-' Sudan AcademyAcademv of Science (SAS)(sAs) Atomic Energy Researches Coordination Council Extraction and Purification of Yellow Cake A Dissertation Submitted in Partial Fulfillment of the Requirement for Diploma Degree in Nuclear Science (Chemistry) By Elshafeea Hassan YYousif ousif (B.Sc.) Supervisor: Dr. Adam Khatir Sam January 20062006 J I , •-. ~ I • )J b .. r-Q -I 11r •t ACKNO\VLEDGMENTACKNOWLEDGMENT t I would like to thank honorable sllpervisorsupervisor D.AdamD.Adarn Khatir SamSanr forfcrr his • continuouscontitiuoussupport and guidance, supportsupport. and valuable instructions from || which I have benefited muchnruch in executing this work.rvork. • And also I would like to thank everyoneevery one who aided me in this work.rvork. || •I : ~J IIIIi Elshafeea Hassan Yousif -. (High DiplomaDiplornaStudent) ~-.T-_-, t • ABSTRACTABSTRACT I 'l'ltis • This dissertationdisscrtationhashas reviewedrcvicrvedcurrentcurre nt studiesstudiesonon productionproductiorrandand T purificationpurilicationofol'yellorv yellow cakecake fromlionr llranium uraniumoresores byby both bothacidaci<J andancl alkalinealkaline • leachingleaclringprocesses.processcs. Itlt comprisescotnprisesthreethree chapters,chapters, thethe first firstone onedeal rjealwithwit| T uraniumuraniumminerals,minerals, uraniumuraniunr deposits,deposits, geologygeology ofof uraniumuraniumandand uranium uranium • 'l'hc l isotopes.isottlpes.The secondsecottdchapterclrapter coverscovers mining nriningand and millingmilling methods,methods, • uraniumuraniurnleachingleacltirtg chemistry,chernistry, precipitation,precipitation, andand purification purificationofof uraniumuraniunr t concentratecotlccntratebyby solventsolventextractionextractiotr andand possiblepossible impuritiesimpurities thatthat commonlycontmonly ,t • interferedinterl'eredwithrvith yellowyellorv cake.cake. The"t'he lastlast chapterchapter presentedpresented ongoingongoing literatureliterature I review.review. •t •I •T •T •T •t •r r• •I II II I I I~: {~ II I ·r I -'l I I \il it IIIIII i t.. 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I • Abstract .,. II t Abstract (Arabic) . III • Table of contents . IV l of IV • List of tablestablcs . VI •f, List of figuresfirgures ' " '" VI il CHAPTERCI{AI'T'BITONEONtr UraniumUraniurnand it's deposits...............................................deposits 2 I 1.1l.l Introduction......................................................Introduction... 2 ,2 rF 1.2 UraniumUraniunrminerals...............................................minerals I 2 1.3L3 Geology ofo[ UraniumUraniurn .. 4 II 1.3.1 UnconfonnityUnconformity related deposits . 4 I 1.3.2 Sandstone deposits .. 4 I I 1.3.3 Quartz pebble conglomerateconglonrerate deposits ... 5 1.3.41.3.4Vein deposits . 5 I, ~ . -- 1.3.5 Brecciasllreccias complexcornplex deposits .. 5 : 1.3.61.3.6Intrusivelntrusive deposits .. 5 • 1.3.7I.3.7PhosphoricPhosphoric deposits . 6 ..I 1.3.8t.3.8CollapseCollapsc breccias pipe deposits . 6 T 1.3.91.3.9Volcanic deposits . 6 • 1.3.10I .3.I 0 SurficialSurhcialdcposits . 6 1 T 1.3.111.3.1I MetasomatiteMetasonratitedeposits . 7I I 1.3.12| .3.12Metamorphic deposits . 7I I ; JI IVIV I J-l f 1.3.13I I ligrites deposits . If .3. 3 deposits 7 I 1.3.141.3.I 4 BlackIllackshale deposits ' . 7 * 1.15I .I 5 Other type of deposits . 7 I 1.4 Uranium isotopes . 7 t• CHAPTERCIIAP'TBITTOIVTO\V • Nuclear fuel cyclecvcle " . 12r2 I 2.1 Uranium mining . 12t2 • 2.2 Uranium millingnrillirig . 12 I 2.3 Uranium Leaching .. 12l2 • 2.3.12.3.t Acid leach chemistrychemistrv for uraniuranium urn . 13 t lea~h 15 • 2.3.2 Alkaline leach chemistrychemis[ry for uranium . 15 2.4 Purification . 16 •il 2.5 Solvent extraction . 16l6 I 2.6 Stripping .. 18l8 2.7 Precipitation . 18l8 'THTTBE CHAI1TERCHAI'TBIt THREE I • Literature Review . 22 I ConclusionConclusiort . 272'7 f. ReferencesReflerences •••••••••••••••••••••••• 11 . 282;8 I ..I I ..I FI I Ii tI •I lfI vV ! .| IIIt t 'I'AI]L[S • LISTt,ISI OFOiI TABLES T Table (1.1):(l.l): list of somesonrecommoncontnron uraniumuraniunr mineralsnrinerals . 3 • J Table (1.2): uraniumuraniunrisotopes .. 8 •; •t -­t lISI'L[ST'OFOF FlCURESFICURIS tillI FigureFigurc(1.1): Uranium decay seriessenes . 9 I FigureFigurc(1.2): UraniumUraniunrActinium decay series .. 10l0 Figure (2.1): Generalized process for uranium extraction ........ .... J199 • t I Figure (2.2): SchematicSchernaticflow sheet of purificationpurihcationby • Solvent extraction .. 20 IIIT IIII •; •I •; •T •t •T •t •t LIrl VI Ili ... ~ .J ----~~~~--~- II 11I •I •I •I ••I I •I • CHAPTER ONE •t URANlUMURANTUM AND IT'S DEPOSITS II ••I ..; I Il -.I I •I •t •I -­t •I II :'" I .JJ !:.-t, II It URANIUMUIIANIUI\lANDr\ND IT'SlT'S DEPOSITSDEI'OSIT-S It 1.1l.l Introduction:Introtluctiou: I FollowingIrollowing the developmentdeveloprnentof the nuclear industry during and I• immediately after World War Il,II, attention was focused on developing • technologies, which could be used to upgrade and purify uranium from l low-grade sources. Initially the nuclear industry had relied on high-grade • uraniumuraniunrores fromltorn the BelgiumBelgiurnCongo and Canada. One of the main I participants in this developmentdevelopnrcntwas\\,as Union of South Africa. The I• production of yellowyellorvcake was an essential step in this developmentcleveloprnentr. 1• • 1.2 UraniumUrlniurn minerals:rninerals: II An understandingurrdcrstandingof mineralizationrnineralizationconcepts ofo{'uranium uranium lead to better understandingundcrstandingof expected leaching behavior. In nature exist mainly in I! 4 the valencevalcnccstate UUa* ' (tetravalent)ltetravalent) and U<J+ U6*(hexavalent).The mineralogy ..F and geochemistrygeochernistry of the valencevalence states dissimilar.dissirnilar. Tetravalent uranium is I readily oxidized and is stable only under reducing conditions. Hexavalentllexavalent I uraniumuraniurnforms a complexcornplexuranyl ion (U0(UO22 )2+)2" that combinescornbineswith other elementselententsin oxides, silicates, sulphates, vanadates, arsenates, carbonates, I 2 phosphates and molybdatesmolybdatesz. • II UraniumUraniurnminerals may be termedtennedprimaryprirnary or secondary, depending upon ; their degree of oxidation and origin. The commoncomrnonUranium minerals are I listed in TableT'able(1.1).( l.l ). H ~I The mostnrost importantinrportantpnmaryprimary ore minerals are uraninite, an oxide, T coffinite, a silicate. Pitchblende, also a primary mineral, is a caliform h variety of uraninite. fl l.r·.1 2 l:t,r It It t The secondary minerals may be formedfornredfromfi'onr elementselenrents and ions derived • fromtiom the primaryprirnarymineralsnrinerals fromfl'orn the intrinsic hosthosl constituents, or from I t migrating ground water, underurider varying pHpll conditions. The transformationtranslbrnration fromlrom primary to secondary minerals is gradual and complex.conrplex. •II t• I • The most commonconrnronand widespread secondary minerals are carnotite, t tyuyamurite, metatyuyamurite, saleeite, sklodowskite, torbernite, • metatorbernite,metatorbemite,autunite, metaautunite,rnetaautunite, uranophate, schroeckingarite and I zeunerite. Minerals prefixed by Meta are chemically ahdaird physically the , • content~ I same but have lowerlorver water\\,ater content2. • ( l Table (1.1 l.l ): list of some commoncomnron uraniumuraniun-t mineralsnrinerals • ~lineralSlvlirrerals =r--CompositionCortrpositiorr-----~-------~~._------------ F.irn'uryPrimary I - -_.--ltu,.,t'utt)o;----- .j ------ 6----------- --~ Uraniteljranite (l)I-, ' U,)t ) 0 21 , • .--_._+ I PitchblendePitchblcnde U,O~UrOs Becqllurelite8..qr',r',*lite Tuq.tut-,o7U02.11 H2O ' • - - - . I BarreneriteB^.erterit" (U,Ca,Fe,Th,Y)(Ti,Fe)2ttj,c r, r.Fti,\)( f r,F")zC), 0 c> • DaviditeDa"i,tite UFe5Tilj025Ue.rf,rO* I Coffinite U(SiO.j)I_x(OH).hU(SiOr)r.,_(OH).* • Secondary I uranophate Ca(U0Ca(UOz)z(SiO3)2(OH)2.5H2h(Si03)2(OHh.5H2zOO • sklodowskite (H30hMg(U0(FI3O)2M g(U02)2(Si04).211 2)2(Si04).2H22OO I schfoeckingarisclqoeckingaritete NaCa3(U02)(C03)(SO.j)F.10H20NaCar(UOzXCOTXSOT)F.I 0lI2O ----- • alltuniteautunlte Ca(U02h(PO.j)2.10-121120Ca(UO:):(l'Or)2.I 0- I 2l lrO ---_. ------- I zellneritezeunente ClI(Cu(U0[JO:):(AsOr):. 2b(As04b·1I 0-12110- I 2l lrO20 ---'-- ----,-". • torbernitetortlernite ClI(U0Cu(UO:)r(POr)2.2)2(P04h. 12HI 2ll?O 2O --- I saleeitesalccite Mg(U0Mg(UOu 2b(PO.jh.101hO):(l'Or)2. I 0l lrO _._----- ----------_.-. • camotitecam()tlte KK2(UO2XVOl).1-3H202(U02)(V04).1-3H2O -8 rII tyuyamuritelvuvamul'lte Ca(U0Ca(UOz 2)(VO.j).5-8IhO)(V O.r ). 5 ll 20 •T -- -. I 3 :t {. i,lr II It 1.31.3GeologyGeolugy of0f Uranium It According tott-r thethe geologicalgcological setting,setting,