The document describes a process for recovering uranium from magnesium fluoride slag produced during the production of uranium metal. The process involves finely grinding the slag, roasting it in air to convert uranium to U3O8, and leaching the roasted slag with an aqueous solution of sodium bicarbonate. This separates the uranium into a product liquor, while leaving the other components in a residue. Alkali metal hydroxide is then added to the liquor to precipitate uranium as a diuranate. This process overcomes issues with prior acid leaching processes and produces a very pure uranium product suitable for refinery treatment.
The document describes a process for recovering uranium from magnesium fluoride slag produced during the production of uranium metal. The process involves finely grinding the slag, roasting it in air to convert uranium to U3O8, and leaching the roasted slag with an aqueous solution of sodium bicarbonate. This separates the uranium into a product liquor, while leaving the other components in a residue. Alkali metal hydroxide is then added to the liquor to precipitate uranium as a diuranate. This process overcomes issues with prior acid leaching processes and produces a very pure uranium product suitable for refinery treatment.
The document describes a process for recovering uranium from magnesium fluoride slag produced during the production of uranium metal. The process involves finely grinding the slag, roasting it in air to convert uranium to U3O8, and leaching the roasted slag with an aqueous solution of sodium bicarbonate. This separates the uranium into a product liquor, while leaving the other components in a residue. Alkali metal hydroxide is then added to the liquor to precipitate uranium as a diuranate. This process overcomes issues with prior acid leaching processes and produces a very pure uranium product suitable for refinery treatment.
whereby the uranium is dissolved, separating a product 2,897,048 liquor containing the uranium from a residue, and adding . URANUM RECOVERY PROCESS alkali metal hydroxide to the product liquor whereby uranium is precipitated as: diuranate. John W. Stevenson, Webster Groves, Mo., and Robert G. 5 Disintegration of the magnesium fluoride slag can be Werkema, Granite City, , assignors to the United carried out by any method known to those skilled in the States of America as represented by the United States art, for instance in a ball mill. Wet-grinding is preferred Atomic Energy Commission to a dry-grinding procedure." It has been found that the - No Drawing. Application May 2, 1956 - particle size of the slag has a great effect on the degree - Serial No. 582,304 . . 0 of leaching obtained. The slag should be ground to a fineness that at least 70%, but preferably about 95%, 6 Claims. (CI. 23-145) pass through a 325-mesh screen and 100% of the slag through a 200-mesh screen. This amounts to an average ... This invention deals with the recovery of uranium particle size of less than 44 microns. Particle, sizes from magnesium fluoride slag obtained as a by-product in 5 considerably smaller than this do not give as satisfactory the production of uranium metal by the “bomb reduction results as those specified. - process.” - - -- After disintegration the slag is classified to remove In the bomb reduction process uranium tetrafluoride is coarse particles that mostly consist of uranium and/or magnesium metal which are not easily disintegrated; this reduced with magnesium. metal in an autoclave or 20 coarse fraction is advantageously recycled to the ball 'bomb. The bomb, in order that attack of its walls during reaction is reduced and also contamination of the :". .millIt or is other grinding device. necessary to convert the slightly soluble .. .. metallic uranium, is lined with a refractory material. Crushed uranium to the better-soluble oxide by roasting; the oxide and ground magnesium fluoride slag formed in the bomb predominantly process proved suitable for this purpose and economical. 25 be carried out obtained thereby is U3O8. Roasting can in any device, for instance in a rotary The excess slag not recycled for lining and to some degree also the "recycled slag' contain small quantities of , furnace370 C. which preferably has been preheated to about Roasting between 350 and 525 C., but prefer uranium metal due to incomplete agglomeration; this ably between 400 and 500° C., was used; the very best uranium content fluctuates between about 2 and 7% and results were obtained at temperatures between 425 and averages about 5%. It is desirable to recover this 30 485 C. An atmosphere of air was maintained during uranium from the slag and thereby to reduce its content the roasting step, and this was preferably accomplished at least to 0.05% prior to discarding it. The slags usually by introducing a stream of air during the operation and contain, in addition to magnesium fluoride and uranium, at the same time moving or stirring the slag, at least from excess magnesium metal and compounds, e.g., oxides, of time to time, in order always to expose new surfaces uranium and magnesium. . . . . . . . . . . . . ; and thereby to accelerate and improve roasting. Roasting The uranium has been recovered from bomb slags by 35 for about three hours at the temperatures specified above leaching with mineral acid, and good results have been was found optimal, a longer roasting period converting cbtained thereby. However, the acid leaching process the uranium to a compound less reactive than U3O8. proved disadvantageous in several respects. Filtration of whereby the leaching efficiency is impaired. the leach solution from the leach residue was rather slow, 40 It was found that the addition of small quantities, for and a large filtration capacity was consequently necessary. instance of about 1%, of sodium carbonate or sodium Hydrofluoric acid was formed during the reaction which bicarbonate to the slag before roasting improved the created quite a corrosion problem. Furthermore, part roasting and thus the leaching efficiency. Also cooling of the slag was dissolved by the acid which eventually of the roasted slag in a carbon dioxide atmosphere instead resulted in a fluoride-contaminated uranium....The 45 of air was found to have a beneficial effect. . .. uranium compound, to be suitable for treatment in the The roasted slag is then ready for the leaching step. refinery, should contain not more than one part of fluoride Uranium extraction with the leach solution was found to per 1000 parts of uranium. . . . . . . . .. be better at lower pH values, preferably at pH values . It is an object of this invention to provide a process of below 9.5. For this reason the addition of dilute sulfuric recovering uranium from magnesium fluoride slag where 50 acid for neutralization of the roasted slag to a pH value by these drawbacks are overcome. ... . . of about 7 proved advantageous. It is thus an object of this invention to provide a A mixture of sodium bicarbonate and sodium car process of recovering uranium from magnesium fluoride bonate in aqueous solution yielded satisfactory leaching slag for which a comparatively small filtration capacity is results. For instance, an aqueous solution containing needed. 100 g. of sodium carbonate plus 10 g. of sodium bicar It is another object of this invention to provide a 55 bonate process of recovering uranium from magnesium fluoride per liter was found suitable; however, mixtures slag whereby the uranium content of said slag is reduced in any other proportion containing at least about 8% of to an amount negligible from the economical point of bicarbonate were operative. The use of sodium bicar WeW. bonate alone, though, was found to give the best results; It is a further object of this inventions to provide a 60 this probably is due to the better leaching efficiency ob tained at lower pH values. While the concentration of process of recovering uranium from magnesium fluoride sodium bicarbonate can vary widely, a solution about 0.7 slag in which no free hydrofluoric acid is formed and thus no corrosion problem exists. . . .. Min NaHCO3 was found optimal. The quantity of car It is finally also an object of this invention to provide bonate (bicarbonate alone or the carbonate-bicarbonate a process of recovering uranium from magnesium fluoride 65 mixture) was advantageously adjusted so that an excess slag by which a very pure uranium product, especially of about 25% was present over the stoichiometric quan in regard to fluoride content, is obtained...so that it is tity for the conversion of UOs to the carbonate com suitable for direct treatment in the uranium refinery. plex UO(CO3)34, the complex predominantly formed; These objects are accomplished by finely grinding the 70 minor quantities of UOa(CO3) are also obtained in slag, roasting the slag in air, leaching the roasted slag this reaction. This, in the case of using sodium bicar with an aqueous solution containing sodium bicarbonate -- - - bonate, amounted to about 1.88 lbs. of sodium bicar 2,897,048 3. bonate per 1 lb. of uranium or about 1 to 3 lbs. of slag Table 2 per 1 gallon of leach solution. While the process is satisfactorily operative when a Washed cake U analyses, percent leach solution as described above is used, a further con (dry basis) siderable improvement was accomplished by adding an 5 Oxidizing agent oxidizing agent to the leach solution. Various types of 1st leach 2nd leach 3rd leach oxidizing agents are suitable, but best results were ob tained with calcium hypochlorite, Ca(OCI)2, potassium None-------------- 40 2, 20 0.50 permanganate and hydrogen peroxide. Hydrogen per 10 g. KMnOf---- 0.30 0.22 0.4 oxide was preferably added in installments, for instance, the addition of 10 ml. of a 30% solution per each liter EXAMPLE III of leach solution every /2 hour during leaching was found A series of runs on carbonate-bicarbonate leaches to yield good results. The effect of an oxidizing agent Were made in which calcium hypochlorite was used as on the leaching step is obvious from Examples I, II, the oxidizing agent in varying concentrations. For run and III. All examples in this specification are given for 5 No. 1 the leach solution contained 40 g./I. of sodium illustrative purposes only, and the data given therein bicarbonate and 60 g./I. of sodium carbonate, while for are not to limit the scope of the invention. the other 4 runs the leach solutions contained 5% each EXAMPLE I of sodium carbonate and sodium bicarbonate. The leach Two parallel runs were made to determine the rate '' temperature was between 80 and 90° C. The conditions and leach results of 4 stages are compiled in Table 3, of uranium dissolution from magnesium fluoride slag in carbonate and in carbonate-peroxide solutions, respec Table 3 tively. The first run was made using a leach solution containing 100 g. of Na2CO3 and 10 g. of NaHCO3 per Percent uranium in each cake liter heated to 70° C. The solids content of the slurry 25 . Ca(OC) was 100 g. of slag per liter of leach solution. Samples Ruin per 100g. First Second Third Fort of slurry were obtained from time to time and filtered of slag leach each each each as rapidly as possible on a Bichner filter. Seventy-five (1 hr.) (2 hrs.) (3hrs.) (8 hrs.) gram portions of the "Bichner cake" each were washed 0 -------------------- 63.5 ---------- with a solution containing 20 g. of Na2CO3 per liter. 1. 0.49 0.10 0.03 0.02 The second run was similar to the first run with the 2 0.30 0.07 0.02 0.0 5 0.26 0.06 0.02 O. O1 exception that 10 ml. of a 30% hydrogen peroxide solu O 0.1 0.05 0.01 0.01 tion was added every 30 minutes to each liter of leach solution. The analytical data obtained from these runs The above results indicate that a cake having less than are shown in Table 1. the specified limit of 0.05% of uranium can be obtained by three carbonate leaches in the presence of from 1 Table I to 10 g. of calcium hypochlorite per 100 g. of slag, and in 2 leaches with 10 g. of calcium hypochlorite. Higher quantities of hypochlorite increased the leaching efficiency 40 to a negligible amount only. Washed cake U analyses, percent (dry basis) EXAMPLE IV Time of sampling, minutes Seven sets of leaching runs were made to study the Car-, bonate Carbonate peroxide effect of roasting and roasting temperature on the leach leach each ing efficiency. Roasting was carried out in air before each run. The leaches were made with a solution con 4.9 4.8 4.9 1.0 taining 100 g. of sodium carbonate and 10 g. of sodium 4.5 0.24 bicarbonate per liter at 70 to 80° C. One liter of this 4.5 4.5 0.3 0.2 leach solution was used for each 360 g. of slag, and five 4. 4. 0.6 3-hour leaches were used in each instance each stage 4.0 2.9 0.1 0.092 being carried out with fresh leach solution. Two paral 2, 3 0.10 lel runs were made in each set, one without hydrogen peroxide and the other one with hydrogen peroxide. The hydrogen peroxide was added in installments of 10 ml. The table shows the improvement obtained by the use 55 per liter of slurry every 30 minutes. The results as well of hydrogen peroxide in the leach solution as the oxidiz as the varied conditions are listed in Table 4. ing agent. A single carbonate-peroxide leach produced Table 4 a residue containing about 0.1% uranium in a leaching time of 2 hours. Extension of the leaching time to 4 Uranium content of washed caires, percent U (dry basis hours did not result in additional extraction. While 60 Run No. S ) leaching with a carbonate solution extracted 53% of the Roasting Carbonate Carbonaic uranium present, the carbonate-peroxide leach solution temp., C. each HO2 lead extracted about 97% of the uranium. (1) 0.86 0.23 EXAMPLE I 200 0.82 0.20 275 0.64 0.4 350 0.3 0.033 Two parallel runs were made to study the effectiveness 425 0.03 0.030 of potassium permanganate. The same slag as that used 500 650 0.4 0.30 0.03 0.4 for Example. I was treated in this instance, The leaching treatment consisted of three 3-hour con 70 1No roasting. tacts of the slag, each time with fresh leach solution. The leaching temperatures were maintained at 70 to 80° The above results prove that roasting at temperatures C. Samples of leached cake were washed prior to of at least 350 C. and also the presence of an oxidizing analysis as described in Example I. The results of the agent in the leach. Solution are necessary to deplete the two runs are compiled in Table 2. 75 slag to a uranium content of below 0.05%. 2,897,048 - 5 6 - EXAMPLE V a solution of at least 60° C., but preferably of 70 to Two sets A and B of parallel experiments were carried 95° C. out, each set consisting of 2 experiments using identical While leaching at atmospheric pressure was found satis conditions except that in one experiment of each set factory, the use of superatmospheric pressure improved dilute sulfuric acid was added to the slag before leaching the results. In this case a carbon dioxide atmosphere until a pH of 7 was obtained. In one of the sets (both and a leach solution containing sodium bicarbonate only experiments) potassium permanganate was used as the and no sodium carbonate were found best. Higher leach : oxidizing agent, while in the other one hydrogen peroxide ing temperatures and lower pH values are obtained under was the oxidizing agent. The slag contained 4.5% of these conditions. The use of an oxidizing agent proved uranium, 0.20% of magnesium and 5.5% of MgO; 100 g. O unnecessary if pressure-leaching was employed; in fact the of the slag each were treated with one liter of the leach results obtained under these conditions were better when solution, and each leach was carried out for 3 hours at no oxidizing agent was present. Example VII confirms these facts. . 70 to 80° C. The results are compiled in Table 5; the uranium contents are expressed on a dry basis. 15 EXAMPLE VII Table 5 - A magnesium fluoride slag which had been leached once at atmospheric pressure and contained, on a dry - ,, . . .. . . Insoluble uranium in leached slag, percent basis, 0.058% uranium was used for pressure-leaching Leach conditions --- 20 in an autoclave. Two hundred grams of this preleached -- - - - - 1st leach 2d leach 3d leach slag were used per liter of leach solution. The leach temperature was 140 C., the pressure 150 p.s.i.g., and A.100 gll. NaC9s. 10 g/l. NaHCO3, the leaching time was 2 hours. The results are compiled 10 ml.30%I2O2,30: Without O neutralization------------- W 0.085 0.068. . . . 0.058 in Table 7. With neutralization.----------------- 0.033 0.015 0.010 25 Table 7 B100 gll, Na2CO3, 10 g/l, NaHCO3, 10 g/l. KMnO4: Without neutralization.-------------- 0.17 0. 0.06 With neutralization.----------------- 0.031 0.017 0.00 Insoluble uranium -- in leached The above results show that the pH value affects the 30 Leach liquor composition Oxidant E. - Cen y leaching, neutralization of the slag prior to leaching in basis) proving the leaching efficiency greatly. -- -- - . . If potassium permanganate is used as the oxidizing 100 g/l. Na,CO. agent a quantity of at least 0.22 lb. per 1 lb. of uranium, SINESS "IOUgll. Na2CO3- m. H2O,----- 0.048 but preferably a 50% excess, should be used. This cor 35 1000g.fl.g-fi.NaCO3--- None.-- NaHCO3------------------------------ None------ o responds to a minimum quantity of 2 g. KMnO4 per liter of solution; the preferred concentration of the perman ganate ranges between 0.05 M and 0.2 M. . . It is obvious that the use of sodium bicarbonate alone In the case of potassium permanganate as the oxidiz yields better results than the carbonate mixture when ing agent it was also found that the leaching efficiency 40 pressure-leaching is employed. could still furthermore be improved by adding calcium It is understood that a series of leaching steps brings nitrate to the leach solution. The calcium nitrate pos about a more complete uranium extraction than just one sibly has a catalytic effect. The improvement obtained step. Considering the economical angle, a countercur with calcium nitrate is obvious from Example VI. rent two-step operation was preferred for most purposes, EXAMPLE VI 45 and pressure was advantageously applied for the second leaching step... Carrying out the second leaching step at Experiments are reported in Table 6 in which between atmospheric pressure but extending it for a period of be 0 and 0.2 N calcium nitrate respectively, was added to tween 3 and 5 hours, preferably 5 hours, at 90 to 95° C. the solution. The leach conditions in these experiments was also found satisfactory. were 5 hours with a solution containing 50 g/l. of each 50 Some of the uranium-containing product liquor is ad sodium carbonate and sodium bicarbonate; the slurry vantageously recycled either to the leaching vessel or to contained 50 g. of slag per one liter of leach solution. the hydroclassifier for the purpose of enriching the leach The slag used contained 8.5% of uranium. solution in uranium and in the latter case also in order Table 6 to dilute the classifier feed to operative solids levels. 55 The product, liquor preferably contains about 20 g. of Insoluble uranium per liter before it is further processed for urani uranium in um recovery. Molarity of NO3- from Ca (NO3)2 addition leached slag, per After completion of the leaching steps the solids are cent (dry removed from the slurry by filtration whereby the "prod basis) 60 luct liquor' and the "filter cake' are obtained. A tem perature of about 80° C. was found best for the filtration. - 0.22 0, 12 The filter cake is then advantageously washed with water 0.082 to remove any soluble uranium adhering thereto. 0.069 0.053 In the following an example is given which represents 65 a comparison of the acid leach process as used heretofore . with the process of this invention. It was found that the leaching efficiency could be still furthermore improved by presaturating the leach solution EXAMPLE VIII with magnesium fluoride; by this, leaching was acceler For both, the acid and the carbonate process, a two ated and the number of leaching steps necessary was 70 stage leach was carried out using a magnesium fluoride reduced. This presaturation was conveniently accom slag that had been roasted for 2 hours at 450 to 500° C. plished by digesting the leach solution with leached slag. and 91% of which had a particle size of -325 mesh. ; : As is obvious from the examples given above, the use The uranium content of this slag was 1% and a quantity of elevated temperature is preferred for the leaching step. of 400 g. was used for each experiment. The data of It was found that leaching should be carried out with 75 these two parallel runs are compiled in Table 8. 2,897,048 7 3. Table 8 Sodium hydroxide was preferred as the caustic and it ERS STAGE was best added in the form of a concentrated aqueous solution, for instance of about 50%. The quantity had to be sufficient to neutralize all sodium bicarbonate to Acid leach Carbonate leach 5 sodium carbonate and to precipitate all uranium. The precipitation starts just about at the bicarbonate-neutrali Leach Solution.------ 1,006 ml, 2N HSO4 contg.8 g. KClO3. 1,000 ml, HO contg. 100 g. zation point. An excess of about 0.07 to 0.1 lb. of sodium Na2CO3, 10g. NaHCO3 total of 80 ml, 30% EI2O2 hydroxide per gallon of product liquor over the stoichi (10 m. added every i5). ometric amount was found necessary for complete urani Leachg. time and 2hrs., 82-89 C--...- 2 hrs., 78-90° C. temp. Filtration index---- um precipitation. A digestion for at least 15 minutes at 0.72 Inl.fcm.2fmin. 0.655 ml.fcm.inin. a temperature between 60 and 95 C. prior to filtration Wolume of filtrate.-- 880 Inl--------------- 1,000 ml. Weight of wet cake 564.9 g. of the precipitate was found to improve the uranium H2O in wet cake.---- Fluoride content of 26.9%. 0.14g.il. recovery and filterability. In the following Example IX filtrate. U content of dried some experiments are described showing uranium precipi 0.15%. tation from product liquor. cake. EXAMPLE X SECOND STAGE A product liquor was used which contained 3.8 g. U/1. Dry filter cake used. 295 g---------------- 352g. and 0.30 g. F/I. Four runs were made each with a 50% - Leach Solution.----- 746 ml. 2 N ESO 880 ml. EO contg. 88 g. 20 sodium hydroxide solution in an excessive quantity of contg.8 g. KClO3. NaCO3-8.8 g. NaHCO3 0.08 lb. NaOH/gal. of product liquor over the stoichio --total of 80 ml. HO added as in 1st stage. metric amount, but using different digestion times and Lali emp. time and 2 hrs., 83-94 C-...--- 2hrs., 75-89° C. temperatures. The conditions and results are compiled Filtration index.-- 0.137 ml.fc.n.min- 0.456 Inlicn.pnin. in Table 9. Volume offiltrate--- 827ml, o5 Weight of wet cake- 580 g. al Table 9 Olin wet cake- 36.7%. r Fluoride content of 0.20 g.fl. r filtrate. Digestion Concentra U content of dried 0.058%. Digestion time, min. temperature, tion of U in cake. ofC. residual liquor, gil. 30 It will be obvious from the above parallel experiments i0--- 5. 77-87 90-97 0.03 0.05 that although the leaching efficiency is greater with sul 20 60-80 0.016 furic acid than with the carbonate solution (one acid 45- 25 0.042 step accomplished the same result as two carbonate steps), the filtration index is significantly higher and the fluoride 35 The above data show that digestion at room tem content of the uranium-containing product liquor is lower perature (25 C.) does not yield too good results and in the carbonate process. The addition of further leach that for optimal uranium recovery a digestion of at least ing stages or extension of the second leaching stage for a 15 min. at a temperature between 60 and 95° C. should longer period of time brought about the same leaching 40 be allowed to take place. efficiency in the carbonate process as are obtained by the The precipitates of the four runs were combined and sulfuric acid treatment. The lower fluoride content has analyzed. The uranium content was found to be 50% the advantage of less corrosion when, in later processing, and the fluoride content 0.09%. the product is acidified, and also that of a pure final The Supernatant or filtrate, as the case may be, from product. the uranium recovery step by precipitation as just de The uranium may be recovered from the product liquor scribed can be recycled for utilization of its carbonate by any method known to those skilled in the art. Con values. tact of the uranium solution with anion exchange resins, The precipitate can be dissolved in nitric or other for instance, proved very satisfactory. The anion ex acid as indicated above. This is preferably done after change resin is preferably in the sulfate, chloride or bi washing with water. The uranium can then be recovered carbonate form, and elution is best with sodium chloride from the acid solution by any method customary in the or Sodium nitrate solution, preferably of a concentration art. of about 4 M. For instance, a cycle comprising passing The optimal process conditions then comprise (1) the carbonate product liquor over the anion exchange roasting at 325 to 525 C. for not more than 3 hours; resin in its bicarbonate form, eluting with a 4 M sodium (2) the use of an oxidizing agent-containing leach solu nitrate solution, regenerating the depleted resin with a 55 tion, preferably potassium permanganate to reduce the 1 M Solution of sodium bicarbonate proved most satis cost of the process (although hydrogen peroxide was factory. Since permanganate interferes with the adsorp found to be a more effective oxidizing agent) in a quan tien of the uranium carbonate complex and the adsorption tity of at least 0.22 g. KMnO4/g. U; (3) leaching at pH from hypochlorite-containing solutions is not too good, values below 9.5 and at a temperature of at least 60° C., the use of hydrogen peroxide as the oxidizing agent is 60 optionally under pressure and with sodium bicarbonate preferred in the case of the uranium recovery by anion only; (4) neutralization of the roasted slag with sulfuric exchange methods. or other acid to a pH value of about 7 prior to leaching; The method preferred by the inventors for the recovery and (5) filtration of the product liquor prior to uranium of the uranium values from the carbonate product liquor, precipitation. though, is precipitation as the diuranate by a caustic, e.g., 65 It will be understood that this invention is not to be by an alkali metal hydroxide. It was found advisable limited to the details given herein and that it may be to filter the product liquor prior to the precipitation step modified within the scope of the appended claims. in order to remove minute amounts of magnesium fluo What is claimed is: - ride crystals which had leaked through the filter used for 1. A process of recovering uranium values from the separation of the product liquor from the slurry. By Imagnesium fluoride slag obtained in the. reduction of this filtration step the fiuoride content of the diuranate uranium tetrafloride with magnesium, comprising grind precipitate was considerably reduced, and when the ing said slag to a particle size of about -325 mesh; precipitate was dissolved in nitric acid, for instance, for roasting the slag in air at a temperature of between 350 further processing, corrosion problems due to free hydro and 525 C. for a maximum period of time of approxi fluoric acid were kept to a minimum. 15 mately three hours; cooling the roasted slag in an at 2,897,048 9 mosphere of carbon dioxide; neutralizing the slag with 10 uranium tetrafluoride with magnesium, comprising grind dilute aqueous sulfuric acid to a pH value of below 9.5; ing said slag to a particle size of about -325 mesh; leaching the neutralized slag with an aqueous solution roasting the slag in air at a temperature of between 425 containing at least 8 percent by weight of sodium bicar and 485 C. for a maximum period of time of approxi bonate and an oxidizing agent, the total quantity of mately three hours; cooling the roasted slag in an atmo carbonate in said solution being about 25 percent in sphere of carbon dioxide; neutralizing the slag with dilute excess of that stoichiometrically required to convert the aqueous sulfuric acid to a pH value of about 7; leaching uranium oxide to a carbonate complex; filtering an in the neutralized slag with an aqueous solution at between soluble uranium-depleted residue from a uranium-con 60 and 95 C. and under superatmospheric pressure, said taining supernatant; adding an aqueous solution of so 10 solution consisting of an at least 8 percent solution of dium hydroxide to said supernatant whereby the uranium sodium bicarbonate, the quantity of said solution being values are precipitated, and separating the uranium-con such that about 25 percent bicarbonate in excess of taining precipitate from the aqueous solution. that stoichiometrically required to convert the uranium 2. The process of claim 1 wherein about 1 percent oxide to a carbonate complex are added; and filtering of a carbonate selected from the group consisting of so 5 an insoluble uranium-depleted residue from a uranium dium carbonate and sodium bicarbonate is added to containing supernatant. the ground slag prior to roasting and the roasting tem References Cited in the file of this patent perature is between 400 and 500 C. 3. The process of claim 1 wherein the roasting tem UNITED STATES PATENTS perature is between 425 and 485 C. 20 2,733,126 Spiegler ---------------- Jan. 31, 1956 4. The process of claim 1 wherein neutralization with OTHER REFERENCES sulfuric acid is carried out until a pH value of about 7 is obtained. Bearse et al.: AEC Document BMI-JDS-130, June 30, 5. The process of claim 1 wherein the oxidizing agent 1948; pages 8, 15-17, 48, 65-66. is hydrogen peroxide and leaching is carried out at a tem 25 Richardson et al.: AEC Document BMI-JDS-195, perature of between 60 and 95°C. June 30, 1948; pages 21-36. 6. A process of recovering uranium values from Brown: AEC Document ACCO-36, Oct. 15, 1953; magnesium fluoride slag obtained in the reduction of pages 7-10 and 29-30.