Oct. 14, 1958 J. M. CARTER ET AL 2,856,263 PROCESS for the RECOVERY and PURIFICATION of URANIUM DEPOSITS Original Filed April 21, 1944 ‘7 Sheets-Sheet 1

Home , Uranium pentachloride

Oct. 14, 1958 J. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS Original Filed April 21, 1944 ‘7 Sheets-Sheet 1

IN VEN TORS James M Car/‘er Mar?n D. ?ame/7 BY ATTORNEY

Oct. 14, 1958 J. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS Original Filed April 21, 1944 7 Sheets-Sheet 55

QQOUMM,vRMmG

w.9386mmE

IN VEN TORS James M. Car fer By Marfin 0 Home/7 W4 W ATTORNEY Oct. 14,1958 J. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION _ OF URANIUM DEPOSITS Origlnal Filed April 21, 1944 7 Sheets-Sheet 4

SCRUBBYING. AND WASHING PARTS OF CALUTRON ' WITH HOT WATER Lf- WASH WATER :FCONDENSATE ' \WATERANDMAKE UP snevmc SOL/D IMPUR/ TIES

— WASH WA TER -—p>- CONDENSING To DISCARD I OXIDIZING ORSALVAGE

SOLUTION U02” Cu?! Few’! Cr!!! Ni“ FILTERING‘ - '3 PREC/P/TATE 0*

|——‘———/ F/LTRA TE _ U024!- TO DISCARD __ EVAPORATING gel”,++ OR SALVAGE

PRECIPITATING Z/VH OH AND F'LTER'NG gFlLTRA TE

TO FURTHER T REATMENT Fig. 4 I

INVENTORS ‘James M Cor fer, BY Mar/7'0 D. Kama/7 ' @ M A TTORNEY Oct. 14,1958 J. M. CARTER ET AL . 2,356,263 PROCESS FOR THE RECOVERY AND PURIFICATION 0F URANIUM DEPOSITS Original Filed April 21, 1944 7 Sheets-Sheet s

DISSOLVING URANIUM METAL DEPOSITED ON COPPER COLLECTOR IN COLD HNo3 (8N)

CONDENSATE I AND MAKE UP SOLUTION HNO3 U02" ' Cu ** 7—>— CONDENSING ' HN03 .

EVAPORATI NG

CONCENTRA TED \ soburj'o/v _ F/LTRA TE C35 cu {NHJLF H PRECIPITATING ‘ -[—-~’—NH4OH A ND F ILTERING '

f/RECIP/ TA TES *Cu/‘OHZH4 :0 01 ORTO SALVAGEDISCARD *Trace

T__>_ DISSOLVING HN 0 3 '

- SOLUTION U02 +4 *cuvf *Tme F/LTRA TE

PRECIPITATING _l—_'_NH OH AND FILTERING 4 { PREClP/TATE NH U 0 TO DISCARD ( ‘)2 2 ’ OR SALVAGE , r---‘“—? TO FURTHER TREATMENT 5

I N V EN TORS' James M Car/‘er ' Mar/"in D. Kama/7

A TTORNEY Oct. 14, 1958 .1. M. CARTER ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS Original Filed April 21, 1944 7 Sheets-Sheet 6

STARTING MATERIAL FROM PRIOR PREC/P/MTES TREATMENT (NH )2U 07 CrFe (0Oil/25 )3

-r-—>— 'oIssoLvINc . 0| so VINc HNO3 ‘HNOa s L SOLUTION SOLUT/ON U02 ++ U02 ++ Fe+++ Pe+++ C,.+++ cr+++

. ADJUSTING ADJUSTING [NH4OH P H (2) 2NH4OH P H (2) SOLUTION ' SOLUTION U02** U0g*+ Fe*** Fe*** c,-+++ Cr+++

PRECIPITATING PRECIPITATING THWH AND FILTERING {TI/H40"; AND FILTERING (Ni/#2 C03 (/I/mlcoa PREC/P/TATES Fe (OH) Fe 0H3 Cr(OH)§ cam/)3 TO DISCARD *(NH4)2U2 0, OR SALVAGE ' I *7?“ ' TO oIscARo OR SALVAGE F/L TRA TE F/LTRA TE (NH4)4UO2(C03)3 I v (/I/H,),u02(co3)3

AcIDIFYINc ‘ TWO?‘ AND HEATING ''_F_''''’_c02 6“

SOLUTION (1020/03): F/LTRATE PRECIPITATTNG TWO” AND FILTERING

émsc/p/ursNH U 0 ‘)2 2 ’ TO DISCARD ,To FURTHER oR sALvAcE TREATMENT~ Fig. 6

INVENTORS James M C‘arfer BY Marf/n Q Kama/7 % . ATTORNEY Oct. 14, 1958 . J. M. CARTER- ET AL 2,856,263 PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS Original Filed April 21', 1944 ’ '7 Sheets-Sheet 7

MATERIALSTARTING /NH4)2Uz0r FRoM PRIOR TREATMENT ' VAPORS CALCINING ‘ NH,

T ' H10 '

' U03

GASES ‘égséfzs 7——->— REDUCING ¢°z REACTING co CH4 Y " C0 2c014 CO2

—uoz ——uc/5

GASES 7—>- REACTING ggc'z CALCINING GAS (SC/4 (x)2 ‘5'2 Clz ' 0014- -uc/4

RES/DUE (/0; 006/; SUBLIMING m VACUUM jsuauMA'rE TO SALVAGE 1U (.74

. END PRODUCT Fzlq. 7

INVENTORS James M Coffer BY Mar-?n D. Kama/7

A TTORNEY 2,856,263 hired States Patent [0 " CO Patented Oct. 14, 1958

1 2 ing uranium both in metallic and compound forms in con 2,856,263 junction with the calutron method of enriching the ura nium with U235, whereby minimum handling of the ura PROCESS FOR THE RECOVERY AND PURIFICA nium and maximum ef?ciency of the process are obtained. TION OF URANIUM DEPOSITS . 5 The invention, both as to its organization and method James M. Carter, Los Angeles, and Martin D. Kamen, ' of operation, together with further objects and advan Berkeley, Calif., assignors to the United States of tages thereof, will best be understood by reference to the America as represented by the United States Atomic following speci?cation taken in connection with the ac ' Energy Commission companying drawings, in which Figure 1 is a perspective Original application April 21, 1944, Serial No. 532,159. 10 view, partly broken away, of a calutron that is suitable and this application April 26, 1945, Serial No. ' for use in carrying out the process of the present inven

9 4 . tion; Figs. 2 and 3 taken together, when arranged end to end, illustrate the overall ?ow diagram of the present 9 Claims. (Cl. 23—14.5) process; Fig. 4 illustrates in greater detail a portion of the 15 ?ow diagram of the present process, indicating the re The present invention relates to processes of producing covery of the residue of UCL, from the parts of the calu an element enriched with a selected isotope, and more tron disposed in the source region thereof upon which it particularly uranium enriched with U235. This applica is deposited, and the initial steps of the subsequent puri tion is a division of our copending application, Serial ?cation of the uranium; Fig. 5 illustrates in greater No. 532,159, ?led April 21, 1944, now Patent. No. 20 detail another portion of the ?ow diagram of the present 2,758,006, issued August 7, 1956. process, indicating the recovery of metallic uranium from It is an object of the invention to provide a process of the collector of the calutron upon which it is deposited, increasing the proportion of a selected isotope in an ele; and the initial steps of the subsequent puri?cation of the ment containing a plurality of isotopes that can be carried uranium; Fig. 6 illustrates in greater detail a further por out on a large scale to produce quantities of the elements 25 tion of the flow diagram of the present process, indicating thus enriched for commercial use. the subsequent steps of the puri?cation of the recovered Another object of the invention is to provide a process uranium; and Fig. 7 illustrates in greater detail a still fur of producing .an element enriched with a selected isotope, ther portion of the ?ow diagram of the present process, which process utilizes a calutron for the purpose of ob indicating the ultimate conversion of the puri?ed uranium taining the enrichment. ' - 30 back to U014. ' Another object of the invention is to provide a process At the outset, it is noted that a “calutron” is a machine of producing an element enriched with a selected isotope,‘ of the character of that disclosed in the copending applica which process utilizes ?rst-stage and second-stage calut tion of Ernest 0. Lawrence, Serial No. 557,784, ?led 0c trons arranged in tandem for the purpose mentioned. tober 9, 1944, now Patent No. 2,709,222, and is employed A further object of the invention is to provide'a process 35 to separate the constituent isotopes of an element and of recovering the residue of a material whichhas been more particularly to increase the proportion of a selected subjectedto treatment in a calutron from the parts of the isotope in an element containing several isotopes in order calutron disposed in the source region thereof upon which to produce the element enriched with the selected isotope. the residue is deposited. . For example, the machine is especially useful in producing A further object of the invention is to provide a‘ process‘ 40 uranium enriched with U235. Moreover, in such a ma of recovering an element enriched with a selected isotope chine it is not essential that the material initially intro from the collector of a calutron upon which the enriched duced be a naturally occurring polyisotope, such as nat element is deposited. urally occurring uranium. It is feasible to separate any A further object of the invention is to provide a process intermixed or intermingled materials capable of produc of treating the residue of a material whichhasbeen pre 45 ing ions distinguishable from each other by differences in viously treated in a calutron in order to render the ma: nuclear mass. Since this is true, it is not essential that terial suitable to be retreated in the calutron. . > , the initial material mixtures be made up necessarily of A further object of the invention is to provide a proc the same chemical elements, as various different elements ess of treating material which has been enriched with a in intermixed form can readily be separated. selected isotope in a ?rst-stage calutron in order torenderi 50 Such a calutron essentially comprises means for vapor the material suitable to be'further enriched with the se izing a quantity of material containing an element which lected isotope in a second-stage calutron. - is to be enriched with a selected one of its several isotopes; A further object of the invention is to provide a process means for subjecting the vapor to ionization, whereby at of purifying material which has been treated in ?rst-stagev least a portion of the vapor is ionized causing ions of the and second-stage calutrons arranged in tandem in order ' 55 several isotopes of the element to be produced; electrical to render the material suitable for commercial use. means for segregating the ions from the un-ionized vapor A further object of the invention is to-provide- a proc-v and for accelerating the segregated ions to relatively high ess of treating an element which has been impoverished velocities; electromagnetic means for de?ecting the ions with respect to a selected isotope by treatment in ,a second alongcurved paths, the radii of curvature of the paths of stage calutron in order to render the material suitable to 60 ions being proportional to the square roots of the masses be retreated in a ?rst-stage calutron in order again to. en of the ions, whereby the ions are concentrated in accord rich the element with respect to the selected isotope. ance with their masses; and means for de-ionizing and A further object of the invention is to provide a proc-' collecting the ions of the selected isotope thus concen ess of producing uranium enriched with U235, which proc trated, thereby to produce a deposit of the element en ess utilizes a calutron in which a halide of uranium is 65 riched with the selected isotope. It will be appreciated treated. that in the event that an element is being separated from A further object of the invention is to provide a process of producing uranium enriched with U235, which process other elements, then said element occupies a position with utilizes ?rst-stage and second-stage calutrons in which the respect to said other elements as said selected isotope compound UCl, is treated. _ 70 occupies with respect to the several other isotopes of the A still further object of the invention is to provide a element being enriched with respect to said selected iso processof recovering, reclaiming, purifying and convert-J . , tope. 2,866,263.

4.. A. _ Referring now more particularly to Fig. 1, there is The removable end wall 19 carries an insulator 34 illustrated a representative example of a calutron 10 of which supports an upstanding collector block 35 formed the character noted, which comprises magnetic ?eld of copper or the like and, provided with two laterally structure including upper and lower pole pieces, 11 and, spaced-apart cavities or pockets 36 and 37 which com 12, provided with substantially ?at parallel spaced-apart: municate with aligned slots 38 and 39 formed in the wall pole faces, and a tank 13 disposed between; the pole faces of the collector block 35 disposed remote from the re of the pole pieces 11 and 12. The pole pieces 11 and movable end wall 19. It is noted that the pockets 36 12 carry windings, not shown, which are adapted‘ to be‘ , and 37 are adapted to receive two constituent isotopes energized in order to produce a substantially uniform of an element which have been separated in the calutron and relatively strong magnetic ?eld th‘erebetween', which 10, as explained more fully hereinafter. Finally, the magnetic ?eld passes through the tank 13 and the various inner wall 16 carries a number of insulators 40 which parts housed therein. The tank 13 is of tubular con support a tubular liner 41 formed of copper or the like, ?guration, being substantially crescent-shaped‘ in plan, rectangular in vertical cross-section, disposed within the and comprising substantially ?at parallel spaced-apart, tank 13' and spaced from the walls 14, 15, 16 and 17 top and bottom walls 14 and 15, upstanding curved, inner 15 thereof‘. One end of the tubular liner 41 terminates and outer walls‘ 16 and 17, and end walls 13 and 19. adjacent the accelerating structure, including the plates The end walls 18 and 19 close the opposite ends of the 32; and the other end of the. tubular liner 41 terminates tubular tank 13 and are adapted to be removably secured adjacent the collector block 35; the tubular liner 41 con in place, whereby the tank 13 is hermetically sealed. stituting an. electrostatic shield for the high-velocity ions Also, vacuum pumping apparatus, not shown, is associ 20 traversing the curved paths between the slit 33 formed ated with the tank 13, whereby the interior of the tank‘ by the plates 32 of the ion accelerating structure and 13 may be evacuated to a pressure of the order of 10"5 the slots 38‘ and‘ 39 formed in the collector block 35, as to 10"4 mm. Hg. Preferably, the component parts of‘ explained more fully hereinafter. the tank 13 are formed of steel, the bottom wall 15 In view of the above description, it will be understood thereof resting directly upon the pole face of the lower 25 that the parts of the calutron 10‘ carried by‘ the removable pole piece 12,, and the top wall 14 thereof being spaced end wall 18 constitute a source unit, and the end of the at suitable distance from the'pole face of the upper pole tank 13 disposed‘ adjacent the source unit constitutes the piece 11, whereby the top and bottom walls 14 and 15 source region of the calutron. Similarly, the parts of constitute in effect pole pieces with respect to the interior the calutron carried by the removable end wall 19 con of the tank 13, as explained more fully hereinafter. 30 stitute a collector unit, and the end of the. tank 13 dis The removable end wall 18 carries an insulator 29 posed adjacent the collector unit constitutes the collector which supports an upstanding charge block 21, provided region of‘ the calutron. ' with a hollow central cavity 22 constituting, a charge Considering now the general“ principle of‘ operation of receiving pocket surrounded by rather thick side walls. the calutron 10, a charge comprising a compound. of the Electrical ‘heating elements 23 are embedded in the side 35 element. to be. treated is, placed in the charge pocket 22 walls of, the charge block 21 and are adapted to be con in the charge block‘ 21, the compound of the element nected to a suitable source of current, whereby the mentioned‘ being one which may be readily vaporized. charge block 21 may be appropriately heated, the charge The cover, not shown, is then secured on the charge block 21 being formed of cast steel or the like. Also, block 21 and‘ the end walls 18 and 19 are securely at the charge block; 21 is provided with a removable cover,“ 40 tached' to the open ends of the tank 13; whereby the tank not shown, and supports a tubular member 24 which in 13‘ is hermetically sealed. The variouselectrical connec turn supports an arc block 25 formed of carbon or tions are completed and operation of the‘ vacuum pump— graphite. The are block 25 is substantially C-shaped in ing apparatus, not shown, associated with the tank 13 is‘ plan, an upstanding‘ slot 26 being formed in the wall initiated. When a pressure of the order of 10-5 to 10-4 thereof remote from the charge block 21. Thus, the arc mm, Hg is established within the tank 13, the electric block 25 is of hollow construction, having a central arc circuits for the windings‘ associated with, the pole pieces cavity 27 formed therein, the arc cavity 27 formed in 11 and 12 are closed and adjusted, whereby‘ a predeter the arc block 25 communicating through the tubular mined magnetic ?eld is established therebetween, travers member 24 with the cavity' 22 formed in the charge ing the tank'13‘. The electric circuit for-the heatingele ments 23 is closed, whereby the charge in the charge blockv 21. 50 Also, the removable end‘ wall‘ 18 carries an insulator pocket 22 in the charge block 21‘ is heated and vaporized. 28, disposed above the insulator 20, which supports hori The vapor ?lls the charge pocket“ 22 and is conducted zontally projecting cathode structure 29, including a ?la through the tubular member 24 into the cavity 27 formed mentary cathode 30 adapted to be connected, to a suitable in the arc block 25. The electric circuit‘ for the ?la source of current. The cathode structure 29 projects mentary cathode 30 is closed, whereby the ?lamentaryv over the upper end of the charge block 21, whereby the cathode 30 is heated and rendered‘ electron-emissive. ?lamentary cathode 30 overhangs and‘ is aligned with Then the electric circuit‘ between the ?lamentary cathode respect to the upper end of the cavity 27' formed in the 30 and the anode 31 is closed, whereby an arc discharge arc block 25. Further, an anode 31 is arranged, below is struck therebetween, electrons proceeding from the ?la mentary cathode 30 to the anode 31. The electrons pro and in alignment with respect to the lower end of the 60 cavity 27 formed in the arc block 25, the‘ anode 31, being ceeding from the ?lamentary cathode 30 to the anode 31 supported by the charge block 21. The ?lamentary‘ break up the molecular form of the compound of the cathode 30 and the cooperating anode 31- are adapted, vapor to a considerable extent; producing positive‘ions‘of‘ to be connected to a suitable source of current; the element which is to‘be enriched'with' a‘ selected one 0 its isotopes. ‘ Ion accelerating structure, including- a pair of upstand 65 ing plates 32 formed of‘ carbon or graphite, is supported‘ The“ electric circuit‘ between‘ the‘ are black 25 and the by insulating structure, not shown, carried‘ by‘the remov ion accelerating structure, including‘ the plates 32, is able end wall 18. The pair of upstanding plates 32 are‘ completed, the plates 32 being at a high negative poten- arranged in spaced-apart relation in order to. de?ne a tial with respect to-the arc block 25, whereby the positive ions are attracted and accelerated to the voltage impressed‘ slit 33 therebetween, arranged in substantial. alignment between the arc block- 25‘ and‘ the ion accelerating struc with respect to theslot 26 formed: in. the wall of the arc ture. More‘particularly, thepositive ions proceed from block 25. A suitable source of‘ voltage is- adapted‘ to the interior of the cavity 27‘ formed in the arc block 25. be connected between the arc block 25 and". the ion through the slot 26 formed in the wallthereof, and across accelerating structure, including: the‘ plates. 32’, for a‘ pure the- space between the plates 32' and the adjacent'wall“ of pose more fully explained hereinafter. theiaroblock 25,.and thencetthrough. the. slit 33 formed assessa ' 3 d between thevplate's 32 into the interior of the tubular liner ' tities of uranium enriched with U235 foi'vc‘omr'nercial pur- 41‘. The high-velocity positive ions form a verticaliup poses. Accordingly, in this example the uranium de standing ribbon proceeding from the cavity 27 formed‘ posited in the pocket 36 of the collector block 35 is'con in the arc block 25 through the slot 26 and the aligned siderably enriched, both with U234 and U235, and consider slit 33 into the tubular liner 41. v ably improverished with respect to U233 as compared to ' The collector block 35, as well as the tubular liner 41, natural or normal uranium. is electrically connected to'the ion accelerating structure, -During the operation of the calutron 10 in the produc including the plates 32, whereby there is an electric ?eld tion of uranium enriched with U235, the compound UCl; ' free path for the high-velocity positive ions, disposed be-‘ is vaporized in the charge block 21 and conducted through tween the plates 32- and the collector block 35 within the 10 the tubular member 24 into the cavity 27 formed in the tubular liner 41. The high-velocity positive ions enter are block 25, where it is subjected to ionization as pre ing the adjacent end of the liner 41 are de?ected from viously explained. Only a minor fraction (about 5%) their normal straight-line path and from a vertical plane, of the UCL, vapor is actually ionized in the cavity 27 passing through the slot 26 and the slit 33, ‘due to'the formed in the arc block 25 and drawn through the slot effect of the relatively strong magnetic ?eld maintained 15 26 due to the ion accelerating structure, including the through the space within the tankv 13 and the liner 41 plates 32. The major fraction (about 95%) of the UCL, through which the positive ions travel, whereby the posi vapor is un-ionized in the cavity 27 formed in the arc tive ions described arcs, the'radii of which are propor block 25 and ?ows through the slot 26 due to the pres tional to the square roots of the mass'esof the ions and sure differential between the cavity 27 and the interior'of consequently of the isotopes of the element mentioned. 20 the liner 41. This major fraction of the UCl, vapor,‘ Thus, ions of the relatively light isotope of the element being un-ionized, is not at all alfected by the ion accelerat describe and interior arc of relatively. short radius and ing structure, including the plates 32, and travels into are focused through the slot 38 into the pocket 36 formed contact with the various parts of the calutron disposed in in'the collector block 35; whereas ions of the relatively the source region thereof, upon which parts it is con heavy isotope of the element ‘describe an exterior arc of densed primarily in the compound formUCl, as a resi relatively long radius and are focused through the slot due. More particularly, this residue is condensed princi 39 into the pocket 37 formed‘ in the collector block 35.{ pally upon the interior of the adjacent end of the liner Accordingly, the ions of thevrelatively light isotope of 41, but to some extent upon the exterior thereof, the the element are collected in the pocket 36 and are de-. walls of the tank 13 in the region of the source and upon ionized to produce a deposit of the relatively light isotope 30 the exterior surfaces of the various elements of the of the element therein, while the ions of the relatively source unit including the arc block 25, the charge block heavy isotope of the element are collected in the pocket 21, etc. ' 37 and deionized to produce a deposit of the relatively More particularly, the minor fraction of the UCl4 heavy isotope of the element therein. ' t - vapor is ionized to form positive atomic ions including , After all of the charge in the charge pocket 22 formed 35 Ui', U++, Cl’r and Cl++; and positive molecular ions in in the charge block 21 has been vaporized, all of the elec-, cluding Cl2+, C12”, UCI4+, UCl4++, UCl3+, UCl3++, tric circuits are interrupted and the end wall 18 is removed UClg’t, U012“, UCl+ and U0“. Of these atomic and so that another charge may be placed in the pocket 22 molecular ions only the singly ionized atomic ions U+ and subsequently vaporized in the manner explained; have the required ratio between mass and charge such above. After a suitable number of charges have-been 40 that they are focused through the slots 38 and 39 into the vaporized in order to obtain appropriate deposits of the pockets 36 and 37 formed in the collector block 35; the isotopes of the element in ,the pockets 36 and 37 of the atomic ions U+ of masses 234 and 235 focusing through collector block 35, the end wall 19 may be removed and the slot 38 into the pocket 36, and the atomic ion U+ the deposits of the collected isotopes in the pockets 36 of mass 238 focusing through the slot 39 into the pocket and 37 in the collector block 35 may be reclaimed. Of course, it will be understood that the various di 45 37, as previously noted. ' mensions of the parts of the calutron 10, the various elec The doubly ionized atomic ions U++ have such a ratio vtrical potentials applied between the various electrical between mass and charge that they are deflected along an parts thereof, as well as the strength of the magnetic ?eld arc of shorter radius into engagement with the inner wall between the pole pieces 11 and 12, are suitably correlated of the liner 41, where they are de-ionized to form a de with respect to each other, depending upon the mass 50 posit thereon. The singly and doubly ionized atomic numbers of the several isotopes ofthe element which is ions Cl+ and Cl++ and the singly and doubly ionized mo‘ to be treated therein. In this connection, reference is lecular ions (312+ and (312+Jr have such small ratios between again made to the copending application of Ernest 0. mass and charge that they are deflected along arcs of Lawrence for a complete speci?cation of a calutron especi very short radii into engagement with the inner wall of ally designed for the production of uranium enriched with the liner 41 adjacent the source region, where they are the isotope U235. By way of illustration, it is noted that de-ionized to form neutral chlorine molecules, which gas when the calutron 10 is employed in order to produce is subsequently pumped from the tank 13.due to the uranium enriched with U235, the compound of uranium operation of thevacuum pumping apparatus previously which is suggested as a suitable charge in the charge block noted.‘ Similarly, the doubly ionized molecular ions 21 is UCl4, as this compound may be readily vaporized UC14++, UCI3++, UClzJr’r and UC1++ have intermediate and the molecular form of the vapor may be readily ratios between mass and charge such that they are de— broken up to form positive ions of uranium with great ?ected along'arcs of intermediate radii into engagement facility. In this case, uranium enriched with U235 is col with the inner wall of the liner 41 intermediate the source lected in the pocket 36 of the collector block 35, and region and the collector region, where they are de-ionized uranium comprising principally U23? is collected in the 65 to form a deposit ‘thereon. Finally, the singly ionized pocket 37 of the collector block 35. Also, it is noted molecular ions UCl4+, UCl3+, UC12‘r and UCl+ have that froma practical standpoint, the deposit of uranium large ratios between mass and charge, such that they are collected in the pocket 36 of the collector-block 35 con de?ected along arcs of large radii into engagement with tains considerable amounts of U238, in view of the fact the outer wall of the liner 41 intermediate the source that this isotope comprises the dominant constituent ofv 70 region and the collector region, where they are de-ionized ordinary uranium. Furthermore, the deposit of uranium to form a deposit thereon. . collected in the pocket 36 of the collector block 35 con Accordingly, it will be understood that, after operation tains a considerably increased amount of U234, in view of the calutron 10 to vaporize a reasonable number of of the fact that it is not ordinarily feasible to separatev charges of UCll in the charge block 21, a considerable U234 and U235 in the production of relatively largequan 75 deposit of UCl.‘ is formed on the adjacent end of the liner ~ 7 8 4.1,. and] that; a. reasonable deposit. of. metallic; uraninml. and is: termed. "singly; enriched” uranium, the enrich-y as. well. as. the various.» uranium; chlorides.v is. formed. on; ment being». with respect. to; the desired. isotope» U235; the; intermediate. : portiono?tha liner 4.11.. These deans. s 0.11.: the; other“. hand. in a. secondestage. ealutron the. de represent. uranium‘ which contains the, various isotopes posit of metallic uranium. inthe noeket 36. in. theC col-l U238, U235 and: Uztal in. natural. or‘: normal; amounts; such.v 5... lector block 35 has been . subjected. to. two; treatments, that these deposits should be recovered fen-recycling; pur.. and is... termed: “doubly enriched.”- uranium,. the. enrich poses as; well ,as .to clean. thez..linen 4L and ‘ the;v QthQKE?ItS merit; heinggrwith resneetrto the.‘ desired. isotope, U235» of the calutron. 10; in. order- to.‘ insure: e?icient: operation. Gonsitierins new the; present. process in sreaterdetailt. thereof. . and." referring to» the. composite. flow diagram. illustrated‘ Considering. the present proeessin greater.- detail with. in» Figs-r211 and hit. wilL herunderstood. that; a; plant 317-. reference. to the. production; of‘ unaniume enriched with ranged to carry out: thiQ-PI‘QCESS; Willcomprisea relatively U235, it. is pointed out that; natural. or normal uranium large: number‘ of: ?rst-stage cahltrons and. a. relatively comprises three isotopes, U?3B,.UF35 and; U234, inthe ap small’. numherrlof seeonthstage:calutronsin addition to. proximate relativeabundancesl; 1/139 and 1/ l6;700. (in facilitiestiol‘ liandl'ina; stories. recovering, purifying and. numbers; of; atoms; with. referencev to. U238) , respectively, converting; the. variousmetallio and; compound». forms- of or. approximately 16,700,, 12.0; and. 1. atoms, repectiyely, uranium; As illustnatediinz the; diagram,‘ the» Starting‘: ma» ' in 16,82]. atoms; of a; sample. It is highly desirable to terial. employed. as a: charges in ‘the; ?rst-stage. calutron is. prepare large. quantities. of‘ uranium enriched, with, the UCl4, comprisingwnatur‘al 0171101111131 uranium, whereby‘ thermalrneutron.?ssionable. isotop.e;.U235 for, commercial metallic. uranium: singly enriched‘. with U235 isrdepositedi purposes, and it: has been; found, that; this end can be 2.05 in. thea?rste pockets‘ of the . collector ‘ and. metallic uranium > accomplished by employing. thecalutron method. How.- ‘ impoverished with, respeemtor U23?1iSr deposited in the ever, it is desirable that the uranium. product‘ have an second: pocket of: the‘ collector. Also, a large amount enrichment factorwith respect‘ to U235 of the order of 40.0, oftUCl; is'dcpositedi as: at. residue upon the parts of the this factorbeing de?ned as. the quotient obtained by di ?rst-stage-lcalutron" disposed in. the source region thereof, viding the ratio of U235‘ to U238 in the product. with ‘the 2.5, the ‘deposit being; primarily.‘ on the. source-region end ratio of U235 to U238 in the original material.. Now as of. the‘ liner; Aften-several‘eharges of‘UClg, comprising‘ . > suming that the product is enriched by 400 in both U235 natural? or normallluraniuml, have‘been- employed in the and U234, it comprises U238, U235 and; Umin. the approxi~ ?rst-stagei calutron, reasonable» deposits of metallic mate relative abundances. 1,. 400/139.‘ and 400/1.6.700 (in uranium have!“ been~ collected-i in‘ the ?rst and second‘ numbers of atoms with. referencesto U2“), respectively, 302 pocketsrofi the collector, andlthervmetallic uranium deposits i orapproximately 16,700,. 48.05.;7 and. 400 atoms, respec in‘ the: collecton and'i the», U61; residue on‘ the liner are tively, in 65,157 atoms of a sample. Thus the enriched? recovered; - A uranium. product comprises. approximately 25.7%“ U238, "More particularly, theemetalli'c»; uranium‘ singly» en 73.7% U235 and.0..6%rU23‘*.. ‘ ‘ > > riched with U235 and“ deposited in the ?rst pocket of In order. to obtain. this desired’ enrichment of?‘ the; the» collector» is“ recovered by’ an‘ acid-l wash process, uranium. product. by utilizing the. calutronmethod, it has whereby“ various: impurities» including copper are intro been foundmost convenient.‘ to use: ?rst-stage and. second? d‘lucedL ‘in the‘ wash‘ solution; ‘due to the‘ fact that‘ the stage calutrons, the. ?rst~stage calutrons ; employingnatural. collector of the ?rst-stage calutron which is- thus washed or normal, uranium. and producing‘, a ?rst-stage enriched‘ with acid" is. formed of the metal‘ mentioned. Accord producthaving an. enrichment faCiOrgOf' the. order. of 2.0.. ingl‘y; the1 wash solution containing-A‘ the uranium singly-e with respect to natural. or: normal uranium; and. the enriched-‘with U235‘ which has‘ been‘ reclaimed contains‘ second-stage calutrons employing ?rst-stage enriched clonsiderableimpurities; This; wash solution. is‘ stored‘ uranium and producing a. second-stage enriched, product and“ subsequently‘ employed as“ makeup" material in‘ a having‘ an. enrichment factor‘ of the order of 20. with re; puri?cation process‘ utilized‘ in; conjunction. with the spect to the ?rst-stage enriched uranium, whereby the sec 45 s'econdestaggé-calhtrom'in a manner‘more fully-explained end-stage enriched uranium product,- has a ?nal enrich hereinafter.v The metallic; uranium impoverished“ with ment factor of. the order of; 4QQ‘WlthIQSPBCt to natural or. respect-to Uzai'and" dcpositcdfin; thesecond.‘ pocket of. the normal. uranium. By employing. the present process, collector is‘ recovered‘ by ‘an acid wash process‘ and dis whereby the ultimate: enrichment of: the ?nal uranium, carded‘; asi't‘contains solittl'e U235‘and further processing product is obtained in two stages, as‘indicated above, each 50 thereof’ is‘ not‘ feasible. ‘ - of the ?rst-stage and the second-stage calutrons may be ‘ The residue’ of“ U614“ deposited. on the parts of .the operated in the stable rangeand to give. a maximum yield‘ ?rst-stage cal‘utrons disposed in the‘source region thereof,‘ of enriched material. principally upon the liner, is recovered by a water wash Accordingly, in the present. process it will be under process, whereby various impurities including copper, stood that in the event the calutron 10 comprises a -‘ iron,‘ chromium,ynickel' and‘carbon are introduced in the ?rst-stage calutron, the. deposit of. uranium in the pocket. wash solution,’ due to‘ thefact that the various parts of 37 in. the collector block 35 has been impoverished with the ?rst-stage calutron which are. thus washed with respect to the desired isotope U235, and is recovered water are formed of the materialsmentioned. According therefrom and discarded; while the deposit. of uranium ly,_ the wash solution containing‘ natural or normal in the pocket 36 in the collector block 35 has been . uranium which has been reclaimed‘, contains considerable singly enriched with respect. to the desired. isotope U235, impurities... To. thiswash... solution there is added makeup‘ and is recovered. therefrom. and, subsequently treated in material, in the.‘ form. of awash, solution derived‘ from a second-stage calutron. On, the other hand, in the the. second-stage cal‘utron, and. comprising the Wash event the calutron 10 comprises: a. second-stage calutron, solution. from. the, second. pocket. of. the, collector,. and the deposit of uranium in the pocket 37. in the collector q ‘ containing. uranium whichhas been ?rst. enriched with block 35 has been ?rst enriched and thenimpoverished U235 in. the ?rst-stage calutron. and. subsequently im with respect to. the desired. isotope U235, and is. recovered poverishecl with. respechtollm‘ in the second-stage calu therefrom and analyzed for possible recycling in a ?rst tron, as explained morefully hereinafter. This com stage calutron; while the deposit. of uranium in the‘ posite. wash solution islthenpuri?ed in. order. to. eliminate pocket 36. in the collector block 35 has been doubly 7.0, the impurities mentioned;.the impurities thus eliminated enriched with respect to the desired. isotope U235, and is‘. are. discardedpand. the uranium. thus puri?ed is then recovered therefrom for commercial. use. converted back to. thecompound. UCl4. This compound. Thus it will be understood that in a ?rstestage calutron, of U514. is‘v then employed, along. with. a suitable amount. the deposit of metallic uranium inthe pocket 36 in the of makeup UClzb. as azcharge in. the ?rst-stage calutron. collector‘block 35 has. been subjected to. one. treatment 75“. Accordingly,..the. residue. of. UCIM deposited in. the steam > a same region of the ?rst-stage calutron is treated to used commercially; and thesecond-stage impoverished render it recyclable therein; the ?rst-stage enriched uranium is stored for use in the ?rst-stage calutron. uranium is stored for use in, the second-stage calutron; Considering now the details of the recovery of the and the ?rst-stage impoverished uranium is discarded. UCL, residue from the parts of either a ?rst-stage or a The starting material'employed as a charge in the 5 second-stage calutron disposed in the source region there second-stage calutron is UCl4, comprising singly enriched of, and the initial steps of the subsequent puri?cation of uranium, whereby metallic uranium doubly enriched with the uranium thus recovered, reference is made to the U235 is deposited in the ?rst pocket ‘of the collector portion of vthe'?ow diagram illustrated in Fig. 4. The. and metallic uranium which has been ?rst enriched in parts of the calutron disposed in the source region thereof, the ?rst-stage calutron and then impoverished in the 10' principally the source-region end of the liner, are scrubbed second-stage calutron is deposited in the second pocket and washed with hot water, whereby the residue of UCL; of the collector. Also, alarge' amount of UCL; is de deposited thereon is dissolved; and various impurities, in posited as a residue upon the parts of the second-stage cluding copper, iron, chromium, nickel and carbon are calutron ‘disposed in the source region thereof, the de introduced in the water wash, due to the fact that the posit being primarily on the source-region end of the various parts of the calutron which are thus washed with liner. After several charges of UCl4 comprising singly the hot water are formed of the materials mentioned. enriched uranium have been employed in the second The wash water is then sieved in order to remove any stage calutron, reasonable deposits of metallic uranium solid impurities which may be picked up, such, for exam have been collected in the ?rst and second pockets of the ple, as small pieces of metal and carbon. These solid collector, and the metallic uranium deposits in the col 20 impurities may be either discarded or subjected to salvage lector and the UCL; residue on the liner are recovered. treatment in order to recover any occluded uranium. More particularly, the metallic uranium doubly en The sieved wash water is then treated with H202 by add riched with U235 and deposited in the ?rst pocket of the ing a slight excess of 10% H202 and agitating the solu collector is recovered by an acid wash process, whereby tion, in order to oxidize the various contained materials. various impurities including copper are introduced in the For example, the wash water may contain suspended wash solution, due to the fact that the collector of the U(OH); and bits of copper and carbon; dissolved-uranium second-stage calutron which is thus washed with acid is in the +4 and +6 valence states; as well as dissolved formed of the metal mentioned. Accordingly, the wash copper, iron, nickel, chromium and possibly other metals solution containing the uranium doubly enriched with in one or more of the positive valence states. Hence, all U235 which has been reclaimed contains considerable im 30 of the uranium is put in solution as uranyl ion, suspended purities. This wash solution is then puri?ed in order to copper is put in solution as cupric ion, and other dis eliminate the impurities mentioned; the impurities thus solved metals are put in solution in their higher stable eliminated are discarded or salvaged; and the uranium valence states. Carbon is not oxidized by this treatment. thus puri?ed is converted into a standard compound of The effect of the oxidation on the various materials con uranium for commercial use. The metallic uranium 35 tained in the Wash solution may be indicated as follows: , ?rst enriched with U235 and subsequently impoverished with respect to U235 and deposited in the second pocket of the collector is recovered by an acid wash process, whereby various impurities including copper are intro duced in the wash solution, ‘due to the fact that the col 40 lector of the second-stage calutron which is thus washed with acid is formed of the metal mentioned. According ly, the wash solution containing the uranium ?rst en riched with U235 and’subsequently impoverished with re spect to U235 which has been reclaimed contains consid erable impurties. The uranium in the wash solution is then analyzed, and in the event it contains at least Accordingly, the oxidized wash water contains at least as much U235 as natural or normal uranium, it is em the following: UO2++, Cu++, Fe+++, Cr+++, Ni++ and ployed as makeup material in the puri?cation processv CD (carbon). The oxidized wash water is then ?ltered utilized in conjunction with the ?rst-stage calutron. 50 in order to remove C0, which may be discarded or sub The residue of UCL; deposited on the parts of the sec jected to salvage treatment in order to recover any urani ond-stage calutron disposed in the source region thereof, um occluded. ' principally upon the liner, is recovered by a water wash In the event this ?ltrate is rather dilute, it may be process, whereby various impurities including copper, iron, concentrated by evaporation; otherwise, this step is omit— chromium, nickel and carbon are introduced in the wash ted. In the event the ?ltrate is concentrated by evapora solution due'to the fact that the various parts of the tion, the water vapor which is driven oil is condensed second-stage calutron which are thus washed with water and to it is added enough makeup water in order to pro‘ are formed of the materials mentioned. Accordingly, vide a new wash solution, which is used again to‘wash the wash solution containing the singly enriched uranium the parts of the ?rst-stage calutron disposed in the source which has been reclaimed contains considerable impuri region thereof, in the manner previously explained. This ties. To this Wash solution there is added the previously step, comprising condensing and reusing the ‘water vapor stored makeup material in the form of the wash solution which is driven off the ?ltrate incident to concentration derived from the ?rst-stage calutron and comprising the by evaporation, is advantageous in view of the fact that acid wash solution from the ?rst pocket of the collector any uranium entrained in the water vapor is not lost to of the ?rst-stage calutron and containing singly enriched the outside. uranium. This composite wash solution is then puri?ed The original ?ltrate mentioned above, or the concen in order to eliminate the impurities mentioned"; the im trated ?ltrate following evaporation, in the event this purities th'us eliminated are discarded or salvaged; and step is employed, is then subjected to ammonia treat the uranium thus puri?ed is then converted back to the ment, either with excess NH3 gas or carbonate-free compound UCl4. This compound of UCl, is then em-' . NH4OH, whereby (NH4)2U207, and ployed as a charge in the second-stage calutron. are precipitated away from most of the copper and nickel Accordingly, the residue of UCl4 deposited in the source in solution, in the form of ammonia complex ions, region of the second-stage calutron is treated to render Cu(NH3)4++ and Ni(NH3)4++. The solution is then it re-cyclable therein; the second-stage enriched uranium ?ltered and the precipitate consisting of ammonium di isconverted-to a standardcompound. ofuranium. to be , uranate, ferric hydroxide and chromic hydroxide is then dosages. 1:1 re washed with, water. containing’, about 1%.; NH4QH and The. metallic. uranium» impoverished ‘with respect‘. to.» 1% NHrNOs; in orderv to eliminate.occludedcopper-and 111.235“ and. deposited in the secondpocketof the collector. nickel ammonia, complex ions. The ?ltrate. containing of . the ?rstrstage»; calutron: may. be recovered merely. by». the copper. and nicltel; ammonia complex. ions; is. then. etching, the inner surfaces of the. secondpocket of;this. discarded or- subjected to. salvage treatment. in order. to 5 collector. with-i 8N HNO3, whereby this. deposit. of me recover any. uranium contained; andthe initially; puri tallic. uranium:is..dissolved. This acid wash solutiontis, ?ed. precipitate of (NH4_)2U2O7,.Ee(QH).3, aILCLCJ.'(OI‘I)s1 then.,discarded,_ as. it- contains so little U235 that further is then stored for: further treatment, processing thereof is not feasible, It will be understood- that_the storedprecipitate de Onthe. other hand, themetallic uranium which. has. rived fromv the. parts. of. the ?rst-stage calutron. disposed been ?rst. enriched withrespect to U235 and subsequently‘ in‘ the source region thereof, as explained above, com impoverished with'..respe.ct‘to..Uz35, and‘deposited hither prises. uranium of. natural or normal. composition with second pocket: of .the. collector of the second-stage caluL reference to U235; while the stored precipitate derived. tron, “may. be recovered by etching the inner surfacesof from the partsof the secondrstagetcalutron disposed. in‘, the; second. pocket of. this; collector. with 8N HNQ-b, the; source. region thereof, as explainednbove, comprises, 15 whereby this deposit of. metallic uranium‘. is dissolved;.. uraniumwhich is singly enrichedwith U235. and. various‘ impurities, principally copper, . are‘. intro» Considering. now the details of the recovery of the: duced in the acid wash. solution,‘ due to thefact; that. metallic uranium, singlyxenriched. with U235, from the the. collector: of. the. secondfstage, calutron thus‘ etched; ?rst pocket of the collector of the ?rst-stage calutron,‘ with‘nitric; acid is formedof: the material mentioned. or of the. metallic. uranium, doubly enriched. with. U235, 20 Accordinglypthe wash. acid contains at least the ‘follow from- the ?rst pocket of the. collector of the second~stage ing. ions: UO2++ and. Cu.++. The considerations con-. calutron, and the initial steps of the subsequent puri? cerning, whether the. wash acid should be concentrated cation of the'uranium thus recovered, reference is made. are the same as those previously noted. in any case, to the portion of‘ the flow diagram illustrated in Fig. .5... either the original wash: acid mentioned. above, or the. The inner surfaces of the ?rst pocket of the. collector 25 concentrated wash acid1 following. evaporation,..in. the‘. of the calutron are. etched with HNO3, about ‘8N, whereby event this step is. employed, is‘ then. ‘analyzedin order. the deposit of metallic uranium, either singly orzdoubly to determine the U235 content thereof. Inthe‘ eventthe enriched withU235, is dissolved; and various impurities, analysis. indicatestthat the Ug35icontent of. this. wash acid‘. principally copper, are introduced in the; acid wash solu: is1at.least asgreat asnatural or normal; uranium,,. it. is: tion, due. to the fact that thecollector of the. calutronl 3.0 conserved. for. further treatmentgyon the. other hand, in. which is thus. etched with nitric acid, is-formedx of. the‘ the event the. analysis. indicates thatthe U?35 contents material mentioned. Accordingly, the wash acid, contains of..this_, wash, acid. is. less. than that. of natural. or :normal. atleastthe following ions: U02?” and Cu++.. uraniumit. is discarded. as further; processing; thereof; In the. event this wash, acid. is rather dilute in. these. isnot. feasible. . ions, it may be-concentratedrby evaporation; otherwise,, Assumingjhat the. analysisindicates that: the‘ Uimccorra this step is omitted. In the event the wash acid is con tentrof this.conserved. wash acid is'atleast as great .aszr centrated by evaporation, the HNO3 vapor which is driven that-.of natural‘ or nonmahuranium, ittis subjected. to ini--‘ off is condensed and to it is added‘enough makeup HNO3 tial, puri?cation by.‘ the. ammonia. process previously deal in order to provide a new- wash‘ acid, which is again scribed, whereby a .preciiptate of. (.NH4,) 2U2Oq‘ is‘obtained, used to wash the ?rst pocket-ofthe collector of the calu 40. which. isv then stored, for. further- . treatment. tron in the manner previously explained. This step, To the storedipl‘ecipitate derived‘ after initial puri?cation comprising condensing the HNO3 vapor which is driven fromjthe parts .o?the ?rstsstage calutrondisposedlin the. off the wash acid incident to concentration by evapora source regionthereof, there-is added the stored precipitate tion, is advantageous in view of the fact that any uranium derived after initialpuri?cation from-the ‘second; pocket of . entrained in the HNO3 vapor is-not lost to the outside. 4:5. ' the. collector. ofthe. second-stage ca‘lutron, in order. to. The original wash acid mentioned above, or the con produce a ?rst. composite. . precipitate; ‘ this. ?rst » composite. centrated. wash acid following evaporation, in_ the event precipitate . comprises uranium: of , substantally“ natural or. this step is, employed, is then subjected to. ammonia. normahcomposition. with reference to U235. Also, to the‘ treatment, either with NH3 gas or carbonate-free NHrOH, stored precipitateden'ved after: initial puri?cation from whereby (NI-LQZUQOq is precipitated away from most 50 the parts of the second-stage. calutron disposed in the‘ of the copper which remains insolution“ as ammonia sourceregion thereof, there is added. the stored precipitate complex ion, Cu(NI-l;;)4++. The solution is then ?ltered derived after initial puri?cation. from the ?rstpocket of and the precipitate, ammonia diuranate, is then washed the collector of, the?rstfstage‘calutron, in order-to pro with water containing. about 1% NH4OH and. 1% duce ansecondcompyosite precipitate; this. second com NH4NO3, in order to eliminate occluded copper‘ complex 55 posite precipitate comprises‘ uranium which is; singly en ion. The ?ltrate containing the copper ammonia. com richcd With U235. Finally, the stored precipitate. derived. plex ion is then subjected to salvage treatment in order after initial puri?cation. from the ?rst pocket of. the. col to recover any uranium contained‘. Preferably, the; pre lector of the. second-stage calutron. constitutes a third com-. cipitate of ammonium diuranate, and perhaps a trace of posite. precipitate; this. thirdv composite precipitate. com Cu(OI-I)2, is dissolved in HNO3, re-precipitated with. 60 prises uraniumwhich isdoubly enriched with U235. NH4OH- and- re-washed with water containing‘about 1% Considering now i the; details. of; the. subsequent. Plll'l?r NHlOH. and 1% NHrNOa- in‘. the manner explained cation; of one. of: the. composite precipitates. described above. This‘ solution is then‘ ?ltered and‘ the ?ltrate, above, . comprising. .(NH4“)2U2O7, Fe.(QH)3 and. Cr( O.H)3,. consisting principally of €u(NI-I3)4++ ‘ion, is then; dis. reference. is, made. to. the. portionof, the; ?ow diagram carded or subjected to further salvage treatment in iorder. 65 illustrated in. Fig. .6.. The, compositeprecipitate is ?rst to recover any uranium contained; and the precipitate dissolved in HNOisandtheip‘H.oftthe.solution.is adjusted of‘ ammonium diuranate is then stored for further treat, to about 2,. usingI 6N ‘ NH4.OH, whereby‘ the. solution ment. contains the. ‘following \ ions: . UOfhEeiH and . Cr+++, It will be understood that the stored precipitate de-. the; ions beingninnthehigher stablewalence states. The rived from the ?rst pocket of ‘the collector of the ?rst solution is then treatedwith,anexcess of» a .:NH4QH.~. stage calutron, as explained above, comprises uranium (NH4)2CO3 reagent,.comprising an approximately satu which is singly enriched with U235; while the stored pre~‘ rated solution. of. (-NH4_)_2_CO3‘ in. 3N NH4OH,. whereby cipitate derived from the ?rst pocket of the collector Fe(.OI-I_)3 and .Cr,(1O,H)3“areprecipitatedp While theura~~ of‘ the second-stage calutron comprises uranium which niumi remains ‘in . solution; as .- the :uranyl.‘ carbonate. com is doubly enriched withU235. plex ion.‘ UO2(CO3)3T*"-. The. solutiomisthen‘?lteredi 2,868,263 13 i4 ' and the precipitate is washed with water containing Evers', ‘Serial No; 55'/,JJ4,'?leu October 6, ‘1944, now NH4OI-I and (NH4)2CO3 in order to recover any occluded Patent No. 2,734,795, issued February 14, 1956, whereby uranium. COCIZ, CO2 CO and C12 gases are given oif incident In the event that it is felt necessary to recover traces to the reaction. The uranium pentachloride thus pro! of ammonium diuranate from the ferric hydroxide and duced is then calcined or decomposed to produce crude chromic hydroxide precipitate, the precipitate mentioned UCL, by heating to approximately 350° C., whereby C12" may be again dissolved in HNO3, the pH of the solution gas is given o? incident to the calcination. adjusted to about 2, the solution retreated ‘with. the In any case, the crude uranium tetrachloride produced NH4OH—(NH4)2CO3 reagent, and the solution again by either of the alternative processes indicated above is ?ltered‘and washed with water containing NH4OH and 10 then sublimed in a suitable molecular still at approximately (NH4)2CO3, all 'in the manner explained above. In 600° C., in order to produce a sublimate of UCl4, where this case, the precipitate of ferric hydroxide and chromic by residues of U02 and 'UOC12 are produced incident to hydroxide may be discarded or subjected to salvage treat- ‘ the sublimation. The residues of U02 and UOC12 are ment in order to recover any trace of occluded uranium. ultimately converted to UCl4. The UCL, thus produced Also in this case, the ?ltrate containing the uranyl carbon 15 is of very pure form and is suitable for recycling in the ate complex ion is added back to the original ?ltrate con appropriate one of the ?rst-stage or second-stage calutrons, taining the uranyl carbonate complex ion, and the ?ltrate in the manner previously explained. More particularly, is then subjected to further treatment. ‘ the conversion of the ?rst'batch of (NH4)ZU2O7 is pro In any case, regardless of whether one or more precipi ductive of a ?rst batch of U014 containing uranium of tations with NH4OH and (NH4)2CO3 are employed, the 20 natural or normal composition with reference to U235; ?ltrate containing (NH4)4UO2(CO3)3 is acidi?ed with this ?rst batch of UCL; is recycled in the ?rst-stage calu concentrated HNO3 and heated, in order to break up the tron. Also, the conversion of the second batch of uranyl carbonate complex ion to produce UO2(NO3)2,‘ (NH4') 2U2O7 is productive of a second batch of IJCL, con whereby CO2 is given o? from the heated solution. This taining uranium singly enriched with U235; this second uranyl nitrate solution is then treated with carbonate-free 25 batch of UCl4 is recycled in the second-stage calutron.‘ NH4OH, whereby (NH4)2U2O7 is precipitated. The Other examples of detailed chemical procedures which solution is then ?ltered, whereby the ?ltrate containing may be followed in order to recover uranium from the NH4NO3 is discarded or subjected to salvage treatment parts of a calutron upon which it is deposited, to pur1fy in order to recover any (NHgzUzOq contained; and the the recovered uranium thus eliminating_ the metal‘ im-, uranium thus puri?ed and in the compound form 30 purities or contaminants, and to reclaim or salvage any (NI-I4)2U2O7 is stored for further treatment or commercial uranium carried by the various precipitates and ?ltrates, use, as previously noted. . t resulting from puri?cation, are'disclosed in the copend It will be understood that the puri?cation of the ?rst ing applications of Martin D. Kamen, Serial No. 532,160, composite precipitate in the manner described above is ?led April 21, 1944, now abandoned; Martin D. Kamen productive of a ?rst batch of (NH4)2U2O7 containing 35 et al., Serial No. 542,378, ?led June 27, 1944, now uranium of natural or normal composition with reference Patent No. 2,771,340, issued November 20, 1956; James to U235. Also, the puri?cation of the second composite M. Carter et al., Serial No. 559,624, ?led October 10, precipitate in the manner described above is productive of 1944; Robert Q. Boyer, Serial No. 552,548, ?led Septem a second batch of (NH4)2U2O7 containing uranium which ber 2, 1944, now Patent No. 2,771,339, issued Novem is singly enriched with U235. Finally, the puri?cation ofv 40 ber 20, 1956; Scott B. Kilner, Serial No. 558,954, ?led, the third composite precipitate in the manner described October 16, 1944; Ross Cummings, Serial No. 532,161, above is productive of a third batch of (NH4)2U2Oq con ?led April 21, 1944, now Patent No. 2,772,142, issued taining uranium which is doubly enriched with U235. The November 27, 1956; and Sam Rosenfeld, Serial No. 567, ?rst and second batches of (NH4)2U2O7 are then con 286, ?led December 8, 1944. verted back to UCL, for retreatment in the ?rst-stage and In view of the foregoing, it is apparent that there second-stage calutrons, respectively; while the third batch has been provided a process of recovering, reclaiming, of (NH4)2U2O7 is available for commercial use. purifying and converting uranium, both in metallic and Considering now the details of the ultimate conversion compound forms, in conjunction with the calutron meth of either the ?rst batch or the second batch of (NI-I02 od, whereby uranium enriched with U235 may be produced UZOqYto UCl4, reference is made to the portion of the 50 on a large scale in commercial quantities. ?ow diagram illustrated" in Fig. 7. More particularly, a Also, it will be understood that the present process batch of (NH4)2U2O7 is calcined at approximately 300° may be suitably modi?ed so that a compound of uranium C. in order to produce U03, whereby NI-I3 gas and water other than UCL; may be treated either in the ?rst-stage vapor are given off incident to the calcination. The ura or in the second-stage calutron. For example, the calu nium trioxide thus produced may be converted by alter tron, as well as theconversion steps of the process, may native processes into crude UCl4. In accordance with be modi?ed, whereby UClS, UBr4, etc. may be treated one process, the U03 is ?rst reduced to U02 by heating in order to produce uranium enriched with U235. with CH, at approximately 450° C., as disclosed in the Furthermore, it will be understood that the present proc copending application of Milton J. Polissar, Serial No. ess may be further modi?ed in order to accommodate 494,448, ?led July 13, 1943, now Patent No. 2,678,257, 60 the enrichment of other elements in one or more of issued May 11, 1954, whereby CO2 and CO gases and their isotopes. For example, potassium may be en water vapor are given off incident to the reduction. The riched with respect to the radioactive isotope K4", ru uranium dioxide is then reacted with C014 in the vapor bidium with respect to the radioactive isotope Rb“, or phase at approximately 450° C.. in a suitable reaction samarium with respect to the'radioactive isotope 8mm. chamber, in order to produce crude UCl4, as disclosed in 65 Further, it will be understood that the present proc the copending application of James M. Carter, Serial No. ess contemplates subjecting the element that is to be 490,293, ?led June 10, 1943, now Patent No. 2,677,592, issued May 4, 1954, whereby COClg, CO2, CO and C12 enriched with respect to-a selected one or more of its gases are given o?i incident to the reaction. In accordance isotopes to successive calutron treatments until the ele ment contains the desired enrichment of the selected one ' with an alternative process, the U03 may be reacted di 70 rectly with CCl4 in the liquid phase in an autoclave at or more of its isotopes, whereby the process may in fact a temperature approximately 140° to 160° C. and at a be carried out in three or the required number of calu pressure approximately 200 pounds per square inch trons, arranged in tandem relation. gauge, in order to produce UCl5, as disclosedin the co The term “uranium” is employed in the present pending application of Charles J. Carignan and Ernest C.' 75 speci?cation and claims in a generic sense, i. e., as apply 2,856,268’ 15 Iii ing; to uranium whether in elemental, combined. or ionic‘ depositsI formed on.the partsnof aicalutron, disposed in form, unles'srindicated otherwise by the context. the‘ source. region. thereof. as a result of processing a While.there has been described what. is at present. con uranium halide compound therein, comprising washing sidered to‘ be thepreferred. embodiment of‘ the‘ inven said‘ parts with water to form a solution containing said tion,,it will be understood that‘ various‘ modi?cations ‘ uranium: values together. with metal impurities» including may be made therein and it is intended to cover. in.the nickel“ and copper ions- which form soluble ammonium appended claims‘ allv such‘ modi?cations as- fall within, complex; ions in alkaline solution and; impurity ions in thgtruewspirit and scope of. the invention. eluding-,1 ironitand chromium which form insoluble‘ hy Whatis claimedis: droxides: in ‘mixed. ammonium. carbonate-ammonium thy; 1. The? process of recovering uranium'values‘ froml 10 droxid'e‘ and ammonium‘ hydroxide solutions,‘ oxidizing‘ deposits formed on. the-.partsofacalutron as a result said solution with: an- agent therefonadding ammonia ofthe processing of UCL; therein,.comprising, washing‘ to» saidl oxidized solution; to precipitate said' uranium said parts‘ to an‘ aqueous wash solution containing. said values; and said’ impurities including. iron. and chromium uranium values together withimpurities of. a.?rst, class. insoluble: in,said1 solutionand away from the copper and including nickel. and copper ions‘. which form: soluble 15 nickel. impurities remaining as soluble ammonium. com complexiions' in the presence of" ammonium. hydroxide plex. ions in the solution, dissolving said precipitate in and impurities‘ of ‘a‘ second. class including iron‘ and chrow acid, treating. said‘ solution with ammonia‘ and. am mium ions which‘ form insolublerhydroxides. in- the pres-' monium carbonate to precipitate said impurities includ ence-o-iI ammoniumrhydroxidecfand mixtures‘ of ammonium ing» iron and. chromium; away from‘ the‘ uranium values hydroxides and ammonium carbonate, treating the;washtt 20 remaining.inwthesolution, acidifying the solution‘ contain solution with an oxidizing» agent, treating the: oxidized in‘gathe: uranium valu‘es,, addingammoniat to said acidi?ed wash solution with ammonia‘. toprecipitate‘ the- uranium. solution to. precipitateiuran'ium‘ values therefrom, ‘calcin values as‘ (NH4)2U2O7 andrthermetal. impurities: of the. ing, said precipitate to uranium oxide,,andr halogenating second‘ class as hydroxides‘ away from the.‘ metal 1‘ im said oxide: to reconstitute, said uranium halide ‘compound. purities of the ?rst class‘ remaining as solublelammonium. 25. 6:‘.The: process‘ of! recovering uranium values from complex‘ ions‘ in the solution,‘ ?ltering‘ the‘. solution 3 in deposits. formed on: the collector of a. calutron as a result order‘ to separate the‘ (NH4J2UZOT and‘ the: metal? hy of: the‘ processingiof a uranium material. therein, com droxide precipitates from the metal.impurities-ofa‘the ?rst-t prising washingrsaid‘ collector‘to produce a solution con class in the ?ltrate, dissolving‘the. (NHQZUZOFI andmetal taining: said. uranium values ‘ and copper, oxidizing; said hydroxide precipitates in acid, treating: thetacid: SO'llliiOnr 30 solution. with an agent therefor, treating said oxidized with ammonia and ammoniumwarhonate to'precipitater: solutionwith ammonia to precipitate said uranium values the metal impurities’ of the: second: class, asi hydroxides“. as (NH4)2UZOq, calcining said (NH4)2U2O7 to produce away from‘ the uranium in the solution; an‘dw‘tlrent filtera U03, convertingtsaid; U03. to UCl4, and‘ purifying said ing‘ the solution‘ in order to separate the; precipitatemf.v 35: U614. metal hydroxides from the-uranium valuesiiinether?ltrate: 7.‘ The‘ processsof‘recovering uranium values from. 2'. The process of reclaiming uranium values fromv deposits‘ formed on:the parts=of a calutronl as-aresult of deposits formed in a‘ calutron as ‘a1resultro?processing theprocessing of UCL, therein, comprising. Washing‘ said‘ UCL, therein, comprising removing‘ said-deposits‘: from parts. with an aqueous solvent'to form a solution contain; ingsaid. values and‘ impurities including iron and chro said calutron, forming an aqueous solution from‘said no deposits; treating said solution with ammonia» to tprecip‘il mium ions which‘v form insoluble‘ hydroxides. in the‘ tate‘ (NH4)2U2O7 therefrom in- purified form, calcining. presence of. ammonium carbonate and ammonium said (NH4)2U2O7 to-produce U03, chlorinating said?UOg: hydroxide', oxidizing: said solution with an agent therefor, to\ produce UCl5, converting-said UCl5 into U014, and treating‘ said‘ oxidized solution with‘ ammonia and? am purifying said UCL; to be recycled in‘ the calutron; monium; carbonate ‘to. precipitate‘ said impurities, and: 3‘. The process of recovering uranium valuesi'from ?ltering, said solution to remove said precipitaterand leavet deposits‘ formed on‘ the parts of‘al calutron disposed in said‘ uranium values in solution the source region thereof‘as a-‘ result' of the-processing 8. The process as’in claim 7‘ with the additional‘stept of‘ a‘ halide compound of uranium. therein‘, comprising of. adjusting the‘pH of‘said oxidized‘ solution. to‘a' value washing said parts‘ with water to form‘ a‘ s'olutiontrcon of‘about 2, prior to1 said- precipitation step. taining said values and metal impurities including cop‘ 9; The‘ process of recovering‘ uranium values‘ from per and nickel ions which form‘ alkaline soluble am depositst‘formed on the parts of a calutron' as a ‘result of monium complex ions, treating said‘ solution with an ox» the processing of a uranium‘ material therein, comprising idizing agent, adding ammonia to precipitate said uranium washingsaidlparts to form. an aqueous ‘solution containing values, while said impurities‘ remain in solution as am” said-values andlimpuritiesr including. iron and chromium monium complex ions, separating the‘ uranium ‘values ions. which form insoluble hydroxides in the presence of from said solution, calcining said precipitate‘totpro-duce‘ ammonium carbonate and. ammonium‘ hydroxide, oxi uranium oxide, andthalogenating'the oxide-to reconstitute‘ dizing'said solution with‘ hydrogen peroxide, treating said said uraniumhalide compound. oxidized'lsolution with ammonia and ammonium‘ carbon-r 4. The process of recovering uranium values from ate. toprecipitate saidimpurities and leave said‘ uranium deposits formed on1 the parts‘ of a. calutron‘ disposed in 60 valuesrin solution, ?ltering said solution to removetsaid the source region: thereof as a result of processing a precipitate, and adding HNO3 to said'?ltrate to produce uranium halide compound therein, comprising washing“ UO2(NO3)2-“therein. said deposits with water to form a solution containing said values and metalximpuritiesr including; ironti and' References’ Cited‘ in the ?le of‘ this patent‘ chromium. ions which are insoluble inv an ammonium 6,5 carbonate-ammonium hydroxide solution, treatingsaid UNITED STATES PATENTS‘ solution with an oxidizing agent, treating. said oxidized. 1,081,949 Du Pont ______.._ Dec. 23, 1913 solution with ammonia and ammonium carbonate, to, 1,461,067 Moser ______July 10,1923 precipitate said impurities and ‘leave said uranium values 1,463,154 Cummins ______.__ July 31, 1923 in solution, recovering said uranium values from said 70; solution, calcining the uranium. values to produce uranium OTHER REFERENCES oxide, and halogenating said‘ oxide to reconstitute said Friend: Textbook of Inorganic Chemistry, vol. VII, uranium halide compound. part III, page 294 (1926), publ. by Charles Gri?in &‘Co., 5. The process of‘ recovering uranium values from 75 . Ltd., London.