Uranium ore processing

Leaching:

Roasted uranium ores are leached of their uranium values by both acidic and alkaline aqueous solutions. For the successful operation of all leaching systems, uranium must either be initially present in the more stable hexavalent state or be oxidized to that state in the leaching process.

Acid leaching is commonly performed by agitating an ore-leach mixture for 4 to as long as 48 hours at ambient temperature. Except in special circumstances, sulfuric acid is the leachant used; it is supplied in amounts sufficient to obtain a final leach liquor at about pH 1.5. Sulfuric acid leaching circuits commonly employ either manganese dioxide or chlorate ion to oxidize the tetravalent uranium ion (U4+) to the hexavalent uranyl ion (UO22+). Typically, about 5 kilograms (11 pounds) of manganese dioxide or 1.5 kilograms of sodium chlorate per ton suffice to oxidize tetravalent uranium. In any case, the oxidized uranium reacts with the sulfuric acid to form a uranyl sulfate complex anion, [UO2(SO4)3]4-.

Uranium ores that contain significant amounts of basic minerals such as calcite or dolomite are leached with 0.5 to 1 molar sodium carbonate solutions. Although a variety of reagents has been studied and tested, oxygen is the uranium oxidant of choice. Typically, candidate ores are leached in air at atmospheric pressure and at 75° to 80° C (167° to 175° F) for periods that vary with the particular ore. The alkaline leachant reacts with uranium to form a readily soluble uranyl carbonate complex ion, [UO2(CO3)3]4-.

Prior to further processing, solutions resulting from either acidic or carbonate leaching must be clarified. Large-scale separation of clays and other ore slimes is accomplished through the use of effective flocculants, including polyacrylamides, guar gum, and animal glue.

Treatment of uranium leachates

The complex ions [UO2(CO3)3]4- and [UO2(SO4)3]4- can be sorbed from their respective leach solutions by ion-exchange resins. These special resins—characterized by their sorption and elution kinetics, particle size, stability, and hydraulic properties—can be used in a variety of processing equipment—e.g., fixed-bed, moving-bed, basket resin-in-pulp, and continuous resin-in-pulp. Conventionally, sodium and ammonium chloride or nitrate solutions are then used to elute the sorbed uranium from the exchange resins.

Uranium can also be removed from acidic ore leach-liquors through solvent extraction. In industrial methods, alkyl phosphoric acids—e.g., di(2-ethylhexyl) phosphoric acid—and secondary and tertiary alkyl amines are the usual solvents. As a general rule, solvent extraction is preferred over ion-exchange methods for acidic leachates containing more than one gram of uranium per litre. Solvent extraction is not useful for recovery of uranium from carbonate leach liquors, however.

Precipitation of yellow cake:

Prior to final purification, uranium present in acidic solutions produced by the ion-exchange or solvent-extraction processes described above, as well as uranium dissolved in carbonate ore leach solutions, is typically precipitated as a polyuranate. From acidic solutions, uranium is precipitated by addition of neutralizers such as sodium hydroxide, magnesia, or (most commonly) aqueous ammonia. Uranium is usually precipitated as ammonium diuranate, (NH4)2U2O7. From alkaline solutions, uranium is most often precipitated by addition of sodium hydroxide, producing an insoluble sodium diuranate, Na2U2O7. It can also be precipitated by acidification (to remove carbon dioxide) and then neutralization (to remove the uranium) or by reduction to less soluble tetravalent uranium. In all cases, the final uranium precipitate, commonly referred to as yellow cake, is dried. In some cases—e.g., with ammonium diuranate—the yellow cake is ignited, driving off the ammonia and oxidizing the uranium to produce uranium trioxide (UO3) or the more complex triuranium octoxide (U3O8). In all cases, the final product is shipped to a central uranium-purification facility.

Abundance:

Uranium is more plentiful than antimony, tin, cadmium, mercury, or silver, and it is about as abundant as arsenic or molybdenum.Uranium is found in hundreds of minerals, including uraninite (the most common uranium ore), carnotite, autunite, uranophane, torbernite, and coffinite.

The discovery of the element is credited to the German chemist Martin Heinrich Klaproth. While he was working in his experimental laboratory in Berlin in 1789, Klaproth was able to precipitate a yellow compound (likely sodium diuranate) by dissolving pitchblende in nitric acid and neutralizing the solution with sodium hydroxide.[27] Klaproth assumed the yellow substance was the oxide of a yet-undiscovered element and heated it with charcoal to obtain a black powder, which he thought was the newly discovered metal itself (in fact, that powder was an oxide of uranium).He named the newly discovered element after the planet Uranus.

Worldwide production of U3O8 (yellowcake) in 2013 amounted to 70,015 tonnes, of which 22,451 t (32%) was mined in Kazakhstan. Other important uranium mining countries are Canada (9,331 t), Australia (6,350 t), Niger (4,518 t), Namibia(4,323 t) and Russia (3,135 t).

Mining:

Uranium ore is mined in several ways: by open pit, underground, in-situ leaching, and borehole mining (see uranium mining).Low-grade uranium ore mined typically contains 0.01 to 0.25% uranium oxides. Extensive measures must be employed to extract the metal from its ore.High-grade ores found in Athabasca Basin deposits in Saskatchewan, Canada can contain up to 23% uranium oxides on average.Uranium ore is crushed and rendered into a fine powder and then leached with either an acid or alkali. The leachate is subjected to one of several sequences of precipitation, solvent extraction, and ion exchange. The resulting mixture, called yellowcake, contains at least 75% uranium oxides U3O8. Yellowcake is then calcined to remove impurities from the milling process before refining and conversion.

The most common forms of uranium oxide are triuranium octoxide (U3O8) and UO2.Both oxide forms are solids that have low solubility in water and are relatively stable over a wide range of environmental conditions. Triuranium octoxide is (depending on conditions) the most stable compound of uranium and is the form most commonly found in nature. Uranium dioxide is the form in which uranium is most commonly used as a nuclear reactor fuel.At ambient temperatures, UO2 will gradually convert to U3O8. Because of their stability, uranium oxides are generally considered the preferred chemical form for storage or disposal.

Enrichment:

In nature, uranium is found as uranium-238 (99.2742%) and uranium-235 (0.7204%). Isotope separation concentrates (enriches) the fissionable uranium-235 for nuclear weapons and most nuclear power plants, except for gas cooled reactors and pressurised heavy water reactors. Most neutrons released by a fissioning atom of uranium-235 must impact other uranium-235 atoms to sustain the nuclear chain reaction. The concentration and amount of uranium-235 needed to achieve this is called a 'critical mass'.

To be considered 'enriched', the uranium-235 fraction should be between 3% and 5%.This process produces huge quantities of uranium that is depleted of uranium-235 and with a correspondingly increased fraction of uranium-238, called depleted uranium or 'DU'. To be considered 'depleted', the uranium-235 isotope concentration should be no more than 0.3%.

At room temperatures, UF6 has a high vapor pressure, making it useful in the gaseous diffusion process to separate the rare uranium-235 from the common uranium-238 isotope. This compound can be prepared from uranium dioxide and uranium hydride by the following process:

UO2 + 4 HF → UF4 + 2 H2O (500 °C, endothermic)

UF4 + F2 → UF6 (350 °C, endothermic)

The resulting UF6, a white solid, is highly reactive (by fluorination), easily sublimes (emitting a vapor that behaves as a nearly ideal gas), and is the most volatile compound of uranium known to exist.