Patent Number: 042017386
Section: description

DESCRIPTION OF A PREFERRED EMBODIMENT The starting solution for the process of the present invention is uranyl nitrate preferably in a concentration range of between about 200 and 300 gU/l at about 2M HNO.sub.3. The concentrated uranyl nitrate is batch denitrated using conventional apparatus and procedures by the controlled addition of formic acid to the hot uranyl nitrate solution. One conventional technique is described in Denitration of Nitric Acid Solution by Formic Acid, USAEC Report DP-1299, 1972. While the formic acid concentration by itself is not critical, the rate of addition of formic acid should be in the range of between about 0.30 to about 0.70 moles/(min)(liter of uranyl nitrate feed). The preferred concentration for the use of this feed rate is a concentration at or in excess of 77.5% or 19.9 M formic acid. Formic acid concentrations as low as 50% and as high as 90% may be used provided appropriate adjustment is made for the feed rate, the solution temperature, and the off gas removal system. As in conventional denitration, the solution temperature is maintained at about 90.degree. C. for a period of about one to two hours in the presence of excess formic acid to assure complete denitration. Although excess formic acid is added during denitration, the solution acid concentration must be controlled to about 0.3 moles per 100 grams of solution to prevent uranyl formate monohydrate precipitation during the denitration step. Such uncontrolled or premature precipitation could adversely effect the particle size distribution of the precipitated salt. Thus, the carefully controlled denitration step produces an unsaturated solution of uranyl formate containing all of the uranium from the feed uranyl nitrate solution. Unsaturated uranyl formate solution from the denitration step and at the denitration temperature of about 90.degree. C. is then contacted with additional formic acid to precipitate uranyl formate monohydrate. The formic acid is added in sufficient stoichiometric excess and at a rate selected to control the nucleation and growth of crystalline particles during precipitation and to yield the desired particle size distribution for powder metallurgical requirements. Formic acid preferably at or in excess of 19.9 M concentration is added at a rate of between about 0.40 and 1.27 moles/(min)(liter of uranyl nitrate feed) to raise the solution acid concentration from about 0.3 to about 1.4 moles/100 g of solution. A higher concentration of formic acid (about 1.6 to 1.7 moles/100 g solution) is achieved by conventional volume reduction (evaporation) and controlled addition of small quantities of 90% formic acid. At this concentration the solution and precipitate are cooled to ambient room temperature (about 25.degree. C.). The precipitate is then recovered by filtration. The precipitate is washed during this step with 90% formic acid to remove residual contaminants. The filter cake, consisting essentially of substantially pure uranyl formate monohydrate (UO.sub.2 (HCOO).sub.2.H.sub.2 O), is then dried at 110.degree. to 120.degree. C. for one to four hours to provide a crystalline uranyl formate monohydrate salt. At this stage the crystalline formate salt, which has a uniform particle size distribution, is suitable for calcining to U.sub.3 O.sub.8. Calcining is conducted in a conventional manner in a static bed by heating the salt in air at about 10.degree. C. per minute to a final temperature of about 800.degree. C. to produce a free-flowing crystalline U.sub.3 O.sub.8 powder having a controlled particle size distribution. The calcination temperature is maintained for 4 to 8 hours to ensure complete conversion to U.sub.3 O.sub.8 product. For the purpose of this specification, the word "controlled" when used in connection with "particle size" may be defined as having a "uniform narrow range" of particle size compatible with powder metallurgical grade aluminum powder and suitable for powder metallurgical use. The U.sub.3 O.sub.8 product may be further characterized as a U.sub.3 O.sub.8 powder consisting essentially of discrete crystalline U.sub.3 O.sub.8 particles with a minimum of particle agglomeration. The bulk morphology of the calcined U.sub.3 O.sub.8 powder is very similar to the crystalline uranyl formate monohydrate prior to calcination. Also, because of the crystalline morphology of the uranyl formate monohydrate, calcination to U.sub.3 O.sub.8 does not result in significantly reduced particle size. Having described a preferred embodiment, the following specific examples will serve to further illustrate the present method of preparing U.sub.3 O.sub.8 for powder metallurgical use: EXAMPLE I To demonstrate the feasibility of preparing U.sub.3 O.sub.8 having a controlled particle size distribution, an exemplary feed solution (85 ml) was prepared of uranyl nitrate having a concentration of 250 gU/l at 2 M HNO.sub.3. Feed solution was contacted in suitable denitration apparatus with 70 ml of 19.9 M formic acid at a feed rate of 0.70 moles formic acid/(min)(liter of uranyl nitrate feed) solution at a temperature of 90.degree. C. Sufficient formic acid was added to achieve a concentration of 0.3 moles /100 grams of solution at the completion of denitration. The solution was digested for one hour after completion of the formic acid addition to assure complete denitration and formation of an unsaturated solution of uranyl formate. An additional 365 ml of 19.9 M formic acid was added to the unsaturated uranyl formate solution at a feed rate of 1.27 moles/(min)(liter of uranyl nitrate feed) at 90.degree. C. to precipitate uranyl formate monohydrate. To maximize uranium precipitation the formic acid was added until the solution acid concentration reached 1.4 moles/100 g of solution. The solution was evaporated to reduce the solution volume by 60% and adjusted with 75 ml of 90% formic acid. The slurry was cooled to ambient temperature and the precipitate recovered by filtration at a formic acid concentration of 1.7 moles/100 g solution. The precipitate was washed with 90% formic acid and the resulting filter cake was dried at 110.degree. C. for 2 hours to provide crystalline uranyl formate monohydrate salt. This salt was then calcined in a static bed in an air atmosphere at 800.degree. C. for 6 hours. The resulting product was a crystalline free-flowing U.sub.3 O.sub.8 powder having the particle size distribution shown in the FIGURE of the attached drawing. EXAMPLE II Using the same feed solution, concentrations and procedure as in Example I, and with volumes adjusted to reflect the larger quantity of feed, U.sub.3 O.sub.8 was prepared from a 170 ml uranyl nitrate sample. In this example, formic acid was added to the feed solution for denitration at a rate of 0.36 moles/(min)(liter of uranyl nitrate feed) and to the precipitation step at a rate of 0.63 moles/(min)(liter of uranyl nitrate feed). Calcination of the resulting precipitate produced a crystalline U.sub.3 O.sub.8 powder having the particle size distribution shown in the attached FIGURE. EXAMPLE III Another feed solution containing uranyl nitrate at a concentration of 207 gU/l was processed using 90% formic acid at denitration and precipitation feed rates of 0.35 and 0.63 moles/(min)(liter of uranyl nitrate feed), respectively. The crystalline U.sub.3 O.sub.8 powder resulting from calcination of the uranyl formate monohydrate precipitation had a particle size distribution as shown in the attached FIGURE. EXAMPLE IV A uranyl nitrate solution having 227 gU/l was processed using 90% formic acid at denitration and precipitation feed rates of 0.24 and 0.42 moles/(min)(liter of uranyl nitrate feed), respectively. The U.sub.3 O.sub.8 powder particle size distribution resulting from this example is also shown in the attached FIGURE. It will be noted from an examination of the accompanying FIGURE that the particle size distribution of U.sub.3 O.sub.8 prepared by the process described in Examples I through IV compare favorable with powder metallurgical grade aluminum powder. In all cases the U.sub.3 O.sub.8 powder prepared from the controlled precipitation of uranyl formate monohydrate displayed the desirable physical characteristics of (1) no large particles, (2) crystalline particle morphology, and (3) a narrow uniform particle size distribution that matched that of the aluminum powder.