6307 U-003-307 .8 SUMMARY TECHNICAL REPORT FOR THE PERIOD APRIL 1, 1959 TO JUNE 30, 1959 - (USED AS A REFERENCE IN OU 1 RI) 07/20/59 NLCO-790 NLO 75 REPORT SUMMARY TECHNICAL REPORT I. For t le Period April 1, 1959 to June 30, 1959 I I AEC RESEARCH AND DEVELOPMENT REPORT NLCO- 790 -w6307 Technology -Feed Materials ..:i (M- 3679, 22nd Ed.) 8 - SUMMARY TECHNICAL REPORT FOR THE PERIOD - APRIL 1, 1959 TO JUNE 30, 1959 F. L. CUTHBERT, DIRECTOR c. E. CROMPTON, ASSOCIATE DIRECTOR TECHNICAL DIVISION ._. EDITED BY JOHN W. SIMMONS Date of Issuance: July 20, 1959 NATIONAL LEAD COMPANY OF OHIO p ' I Box 158, Cincinnati 39, Ohio *I Contract No. AT(30 -1) -1156 "630'7 -3- Page No. .' - .. SUMMARY. .. '. 7 - Feed Materials Evaluation :...I '. 11 I. .- . .. 2. Selective Digestion . :-;. 17 ,>+ 3. Bondingin theTri-n-butylPhosphate-H20-U-AcidSy$tem . 27 4. Extraction Column Control . ..: . 37 5. Activation of Pot-Produced Orange Oxide . .' . 41 . Hydrofluorination of Sodium-ContamGated Uranium Oxides. 41 Thermal Decomposition of AnhydibusUranylSulfate . 44 i .. 6. ADU ("Ammonium Diuranate") Process Development . 49 . Laboratory Determination of Impurity Decontamination by an ADU Process . 49 '- Thermobalance Hydrofluorination Investigation of Pilot Plant ADU . 52 7. Analyses of Variations in Visually Determined Derby Grades . 57 8. Recovery of Uranium from a Mixture of Uranium, Magnesium, and Magnesium Fluoride . 61 9. Scrap Processing by an Aqueous UF4 Process . 67 Labomtory Preparation of Green Salt from Plant-Produced UAP and Black Oxide . 67 Green Salt Preparation from Pickle Liquor, Black Oxide, and Reduction Pot Residues . 71 io. The Recovery of Magnesium and HF from MgF2 Slag . 77 The Recovery of Magnesium from MgF2 Slag .. 77 Laboratory Autoclave Study of the MgF, Slag-H$04 Reaction for the Preparation ofHF . 78 11. A Rotating Sample Holder fm Preferred Orientation Studies . 81 ' 12. Determination of Microgram Amounts of Fluoride in Uranium Metal . 83 ::I 13. Direct Flame Photometric Determination of Magnesium in Uranium Ore Concentrates . 89 000003 -6301 -5- .. .. TECHNICAL PROJECT SUPERVISION NATURE OF ACTIVITY PERFORMED UNDER (Projects) SUPERVISION OF C hemica 1 Projects Relating to Feed M. A. DeSesa, Head, Evaluation, Refining and Chemical Chemical Department. Processing . * Metalluraical Projects Relating to Fabrication, C. E. Polson, Head, Foundry Technology and Physical Metallurgical Department. Metallurgy. Pilot Plant Metals Development, Pilot J. 0. Davis, Head, Production, Process Engineering Pilot Plant. and Refinery Operations. Analytical Chemistrv J. W. Robinson, Head, Investigations in Wet Chemical Analytical Department. and Instrumental Analysis. P. N. McCreery, Head, Statistical Studies and Technical Accountability - Quality Illustration Services. Control Department. -7 - SUMMARY , Page No. Anaconda Acid, Kermc, Moab, Rifle, and Texas Zinc urc&um concentrates were evaluated "(.the laboratory portion of feed material evaluation). .........- 11 Laboratory equilibrium tests and Pilot Plant 2 -inch- column extraction tests have demonstra- ted effective distribution of uranium into a TBP-kerosene solvent from aqueous phases containing as little as 0.5u HNG and varying amounts of added metal nitrates (NaN03). 17 The concentration of associated nitric acid in dilute aqueous nitric acid solutions was determined after values were obtained for the equilibrium constant for the reaction of tri-n- butyl phosphate with associated nitric acid and for the equilibrium distribution constant for the partition of associated nitric acid into tri - n - butyl phosphate. Optimum partition of uranium into tri-n-butyl phosphate was realized in the laboratory by using an aqueous uranyl nitrate solution containing sufficient hydrogen ions to promote extraction and a low concentration of associated nitric acid. ....... 27 r An Ohmart system for controlling the uranium profile in the "A" extraction column was * installed on Refinery pulse columns. Use of this system improved control but did not stop all column upsets. ................ 37 The effect of 13 to 189 ppm sodium contamination upon hydrofluorination conversion of UOI toUF4can be decreasedor eliminated by reducing the temperature at the site of the reaction. Uranyl sulfate was shown to undergo an enantiotropic transition at 755°C and to decompose to U308 in an atmosphere of oxygen and sulfur dioxide, which gases are evolved during decomposition. ................. 41 Decontamination of sodium, calcium, nickel, magnesium, gadolinium, and dysprosium was achieved in a laboratory investigation of the ADU process. c U02 produced by reductions programid fioiii 700" to 1100°F was hydrofliiciiinaied at pro- grammed temperatures of 550" to 1100°F and isothermally at 1100°F. Good conversion was obtained for material whose source was ADU calcined at 1200°F. ...... 49 Uranium derbies were classified by the present method of derby grading and were then exam- ined fcr slag coverage, slag volume, and slag weight. There was a high degree of overlap of these parameters for adjacent grades. ............ 57 A hydraulic separator for separating uranium from magnesium and magnesium fluoride has been fabricated. Excellent separation was obtained for t16 mesh material. .... 61 -9- Page. No. A hydrochloric acid dissolution- UF4 precipitation process for routing scrap materials to the reduction- to- metal step was examined. The purification- obtained was noted, and process conditions were varied to determine their effect upon UF, density, UF4 purity and precipi- tation time in this laboratory study. - Three types of uranium scrap were subjected to the HC1 dissolution-aqueous precipitation Winlo process to determine the purification achieved. Green salt made from dolomitic bomb liner residues was found to be grossly contaminated. Acceptable green salt was made from pickle liquor treated with formaldehyde and from pickle liquor plus black oxide. ... 67 L Nominal 80 per cent yields were obtained (1) in the recovery of magnesium metal by reaction of calcium carbide with magnesium fluoride slag and (2) in the recovery of HF by the reaction of sulfuric acid with magnesium fluoride slag. ........... 77 A sample holder fcr use in quantitative preferred orientation studies was fabricated. The holder, designed to fit a North American Philips Goniometer, will accommodate specimens up to 1 '2, inches in diameter and incorporates a precision ball bearing. ...... 81 1- A satisfactory technique has been developed for the analysis of uranium metal for traces of fluoride. ................... 83 .4 direct flame photometric method is given for the determination of magnesium in uranium ore concentrates. No chemical separation step is required, except for high - iron - content ores. 89 \ -- -11 - 1. FEED MATERIALS EVALUATION C. T. Hicks J. R. Nelli Abstract fa t.Jk five uranium concentrates. Texas Zinc has been found to exceed the FMPC impurity tolerance Laboratory digestion and extraction evaluations limit for total arganic material, and Moab to con- ad complete chemical analyses of five feed mat- tain excessive amounts of insoluble uranium. erials (Anaconda Acid, Kermuc, Moab, Rifle, and Texas Zinc) are reported. Chemical Analyses of the Concentrates Introduction An official assayer's sample of each concentrate investigated is submitted to the Analytical Depart- The digestion and extraction characteristics of menk at this site fm (1) complete spectrochemical new feed muterials must be evaluated prior to their analysis and (2) chemical analyses of constituents processing in the solvent - extraction pulse column for which feed materials impurity tolerance limits7 system in the Refinery. Also, the chemical anal- exist. Wet chemical and complete spectrochemical yses of the concentrates must be compared with analyses of the five new feed materials are pre- FMPC impurity tolerance limits for feed materials, sented in Tables 1.1 ad 1.2, respectively. as blending may be necessary to obtain acceptable The analyses of the feed materials show that: process in^ operations with respect to column (1) Anaconda Acid, Kermac, Moab, and Rifle con- scale, corrosion, etc. centrates meet all tolerance limits, and (2) Texas Test lots of five Colorado feed materials be- Zinc concentrate meets all tolerance limits except came available this quarter for evaluation and the limit for total organic material(0.12 per cent, official assayer's samples of each lot were made uranium basis). The Texas Zinc concentrate available for labaatory studies. will have to be either blended or processed further to meet this tolerance limit. Prior Work on Project Laboratory Digestion Tests The feed materials evaluation program has been in existence since January, 1957. It was pre- Standard digestion tests6 consist of (1) labora- tory digestion of the concentrates in dilute nitric viously reported' -7 that feed material evaluations of 21 feed materials had been completed. acid, and (2) determination of the following data from G feed S!LI containing 250 2 10 q,'! uraRinm ad having a nitric acid concentration of 3.0 Objective for This Quarter f 0.1N: consumption To initiate and complete the laboratory part of 1. HN03 the feed material evaluations for Anaconda Acid, 2. Volume change factor Kermac, Moab, Rifle, and Texas Zinc uranium 3. Digestion efficiency concentrates. 4. Solids content of slurry 5. Any unusual behavior Summary of Results Digestion data are tabulated in Table 1.3. The results indicate that: Chemical analyses, laboratory digestion tests, 1. Anaconda Acid, Kermac,