum compound. 

Molybdate orange and red are pigments (qv) that contain lead(II) molybdate [10190-33-3], PbMoO, formulated in mixed phases with PbCrO and PbSO. The mixed phase is more intensely colored than any of the component phases. Concerns about lead content are lessening the use of these materials (see also Paint). Various organic dyes are precipitated with heteropolymolybdates. This process allows the fixation of the dye in various fabrics. The molybdenum anion generally imparts light stabiHty to the colorant as weU (91). 

Soil Nutrient. Molybdenum has been widely used to increase crop productivity in many soils woddwide (see Fertilizers). It is the heaviest element needed for plant productivity and stimulates both nitrogen fixation and nitrate reduction (51,52). The effects are particularly significant in leguminous crops, where symbiotic bacteria responsible for nitrogen fixation provide the principal nitrogen input to the plant. Molybdenum deficiency is usually more prominent in acidic soils, where Mo(VI) is less soluble and more easily reduced to insoluble, and hence unavailable, forms. Above pH 7, the soluble anionic, and hence available, molybdate ion is the principal species. 

Biomedical Uses. The molybdate ion is added to total parenteral nutrition protocols and appears to alleviate toxicity of some of the amino acid components in these preparations (see Mineral NUTRIENTS) (97). Molybdenum supplements have been shown to reduce iiitrosarnine-induced mammary carcinomas in rats (50). A number of studies have shown that certain heteropolymolybdates (98) and organometaUic molybdenum compounds (99) have antiviral, including anti-AIDS, and antitumor activity (see Antiviral agents Chemotherapeutics, anticancer). 

In this process, catalysts, such as boric acid, molybdenum oxide, zirconium, and titanium tetrachloride or ammonium molybdate, are used to accelerate the reaction. The synthesis is either carried out in a solvent (aUphatic hydrocarbon, trichlorobenzene, quinoline, pyridine, glycols, or alcohols) at approximately 200°C or without a solvent at 300°C (51,52). 

Phosphate. Phosphoms occurs in water primarily as a result of natural weathering, municipal sewage, and agricultural mnoff The most common form in water is the phosphate ion. A sample containing phosphate can react with ammonium molybdate to form molybdophosphoric acid (H2P(Mo202q)4). This compound is reduced with stannous chloride in sulfuric acid to form a colored molybdenum-blue complex, which can be measured colorimetrically. SiUca and arsenic are the chief interferences. 

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... 

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