96

URANIUM PROCESS METALLURGY

are an insoluble sodium uranate and a soluble vanadate that can be

leached away from the uranium.

Most precipitates from uranium leach solutions are taken up directly

or indirectly in nitric acid. According to a widely used procedure, the

uranium is then crystallized as a nitrate or is precipitated as a peroxide,

the nitrate or peroxide is dried and calcined to U03, the U03 is reduced

with hydrogen to U02, and the U02 is converted to a halide, which is

ultimately reduced to metallic uranium.

Numerous methods of recovery of uranium from solution depend on

the reduction of hexavalent uranium to tetravalency. The reduction,

whether accomplished chemically or electroehemically, results in the

selective formation of an insoluble uranium compound, which can be

separated by filtration or decantation from associated elements in solu-

tion.

Passing acid liquors over zinc amalgam, aluminum, or iron reduces

the uranium to tetravalency so that it can be precipitated as phosphate,

arsenate, or fluoride. Addition to the liquor of S11CI2, C11CI2, or TiCU

also can accomplish this reduction. This avoids the cost of neutralizing

acid solutions and permits them to be recycled for further use.6

In some instances a combination of chemical and electrochemical

methods is used. For example, hexavalent uranium can be reduced to

tetravalent in 30% H3P04 by electrolyzing at 0.5 v by the use of an

attackable iron anode and an inert cathode of stainless steel or platinum.78

Reduction is continued from a redox potential of 300 to 180 mv, as

measured with a platinum-calomel electrode couple. With carbonate

liquors at elevated temperature and pressure, the reduction and conse-

quent precipitation (in the presence of phosphate, arsenate, or fluoride)

can be accomplished with hydrogen in the presence of a nickel catalyst.

The hydrogen reduction of uranyl salts and oxides and the precipitation

of the reduction product can be accomplished, even in the absence of

phosphate, arsenate, or fluoride, by any of several methods.

Hydrogen reduction in an autoclave at 100 to 150C precipitates

high grade UO2 directly from either acid or carbonate solutions if nickel

powder is present as a catalyst.666679 The nickel can be recovered by

magnetic separation and in other ways, and the chemical reagents can

be recycled.

Despite the theoretical simplicity of this direct process operators of

plants already equipped to use another procedure are understandably

unlikely to be in a hurry to have them converted so that they can use

direct-reduction precipitation.

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