Bismuth plant

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. 

In the Betterton-KroU process the dezinced lead is pumped to the debismuthizing kettie, in which special care is taken to remove drosses that wastefuUy consume the calcium and magnesium. The skimmed blocks from the previous debismuthizing kettie are added to the bath at 420°C and stirred for a short time to enrich the dross with the bismuth being extracted from the new charge. This enriched dross is skimmed to blocks and sent to the bismuth recovery plant. 

Slag and Htharge formed during cupeUation are segregated and reduced to a metal containing 20—25% ore more bismuth, depending on the bismuth content of the original buUion, and transferred to a bismuth recovery plant. 

The washed slime is dried and melted to produce slag and metal. The slag is usually purified by selective reduction and smelted to produce antimonial lead. The metal is treated ia the molten state by selective oxidation for the removal of arsenic, antimony, and some of the lead. It is then transferred to a cupel furnace, where the oxidation is continued until only the silver—gold alloy (dorn) remains. The bismuth-rich cupel slags are cmshed, mixed with a small amount of sulfur, and reduced with carbon to a copper matte and impure bismuth metal the latter is transferred to the bismuth refining plant. 

The effect of impurities in either structural material or corrosive material is so marked (while at the same time it may be either accelerating or decelerating) that for rehable results the actual materials which it is proposed to use should be tested and not types of these materials. In other words, it is much more desirable to test the actual plant solution and the actual metal or nonmetal than to rely upon a duphcation of either. Since as little as 0.01 percent of certain organic compounds will reduce the rate of solution of steel in sulfuric acid 99.5 percent and 0.05 percent bismuth in lead will increase the rate of corrosion over 1000 percent under certain conditions, it can be seen how difficult it would be to attempt to duplicate here all the significant constituents. 

Bismuth oeeurs mainly as bismite (a-Bi203), bismuthinite (Bi2S3) and bismutite [(Bi0)2C03] very oeeasionally it oeeurs native, in assoeiation with Pb, Ag or Co ores. The main eommereial souree of the element is as a byproduet from Pb/Zn and Cu plants, from whieh it is obtained by special processes dependent on the nature of the main product. Sulfide ores are roasted to the oxide and then reduced by iron or charcoal. Because of its low mp, very low solubiUty in Fe, and fairly high oxidative stability in air, Bi can be melted and cast (like Pb) in iron and steel vessels. Like Sb, the metal is too brittle to roll, draw, or extrude at room temperature, but above 225°C Bi can be worked quite well. 

The reason for the ultramicrochemical test was to establish whether the bismuth phosphate would carry the plutonium at the concentrations that would exist at the Hanford extraction plant. This test was necessary because it did not seem logical that tripositive bismuth should be so efficient in carrying tetrapositive plutonium. In subsequent months there was much skepticism on this point and the ultramicrochemists were forced to make repeated tests to prove this point. Thompson soon showed that Pu(Vl) was not carried by bismuth phosphate, thus establishing that an oxidation-reduction cycle would be feasible. All the various parts of the bismuth-phosphate oxidation-reduction procedure, bulk reduction via cross-over to a rare earth fluoride oxidation-reduction step and final isolation by precipitation of plutonium (IV) peroxide were tested at the Hanford concentrations of... 

Irradiated Fuel A historically important and continuing mission at the Hanford site is to chemically process irradiated reactor fuel to recover and purify weapons-grade plutonium. Over the last 40 years, or so, several processes and plants— Bismuth Phosphate, REDOX, and PUREX—have been operated to accomplish this mission. Presently, only the Hanford PUREX Plant is operational, and although it has not been operated since the fall of 1972, it is scheduled to start up in the early 1980 s to process stored and currently produced Hanford -Reactor fuel. Of nine plutonium-production reactors built at the Hanford site, only the N-Reactor is still operating. 

M. Lancien, S. Ferrario-Mery, Y. Eoux, E. Bismuth, C. Ma.sclaux, B. Hirel, P. Gadal, and M. Hodges, Simultaneous expression of NAD-dependent isocitrate dehydrogenase and other Krebs cycle genes after nitrate resupply to short-term nitrogen starved tobacco. Plant Physiol. 120 1X1 (1999). 

In 1962, Pierre Eymard, a graduate smdent at the University of Lyon, synthesized a series of khellin derivatives. Khellin is a biologically active substance that occurs in the fruit of the wild Arabian Khell plant and which has been used for centuries by herbalists for the treatment of kidney stones. Eymard arranged to have his new compounds biologically evaluated at the Ecole de Medecine et de Pharmacie in nearby Grenoble. When attempts to produce a solution of these khellin compounds failed, advice was sought from H. Meunier of the nearby Laboratoire Berthier. In view of Berthier s recent peripheral interest in valproic acid as a solvent for bismuth compounds, Meunier recommended valproic acid as a nontoxic inert solvent. 

During the history of a half century from the first discovery of the reaction (/) and 35 years after the industrialization (2-4), these catalytic reactions, so-called allylic oxidations of lower olefins (Table I), have been improved year by year. Drastic changes have been introduced to the catalyst composition and preparation as well as to the reaction process. As a result, the total yield of acrylic acid from propylene reaches more than 90% under industrial conditions and the single pass yield of acrylonitrile also exceeds 80% in the commercial plants. The practical catalysts employed in the commercial plants consist of complicated multicomponent metal oxide systems including bismuth molybdate or iron antimonate as the main component. These modern catalyst systems show much higher activity and selectivity... 

Investigations into the scheelite-type catalyst gave much valuable information on the reaction mechanisms of the allylic oxidations of olefin and catalyst design. However, in spite of their high specific activity and selectivity, catalyst systems with scheelite structure have disappeared from the commercial plants for the oxidation and ammoxidation of propylene. This may be attributable to their moderate catalytic activity owing to lower specific surface area compared to the multicomponent bismuth molybdate catalyst having multiphase structure. 

Bismuth, antimony, arsenic, arsenate, vanadate, thallium, lead, tin, dichromate, nitrate and iron all interfere in this procedure but the interferences by all of these except thallium, tin and dichromate can be overcome by suitable modifications to the method. Plant digests for analysis when prepared by nitric acid-perchloric acid digestion [70]. 

Schramel [103] discusses the conditions for multi-element analysis of over 50 trace elements, giving detection limits. Wolnik [104] described a sample introduction system that extends the analytical capability of the inductively coupled argon plasma/polychromator to include the simultaneous determination of six elemental hydrides along with a variety of other elements in plant materials. Detection limits for arsenic, bismuth, selenium and tellurium range from 0.5 to 3 ng/ml and are better by at least an order of magnitude than those obtained with conventional pneumatic nebulisers, whereas detection limits for the other elements investigated remain the same. Results from the analysis of freeze-dried crop samples and NBS standard reference materials demonstrated the applicability of the technique. Results obtained by the analysis of a variety of plant materials are presented in Table 7.10. 

Hahn et al. [105] used a hydride generation/condensation system with an ICP polychromator for the determination of arsenic, bismuth, germanium, antimony, selenium and tin in plant materials. 

At first, George Merck merely ran the American branch of dad s export business. However, in that era of high tariffs, he figured it would make sense to start manufacturing his own supply. In 1900 he bought some 120 acres of swamps and woodland in Rahway, New Jersey, for a manufacturing plant, followed by a factory in St. Louis. Among his products were iodides, bismuths, morphine, and cocaine—the last two considered medicines at the turn of the century. 

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