Uranium oxidation reactions

Dioxygea difluoride has fouad some appHcatioa ia the coaversioa of uranium oxides to UF (66), ia fluoriaatioa of actinide fluorides and oxyfluorides to AcF (67), and in the recovery of actinides from nuclear wastes (68) (see Actinides and transactinides Nuclear reaction, waste managel nt). 

CP-1 was assembled in an approximately spherical shape with the purest graphite in the center. About 6 tons of luanium metal fuel was used, in addition to approximately 40.5 tons of uranium oxide fuel. The lowest point of the reactor rested on the floor and the periphery was supported on a wooden structure. The whole pile was surrounded by a tent of mbberized balloon fabric so that neutron absorbing air could be evacuated. About 75 layers of 10.48-cm (4.125-in.) graphite bricks would have been required to complete the 790-cm diameter sphere. However, criticality was achieved at layer 56 without the need to evacuate the air, and assembly was discontinued at layer 57. The core then had an ellipsoidal cross section, with a polar radius of 209 cm and an equatorial radius of309 cm [20]. CP-1 was operated at low power (0.5 W) for several days. Fortuitously, it was found that the nuclear chain reaction could be controlled with cadmium strips which were inserted into the reactor to absorb neutrons and hence reduce the value of k to considerably less than 1. The pile was then disassembled and rebuilt at what is now the site of Argonne National Laboratory, U.S.A, with a concrete biological shield. Designated CP-2, the pile eventually reached a power level of 100 kW [22]. 

Fluidized bed reactors were first employed on a large scale for the catalytic cracking of petroleum fractions, but in recent years they have been employed for an increasingly large variety of reactions, both catalytic and non-catalytic. The catalytic reactions include the partial oxidation of naphthalene to phthalic anhydride and the formation of acrylonitrile from propylene, ammonia, and air. The noncatalytic applications include the roasting of ores and Tie fluorination of uranium oxide. 

Dining outgassing of scrap uranium-aluminium cermet reactor cores, powerful exotherms led to melting of 9 cores. It was found that the incident was initiated by reactions at 350°C between aluminium powder and sodium diuranate, which released enough heat to initiate subsequent exothermic reduction of ammonium uranyl hexafluoride, sodium nitrate, uranium oxide and vanadium trioxide by aluminium, leading to core melting. 

Strangely enough, a combination similar to the ammonia catalyst, iron oxide plus alumina, yielded particularly good results (32). Together with Ch. Beck, the author found that other combinations such as iron oxide with chromium oxide, zinc oxide with chromium oxide, lead oxide with uranium oxide, copper oxide with zirconium oxide, manganese oxide with chromium oxide, and similar multicomponent systems were quite effective catalysts for the same reaction (33). 

Uranium is best known as a fuel for nuclear power plants. To prepare this fuel, uranium ores are processed to extract and enrich the uranium. The process begins by mining uranium-rich ores and then crushing the rock. The ore is mixed with water and thickened to form a slurry. The slurry is treated with sulfuric acid and the product reacted with amines in a series of reactions to give ammonium diuranate, (NH4)2U20 . Ammonium diuranate is heated to yield an enriched uranium oxide solid known as yellow cake. Yellow cake contains from 70—90% U3Og in the form of a mixture of U02 and U03. The yellow cake is then shipped to a conversion plant where it can be enriched. 

In the 1960s, a number of binary oxides, including molybdenum, tellurium, and antimony, were found to be active for the reactions and some of them were actually used in commercial reactors. Typical commercial catalysts are Fe-Sb-O by Nitto Chemical Ind. Co. (62 -64) and U-Sb-O by SOHIO (65-67), and the former is still industrially used for the ammoxidation of propylene after repeated improvements. Several investigations were reported for the iron-antimony (68-72) and antimony-uranium oxide catalysts (73-75), but more investigations were directed at the bismuth molybdate catalysts. The accumulated investigations for these simple binary oxide catalysts are summarized in the preceding reviews (5-8). 

Calcium serves as a reductant for such reactive metals as zirconium, thorium, vanadium, and uranium. In zirconium reduction, zirconium fluoride is reacted with culcium metal. The high heat of the reaction melts the zirconium. The zirconium ingot resulting is remelted undet vacuum for purilicatinn. Thorium and uranium oxides are reduced with an excess of calcium in reactors or trays under an atmosphere of argon. The resulting tnetals are leached with acetic acid tu remove the lime. 

A typical nuclear reactor utilizes uranium oxide, whose uranium content is approximately 3 percent uranium-235, and 97 percent uranium-238, by mass. During the fission reaction, the uranium-235 is consumed and fission products form. As the amount of uranium-235 decreases and the amounts of fission products increase, the fission process becomes less efficient. At some point, the spent nuclear fuel is removed and stored. Some of the radioactive fission products, because of their radioactivity and long half-lives, must be stored securely for thousands of years. Thus, nuclear waste management poses a tremendous challenge. 

Thorium oxide fluoride (Th2OF5) (277) has been prepared from ThF4 and ThOF, and the reaction of uranium oxides with UF4 at 400-500°C is said to produce U205F as one of the products (278). 

---