Molybdenum plant

The symptoms of molybdenum deficiency are usually chlorosis, yellowing of the leaves, and stunted growth (Mulder, 1950 Hewitt, 1951). These are the usual indications of nitrogen deficiency which is the result in this case of decreased nitrogen fixation, and interference with nitrogen metabolism in the cells in the absence of the activator, molybdenum. Plants seem to be able to grow normally without this element if adequate nitrogen is supplied as ammonia. 

Molybdenum Plant Thiocyanate complex Spectrophotometry 0.05-1.0 mg r Liquid-liquid extraction... 

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. 

Micronutrients. Attention to meeting the micronutrient needs of crops has greatiy increased as evidenced in an analysis undertaken by TVA and the Soil Science Society in 1972 (99). The micronutrient elements most often found wanting in soil—crop situations are boron, copper, iron, manganese, molybdenum, and zinc. Some of these essential micronutrients can be harmful to plants when used in excess. 

Flotation or froth flotation is a physicochemical property-based separation process. It is widely utilised in the area of mineral processing also known as ore dressing and mineral beneftciation for mineral concentration. In addition to the mining and metallurgical industries, flotation also finds appHcations in sewage treatment, water purification, bitumen recovery from tar sands, and coal desulfurization. Nearly one biUion tons of ore are treated by this process aimuaHy in the world. Phosphate rock, precious metals, lead, zinc, copper, molybdenum, and tin-containing ores as well as coal are treated routinely by this process some flotation plants treat 200,000 tons of ore per day (see Mineral recovery and processing). Various aspects of flotation theory and practice have been treated in books and reviews (1 9). 

Oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was first patented in 1921 (90), followed in 1933 by a patent for an iron oxide—molybdenum oxide catalyst (91), which is stiU the choice in the 1990s. Catalysts are improved by modification with small amounts of other metal oxides (92), support on inert carriers (93), and methods of preparation (94,95) and activation (96). In 1952, the first commercial plant using an iron—molybdenum oxide catalyst was put into operation (97). It is estimated that 70% of the new formaldehyde installed capacity is the metal oxide process (98). 

Chromium is the most effective addition to improve the resistance of steels to corrosion and oxidation at elevated temperatures, and the chromium—molybdenum steels are an important class of alloys for use in steam (qv) power plants, petroleum (qv) refineries, and chemical-process equipment. The chromium content in these steels varies from 0.5 to 10%. As a group, the low carbon chromium—molybdenum steels have similar creep—mpture strengths, regardless of the chromium content, but corrosion and oxidation resistance increase progressively with chromium content. 

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. 

Because of its position in the Periodic Table, molybdenum has sometimes been linked to chromium (see Chromiumand chromium alloys) or to other heavy metals. However, unlike those elements, molybdenum and its compounds have relatively low toxicity, as shown in Table 3. On the other hand, molybdenum has been identified as a micronutrient essential to plant life (11,12) (see Fertilizers), and plays a principal biochemical role in animal health as a constituent of several important enzyme systems (see Mineral nutrients). 

Molybdenum, recognized as an essential trace element for plants, animals, and most bacteria, is present in a variety of metaHo enzymes (44—46). Indeed, the absence of Mo, and in particular its co-factor, in humans leads to severe debility or early death (47,48). Molybdenum in the diet has been impHcated as having a role in lowering the incidence of dental caries and in the prevention of certain cancers (49,50). To aid the growth of plants. Mo has been used as a fertilizer and as a coating for legume seeds (51,52) (see FERTILIZERS Mineral NUTRIENTS). 

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. 

Synthesis. The total aimual production of PO in the United States in 1993 was 1.77 biUion kg (57) and is expected to climb to 1.95 biUion kg with the addition of the Texaco plant (Table 1). There are two principal processes for producing PO, the chlorohydrin process favored by The Dow Chemical Company and indirect oxidation used by Arco and soon Texaco. Molybdenum catalysts are used commercially in indirect oxidation (58—61). Capacity data for PO production are shown in Table 1 (see Propylene oxide). 

It is carried out in the Hquid phase at 100—130°C and catalyzed by a soluble molybdenum naphthenate catalyst, also in a series of reactors with interreactor coolers. The dehydration of a-phenylethanol to styrene takes place over an acidic catalyst at about 225°C. A commercial plant (50,51) was commissioned in Spain in 1973 by Halcon International in a joint venture with Enpetrol based on these reactions, in a process that became known as the Oxirane process, owned by Oxirane Corporation, a joint venture of ARCO and Halcon International. Oxirane Corporation merged into ARCO in 1980 and this process is now generally known as the ARCO process. It is used by ARCO at its Channelview, Texas, plant and in Japan and Korea in joint ventures with local companies. A similar process was developed by Shell (52—55) and commercialized in 1979 at its Moerdijk plant in the Netherlands. The Shell process uses a heterogeneous catalyst of titanium oxide on siHca support in the epoxidation step. Another plant by Shell is under constmction in Singapore (ca 1996). 

Materials of Construction. Resistance of alloys to concentrated sulfuric acid corrosion iacreases with increasing chromium, molybdenum, copper, and siUcon content. The corrosiveness of sulfuric acid solutions is highly dependent on concentration, temperature, acid velocity, and acid impurities. An excellent summary is available (114). Good general discussions of materials of constmction used ia modem sulfuric acid plants may be found ia References 115 and 116. More detailed discussions are also available (117—121). For nickel-containing alloys Reference 122 is appropriate. An excellent compilation of the relatively scarce Hterature data on corrosion of alloys ia Hquid sulfur trioxide and oleum may be found ia Reference 122. 

A U.S. Bureau of Mines survey covering 202 froth flotation plants in the United States showed that 198 million tons of material were treated by flotation in 1960 to recover 20 million tons of concentrates which contained approximately 1 billion in recoverable products. Most of the worlds copper, lead, zinc, molybdenum, and nickel are produced from ores that are concentrated first by flotation. In addition, flotation is commonly used for the recoveiy of fine coal and for the concentration of a wide range of mineral commodities including fluorspar, barite, glass sand, iron oxide, pyrite, manganese ore, clay, feldspar, mica, sponumene, bastnaesite, calcite, garnet, kyanite, and talc. 

Air pollutants that present a hazard to livestock, therefore, are those that are taken up by vegetation or deposited on the plants. Only a few pollutants have been observed to cause harm to animals. These include arsenic, fluorides, lead, mercury, and molybdenum. 

Heavy metals on or in vegetation and water have been and continue to be toxic to animals and fish. Arsenic and lead from smelters, molybdenum from steel plants, and mercury from chlorine-caustic plants are major offenders. Poisoning of aquatic life by mercury is relatively new, whereas the toxic effects of the other metals have been largely eliminated by proper control of industrial emissions. Gaseous (and particulate) fluorides have caused injury and damage to a wide variety of animals—domestic and wild—as well as to fish. Accidental effects resulting from insecticides and nerve gas have been reported. 

Micronutrient An element required by plants and bacteria, in proportionately smaller amounts, for survival and growth. Micronutrients include Iron (Fe), Managanese (MN), Zinc (Zn), Boron (B), and Molybdenum (Mo). 

In the chemical process industry molybdenum has found use as washers and bolts to patch glass-lined vessels used in sulphuric acid and acid environments where nascent hydrogen is produced. Molybdenum thermocouples and valves have also been used in sulphuric acid applications, and molybdenum alloys have been used as reactor linings in plant used for the production of n-butyl chloride by reactions involving hydrochloric and sulphuric acids at temperatures in excess of 170°C. Miscellaneous applications where molybdenum has been used include the liquid phase Zircex hydrochlorination process, the Van Arkel Iodide process for zirconium production and the Metal Hydrides process for the production of super-pure thorium from thorium iodide. 

Although molybdenum is resistant to molten glass, except leaded, molybdenum components not coated with glass but exposed to the oxidising furnace atmosphere corrode rapidly due to volatilisation of molybdenum oxide above 370°C. To overcome this, stirrers etc. for use in glass plant are physically clad with platinum sheet in vulnerable areas. Modern plating techniques have enabled dense platinum coatings to be put onto the surface of the molybdenum and it is expected that this technique will be exploited further in the near future. 

In direct liquefaction, coal is heated in the presence of hydrogen and a catalyst such as cobalt-molybdenum or nickel-molybdenum on alumina to give a greater yield of high-quality hydrocarbons than that produced by pyrolysis. This hydrogenation process has been demonstrated in several 50- to 250-ton-per-day plants. 

Rosa Llusar was born on September 20th, 1960 in Almenara (Spain). She studied chemistry at the University of Valencia (Spain) where she graduated in 1983 with the highest honors. Her doctorate work was devoted to the chemistry of cubane-type molybdenum and tungsten sulfides and she received Ph.D. degrees from Valencia University in 1987 and from Texas A M University (USA) in 1988, under the guidance of Prof. F. Albert Cotton. After working in the Research and Development Department of a Caprolactam Production Plant in Castello (Spain) for three years, she spent one year (1992) with Prof John D. Corbett at the... 

We tend to think of metals as lustrous solids copper, tin, gold, silver, iron. We are less likely to think of individual metal atoms in biological machines. Nevertheless, plants and animals require the presence of tiny amounts of transition metals. Humans require most of the elements in the first transition metal series and at least one element from the second transition metal series, molybdenum. 

H. Heuwinkel, E. A. Kirkby, J. Le Bot, and H. Marschner, Phosphorus deficiency enhances molybdenum uptake by tomato plants. J. Plant Niitr. 15 549 (1992). 

Soil pH is easily tested for and determines the availability of nutrients and the success of white clover. Very acid soils (below pH 5.0) will cause a deficiency of the trace elements iron, boron, copper and molybdenum and conversely will cause injury to plant growth by increasing the availability of aluminium and manganese to toxic levels. Over-liming, on the other hand, which can raise the pH above 6.5, will reduce the availability of certain essential elements such as phosphorus, manganese and boron. 

One of the first considerations in the use of any chemical is possible accumulations of harmful residues in soils. Evidence proves beyond any doubt that many of the newer compounds remain in the soil for at least 5 years. How much longer they may persist, time alone can determine. We know that both selenium and molybdenum can be picked up from soils by plants, which thus become extremely toxic to animals, even when plants themselves are apparently unharmed. Often a given piece of land may be treated safely as far as one crop is concerned but another crop may be injured. For example, potatoes will tolerate large amounts of DDT in the soil as a means of controlling wireworms which are extremely destructive melons, on the other hand, are severely injured by excessive DDT in the soil. There can be no assurance in many cases as to the ultimate use of any... 

Chemical precipitation is used in porcelain enameling to precipitate dissolved metals and phosphates. Chemical precipitation can be utilized to permit removal of metal ions such as iron, lead, tin, copper, zinc, cadmium, aluminum, mercury, manganese, cobalt, antimony, arsenic, beryllium, molybdenum, and trivalent chromium. Removal efficiency can approach 100% for the reduction of heavy metal ions. Porcelain enameling plants commonly use lime, caustic, and carbonate for chemical precipitation and pH adjustment. Coagulants used in the industry include alum, ferric chloride, ferric sulfate, and polymers.10-12... 

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