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Studies of Recovery Processes for Western Uranium- Bearing Ores

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Studies of Recovery Processes for Western Uranium- Bearing Ores STUDIES OF RECOVERY PROCESSES FOR WESTERN URANIUM- BEARING ORES Part VIII EXAMINATION OF CERTAIN ASPECTS OF THE "CARBONATE PROCESSES" AS USED AT MONTICELLO, UTAH By R. S. Lowrie and E:. B. Brown OAK RIDGE NATIONAL LABORATORY Y-12 AREA OPERATED BY CARBIDE AND CARBON CHEMICALS DIVISION UNION CARBIDE AND CARBON CORPORATION OAK RIDGE, TENNESSEE ., Index No. -'----Y::.--'5:..!.7.:::.1'------ Subject Category: Metallurgy Raw­ ·I M9.teria1s STUDIES OF RECOVERY PROCl!SSES FOR limTERN TJRANTUM-BlllARING ORES PART VIII Exam1nation of Certain Aspects of the "Carbonate Processes" as Used at Monticello, Utah R. s. Lowrie K. B. Brown Y-12 ChaRdca1 Research Division Mr. G. H. C1ewett, Division Head OAK RIDGI!: NATIONAL lABORATORY Y - 12 AREA Operated by CARBIDE AND CARBON CHEMICAlS ·DIVISION UNION CARBIDE AND CARBON CORPORATION Oak Ridge, Tennessee Contract No. W-7405-Eng-26 ,v;: ....'"'"' ... >Jm.... _,_:::;:;:::co;w - 2 Index No. Y-571 Metallurg-y-;R;.,a~w:,c-;:;Ma"'te=r"'i7al"s=- Distribution, Series A: No. Copies Atomic Energy Commission, Washington (Jesse Johnson) 2 Atomic Energy Commission, New York (Wilson) 5 Battelle Memorial Institute (Bearse) 1 Dow Chemical Company 1 Massachusetts Institute of Technology (Gaudin) 1 Patent Br'anch, washington 1 Technical Information Branch, ORE 10 U. s. Geological Survey 1 Colorado Area Office (Frank H. MacPherson) 2 Carbide and Carbon Chemicals Division (Y-12 Plant) internal distribution as follows: .Mr. c. E. Center 1 Dr. c. E. larson 1 Dr. A. M. Weinberg 1 Dr. E. D. Shipley 1 .Mr. w. D. Lavers 1 Dr. J. A. Swartout 1 .Mr. c. D. Susano 1 .Mr. w. R. Grimes 1 Dr. c. F. Coleman 1 .Mr. G. H. Clewett 1 Mr. K. B. Brown 1 .Mr. R. s. Lowrie J. C. R. I. o. 2 TOTAL: 38 Plant Records Department, Y-12 Plant Date Issued: MAR 21 1950 - 3 Abstract The following topics are discussed: ( 1) the maximum build-up of uranium in the recycling carbonate leach liquors of both raw and salt-roasted ore, (2) solubilities of certain uranyl vanadates in sodium carbonate solutions, (3) solubility of sodium uranyl tricarbonate in sodium carbonate solutions, (4) analyses for carbonate in the mill liquor, and (5) carbonate consumption during leaching. Some information is also pre- sented on the organic content of the mill liquors, the filter- ing and settling of raw leach slurries, and the recycle of effluent liquors from the "yellow-cake" precipitation. 4 Table of Contents Introduction 7 Ore Samples 10 Cyclic Leaching of Salt Roasted Ores 11 Experimental Procedures 12 Salt Roasting 12 Q,uenching . 12 Leaching .. 12 Leaching with 3% Na2C03 14 Uranium Build-Up • 14 Vanadium Build-Up 17 Build-Up of Contaminants 18 Leaching with 6% Na2 C0 3 18 Uranium Build-Up • 18 Build-Up of Vanadium and Impurities 22 Leaching with 9% Na2 C0 3 • 22 Uranium and Vanadium Build-Up 22 Summary .•...... 24 Cyclic Leaching of Raw Ores 25 Experimental Procedures 25 First Leach 25 Second Leach 26 5 Table of Contents (cont'd) page Leaching with 3% Na2 co3 25 Indian Reservation Ore 25 Stockpile No. 7 Ore 28 Stockpile No. 9 Ore 28 Leaching with 5% Na2 C0 3 . 28 Stockpile No. 7 Ore 28 Swnmary . • • . • • • 32 Organic Content of Na2 co3 Leach Solutions from Raw Ore 33 Carbonate Consumption during Leaching 34 Analysis for Carbonate in Mill Liquors 34 Filtering and Settling of Raw Ore Leach Slurries 35 Carbonate Leach-Sand ·Slime Separation-Acid Leach 38 Solubility of Synthetic and Natural Minerals in Carbonate Solution • . • • . • • • • • 41 Description of Materials 41 Experimental Procedure 42 Effect of Sodium Carbonate Concentration 43 Effect of Sodium Vanadate Concentration 43 Effect of Sodium Chloride Concentration 47 Effect of Sodium Vanadate in Combination with Sodium ·• Chloride . 6 • • • • • • • • • • • .- • • • • • • • • . 49 Solubility of Natural Mineral in Actual Leach Liquors 49 Solubility Studies on Sodium Uranyl Tricarbonate • 51 6 Table of Contents (~ont'd) page Preparation of Sodium Uranyl Tricarbonate 54 Effect of Sodium Carbonate Concentration 54 'Effect of Sodium Vanadate Concentration 54 Effect of Sodium Chloride Concentration 56 Recycle of Effluents from Yellow-Cake Precipitation 58 Effect of Na~so4 on Solubility of Natural Mineral 58 Effect of Na2so4 on Raw Ore Leaching 58 Acknowledgements 61 Appendix A 62 Appendix B 63 7 EXAMINATION OF CERTAIN ASPECTS OF THE "CARBONATE PROCESSES" AS USED AT MONTICELLO, UTAH INTRODUCTION Sodium carbonate leaching has been employed in Western uranium mills for many years. Currently, such "carbonate processes" are being used at Naturita and other mills of the Vanadium Corporation of America and at the plant at Monticello, Utah, which was recently constructed and placed in operation by the Galagher Company of Salt Lake City, Utah under the auspices of the A.E.C. The term "carbonate process" is often used rather loosely to describe somewhat different processing methods. At the VCA mills, a process is used in which the ore is first roasted with salt to form soluble sodium vanadate, and then leached with sodium carbonate to dissolve the vanadium and uranium values1 • Since the roasting step is included only for vanadium recovery, this process is economically feasible only with ores which have a fair concentration of vanadium minerals ( > 1% V205). Also, because of the formation of insoluble calcium vanadates, the ore must be low in calcite. At the new mill at Monticello, Utah, equipment is available for the salt-roast, carbonate-leach treatment, but, in addition, allowances have been made for other types of processing. The rather copious quantities of ores of low vanadium content and/or high calcite content 1 For simplified flowsheet, see Appendix A. 8 will be processed by leaching the raw ore directly with hot sodium carbon- ate solutions. In instances where the vanadium and calcite are both high, the ore will be leached directly and provision will be made later to remove the calcite by flotation, followed by a roast and leach of the flotation tailings for their vanadium content. These innovations will give rise to processing problems not previously encountered in the Western mills. An extensive study of the roasting and leaching treatment has been made by the Battelle Memorial Institute at Columbus, Ohio, and by the U.S. Bureau of Mines, Salt Lake City station. The direct leaching process and the calcite flotation method were also developed and studied by the Bureau of Mines at Salt Lake City. In April, 1949, the laboratories at Y-12 were requested by, the A.E.C. to investigate whatever solution and analytical chemistry was important to the start-up of the Monticello plant1 After conversation with Messrs. M.G. McGrath2 and John \Vhite3 , a program was set up which included the immediate problems of this nature. These problems may be summarized as follows: (1) The supplying of analytical procedures for use in determining uranium at Monticello. The furnishing of Y-12 analysts to set up these procedures at the plant, help organize the plant laboratory, and train the plant personnel. 1 The Monticello plant started operations in September, 1949. 2 Metallurgist for Colorado Raw Material Operation, A.E.C. 3 In charge of construction and start up of Monticello for the Galagher Company. 9 (2) The supplying of analytical methods for plant control of (a) carbonate concentration in the leach circuit, and (b) yellow cake pre­ cipitation. (3) The determination of the limitations that are imposed on uranium build-up and impurity build-ups when using different concentrations of Na2C03 on raw ores in the Monticello leach circuit. Since raw ore leaching is a recent innovation in the Monticello flowsheet, the critical conditions for such a circuit had not been studied. (4) As explained above, past practice in the Western mills has been to roast the ores with salt (to convert vanadium to soluble sodium vana­ date) and then leach the calcines with Na2C03 eolution to derive the uranium and vanadium values. Direct leach solutions are different from those formerly obtained with roasted ores in that these solutions contain less vanadium as well as some organic matter. It was of immediate inter­ est to the Monticello plant to determine whether the standard, yellow-cake, precipitation technique would apply·to the direct leach solutions •. (5) Since the direct leach solutions are very low in vanadium content, it is not possible to use the same precipitation method for vanadium that was formerly employed. Consequently, some satisfactory method for recover­ ing vanadium (economically) from the dilute vanadium liquors should b~ developed. (6) One way to solve the vanadium recovery problem would be to recycle the plant solutions, after the uranium precipitation step, in order to build-up the vanadium concentration to a normal level -- as well as to conserve water in the process. First, it must be determined whether 10 such an operation can be accomplished without harm to the milling oper- ' ation (liquors from the yellow-cake precipitation contain fairly large amount• of Na2S04). (7) Tests should be made to determine the amount of Na2C03 that will be consumed by an average ore during a direct leaching treatment. (8) Methods for improving the settling and filtration of raw ores should be considered. The results of investigations conducted on items 2, 3, 6, 7, and 8 are discussed in this report. The data collected in studying items 1, 4, and 5 are discussed in other sections of this series. The information on which this report is based has been drawn from results presented in greater detail in previous progress reports. A list of these reports is given in Appendix B. ORE SAMPLES The ores used during most studies of the Monticello operations included samples from Radium 7 and Wild Steer Mine and from Stockpile 7 and 9 at the Monticello site.
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