The separation of boron isotopes using ion-exchange chromatography by Gerald Thomas Paulson A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Engineering Montana State University © Copyright by Gerald Thomas Paulson (1990) Abstract: The separation of boron isotopes by ion-exchange chromatography of boric acid was investigated. Two commercially available ion-exchange resins were tested. The maximum separation produced a product containing 24.2 atom percent boron-10 using a feed stream containing 18.4% boron-10. The maximum extent of separation obtained was 0.104 as compared with a previously published maximum of 0.07. The parameters investigated included resin type, length of the resin column, column temperature, volume of boric acid fed to the column, concentration of the feed solution, and flowrate through the column. A model was developed to predict the extent of separation. The model indicates that column length is the most significant parameter. Column temperature and resin type are also significant parameters. Large scale production of enriched boron was considered. The major issue with the use of ion-exchange chromatography to produce enriched boron is the large amounts of water produced in the product. THE SEPARATION OF BORON ISOTOPES USING ION-EXCHANGE CHROMATOGRAPHY by G erald Thomas Paulson A th e s is subm itted in p a r t i a l f u l f i l l m e n t o f th e requirem ents f o r th e degree of Doctor o f Philosophy in Chemical Engineering MONTANA STATE UNIVERSITY Bozeman, Montana August 1990 ii APPROVAL o f a th e s is subm itted by G erald Thomas Paul son This th e s is has been read by each member o f th e t h e s is committee and has been found to be s a t i s f a c t o r y re g a rd in g c o n te n t, English usage, fo r m a t, c ita tio n s , b i b l i o g r a p h i c s t y l e , and c o n s is te n c y , and is ready f o r submission to the C o lle g e o f Graduate S tu d ie s . Date C ha irp ers o n , Graduate Committee Approved f o r th e M ajor Department 7 C - Date Approved f o r the C o lle g e o f Graduate S tu d ie s Date ri. Hdad, M ajor Department Graduate Dean iii STATEMENT OF PERMISSION TO USE In p r e s e n tin g req u ire m e n ts fo r th is a d o c to r a l agree th a t ru le s o f th e L i b r a r y . a llo w a b le th e o n ly p r e s c r ib e d or L ib ra ry degree s h a ll p a rtia l fu lfillm e n t of th is In te rn a tio n a l, 48106, whom copies th e s is 300 Requests f o r e x te n s iv e copying should North be r e fe rr e d to U n iv e rs ity Zeeb Road, Ann A rb o r, Michigan I have granted "th e e x c lu s iv e r i g h t t o reproduce and of th e d i s s e r t a t i o n in and from m i c r o f il m and th e 9 H I a v a i l a b l e to borrowers under r i g h t t o reproduce and d i s t r i b u t e by a b s t r a c t in any fo r m a t ." Date________ ? the a t Montana S t a t e U n i v e r s i t y , make i t in th e U.S. C opyright Law. S ig n a tu r e of I f u r t h e r agree t h a t copying o f t h i s t h e s is is M i c r o f ilm s d is trib u te in f o r s c h o l a r l y purposes, c o n s is te n t w ith " f a i r use" as re p r o d u c tio n to th e s is ________________ iv TABLE OF CONTENTS Page LIST OF TA B L E S ........................................................................................................... vi LIST OF FIGURES................................................................................................................ v i i i ABSTRACT......................................................................................................................... xi INTRODUCTION ............................................................................................................... I Enriched B o ro n -10 ................................................................................................. Chromatography ...................................................................................................... Scope And O b j e c t i v e s ........................................................................................ 2 6 12 A REVIEW OF PUBLISHED WORK.............................................................................. 15 The Enrichment Phenomena ............................................................................... Past Enrichment E xperim en ts.......................................................................... Theory Of General Chromatography ............................................................ The Mathem atical Model ................................... A ds orption Isotherms ............................................................................... K i n e t i c s ........................................................................................................... P l a t e T h e o r y ................................................................................................. S t a t i s t i c a l Approach ............................................................................... T h e o rie s A p p lie d To Boron............................................................................... 15 17 22 22 25 26 27 27 29 AN ANALYSIS OF THE PUBLISHEDWORK................................................................... 32 E f f e c t Of Column L e ngth.................................................................................. E f f e c t Of Resin T y p e ....................................................................................... E f f e c t Of Boron C o n c e n tr a tio n ..................................................................... E f f e c t Of F l o w r a t e ............................................................................................ A p p l i c a t io n Of S t a t i s t i c a l Th e o ry ................................................................ S e p a ra tio n Index For BoronIs o to p e s ........................................................... 32 34 34 37 37 47 NEW EXPERIMENTS........................................................................................................... 62 Equipment.................................................................................................................... S o lu tio n S u p p ly ....................................................... I n j e c t i o n System ........................................................................................ C o l u m n ............................................................................................................... D e t e c t o r ........................................................................................................... 62 62 67 67 70 V TABLE OF CONTENTS (C o ntinued ) Page D e te c t o r E l e c t r o n i c s ................................. R e c o r d e r ........................... A d d i t i o n a l M e t h o d s ................................................... .... . '............................ D a t a ............................................................................................................................. E f f e c t o f S in g le Param eters. . ................................................................. E f f e c t Of L e n g t h ..................... E f f e c t Of Resin T y p e ............................................................................. E f f e c t Of Te m p era tu re ............................................................................. E f f e c t Of Feed C o n c e n t r a t i o n ........................................................... E f f e c t Of Feed Volume.............................................................................. E f f e c t Of F l o w r a t e .................................................................................. E f f e c t Of I n i t i a l E n r i c h m e n t .......................... E f f e c t Of I n t e r a c t i o n s . ...................................................................... E f f e c t Of Feed Q u a n t i t y .......................................................................... E f f e c t Of Cycle Time ............................................................................... C o n d u c tiv ity R e s u lts ........................................................................................ 70 73 77 81 81 83 83 83 87 87 87 90 90 SYSTEM MODELING........................................................................................................... 96 71 71 71 General Model Of The New Experiments . . . ...................................... 96 Model Based On Experimental Parameters ............................................... 98 Comparison Of The Model To T h e o ry .................................... 102 S cale Up Of A S in g le Stage System.................................................................. 103 S cale Up Of A M u l t i - S t a g e S y s t e m .................................................................. 107 CONCLUSIONS................................................................................................................... 117 REFERENCES.......................................................................................................................... 120 APPENDICES............................................................................................ 124 APPENDIX A ..........................................................................................................................125 APPENDIX B 143 vi LIST OF TABLES T a b le Page 1 E x p e r im e n ta lly Determined S e p a ra tio n Factors ........................ 17 2 Summary Of Published Conclusions ................................................... 21 3 Modeling R e s u lts For Boron E nrichm e nt.................................................. 31 4 Past E x p e r i m e n t s ..............................................................................................63 5 Producers Of S y n t h e t ic Ion-Exchange Resins 6 T a b u la t io n Of E xperim en ts..............................................................................72 7 Comparison Of Economics For A S in g le Column System . . . 8 Experiment A ....................................................................................................... 126 9 Experiment B ....................................................................................................... 127 ..................................... 69 108 10 Experiment C ..................................................................................... 128 11 Experiment D .......................................................................................................129 12 Experiment F ....................................... 130 13 Experiment G ..................................... .................................... ' . . . . . 131 14 Experiment H .......................................................................................................132 15 Experiment I 16 Experiment J .......................................................................................................134 17 Experiment K .......................................................................................................135 18 Experiment L .................................................................................................... 1 3 6 19 Experiment M ..................................................................................... 137 20 Experiment N ...................................... 138 ....................................................................................................... 133 LIST OF TABLES (C o n tin u ed ) Tabl e Page 21 Experiment 0 ....................................................................................................... 139 22 Experiment S .................................. 140 23 Experiment T .................................. 141 24 Experiment U ....................................................................................................... 142 25 Data From K a k ih a n a 's Experim ent. ................................................... 144 v iii LIST OF FIGURES F ig u re Rage 1 Types o f Chromatography.......................................................................... 8 2 P roduction Rate as a Function o f Throughput............................ 11 3 Dimensions o f Columns in U s e ............................................................ 13 4 Time Line o f Boron E x p e r i m e n t s ........................................................ 19 5 R e s u lts Found in th e L i t e r a t u r e ........................................................ 20 6 Development o f th e D i f f e r e n t i a l Equation ................................. 23 7 Random Motion o f a M o le c u le ................................................................. 28 8 T h e o rie s A p p lie d to Boron...................................................................... 30 9 E ffe c t o f Column Length........................................................................... 33 10 E ffe c t o f Resin T y p e ................................................................................ 35 11 E ffe c t o f Boron C o n c e n tr a tio n ....................... 36 12 E ffe c t o f F l o w r a t e .................................................................................... 38 13 Enrichment R e s u lts from Kakihana ................................................... 42 14 C o n c e n tra tio n R e sults from K ak iha na ............................................... 43 15 Is o to p e C o n c e n tra tio n s from Kakihana .......................................... 44 16 V e l o c i t y D i s t r i b u t i o n s from Kakihana .......................................... 46 17 E ffe c t o f C o n c e n tra tio n on S e p a ra tio n Fa cto r ........................ 50 18 E ffe c t o f C o n c e n tra tio n on E xten t o f S e p a r a t io n ................... 51 19 E ffe c t o f C o n c e n tra tio n on Change in Enrichm ent................... 52 20 E ffe c t o f F lo w ra te on S e p a ra tio n F a c t o r ...................................... 53 ix LIST OF FIGURES (Continued) F ig u re Page 21 E ffe c t o f F lo w ra te on E xtent o f S ep a ra tio n ............................ 54 22 E ffe c t o f F lo w ra te on Change in Enrichment . . ................... 56 23 E f f e c t o f Feed Q u a n tity on S e p a ra tio n Fa cto r ........................ 57 24 E ffe c t o f Feed Q u a n tity on E xten t o f S e p a r a tio n . 58 25 E ffe c t o f Feed Q u a n tity on Change in Enrichm ent................... 26 E f f e c t o f F lo w ra te on Enrichment F l u x ................................... 27 Equipment Flowpath .................................................................................... 28 B o ric Acid S o l u b i l i t y ........................................................................ 66 29 S e p a ra tio n F a c to r f o r th e New Experim en ts.......................... 74 30 E x te n t o f S e p a ra tio n f o r th e New E x p e r i m e n t s ........................ 75 31 Change in Enrichment f o r th e New E x p e r i m e n t s ........................ 76 32 E ffe c t o f L e n g t h ......................................................................................... 78 33 E x te n t o f S e p a ra tio n as a Function o f L e n g t h ........................ 79 34 In c re a s e in Product Enrichment as a Function o f 35 . . . . 59 61 64 Length . 80 E x te n t o f S e p a ra tio n as a Function o f R e s in ............................ 82 36 E ffe c t o f Feed C o n c e n t r a t i o n ............................................................. 84 37 E ffe c t o f Feed Volume................................................... 85 38 E ffe c t o f F l o w r a t e .................................................................................... 86 39 E ffe c t of In itia l 88 40 In c re a s e in Product Enrichment as a Function o f Feed Q u a n t i t y ................................................................................................ 41 Enrichment ............................................................. Product Enrichment Slope as a Function o f FeedQ u a n t it y . 89 91 X LIST OF FIGURES (Continued) F ig u re Rage 42 S e p a ra tio n F a c to r as a Function o f Cycle Tim e................. 43 E x te n t o f S e p a ra tio n as a Function o f Cycle Time . . . 44 C o n d u c tiv ity R e s u lts 45 B-IO Y i e l d as a Function o f T o ta l Boron Y i e l d ................. 97 46 Y i e l d Data In c lu d in g a L in e a r M odel........................................ 99 47 R e s u lts o f th e L in e a r Model D e a lin g w ith P aram eters. . . 101 48 E xten t o f S e p a ra tio n as a Function o f Time Adsorbed. . . 104 49 S cale Up o f a C o lu m n ............................................................................105 50 Enrichment as a Function o f Y i e l d per H o u r .........................106 51 S i m p l i f i e d Example o f a M u l t i - S t a g e Model............................. 109 52 R e s u lt o f A i d a 's E xperim en t.............................................................. I l l 53 Approach to Steady S ta te w ith th e M u l t i - S t a g e Model. 54 Column Diam eters f o r a M u l t i - S t a g e System..............................113 55 Number o f Columns f o r a M u l t i - S t a g e System ............................ 56 Enrichment versus Product C o n c e n tr a tio n .................................. 116 92 . 93 ............................................................................... 95 . . 112 115 xi ABSTRACT The s e p a r a tio n o f boron iso topes by ion-exchange chromatography o f b o r ic a c id was i n v e s t i g a t e d . Two com m ercially a v a i l a b l e ion-exchange r e s in s were t e s t e d . The maximum s e p a ra tio n produced a product c o n ta in in g 2 4 .2 atom p e rce n t boron-10 using a feed stream c o n ta in in g 18.4% b o ro n -1 0 . The maximum e x t e n t o f s e p a ra tio n o b ta in e d was 0 .1 0 4 as compared w ith a p r e v io u s ly p ublishe d maximum o f 0 . 0 7 . The param eters in v e s t i g a t e d inclu d e d r e s in ty p e , le n g th o f the re s in column, column te m p e ra tu re , volume o f b o r ic a c id fed to the column, c o n c e n tr a tio n o f th e feed s o l u t i o n , and f l o w r a t e through th e column. A model was developed to p r e d i c t th e e x t e n t o f s e p a r a tio n . The model in d i c a t e s t h a t column le n g th is th e most s i g n i f i c a n t p a ram e te r. Column te m p e ratu re and r e s i n type a re a ls o s i g n i f i c a n t param e te rs. Large s c a le p ro d u c tio n o f enric he d boron was c o n s id e re d . The major issue w ith th e use o f ion-exchange chromatography t o produce enriched boron i s th e l a r g e amounts o f w a te r produced in th e p ro d u c t. INTRODUCTION One of th e h a n d lin g , and n e u tro n s . balance than b a s ic use For can th e a be requirem ents of fis s io n a b le system ra te , th e p ro d u c tio n ra te p ro d u c tio n and q u a n t i t y o f f i s s i l e m a t e r ia l ra te on dependent S p e c ific a neutron I f the I f the the system i s s u p e r c r i t i c a l . p r e s e n t. The loss r a t e f o r neutrons o f th e r a t e o f neutrons " le a k in g " from th e system and of dependent of r a t e f o r neutrons is s t r o n g ly dependent upon th e type fu n c t i o n th e c o n tro l th e system is c r i t i c a l . th e loss r a t e , The a th e system is d e fin e d as s u b c r i t i c a l . r a t e equals th e loss r a t e , is is I f th e neutron p ro d u c tio n r a t e is le s s p ro d u c tio n exceeds m a te r ia l c o n ta in in g f i s s i o n a b l e m a t e r i a l c a lc u la te d .^ lo s s ass o c iate d w ith th e p ro d u c tio n , neutron system on th e a d d itiv e s a b s o r p tio n . geometry chemical such and Neutron lea k ag e d e n s ity . c o n s t it u e n t s is s tr o n g ly The a b s o rp tio n r a t e is p re se n t in th e system. as boron in s o l i d or s o l u t i o n form are used to r a i s e th e a b s o rp tio n r a t e s i g n i f i c a n t l y . The s t a b le 11 symbol f o r iso tope s (boron-11 elem ental boron w ith or mass ^ B ). The a p p ro x im a te ly 20% boron-10 d is trib u tio n is known d e p o s i t . 2 ,3 numbers to and v ary is of B. Boron 10 n a tu r a l (bo ro n -10 is o to p ic 80% b oron-1 1 . based on c o n s is ts of two ^B) and abundance is or The n a tu r a l th e lo c a tio n is o to p ic of th e 2 The boron-10 a b s o rp tio n process occurs by th e r e a c t i o n : 1Sb + O n - 3 L1 + 2He (I) The r e a c t i o n is e x o e rg ic r e le a s i n g 2 .7 9 MeV.4 lith iu m The (g L i) ra te and helium at which ( 4He) Both r e a c t i o n products, a re s t a b le n o n r a d io a c tiv e is o to p e s . a b so rp tio n occurs is a strong fu n c tio n o f th e n e u tr o n 's energy. The n u c le a r occurrence n u c le a r fo r a c n r). neutron The In energy cross s e c tio n s e c tio n re a c tio n re a c tio n . (I X as cross s e c tio n B a r n .B of an an used determ ines f o r cross a d s o rp tio n cross in c re a s e s . E ffe c tiv e neutron barns energy p ro b a b ility o f th e s e c tio n s i s s e c tio n s ra te o f a the barn decrease absorbers have a 1,0 0 0 barns in th e energy range below one barn w ith a neutron energy o f IO5 e l e c t r o n energy o f 0 .0 2 5 e le c t r o n v o l t s , 4 ,0 0 0 At la rg e ly o f th e g e n e r a l, o f at le a s t At and u n it e l e c t r o n v o l t and about I v o lts . i s a measure w h ile of boron-10 has a cross boron-11 has a cross s e c tio n o f 0 .0 5 10B e le c t r o n v o l t s , boron-10 has a cross s e c tio n o f 2 b a r n s . 4 Enriched Boron-10 Research U n ite d th e S ta te s Manhattan in th e began area in P ro je c t. of boron iso tope s e p a r a tio n w i t h i n the 1943 a t Columbia U n i v e r s i t y as a p o r tio n o f Seven s e p a r a tio n schemes were c onsidered. 3 One method methods was were firs t th e based Standard la rg e and Hooker p la n t P ro je c t 460 kilogram s p la te s . p la n t has of BF3 . A ll o th e r o f v a rio u s boron compounds. The c o r ro s io n Eagle The i n i t i a l a at p l a n t was shutdown in l a r g e r p l a n t was c o n s tru c te d by Model C i t y , c o n sis te d and in of O p e ra tin g R ic her o p erated In d ia n a designed and operated the New York. The p la n t per y e a r o f boron-10 a t an enrichm ent o f 92% th e o re tic a l by 1953 Company fa c ility decom position, of 1 9 4 4 .6 In The purchased d iffu s io n f o r s e p a r a tin g boron iso to p e s as a p a r t o f in E le c tro c h e m ic a l boron-10.^ 580 Company d is m a n tle d . produced gaseous on d i s t i l l a t i o n O il s c a le Manhattan 1946 on o f (CH3 ) 2OoBF3 was f i n a l l y s e le c t e d . d is tilla tio n The based le a k a g e . e ig h t columns r e s u l t i n g in problems The in c lu d e d Model thermal C i t y p la n t was I n d u s t r i e s and moved t o Quapaw, OK. Oklahoma sin ce The 1973 and c u r r e n t l y produces 1,000 kilogram s per y e a r . A nother is o to p ic exchange re a c tio n (C2H5) 2OoBF3 using was used in England t o produce 2 kilogram s o f boron-10 p e r y e a r . 7 The used enrichm ent com m ercially percent b oron-1 0 ) p e rc e n t b o r o n -1 0 ). BF3 o n ly is of by boron by th e d is tilla tio n o f BF3 has been th e S o v ie t Union ( 0 . 5 kilogram s p e r y e a r o f 83 and 1 .0 0 7 5 . 7 The England ( 2 6 .5 s e p a r a tio n A s e p a r a tio n kilogram s per year o f 95 f a c t o r f o r th e d i s t i l l a t i o n fa c to r is a of dim ensionless 4 index used to compare s e p a r a tio n s . A v a lu e o f one i n d i c a t e s no s e p a r a t io n . Recent boron. In 1974, 14 p e rc e n t CO2 la s e r of work has in a s o lid from dependence on of BF3 . 10 of th e S c ie n tific ra tio of L a b o ra to ry 10BZ11B p r o c e s s .8 fo r by e n r ic h in g re p o rte d a th e use o f a In 1975, th e U n i v e r s i t y th e s e p a r a tio n o f boron iso tope s by d i r e c t The s e p a r a tio n i s based on th e th e exchange r e a c t i o n between gaseous BF3 and s u lfo x id e ). S e p a ra tio n fa c to rs ranged In 1989, Montana S ta te U n i v e r s i t y re p o rte d the boron iso topes S e p a ra tio n novel methods pumping.9 (d im e th y l 1 .0 2 0 and 1 .0 2 8 . s e p a r a tio n Alamos in p a ra m e tric BFgoDMSO th r e e photochem istry r e p o r te d therm al therm al th e Los enrichm ent Kentucky mode id e n tifie d fa c to rs by of gas phase membrane permeation o f 1.0 2 0 and 1.0 9 0 were determined f o r phenyl e t h e r m o d ifie d p o l y v i n y l idene f l u o r i d e membranes. Enriched re q u ire lim it 1943 boron-10 th e fo r th e ra te th e n u c le a r boron. m a te ria l fo r enrichm ent common b o r ic used in c e r t a i n n u c le a r a p p l ic a t i o n s t h a t o f neutron a b s o rp tio n to exceed a maximum physical q u a n tity e n ric h e d an is of weapons n a tu r a l program boron t h a t can be added. has re q u ire d Since th e p roduction o f The c u r r e n t boron-10 p la n t was designed to p rovide th e weapons program. of 75% a c id is The p r i c e per gram o f boron-10 a t boron-10 i s $ 5 . 0 0 . 11 $ 0 .1 7 per g ra m .12 The c ost o f boron-10 in The c o s t d i f f e r e n c e o f 2800% r e f l e c t s th e d i f f i c u l t y a s s o c ia te d w ith the s e p a r a t io n . 5 The in t r o d u c t i o n g e n e ra te two m ajor p r e s s u r i z e d -w a te r emergency w a te r of new enric he d uses. re a c to rs . boron The A ll at firs t such a reduced d e a ls r e a c to r s cost would w ith commercial a re equipped w ith core c o o lin g systems t h a t uses s o lu b le boron in w a te r . is heated c o n c e n tr a tio n to m a in ta in re q u ire d . The th e boron speed at s o lu b ility which above in je c tio n The the systems in tr o d u c e a p p r e c ia b le q u a n t i t i e s o f boron-10 i n t o th e core is u s u a lly slow is and a re s u lt of lim ite d s o lu b ility , system c a p a c ity and pumping ra te s . The E l e c t r i c Power Research I n s t i t u t e has s tu d ie d th e use of e n ric h e d use o f e n ric h e d boron f o r i t s r e a c t o r s and decided a g a in s t c o n v e rtin g boron in r e a c t o r s . 13 V i r g i n i a Power s tu d ie d the due t o th e c u r r e n t high c ost o f th e e n ric h e d b o r o n .14 A in second n u c le a r spent fu el re a c to r During th e m a in ta in th e m ajor r e p ro c e s s in g . fu e l in d is s o lu tio n a s u b c ritic a l re a g e n t a c id . use o f e n ric h e d boron a t a reduced c ost would be makeup N a tu ra lly The Department o f Energy d is s o lv e s s everal of processes fu e l, system. s o lu b le th a t use n a tu r a l boron. boron-10 i s necessary to The boron is added to th e a cid during process in th e form o f n a t u r a l l y o c c u rrin g b o r ic o c c u rrin g boron is ty p ic a lly 1 9 .6 atom p e rcent boron-10 and 8 0 . 4 atom p e rce n t b o r o n -I I . A fte r form th e complete d i s s o l u t i o n o f th e f u e l , th e uranium is in th e o f uranyl n i t r a t e s o lu t io n and i s c r i t i c a l l y uranium c o n c e n tr a tio n w ith o u t s a fe because o f the any neutron poison. In th e f o llo w in g 6 e x tra c tio n fis s io n in a flu id iz e d in liq u id p a rtic le s . components. ra d io a c tiv e The th e aqueous s o l u t i o n w ith th e This waste is e v e n t u a l l y The c a l c i n i n g process evaporates wastes w ith in a heated bed o f c a l c i n e generated is s to re d in s t a in l e s s bins c o n ta in ed in c o n cre te v a u l t s . A r e d u c t io n r e d u c t io n in e n ric h e d le v e l remains c a l c i n i n g process. s o lid ifie s s teel boron products and o th e r fu e l processed and system, in th e re ag e n ts boron-10 to tal used boron c o n c e n tr a tio n would r e s u l t in a and t o t a l waste processed. Using 100% waste p roduction would decrease th e volume o f high r a d i o a c t i v e waste produced by 15%. Chromatography In 1906 d e a lin g w ith coined He a th e th e s c ie n tis t, s e p a r a tio n term of M. p la n t S. T s w e tt, p u b lish e d a paper pigments. In th e paper he "chromatographic method" to d e s c rib e h is te c h n iq u e . s e le c t e d th e name by combining two Greek words, chroma ( c o l o r ) and grapheme (w rite ) bands in could lik e w is e p h y s ic a l are Russian to a column. be th e development o f i n d i v i d u a l c olored However, he a ls o noted t h a t c o l o r l e s s substances s e p a ra te d . Chromatography i s b est d e fin e d as a method o f s e p a ra tio n in which th e components t o be separated d is trib u te d s e p a r a tio n in d ic a te occurs between a s ta tio n a ry and a m obile phase. The as a r e s u l t o f re p e a te d s o r p t io n /d e s o r p t io n s te p s. 7 Chromatography can c l a s s i f i c a t i o n s . 15 become The two L iq u id m ajor s ta tio n a ry liq u id -s o lid , be c la s se s phase is g a s -liq u id , d iv id e d in to chromatography based gas v a rie ty of chromatography on th e mobile phase o f the system. e ith e r and and a a l i q u i d or s o l i d . g a s -s o lid L iq u id -liq u id , chromatography become the f o u r subclasses o f chromatography. Chromatography used. Column can be c l a s s i f i e d based on th e p h y s ic a l equipment chromatography is based on flo w through a packed column. Paper chromatography i s based on the s e l e c t i v e m ig r a tio n o f compounds across based th e two on planes flo w of subclasses a plane paper. T h i n - l a y e r chromatography is o f a m obile phase through a small gap c re a te d by s ta tio n a ry can of lik e w is e m a te ria l. be Four d e fin e d column based on chromatography column packing. Ion-exchange chromatography s u b s t i t u t e s an ion-exchange r e s in f o r the adso rb e n t. Gel pa ck in g . is chromatography uses a c o n t r o l l e d p o r o s i t y gel as a A f f i n i t y chromatography is based on a unique packing which capable of s e p a r a tin g c e rta in p r o te in s based on p r o t e i n - l i g a n d in te ra c tio n s . Chromatography te c hniques are f u n c tio n change firs t. In column. is shown at e lu tio n Each a ls o c l a s s i f i e d based on te c h n iq u e . in Fig u re I . th e in le t. a n a ly s is component moves The th r e e F ro n ta l a n a ly s is in v o lv e s a step The l e a s t adsorbed component e x i t s a pulse through of th e a m ix tu re i s added to a column w ith th e l e a s t A+B A+B A A - F ro n ta l a n a lysis E lu tio n a n a lysis C D is p la c e m e n t d e v e lo p m e n t ICPP-A-16581 (7 -9 0 ) Figure I . Types o f Chromatography 9 adsorbed p ulse component of a p o w e r f u l ly m ix tu r e e x itin g m ix tu re adsorbed through to firs t. Displacement development adds a a column fo llo w e d by th e a d d i t i o n o f a more component. The fin a l component "pushes" th e th e column w ith th e l e a s t s tr o n g ly adsorbed compound e x itin g f i r s t . A fin a l c la s s ific a tio n A n a ly tic a l chromatography of components sample c o n c e n t r a t io n . In v a rio u s P re p a ra tiv e chromatography id e n tific a tio n f o r a q u a n t i t a t i v e assessment o f r e l a t i v e a n a ly tic a l of by chromatography is based on purpose. is used f o r th e q u a l i t a t i v e and re s o lu tio n m a te ria l fo r chromatography, compounds a re th e speed m ajor and the re q u ire m e n ts . i s used t o produce a q u a n t i t y o f p u r i f i e d chromatographic means. In p r e p a r a t i v e chromatography through put and p u r i t y a re the m ajor re q u ire m e n ts . P re p a ra tiv e in d u s tr y have w ith in th e re c e n tly chromatography is chromatography to and o p e r a t in g l a s t th r e e decades. p ublishe d a s y s te m s .16 maximize complete The throughput c o s ts . has been i n t e g r a t e d i n t o the chemical goal P. E. Baker and G. Gauetos re v ie w of pro d u c tio n s ca le o f p r e p a r a t i v e chromatography a t a d e fin e d p u r i t y and m inim ize c a p i t a l D i f f e r e n t s c a le -u p approaches have produced a v a rie ty of p h y s ic a l cost. A ll systems can be c l a s s i f i e d as e i t h e r a batch o r continuous o p e r a t io n . c la s s ifie d The as systems w ith th e i n t e n t o f m in im iz in g c a p i t a l concepts f o r s e p a r a tio n using chromatography can be c o -c u rre n t, c o u n te r-c u rren t, or c ro ss -c u rre n t flo w 10 systems. Ten i n d u s t r i a l Once a concept is m axim izing throughput p ro d u c tio n ra te p u rity per amount of found in th e at an term column were o p tim iz a tio n Guiochon of and focuses C o l i n 17 on d e f in e a compound produced a t a given A d d itio n a lly , throughput i s d e fin e d as th e per u n it tim e (averaged over a number o f i l l u s t r a t e s th e r e l a t i o n s h i p between production The th r e e amount cases process g reater s e p a r a tin g seven amount of shown. feed i n j e c t e d per pulse is The c u t p o i n t i s d e fin e d by a The maximum production r a t e is t y p i c a l l y i n te r m e d ia te of use, th ro u g h p u t. Jones18 has s c a le l i q u i d chromatography. analyzed the He introduces "process s c a le p r e p a r a t i v e " column to i d e n t i f y columns w ith d ia m e te rs w ith 2 fo r p u rity . p u r i t y r e q u ire m e n t. o p tim iz a tio n th e th e th ro u g h p u t. in c re a se d minimum and in je c te d F ig u re and chosen tim e . feed c y c le s ). ra te as u n it types o f columns are in use. than His s p e c i f i c e x p e rim e n ta tio n d e a l t p- n i t r o - a n i l ines in a 15 cm d ia m e te r using a s i l i c a packing. S ix te e n v a r i a b l e s were considered and determ ined p a rtic le pressure s iz e , across m-, cm. and were o -, 10 to column be s t a t is t ic a lly s ig n ific a n t. le n g t h , packing th e column, s o lv e n t ty p e , method, flo w ra te , The seven d iffe re n tia l and th e use o f a precolumn. Hupe and Lauer1^ chromatography. s e p a r a tio n should lik e w is e s tu d ie d o p tim iz a tio n o f p re p a ra tiv e They concluded t h a t th e parameters f o r a p r e p a r a t i v e be s e le c te d based on s e l e c t i v i t y , column l e n g th , Throughput ( l/ h r ) Figure 2. Production Rate as a Function o f Throughput 12 column d ia m e te r, p a rtic le s iz e , flo w ra te , in je c tio n system, and product d i l u t i o n . The in a two o p tim iz a tio n s lig h tly r e p o r ts address p r e p a r a t i v e chromatography d iffe re n t manner. However, both s tu d ie s document r ig o r o u s methods f o r o p t i m i z a t i o n . The re s u lt d e fin itio n la rg e s t column of column is 12 o f a s p e c i f i c p r e p a r a t i v e chromatography study is the a s e p a r a tio n d ia m e te r in m e te rs . column of s p e c ific dim ensions. c u r r e n t use is 4 .7 m e te rs . Figure 3 provides a The The lon g e st s c a t t e r p l o t o f the dimensions o f p r e p a r a t i v e chromatography columns in u s e . 16 Scope And O b je c tiv e s The scope e n ric h e d of boron ion-exchange th is can work be is to determ ine i f l a r g e q u a n t i t i e s o f produced chromatography. e cono m ically using e lu tio n The s p e c i f i c o b j e c t iv e s c o n s is t o f the fo llo w in g : 1. Demonstrate th e enrichment of boron using, ion-exchange chromatography. 2. C o lle c t and compare th e v a rio u s th e o rie s enrichm ent using ion-exchange chromatography. fo r iso tope COLUMN DIAMETER ( COLUMN LENGTH (m ) Figure 3. Dimensions o f Columns in Use 14 3. Develop a s im u la tio n model f o r boron e nrichm ent. 4. Perform fo r a p a r a m e tr ic study f o r both th e q u a l i t y and q u a n t i t y enric h m e n t. c o n c e n tr a tio n The and v a ria b le s te m p e ra tu re , s tu d ie d w i l l feed in c lu d e feed q u a n tity , flo w ra te , r e s i n type and column le n g t h . 5. Compare th e s im u la tio n model t o th e v a rio u s t h e o r i e s . 6. Determine th e s c a le -u p economics o f p ro d u c tio n based on th e s im u la tio n model. 15 A REVIEW OF PUBLISHED WORK The scope fo r th is w ith an chromatography te c h n iq u e fo r scope based is in s ig h t in to encouraging Reactors b o r ic a th e work at a c id th e was exchange re s in . re s in . The With a is lim ite d to ion-exchange packing using p r e p a r a t i v e purpose. on p ublishe d s e p a r a tio n re s u lts of th e liq u id th e column e lu tio n The r e s t r i c t i v e n a tu re o f the which boron p ro v id es is o to p e s . s u b s t a n t ia l The most was re p o rte d by th e Research L a b o ra to ry f o r N uclear Tokyo I n s t i t u t e o f T e ch n o lo g y .20 fe d in to Both a column A p ulse o f common packed w ith w eakly basic anion boron-10 and boron-11 were adsorbed onto th e adsorbed m ig r a t io n work boron le n g th was e lu t e d by d isplacem ent w ith w a te r . o f 256 m e te rs , th e enrichm ent changed from 19.8% t o 91.0% b o ron-1 0 . The Enrichment Phenomena To needs understand to be th e enrichment dis cus s ed. phenomena, th e c h e m is try o f boron When b o r ic a c id is d is s o lv e d in w ater th e r e i s a s l i g h t d i s s o l u t i o n as shown in e quation 2. B(OH)3 + H2O - It (2 ) should be expected t h a t t h i s d i s s o c i a t i o n would occur f o r both th e boron-10 3 B(0H)4 + H+ and boron-11 is o to p e s . What may not seem obvious is t h a t an 16 isotope exchange e q u ilib riu m is maintained in the form o f equation 3. 10B(OH)3 + 11B(OH)^ = 11B(OH)3 + 10B(OH)^ Kakihana^1 given the in calculated equation e q u ilib riu m from 1.0206 constant remains s o lu tio n at the 3 e q u ilib riu m constant to be 1.0186 at 300°K. constant as a 273°K to (3) of the reaction H e ^ l a t e r developed fun ctio n o f temperature th a t varies 1.0177 at 333°K. Because the e q u ilib riu m o f equation 3 is greater than u n ity , boron-10 p r e f e r e n t ia lly as an is anion. in p r e f e r e n t ia lly represented contact adsorb by One should expect th a t when a boric acid with an anion exchange re s in boron-10 would onto the re s in . Such adsorption can be the reaction shown in equation 4 w ith R- representing a re s in . R-11B(OH)4 + H310BO3 -* R-10B(OH)4 + H3l l BO3 The s in g le stage separation fa c to r , a, (4) f o r boron isotopes in contact w ith a resin is given in equation 5, a = where in the [- ] (5 ) and re s in experimenters [ ] denote phases and have the external determined concentration s o lu tio n , of each re s p e c tiv e ly . species Three separation fa c to rs f o r s ix resins and 17 are lis te d in T a b le maximum t h e o r e t i c a l TABLE I . I. In a d d itio n , C h ris to p h 25 c a lc u la te d a s e p a r a tio n f a c t o r o f 1 .0 3 2 . E x p e r im e n ta lly Determined S e p a ra tio n Factors Resin C ondition Reference OC A m b e r lite C G -4 0 0-I 0.03M 1.010 Yoneda22 Dowex l - X - 8 0. IM 1.0272 U r g e ! ! 2^ Dowex l - X - 8 0.03M 1.0262 U r g e l l 24 Dowex l - X - 8 0.015M 1.0269 U r g e l l 24 Dowex 2 -X -8 0. IM 1.0285 U r g e l l 24 Dowex 2 -X -8 0.5M 1.0354 Urgel D ia io n WA-21 0.0107M 1.015 Kakihana21 D ia io n WA-21 0.102M 1.013 Kakihana21 D ia io n WA-21 0.518M 1.011 Kakihana21 D ia io n WA-IO 0 . OlOlM 1.016 Kakihana21 D ia io n WA-IO 0.0991M 1.012 Kakihana21 D ia io n WA-IO 0.501M 1.007 Kakihana21 D ia io n PA-310 0.0104M 1.0 1 9 Kakihana21 D ia io n PA-310 0.109M 1.013 Kakihana21 D ia io n PA-310 0.501M 1.007 Kakihana21 1 24 Past Enrichment Experiments With occurs, th e understand ing th a t p re fe re n tia l a d s o rp tio n o f boron-10 two d i f f e r e n t experim ents using an ion-exchange column can be 18 used to study a n a ly s is . th e In e ffe c t. They are e l u t i o n a n a ly s is and f r o n t a l e l u t i o n a n a ly s is experim ents boron is in tro d u c e d as a s h o rt pulse and is d is p la c e d through th e column. boron is in tro d u c e d saturated a step c o n tin u o u s ly fo llo w e d by e l u t i o n . fu n c t i o n change to u n til th e In f r o n t a l column a n a ly s is is com p lete ly F r o n ta l a n a ly s is can be considered as th e in p u t o f th e column. Experim enters have a ls o used two b a s ic types o f r e s i n s : strong base r e s i n and weak base re s in . th e boron can be d is p la c e d through With th e column displa c em e n t or weak base re s in s o l e l y w ith w a t e r . A strong base r e s i n r e q u ir e s o f th e b o r ic a cid w ith an o th e r a c id such as h y d r o c h lo r ic a c e tic a c id . documents a th e F ig u re 4 prov ides a tim e l i n e o f th e l i t e r a t u r e t h a t fo u r types of boron enrichment experim ents using ion-exchange r e s i n s . F ig u re 5 is a s c a tte r p lo t o f a ll enrichm ent was enrichm ent of c a lc u la te d a given from product re p o rte d d a t a . th e d iffe re n c e fra c tio n (E f) An in c re a se in of th e h ig h e s t and th e in itia l enrichm ent (E0 ) and p l o t t e d versus th e le n g th o f th e r e s i n column. An There ite m iz a tio n is improves general w ith of published agreement in c r e a s in g conclusions between authors column l e n g t h , th e feed and in c r e a s in g amount o f th e fe e d . is th a t g iv en in Table 2. th e s e p a ra tio n in c re a s in g c o n c e n tr a tio n o f Step Change ------ ► Experiment Yoneda (23) Christoph (25) Strong Base Resin Pulse Experiment Urgell (24) Conrard (26) Ir 1955 Step Change Experiment 1960 1965 1970 1975 U 1980 1985 Sakuma (27) - I Itoh (29) Kahihana (22) Weak Base Resin Sakuma (20) Pulse Experiment Kakihana (21) Aida (28) icPP-z-iseeBB (7-eo) Figure 4. Time Line o f Boron Experiments D 150 ; Length of Column (M) Figure 5. Results Found in the L ite ra tu re 21 TABLE 2. Author Summary Of Published Conclusions Reference M aior Conclusions Yoneda 23 a in c re a se s w ith an boron c o n c e n tr a tio n Yoneda 23 a in c re a se s w ith th e o f g l y c e r i n e in th e feed U r g e ll 24 The h ig h e s t a occurred w ith b o r ic a c id . a decreased when mannite or g l y c e r i n e were added. U r g e ll 24 Only a s l i g h t s e p a r a tio n occurred when sodium b o ra te was used U r g e ll 24 S e p a ra tio n improved when th e column le n g th was inc re a se d from 9 to 25 meters Kakihana 21 Weakly ba sic r e s i n r e q u ir e s w a te r as th e e l u t i n g agent C h ris toph 25 The amount o f b o r ic a c id adsorbed on th e r e s i n in c re a se s as th e feed c o n c e n tr a tio n in c re a se s Aida 28 Enrichment in c r e a s in g in c r e a s in g th e feed Aida 28 An optimum f l o w r a t e o f 10 to 20 m l / c n r h r e x i s t s f o r th e column Aida 28 The b u lk o f th e boron e x i t s th e column a t a c o n stan t 19% B-IO Aida 28 In c o n c e n tr a tio n s le s s than m olar no t a i l i n g was observed Sakuma 20 Enrichment in c re a se s w ith len gth Sakuma 20 The s e p a ra tio n fa c to r i s constant i r r e s p e c t i v e o f column le n g th in c re a s e in a d d it io n only in c re a s e s w ith c o n c e n tr a tio n and amount o f b o r ic acid in 0 .3 22 Theory Of General Chromatography There th e o r y a re two general v ie w p o in ts f o r chromatography th e o r y . Rate i s e x p la in e d in terms o f models in v o lv in g m o le c u la r d i f f u s i o n , re a c tio n and produces an outcome s i m i l a r to th e g iven system but does not i d e n t i f y th e mechanisms based or f lo w . on Phenomenological th e o ry is based on a model t h a t w ith in th e system. Rate th e o r y models are t y p i c a l l y th e s t e a d y - s t a t e thermodynamics o f molecules and th e re s in s by th e k in e tic s Phenomenological th e o re tic a l th e o r y of is th e based p l a t e or by s t a t i s t i c a l a d s o r p t io n -d e s o r p t io n e ith e r on th e s te p s. concept of a mechanics. The Mathem atical Model The e q u atio n s ba sis fo r th a t ra te d e s c r ib e th e o ry th e is mass th e development o f d i f f e r e n t i a l tra n s fe r processes. i d e n t i f i e s th e s t a r t i n g p o in t o f th e d i f f e r e n t i a l Mass by th e tra n s fe r in te rn a l c o n c e n tr a tio n C e q u a t i o n s . 30 is caused by th e a p p l i c a t i o n o f e x t e r n a l g ra d ie n t. The e x t e r n a l d e fin e d in e q u atio n 6. AE ^ 5x Figure 6 ~ V j(* 't)C j(x ,t)j) AxAyAzAt fo r c e and fo rc e , E, is Ci (x , t ) C1- (x + A x , t ) V1- ( x , t ) V i (x + Ax,t) ^ (x.y.z) (x,y,z+Az) Figure 6. Development of the D iffe r e n tia l Equation 24 In e q u a tio n 6 th e v a r i a b l e s a re : x = column len g th y and z = d is ta n c e s in th e n o n -flo w d i r e c t i o n t = tim e V1- = v e l o c i t y o f species i C.j = c o n c e n tr a tio n o f species i The tra n s fe r caused by the in te rn a l c o n c e n tr a tio n g r a d i e n t , G, is d e fin e d in e quation 7. / rDi ( x , t ) 3Ci * The o n ly system shown in is and th e F ig u re c o e ffic ie n t. caused 3x a d d itio n a l Di AxAyAzAt (7 ) ' v a ria b le is Di . d i f f u s i o n c o e f f i c i e n t o f species i . 6, Di However, is an Di d iffe re n tia l ^ 2 At re p re s e n ts th e an a ll mass tra n s fe r e ffe c ts By combining equations 6 and 7 in fin ite s im a l e quation is d e fin e d q u a n tity the p a rtia l (e q u a tio n 8 ) . = Di d2 c i - Vi ^ at For to For the case index having the u n it s o f d i f f u s i o n by the c o n c e n tr a tio n g r a d i e n t . reducing In the case o f a one phase ax2 case of ax th e boron ( 8) is o to p e s , equations in the form o f 25 eq u atio n 8 e x i s t f o r both boron-10 and b o r o n -1 1 . Kakihana solved assuming th a t iso tope s do is th e eq u atio n th e to ta l 8 th e case o f a two iso to p e system c o n c e n tr a tio n remains c o n s ta n t and t h a t th e not i n t e r a c t . mole fo r The s o l u t i o n is given in e q u atio n 9 where fra c tio n of is o to p e A and a, b, c and d are c o n s ta n ts . RA ( x , t ) T h is = a [e x p (b t)e x p (c x )] + d e xpre s sion both tim e w ill and (9 ) p ro v id e enrichm ent in a column as a fu n c tio n o f p o s itio n w ith in th e column assuming th e to ta l c o n c e n tr a tio n remains c o n s ta n t. A ds orption Isotherms The is tr e a tm e n t chromatography from a thermodynamic s ta n d p o in t t o assume t h a t th e process is allow ed to reach e q u i l i b r i u m a t each p o in t in re la tin g th e column. th e amount c o n c e n tr a tio n th e of in For adsorbed s o lu tio n . each m olecule th e r e e x i s t s an isotherm on th e r e s in to an e q u i li b r i u m Textbooks in chromatography3 ^ i d e n t i f y r e l a t i o n s h i p s between isotherms and th e c o n c e n tr a tio n p r o f i l e s o f e x i t i n g m olecules. The s im p le s t c o n c e n tr a tio n of isotherm is a lin e a r re la tio n s h ip between the a compound in s o l u t i o n and th e c o n c e n tr a tio n o f the 26 compound in th e m a th e m a tic a lly c o n c e n tr a tio n d e v ia te s re s in . A produce p ro file a of lin e a r normal a isotherm can d is trib u tio n chromatography column. be in shown th e to e x itin g As th e isotherm from a l i n e a r r e l a t i o n s h i p th e e x i t i n g c o n c e n tr a tio n p r o f i l e d e v ia te s from a normal d i s t r i b u t i o n . K in e tic s The of movement o f a m olecule through th e column r e p r e s e n ts a s e r ie s a d s o rp tio n s never reached developed a and at d e s o r p tio n s . any method p o in t fo r in d e a lin g In c e r t a i n systems e q u i li b r i u m is a column. w ith complex J . C a lv in G id d in g s ^ k in e tic processes. However, th e method r e q u ir e s a "near e q u i li b r i u m c o n d itio n " to e x i s t . The k in e tic s of th e ion exchange r e a c t i o n has been s tu d ie d by L e d e r e r ^ in f i v e s te p s: )i( (i) D i f f u s i o n through th e s o l u t i o n up to th e r e s i n p a rtic le . (ii) (iii) (iv ) (v ) D i f f u s i o n through th e r e s i n p a r t i c l e . Chemical exchange onto and o f f o f th e r e s i n . D i f f u s i o n out o f th e r e s i n p a r t i c l e . D i f f u s i o n through th e s o lu t io n away from th e p a rtic le . 27 The work g reater in d ic a te s th a t in a than 0 .1 m o lar, step ( i i ) le s s than 0 .0 0 3 m olar step ( i ) column w ith s o l u t i o n c o n c e n tra tio n s c o n tro ls . With d i l u t e s o lu tio n s o f c o n tro ls . P l a t e Theory Because o f th e d i f f i c u l t i e s w ith n o n - l i n e a r isotherm s and complex k in e tic s , most s o lu tio n . In work discusses chromatography based on an approximate th e p la te zones. The le n g th o c cu r. The le n g th o f th e zone i s c a l l e d th e h e ig h t e q u iv a le n t to a th e o re tic a l p la te each or HETP. by M a r tin zone The a llo w s complete e q u i li b r i u m to phenomenological in widespread p o p u l a r i t y in th e d e s c r i p t i o n o f chromatography. th e o r y has been and Synge.35 th e o ry in tro d u c e d th e 1941 of model th e column is t r e a t e d as N sepa ra te c ritic iz e d as was P l a t e th e o r y continues la c k in g p h y s ic a l However, r e a l i t y and c o n ta in in g l a r g e numbers o f v a r i a b l e s open to m a n ip u la t i o n . 36 S ta tis tic a l A Approach second n a tu re of m u ltip le a u th o rs 3 7 ,3 8 process. phenomenological have The d is trib u tio n . m olecule through d e a ls w ith a d s o r p t io n /d e s o r p tio n tre a te d th e o r y was F ig u re 7 a th e o r y the s ta tis tic a l s te p s . Several chromatographic process as a Poisson expanded illu s tra te s column. th e la te r to avoid th e Poisson th e random motion o f a sample r e p re s e n ts a w a i t tim e f o r th e i^*1 28 A Xi X Distance ICPP-Z-16578 (4 -9 0 ) Figure 7. Random Motion o f a Molecule 29 a d s o rp tio n moves a s te p . re p re s e n ts d is ta n c e d is ta n c e is . th e The sum of a flo w tim e in which th e molecule tim e th e f o r a m olecule to t r a v e l a lte rn a tin g w a it and a given flo w tim e s . OQ S c o tt developed a method f o r c a l c u l a t i n g th e mean and v a ria n c e o f th e e x i t tim e f o r th e m olecules. T h e o ries A p p lie d To Boron A is tim e shown models lin e in fo r F ig u re boron models a re l i s t e d As s ta te d d iffe re n tia l system. iso tope s boron b e fo r e , both column. The c o n c e n tr a tio n I t o h zS113 d a ta on K a k ih a n a ^ of a ls o th e o r y . th e solved chromatography The r e s u l t s o f the fo r th e ge nera l p a rtia l a g e n e r ic tw o -is o to p e solved th e fundamental e q u a tio n assuming non in th e boundary re g io n s . s o lu tio n s c o n s ta n t. e n te r s based in T a b le 3. c o n d itio n s is Seven authors have i d e n t i f i e d mathematical enrichm ent F u jiv ^ th a t 8. e q u atio n s te a d y -s ta te note o f th e chromatographic t h e o r i e s as a p p lie d to boron assume th a t the It to ta l is im porta nt to c o n c e n tr a tio n o f That im p lie s t h a t i f a square shaped pulse o f column, the same square shape pulse w i l l e x i t the r e s u l t s presented by Sakuma20 i l l u s t r a t e t h a t constant is p o s s ib le . a ll c o n c e n tr a tio n c u rv e . show a However, ra d ic a l K a k ih a n a ,21 change in th e A i d a , 28 to ta l and boron Jacques (40) Kokihano (22)----P a rtia l D ifferentialEquation Fujii (42) ------Kakihana (41) 'r 1970 Adsorption Iso th erm s 1975 Kakihana (21) 1980 1985 — Kakihana (2 2 ) CO O P late . Theory Conrad (2 6 ) C hristoph (2 5 ) Sonwalkar (4 3 ) ICPP-A-16577 (7 -9 0 ) Figure 8. Theories Applied to Boron 31 TABLE 3 . Author MODELING RESULTS FOR BORON ENRICHMENT Reference F u jii 42 Equation f o r enrichm ent as a fu n c tio n o f column d is ta n c e Jacques 40 P a rtia l d iffe re n tia l equation s o lu t io n in an e r r o r fu n c tio n form Kakihana 22 P a rtia l d iffe re n tia l equation s o lu tio n in an e x p o n en tia l form Kakihana 41 Numerical enrichm ent tim e as method fo r a f u n c tio n of Numerical enrichm ent tim e as method fo r a f u n c tio n of Sonwalkar The or F in a l R e s u lt 43 Conrard 26 S o lu tio n f o r enrichm ent fu n c tio n o f p l a t e number Kakihana 21 No s o lu t io n th e o ry C hristoph 25 HETP model g iv e s enrichm ent as a fu n c tio n o f d is ta n c e as a f o r thermodynamic f i v e rem aining models d e f i n e enrichment as a f u n c tio n o f tim e d is ta n c e w ith in th e column. None o f the seven models i d e n t i f y both enrichm ent and c o n c e n tr a tio n as a fu n c tio n o f tim e o r d is ta n c e . 32 AN ANALYSIS OF THE PUBLISHED WORK In a d d itio n T a b le 2, a to s e r ie s th e of summary o f published c onclusions l i s t e d in a d d i t i o n a l conclusions can be drawn from the experim ents d e s c rib e d in th e l i t e r a t u r e . E f f e c t Of Column Length F ig u re change th e 9 in ' column ' per a len g th . such ' le n g th . - in - cases Also p l o t t e d is th e maximum enrichm ent per u n i t Two o b s e rv a tio n s can be made. le n g th With of column w ith a column le n g th 3 o b s e rv a tio n is 3 complete 3 p o in ts 3 column le n g th in c re a s e s . D D th e enrichment decreases w ith enrichm ent per meter o f column le n g th does not exceed 2%. per D s u b s ta n tia lly F irs t, meter th a t th e of of column v ery long s e p a r a tio n . approach column a column le n g th o f g r e a t e r than 20 m e te rs , th e change enrichm ent ] th e v a rio u s experim ents d e s c r ib in g the per u n i t le n g th o f th e column as a fu n c tio n o f 3 ] of t h a t a complete s e p a r a tio n is obta ine d f o r a given r e s in le n g th . u n it p lo t enrichm ent column le n g th is From le s s than a m e te r, th e change in le n g th approaches 20%. le n g th s F ig u re 9 are In some r e q u ir e d The second to approach t h i s can be seen as th e data maximum enrichm ent per u n i t le n g th curve as the 100% Enrichment Curve (Ef = 1.0) <o o ^ D 150 ^ Length of Column (M) Figure 9. E ffe c t o f Column Length ICPP-Z-15669 (4-90) 34 E f f e c t Of Resin Tvoe The tim e r e s in s s tu d ie d r e s in s base can It lin e in a fte r 1974. re s in s . be is The eluded a ll in itia l work in the types o f w ith weak base r e c e n t work continues to c o n c e n tr a te on weak main advantage o f these r e s in s i s t h a t the boron w ith pure w a te r w ith o u t any r e g e n e r a tio n o p e r a t io n s . to n o te , however, t h a t strong base r e s in s p rovide a s e p a r a tio n compares K a k ih a n a 's 21 Al I im p o rta n t b e tte r (F ig u r e 4) shows a d i s t i n c t s p l i t per u n it le n g th of r e s in column. Figure 10 th e s p e c i f i c experim ents t h a t used weak and strong base I ( r e s in s d a ta in is th e range o f I to 35 meters o f r e s i n column. s c a tte re d , strong base Although the r e s in s appear to p ro v id e a g r e a t e r ‘i change of in enrichm ent per u n i t l e n g t h . e n ric h e d boron-10 w ith P roduction o f l a r g e q u a n t i t i e s strong base r e s in s would r e q u i r e s h o r te r columns but would r e q u i r e r e g e n e r a tio n f o r each c y c le . E f f e c t Of Boron C o n c e n tra tio n oI Kakihanar^ r e s in s each s e p a r a tio n not in flu e n c e d r e p o r te d D at th re e th e s e p a r a tio n fa c to r boron c o n c e n tr a tio n s . v a lu e s fo r He concluded th r e e t h a t the f a c t o r i s s tr o n g ly dependent on boron c o n c e n tr a tio n and is s e p a r a tio n th e r e p o r te d by fa c to rs by th e determ ined U r g e l l 2^, s e p a r a tio n kind o f fa c to r as and by shown th e re s in used. Kakihana are in F ig u re 11, e ffe c t of it However, when the compared to those appears t h a t both boron c o n c e n tr a tio n are 50 D Strong Base Resin + Weak Base Resin C 0) E JZ O "l— C + .E S 0) o CO LU S1 CjO in + O 1^r C O O 0) + CL + V + "b + ■ fa I 10 I I I I I I 15 20 Length of Column (M) Figure 10. E ffe ct o f Resin Type I I 25 ICPP-Z-15670 (4-90) 1.040 1.035 n Diaion WA-21 1.030 Separation Fac + Diaion WA-tD ° Diaion PA-312 1.025 A Dowex 1-X-8 1.020 0 Dowex 2-X-8 1.015 1.010 1.005 0- -I .2 .3 .4 Boron Concentration (M) Figure 11. .5 E ffe c t o f Boron Concentration ICPP-Z-15672 (4-00) 37 s t r o n g l y dependent on th e r e s in used. E f f e c t Of F lo w rate A id a 28 through and th e Sakumazs F ig u re column. For non-optimum It re s in d a ta , o b s e rv a b le . th e Sakuma20 should high be both concluded column is as shown in 12 uses th e t o t a l la rg e about th e optimum f l o w r a t e 20mL/hrcm2 . F ig u re 12, s c a le flo w ra te th a t an In optimum p lo ttin g is very re sid e n c e tim e o f th e boron in boron-10 enrichm ent th e use o f a may r e s u l t in an optimum pro d u c tio n r a t e . noted t h a t by in c re a s in g re sid e n c e tim e from 27 to 236 hours (770% ), th e change in enrichment improves by o n ly 50%. A p p l i c a t io n Of S t a t i s t i c a l F ig u re to boron 8 id e n tifie s is a th e v a rio u s t h e o r i e s t h a t have been a p p lie d chromatography. chromatography th e o r y s ta tis tic a l Theory One th a t m ajor c a te g o ry of general has not been a p p lie d to boron enrichment th e o r y . The f o l l o w i n g is a development o f such a th e o r y based on th e p ublishe d exp e rim en ts. For column a (T j) given m olecule c o n ta in in g , boron, th e t o t a l is th e sum of th e tim e spent in a tim e spent in motion (Tm) and the tim e spent e f f e c t i v e l y adsorbed w ith no movement (T a ) . 13 CO CO 8 0 100 200 300 Flow Time Required (Mrs) Figure 12. E ffe c t o f Flowrate 400 500 ICPP-Z-15671 (4-90) 39 (10) For a ll Tmand boron in a pulse The V c o n s id e rin g sum v e lo c ity . move a d is ta n c e ( x ) th e r e of The is a d is trib u tio n d is trib u tio n s to tal in a given t o t a l v e lo c ity can be o f each T7 , e lim in a te d by (V7 ) is th e v e l o c i t y to tim e . ( H) Equation to ta l 11 d e fin e s th e v e l o c i t y in motion (Vm) and th e f r a c t i o n o f tim e in motion ( f ) . For a ll d e fin in g boron to tal molecules v e lo c ity th e r e as a e x is ts fu n c tio n a of d is trib u tio n to ta l tim e . (g (V 7 ) ) The d i s t r i b u t i o n can be d e fin e d by the use o f equation 12. g(v7) = g (v mf ) Assuming to tal tim e ( 12) the v e l o c i t y in motion is independent o f th e f r a c t i o n o f in m otion, the to tal d is trib u tio n is th e product o f independent d i s t r i b u t i o n s . 9 (V T ) = g(V mf ) = h(Vm) j ( f ) (13) 40 For th e case o f no a d s o rp tio n ( j ( f ) = I) the n: 9 ( V t ) = I i ( V m) (1 4 ) For th e case when th e v e l o c i t y in motion is c o n s ta n t: 9 (V T ) = c j ( f ) The d is trib u tio n packing method, e ffe c ts . and column th e v e lo c ity v o id s , d e fin e in motion i s a f f e c t e d by th e column channels e x tra-c o lu m n e ffe c ts and extra-colum n as void volumes t o th e packed column, such as th e pump, tu b in g and d e t e c t o r , may fra c tio n of Textbooks extern al th a t (1 5 ) in flu e n c e of to ta l d e s o rp tio n th e outpu t peak shape. The d i s t r i b u t i o n o f the tim e is e f f e c t e d by d i f f u s i o n r a t e s , ra te s, th e th e adsorption shape o f th e a d so rp tio n isotherm and the i n t e r f e r e n c e between competing m olec ule s. Kakihana21 a weak presented base r e s i n and 50 cm lo n g . in to a 40°C A flo w ra te of 19 m l/h r 'c m 2 fo r column (D ia io n WA-21). p ulse o f 10 ml column. a th e d a ta from 10 th e Water was m l / h r ‘ cm2 second two The column p ulse experim ents using was I cm o f 0 . 5 M b o r ic used fo r as th e e x p e rim en t. th e firs t in d ia m e te r a c id was e lu tin g in je c te d agent experim ent at and In both experiments th e e f f l u e n t was c o l l e c t e d in 20 ml volumes and a n alyzed f o r t o t a l boron c o n c e n tr a tio n and atom f r a c t i o n o f boron-10. 41 F ig u re 13 e fflu e n t F ig u re pro v id es volume 14 fo r p ro v id es th e enrichm ent th e th e firs t measured re s u lts as experim ent b o r ic a c id a fu n c tio n o f (10 m l/h r-c m 2 ) . c o n c e n tr a tio n as a fu n c t i o n o f e f f l u e n t volume f o r th e same e xperim ent. The of m a n ip u la tio n th e ure illu s tra te s boron v a ria b le each as shown experim ent e fflu e n t ti m e . volume The v e lo c ity v e lo c ity in w ith t h a t c o n c e n tr a tio n s f u n c tio n of can is run by flo w ra te of ( m o le s ) . volume. of The The independent at a c o n stan t prov ides v a ria b le flo w ra te , a of lin e a r tim e th e d i v i s i o n o f the tr a n s fo r m a t io n to can be transform ed i n t o in be th e F ig u re 15 is th e boron c o n c e n tr a tio n . (moles per l i t e r ) and volume, in to can be transform ed a ccum ulative boron q u a n t i t y o f these th r e e r e p r e s e n ta tio n s o f dependent v a r i a b l e transform ed p o s s ib le v a ria b le 36 (moles) v a ria b le , Each o f the th r e e The shown independent Because a ls o be transform ed i n t o a dim ensionless q u a n t i t y . Each independent p o s s ib le . b o ro n -1 0 , b oron-1 1 , and and q u a n tity lik e w is e form s. e fflu e n t F ig ­ tim e , v a ria b le boron outcome of F ig u re 15 i s th e column e f f l u e n t volume. u n i t s o f boron c o n c e n tr a tio n in to o f th e enrichm ent d a ta . by th e d i v i s i o n o f column le n g th by tim e . dependent can a th e independent re p re s e n ta tio n s The th e raw d a ta begins w ith th e m u l t i p l i c a t i o n c o n c e n tr a tio n d a ta 15 to ta l of in to a dim ensionless tr a n s fo r m a tio n s q u a n tity . The is t h a t th e dependent and f o r a s in g le experim ent can be presented in s ix form ats fo r p r e s e n tin g a s in g le experim ent are 0.3 0 .2 9 0 .2 8 0 .2 7 0 .2 6 - 0 1 CO 0 .2 5 0 .2 4 - ATOM FRACTIi Z 0 .2 3 0 .2 2 - 0.21 - -Pa 0 .2 ro - 0 .1 9 0 .1 8 0 .1 7 0 .1 6 0 .1 5 — 50 70 90 I 10 EFFLUENT VOLUME (m l) Figure 13. Enrichment Results from Kakihana 130 0.1 TOTAL BORON CONCENTRATION (M) 0 .09 0 08 0 .0 7 0 .0 6 0 .0 5 0 .0 4 0 .0 3 0 02 EFFLUENT VOLUME (m l) Figure 14. Concentration Results from Kakihana TOTAL BORON CONCENTRATION (M) 0 .0 9 0 .0 8 0 .0 7 0 .0 6 0 .0 5 0 .0 4 0 .0 3 0.02 0.01 50 70 90 110 EFFLUENT VOLUME ( m l) Figure 15. Isotope Concentrations from Kakihana 130 45 F ig u re g iven 16 minimum id e n tifie s and th e v e lo c ity th a t at is o to p e . 50 For boron-11 in th e p l o t o f th e f r a c t i o n o f recovered boron w ith a th e fa s te s t v e lo c ity mean is are th e v e lo c ity p e rc e n t 7 .9 0 a fu n c tio n fo r both recovered v e lo c ity . experim ent and 8 .0 5 between d iffe re n c e in iso topes is th e th e is mean The f i g u r e 1 4 .8 cm /hr. v e lo c ity the The d i f f e r e n c e in th e iso topes o f 0 .1 5 cm /hr. these of The mean v e l o c i t y f o r boron-10.and cm/hr r e s p e c t i v e l y . range o f is o to p e v e l o c i t i e s magnitude of slowest v e l o c i t y f o r both iso to p e s is 5 . 8 cm/hr th is v e lo c itie s as is 1 0 .8 cm /hr. numbers is a The d i f f e r e n c e The two orders o f measure o f the poor q u a l i t y o f s e p a r a tio n . Using K a k ih a n a 's s im ila ritie s fo r e x p e rim en t, th e boron-10 it and is im p o rta n t boron-11 to note d is trib u tio n s . the The minimum to ta l v e lo c ity was 5 .8 cm/hr f o r both B-10 and B - I l . The maximum to ta l v e lo c ity was 1 4 .8 cm/hr f o r both B-10 and B - I l . The to ta l v e lo c ity n o ta b le d iffe re n c e v e lo c ity T h is mode was 1 3 .8 cm/hr f o r both B-10 and B - I l . was 7 .9 0 a n a ly s is assumption in th a t th e and tends th e 8 .0 5 to d is trib u tio n s cm/hr is th a t th e mean t o t a l f o r B-10 and B - I l r e s p e c t i v e l y . support s e p a r a tio n is The only Kakihana22 and F u j i i zS42 based on an i n t e r a c t i o n between B-10 and B - I l such t h a t a complete s e p a r a tio n is not p o s s ib le . From in motion a s ta tis tic a l (Vm) v iew , th e two iso topes have th e same v e l o c i t y d is trib u tio n and a near i d e n t i c a l f r a c t i o n o f tim e FRACTION OF BORON WITH MINIMUM VELOCITY 5 7 9 11 VELOCITY ( c m / h r ) Figure 16. V e lo c ity D is trib u tio n s from Kakihana 13 47 in motion s h ift (f) in th e v e lo c itie s d is trib u tio n s . mean t o t a l rem aining F irs t, somewhat demonstrated column. a Second, s e p a r a tio n v e l o c i t y w ith th e minimum, mode and maximum e q u a l. drawn. If p e rfe c t by should The e n r ic h in g occurs as a r e s u l t o f a in tru e , s e p a r a tio n th e is c o nclusions could be p o s s ib le . This is not Japanese w o r k ^ t h a t used a 256 meter d ecreasing improve. two A th e f r a c t i o n o f tim e in motion the s e r ie s of new experim ents w ill in v e s tig a te th is p re d ic tio n . S e p a ra tio n Index For Boron Isotopes The s im p le s t s in g le feed stream e n ric h e d in th e type o f a s e p a r a tin g system is one t h a t re c e iv e s a c o n ta in in g a b in a r y m ix tu re and produces one product in a d e s ire d component and one t a i l s d e s ir e d component. For discussed in terms of ra te s. discussed in terms of q u a n titie s a continuous For batch per stream d e p le te d system streams are systems, c y c le or streams ra te s based are on q u a n t i t i e s pe r c y c le tim e . of A v a r i e t y o f indexes have been i d e n t i f i e d to q u a n t i f y the q u a l i t y a s e p a r a t io n . s e p a r a tio n fa c to r, to d e s c r ib e in th e produces The th e re s in . one a. most The common used s e p a r a tio n index is e n t i t l e d 44 the f a c t o r was used p r e v io u s ly i s o t o p i c d i s t r i b u t i o n between boron in s o lu t io n and For th e a p p l i c a t i o n to a pulse boron experim ent t h a t product stream en ric h e d in boron-10 and one t a i l s 48 stream: a where is a amount of product th e (B -Il)7 (B -H )p (B -IO )t th e re s p e c tiv e ly . of B -Il ze ro fa c to r, B-IO and and boron-11 r e s p e c t i v e l y , ta ils amount (1 6 ) s e p a r a tio n boron-10 and approach (B -IO )p = It B -Il re p re s e n t the and P and I re p re s e n t should be noted t h a t as e i t h e r in th e product o r th e amount o f B-IO in the t a i l s th e value fo r th e s e p a ra tio n fa c to r approaches in fin ity . In a s e r ie s of a rtic le s Rony^"^ e n t i t l e d th e e x t e n t o f s e p a r a tio n . Rony c la im in v a ria n t w ith no to an index is d e fin e d as: (B -H )p (B-10)p + (B -IO )t ( B - H ) p + ( B - I l ) 1- (1 7 ) th e f a c t o r is a "U n iv e rs a l S e p a ra tio n In d e x ." based d im e n s io n le s s , in tro d u c e d (B -IO )p contends is It has on th e in v a ria n t in itia l s e p a r a t io n . fa c ts to th a t changes feed p u r i t y . th e between index is The n o rm a lize d , product and t a i l s and A value o f ze ro d e fin e s a system A value o f one d e fin e s a system w ith complete s e p a r a t io n . A id a 28 publishe d th e d e t a i l s o f tw e lv e e x p e rim en ts. The design 49 of th e experim ents was such t h a t th e in f lu e n c e o f th e b o r ic a cid feed c o n c e n t r a t io n , enrichm ent th e could Japanese enrichm ent and feed amount be column e v a lu a te d . a rtic le c u rv e s . enrichm ent and as flo w ra te on th e e fflu e n t The published d a ta is presented in tw e lv e s ets of c o n c e n tr a tio n curves and By r e g e n e r a tin g th e d a ta from th e c o n c e n tra tio n c u rv e s , curves fo r th e s e p a r a tio n indexes can be c a lc u la te d . In th re e experim ents c o n c e n tr a tio n s e p a r a tio n product w ith f a c t o r as is shown c o n c e n tr a tio n of ure a ll v a r ie d o th e r a fu n c tio n in Fig u re The o f th e 17. fu n c tio n o f th e same tr e n d is seen. It b o r ic le ft amount o f is seen c o n s ta n t. The as f a c t o r in c r e a s e s . product amount in the the feed The e x t e n t i s shown in F i g ­ A t h i r d method o f p re s e n tin g the shown Fig u re 19. d iffe re n c e in th e product enrichm ent and th e i n i t i a l in c re a s in g feed th a t is A gain, acid boron-10 s e p a r a tio n fra c tio n . in th e parameters inc re a s e s th e s e p a ra tio n s e p a r a tio n as a 18. Aida The change in enrichment is the c o n c e n tr a tio n feed enrichment in c re a s e s product enric h m e n t. F iv e experim ents e v a lu a te d th e e ffe c t of s o lu tio n flo w ra te . F ig u re 20 i d e n t i f i e s t h a t th e s e p a r a tio n f a c t o r decreases as f l o w r a t e in c r e a s e s . th a t re s u lte d in th e flo w ra te . 5 cc/cm2hr s e p a r a tio n The flo w ra te which was i s shown in minimum F ig u re 21. Again an optimum s e p a ra tio n is th e The optimum extent of flo w ra te is SEPARATION FACTOR 0.60M 0.80M 1.03M 0 02 0 06 0.1 4 MOLES OF B - I O Figure 17. 0 .1 8 0.22 0 26 IN PRODUCT E ffe c t o f Concentration on Separation Factor 0 .3 4 0.045 0 .0 4 0.60M 0.80M 1.03M EXTENT OF SEPARATION 0 .0 3 5 0 .0 3 0 .0 2 5 0.02 0 .0 1 5 0.01 0 .0 0 5 MOLES OF B - I O Figure 18. IN PRODUCT E ffe ct o f Concentration on Extent o f Separation 0.05 0.60M 0.80M 1.03M CHANGE IN ENRICHMENT 0 .0 4 0 .0 3 0.02 0 . 01 0 .0 2 0 .0 6 0.1 0 .1 4 0 .1 8 MOLES OF B - I O Figure 19. 0 .2 2 0 .2 6 0 .3 IN PRODUCT E ffe c t o f Concentration on Change in Enrichment 0 .3 4 5 ml/hr-cm; 8 ml/hr-cm' SEPARATION FACTOR 10 ml/hr-cm; 22 ml/hr-cm; 87 ml/hr-cm' cn CO 0 .0 3 0 05 0 .0 7 0 09 0 15 MOLES OF B - I O IN PRODUCT Figure 20. E ffe c t o f Flowrate on Separation Factor 0.19 0 08 0 .07 EXTENT OF SEPARATION 0 .0 6 0 .0 5 0 .0 4 in 0 03 0 02 0 .0 4 0 .08 0 .1 6 MOLES OF B - I O IN PRODUCT Figure 21. E ffe c t o f Flowrate on Extent o f Separation 0 .2 4 55 5 cc/cm^hr p u rity The and ( F ig u r e change based on in th e tr e n d 22) is re p e a te d . id e n tifie s produce flo w ra te . The improvement in product an optimum f l o w r a t e a t 10 cc/cm2h r . enrichment does not i n d i c a t e a strong tre n d A ll fo u r measures in d ic a te t h a t an optimum s e p a r a tio n occurs a t low f l o w r a t e s . Four th e column. as th e in e v a lu a te d th e q u a n t i t y o f b o r i c a c id added to F ig u re 23 i n d i c a t e s t h a t th e s e p a ra tio n f a c t o r decreases boron q u a n t i t y in c re a s e s . F ig u re 24. 0 .1 6 of experim ents The exten t o f The e x t e n t o f s e p a r a tio n is shown s e p a r a tio n begins at a maximum w ith moles o f boron-10 and progresses through a minimum a t 0 .3 0 moles b o ro n -1 0 . s e p a r a tio n begins improvement measures The f i n a l in to ris e product in c re a s e in c re a s e s . experim ent appears to i n d i c a t e th e e x t e n t o f as as a d d itio n a l p u rity th e ( F ig u r e q u a n tity boron 25) of boron is added. id e n tifie s fed to The th a t the the column The th r e e indexes a r r i v e a t c o n f l i c t i n g conclusions when c o n s id e rin g th e optimum feed q u a n t i t y . The indexes design re s u lts c onclus ion w ill of o p tim iz a tio n of was of any one o f the th r e e o p tim iz e a s e p a ra tio n could be a very s tro n g to o l th e indexes in which " I ess-than-optim um " Aida th e l a r g e s c a le systems. c o n d itio n s of th a t However, in the in c o n s is te n c ie s between the and the economics o f p l a n t design in tro d u c e minimum p la n t costs s e p a r a tio n c o n d i t i o n s . p l o t t e d in Figure 12. may be achieved at P r e v io u s ly th e conclusion As th e c y c le tim e increased 770% 0 .2 9 5 ml/hr-cm; 8 m l/h r ’ em1 10 ml/hr-crrr PRODUCT ENRICHMENT 0 .2 8 22 ml/hr-cnr E7 ml/hr«cm: 0 .2 7 0 .2 6 0 .2 5 0 .2 4 0 .2 3 0.22 0.21 0 .0 3 0 .0 5 0 .0 7 0 .0 9 0.1 I MOLES OF B - I O Figure 22. 0 .1 3 0 .1 5 0 .1 7 IN PRODUCT E ffe c t o f Flowrate on Change in Enrichment 0 .1 9 0.21 0 .2 3 0.16 Moles 0.24 Moles 0.30 Moles SEPARATION FACTOR 0.68 Moles 1.14 AMOUNT OF B - I O IN PRODUCT (m o les) Figure 23. E ffe c t o f Feed Quantity on Separation Factor 0.032 0 .0 3 0.16 0.24 0.30 0.68 0 .0 2 8 0 .0 2 6 0 .0 2 4 EXTENT OF SEPARATI 0 .0 2 2 0 02 0 .0 1 8 0.01 6 0.01 4 0 .0 1 2 0 .0 0 8 0 .0 0 6 0 .0 0 4 0 .0 0 2 AMOUNT OF B - I O IN PRODUCT (m o les) Figure 24. E ffe c t o f Feed Quantity on Extent o f Separation Moles Moles Moles Moles 0 .0 4 5 INCREASE IN PRODUCT ENRICHMENT 0 .0 4 0.16 0.24 0.30 0.68 0 .0 3 5 Moles Moles Moles Moles 0 .0 3 0 .0 2 5 0.02 Ul 0.01 5 0.01 0 .0 0 5 AMOUNT OF B - I O Figure 25. IN PRODUCT (m o le s ) E ffe c t o f Feed Quantity on Change in Enrichment 60 th e change in enrichm ent improves by o n ly 50%. For A i d a 's optimum s e p a r a tio n flo w ra te a th e fiv e of th r e e s e p a r a tio n indexes i n d i c a t e t h a t the tim e in a t low f l o w r a t e s . c y c le tim e . flo w ra te c y c le change a ll occurs in c re a se s fu n c t i o n c o n s id e r work However, a decrease in The improvement in product p u r i t y as in fo r m a tio n in Fig u re 26. (F ig u r e 22) is m o d ifie d to The index shown in th e f i g u r e is th e product enrichment per hour o f c y c le tim e f o r the experim ents w ith v a ria b le flo w ra te s . It is c l e a r t h a t from a " s e p a r a tio n f l u x " s ta n d p o in t th e optimum occurs a t high f l o w r a t e s . The s ig n ific a n c e e x p e rim en tal c o n d itio n s . o p tim ize d a d d itio n a l system. of c o n d itio n s When measure th is do la rg e does experim ents not w ill e va lu a tio n not s c a le equate in to th a t th e chromatography ensure be is an aimed o p tim ize d at is th e optimum optimum p la n t considered system. an Again o p tim iz in g a l a r g e s c a le 0.0002 0 .0 0 0 1 9 (Ef - E0) / t PRODUCT ENRICHMENT CHANGE PER HOUR 0.0001 8 ml/hr-cm1 m l/hr- cnv ml/hr-cm1 m l/hr* cm; ml/hr'cm' 0 .0 0 0 1 7 0 .0 0 0 1 6 0 .0 0 0 1 5 0 .0 0 0 1 4 0 .0 0 0 1 3 0.00012 0.0001 I 0.0001 0 .0 0 0 0 9 0 .0 0 0 0 8 0 .0 0 0 0 7 0 .0 0 0 0 6 0 .0 0 0 0 5 0 .0 0 0 0 4 0 .0 0 0 0 3 0.00002 0.00001 O 0 .0 3 0 .0 5 0 .0 7 0 .0 9 0 .11 MOLES OF B - I O Figure 26 0 .1 3 0 .1 5 0 .1 7 IN PRODUCT E ffe c t o f Flowrate on Enrichment Flux 0 .1 9 0.21 0 .2 3 NEW EXPERIMENTS The lite ra tu re p u b lish e d th e i d e n t i f i e s e ig h t previous e x p e rim e n te rs t h a t have re s u lts e x p e r im e n te r s , seven of f i f t y - o n e e xpe rim ents. parameters have been t r e a t e d as v a r i a b l e s . p u b lish e d experim ents are i d e n t i f i e d The in te n t v a ria b le s ty p e , of of feed Between th e e ig h t perform ing q u a n tity , The in Table 4. new experim ents is to study the feed c o n c e n tr a tio n , te m p e ra tu re , r e s in f l o w r a t e and column le n g th . Equipment The th e equipment same sequence used in as th e th e new experim ents w i l l flo w path through be discussed in th e equipment. The components and th e flo w path are shown in Figure 27. S o lu tio n Supply D is tille d s to re d in a w a te r covered was obta ine d from the l a b o r a t o r y u t i l i t i e s f i v e l i t e r p o ly e th y le n e be a k e r. and The w ater was measured f o r c o n d u c t i v i t y and t y p i c a l l y was 1 .0 [iQ o r l e s s . B o ric th a t was a c id was d is s o lv e d in d i s t i l l e d w ater to produce a s o lu tio n s a tu r a t e d a t room te m p e ra tu re . The s o l u b i l i t y curve48 f o r 63 TABLE 4. Exoerim enter PAST EXPERIMENTS Levels Of Treatments A B C D E F G Number Of Exoeriments Reference U r g e ll 2 3 3 4 I I I 13 24 Conrard I I I I I I I I 26 Kakihana I I I 2 I I I 2 21 Aida I I I 3 4 7 I 12 28 Sakuma I I 4 I I 3 I 7 27 Kakihana I I I I 3 I I 3 22 Sakuma I I 9 I I I I 9 20 Ito h I I I 4 I I 4 4 29 Treatm ents: A B C D E F G - Resin Type Chemical Form o f th e Boron Feed Column Length C o n c e n tra tio n o f Boron in th e Feed Feed Volume F lo w rate Column Temperature Solution supply Column oven D etecto r Column Injection system D ete c to r e le ctro n ics Recorder IC P P -A -16500 (4 -9 0 ) Figure 27 Equipment Flowpath 65 b o r ic a c id c o n c e n tr a tio n in w a te r is given in Fig u re 28. Feed s o lu tio n to th e column was v a r i e d by d i l u t i o n or by h e a tin g the s a t u r a t e d m ix t u r e . The b u lk of th e iso to p e s o b ta in e d Chemical of experim ents as a re ag e n t P h i l l ip s b u rg , Nd. used th e n a tu r a l m ix tu r e o f boron grade The chemical from J . T. Baker boron was a n alyzed to c o n ta in .1835 atom f r a c t i o n boron-10. A small (Id a h o q u a n tity F a lls , In d u s trie s o f enric he d b o r ic a cid was o b ta in e d from WINCO ID ). of The Quapaw, m a t e r ia l OK. The was boron enric he d was by Eagle Richer analyzed to c o n ta in .526 atom f r a c t i o n b oron-1 0 . Two methods c o n ta in in g of sample in je c tio n between through th e column was e x tre m e ly low. flo w th e pump d is tu rb a n c e s and in d is tu rb a n c e s a t th e d e t e c t o r . The to fin a l immerse graduated a d d itio n e v a lu a te d . A s yrin g e th e d e s ir e d volume o f b o r ic a c id was used through a septum lo c a te d la rg e were th e column. T y p i c a l l y th e v e l o c i t y The use o f th e s y rin g e c rea te d column in c lu d in g n e ar immediate The s y rin g e method was d is c o n tin u e d . method used to in tro d u c e b o r ic acid i n t o th e column was th e tu b in g c y lin d e r was th e w ith in connected c o n ta in in g 0 .5 m l. th e to th e pump s u c tio n i n t o a 100 ml feed m a t e r i a l . Accuracy f o r the No d is tu rb a n c e s a t th e d e t e c t o r were BORON CONCENTRATION (g ra m s B /L ) TEMPERATURE (C ) Figure 28. Boric Acid S o lu b ilit y 67 d e te c te d using t h i s method. I n j e c t i o n System An e le c tro n ic Acton, NA) s o le n o id was m e te rin g pump (Model A141, L iq u id M e tr o n ic s , used. The design In c ., o f th e pump uses a s o l i d - s t a t e to move a t e f l o n diaphragm a measured d is ta n c e w ith a spring re tu rn . An a d ju s t a b le s tr o k e le n g th and s tro k e frequency provided a flo w ra te range near continuous re s in re s u lte d compaction from 0 to 38 m l/m in . use is a p p ro p ria te . de te rm in e fo r s ix in th e loss an in d ic a to r A 6 .7 5 meter long column was in months and th e flo w compaction o f the of 4 cm in t o t a l th a t th e column le n g th . packing Such s l i g h t method is A measured volume o f w a te r was added to th e columns to s o lu tio n volume and void f r a c t i o n . In a l l cases the void f r a c t i o n was 0 . 4 9 . Column A ll The new S everal re s in s . There method in s e rte d was used a column w ith a d ia m e te r o f 0 .9 5 cm. s c a le up o f column d ia m e te r is not an issue and w i l l la te r. th e experim ents added is of at le n g th s one to th e o f Nalgene tu b in g were packed w ith v a rio u s c o n s id e ra b le pa ck in g . end be discussed For d is cu s s io n th is work in th e l i t e r a t u r e ^ 0n a plug o f g la s s wool was o f th e column and a vacuum was a p p lie d . o th e r end o f th e column v i a a f u n n e l . Resin Mechanical 68 v ib ra tio n second to was plug used of to move th e r e s i n through th e t u b in g . F in a lly a g la s s wool was i n s e r t e d and th e column was connected th e pump and d e t e c t o r v i a small le n g th s o f tu b in g w ith compression fittin g s . Two w eakly ba sic and Haas th e d e a c id ific a tio n strong re s in a and exchange r e s in s were o b ta in e d from Rohm PA. Both r e s in s are com m erc ially used f o r d e io n iz a tio n o f w ater where th e removal o f and o rg a n ic acids is d e s ir e d . A m b e r lit e IRA-68 is an r e s i n w ith th e ba sic fu n c t io n a l group being a polyam ine. is spheres is o f P h ila d e lp h ia , m inera l a c ry lic anion sold is in a f r e e base form. 0 .4 3 mm. p o ly s ty r e n e IRA-93 is a ls o a The e f f e c t i v e s iz e o f the r e s in A m b e r lite IR A -93 was the second r e s i n used. re s in w ith a The It polyamihe as th e f u n c t i o n a l group. fre e base r e s in w ith an e f f e c t i v e sphere s iz e o f producers o f s y n t h e t ic ion-exchange r e s in s are l i s t e d 0 .4 1 mm. The in w orld T a b le 5 .^ The ta b le in c lu d e d a cross r e fe r e n c e to published boron exp e rim en ts. A column few was experim ents submerged th e rm o s ta tic a lly were conducted a t e le v a te d te m p e ra tu re s . in c o n tro lle d a w a te r h e a tin g bath elem ent. was m a in ta in e d w i t h i n a f i v e degree range. th a t contained The a The bath tem peratu re U U U U U U U U U U L i r ) { ) TABLE 5, Comoanv Akzo Bayer Chemolim fex Diamond Shamrock Diaprosim Dow Ionac M its u b is h i M o n te c a tin i O stion P e rm u tit P e rm u tit A.G. Resindion Rohm & Haas Wolfen r j ___ C l Z- L / PRODUCERS OF SYNTHETIC ION-EXCHANGE RESINS Country Holland FRG Hungary U nited S ta te s France U nited S ta te s U nited S ta te s Japan Ita ly Czechoslovakia U nited Kingdom FRG Ita ly United S ta te s GDR USSR Tradenamefsl Imac L e w a tit Varion D u o lite D u o lite Dowex Ionac Diaion Kastel Ostion Zeocarb, D e a c i d i t e , Z e r o l i t O r z e l i t h , P erm u tit R e lite A m b e rlite W o f a t it AW", A V , KB", KU" Boron Exoerimenters U r g e l l , 2 * Conrardi^b K akihana,22 A ida28 This work Christoph28 70 D e te c t o r The e fflu e n t c o n d u c tiv ity d is s o lv e d from probe. The b o r ic a c i d . a tte m p te d . The the column concept is passed to through d etect th e an in -lin e presence o f I n - l i n e d e t e c t io n o f s p e c i f i c iso tope s was not e fflu e n t from th e probe was c o l l e c t e d in f r a c t i o n s f o r chemical and i s o t o p i c a n a l y s is . Two of probes Chicago, volume small volume were obta ine d from th e C ole-P alm er In s trum ent Company IL . Model N-01481 was a m ic r o - f lo w probe w ith an a c t i v e o f seven m i c r o l i t e r s . volume. of The s ev e ral e x p e rim e n ts . The Model The probe f r e q u e n t l y plugged due to i t s N-05800 m illilite rs , probe probe, which c o n ta in s an a c t iv e was used fo r a ll o f th e re p o rte d accuracy i s 0.1% and c o n ta in s a the rm os ta t f o r te m p e ra tu re compensation. D e te c t o r E le c t r o n ic s A d ig ita l In s tru m e n t c o n d u c tiv ity Company. meter was obta ine d from th e Cole-Palm er The meter measures c o n d u c t i v i t y in f i v e ranges. Most experim ents were conducted in th e range o f 0 to 100 micro-mhos. 71 Recorder A ty p e P r in c e to n , recorder Nd. accuracy. per L6512 The hour to was o b ta in e d from th e L in s e is Company o f The r e c o r d e r is a s in g le channel model w ith a 0.35% r e c o r d e r was used a t a c h a r t speed o f one c e n tim e te r accommodate experim ents th a t la s te d in excess of 100 hours. A d d itio n a l Methods E f f l u e n t samples were subm itted Company was A n a ly tic a l Department. c a r r i e d out using a mass t o th e Westinghouse Idaho N uclear The i s o t o p i c a n a ly s is o f b o r ic sp ec tro m e te r by th e acid use o f a s urfa ce i o n i z a t i o n method. The mass peaks used were those a t m/e 88 (Na ^BO ^) i i + ^ and 89 (Na^11BOg). The a n a l y t i c a l department determ ines a 0.072% standard d e v ia tio n samples. in Atomic c o n c e n tr a tio n s . th e enrichm ent ad so rp tio n was of th e used d ilu te to b o r ic determ ine acid boron Due to th e d i l u t e n a tu re o f th e samples th e standard d e v i a t i o n was determ ined to be 5%. Data Twenty-one experim ents given is experim ents g iven in Appendix A. in were T able 6. perform ed. A summary of the The d a ta from each experim ent is Each o f th e e xpe rim ental r e p o r t s i d e n t i f i e s the TABLE 6. Q R S T U 2 .2 5 m 2 .2 5 m 2 .2 5 m 2 .2 5 m 2 .2 5 m 6 .7 5 m 6 .7 5 m 2 .2 5 m 6 .7 5 m 6 .7 5 m 6 .7 5 m 6 .7 5 m 6 .7 5 m 0 .5 m 6 .7 5 m 6 .7 5 m 0 .5 m 0 .5 m 2 .2 5 m 2 .2 5 m 2 .2 5 m Comments Enriched Feed Hot Feed No S ep a ra tio n O CO CD -O IRA-67 IRA-67 IR A -67 IRA-67 IRA-67 IRA-67 IR A -67 IRA-67 IRA-67 IRA-67 IRA-67 IRA-67 IRA-67 IRA-67 IRA-67 IRA-67 I RA-93 IR A -93 I RA-93 I RA-93 IR A -93 Length -Q Z A B C D E F G H I J K L M N O P Resin CO O C T itle No S eparation No S ep a ra tio n Enriched Feed TABULATION OF EXPERIMENTS Feed Cone. 2 .4 5 .0 2 .4 2 4 .4 1 .2 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 2 .4 5 .0 2 .4 g/L g/L g/L g/L g /L g/L g/L g /L g/L g/L g /L g /L g/L g/L g/L g/L g /L g/L g/L g/L g/L Feed Volume 10 10 10 9 10 15 10 10 10 10 10 25 15 10 I 10 40 5 15 18 30 ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml ml Flow rate 55 44 66 44 56 24 42 34 19 16 25 31 12 12 12 31 10 300 41 25 20 c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r c c /h r Total Time 11 hr 13 hr 10 hr 20 hr 13 hr 70 hr 34 hr 19 hr 57 hr HO hr 100 hr 50 hr 125 hr 8 hr 125 hr 39 hr 9 hr 0 .2 hr 6 hr 7 hr 10 hr Data Table Table Table Table NA Table Table Table Table Table Table Table Table Table Table NA NA NA Table Table Table 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 73 fix e d c o n d itio n s of th e e x p e rim en t, th e outcome in c lu d in g tim e , re c o v e ry and enrichm ent and a n a ly s is o f product s e p a r a tio n . in For an th e ta b le s , (F ig u r e in itia l 29), enrichm ent s c a tte r exten t (F ig u r e is 1 .5 4 . of 1 .6 from a l l exten t i n s i g h t i n t o th e l a r g e q u a n t i t y o f d a ta presented are given f o r th e s e p a r a tio n f a c t o r o f s e p a r a tio n ( F ig u r e 30) and th e change in the 31). The maximum s e p a ra tio n f a c t o r f o r t h i s work T h is compares w ith a maximum c a l c u l a t e d s e p a r a tio n f a c t o r o f th e p r e v io u s ly p ublishe d exp e rim en ts. of s e p a r a tio n p r e v io u s ly publishe d enrichm ent general p lo t s was th e maximized 5.8% fo r th is maximum as s e p a r a tio n work of is 0 .0 7 . 0 .1 0 4 The The maximum as compared w ith a maximum change compared t o Kakihana's maximum o f 7.2%. fa c to r a n d /o r th e in In e x t e n t o f s e p a ra tio n is when th e feed q u a n t i t y and f l o w r a t e are m inim ized in a long column. E f f e c t Of S in g le Parameters 2 Seven parameters j e x p e rim en ts. j d e te rm in e d . ] ] D D D D ) The were e ffe c t tre a te d of each as v a ria b le s in th e tw enty-one param eter on th e s e p a ra tio n was SEPARATION FACTOR D □ 0.001 MOLES OF B - I O Figure 29. 0.002 IN PRODUCT Separation Factor fo r the New Experiments 0 .0 0 3 0.1 I 0.1 - 0 .0 9 - EXTENT OF SEPARATION 0 .0 8 0 .0 7 0 .0 6 0 .0 5 0 .0 4 - □ 0 .0 3 0 .02 - n □ 0.01 O □ ------ 0 — g - gaap— B - = I a I 0.001 MOLES OF B - I O Figure 30. I a 0.002 IN PRODUCT Extent o f Separation fo r the New Experiments D □ ----- 1----------------------B 0 .0 0 3 0.06 CHANGE IN ENRICHMENT FRACTI 0 .0 5 0 .0 4 0 .0 3 0.02 0.01 D__ n 0 .0 0 1 MOLES OF B - I O Figure 31. 0 .0 0 2 IN PRODUCT Change in Enrichment fo r the New Experiments 0 .0 0 3 77 E f f e c t Of Length Data from experim ents comparison fo r th e s e p a r a tio n fa c to r A e ffe c t d a ta (2.25m ) of fo r and le n g th . th e two G (6.75m ) pro v id e d i r e c t F ig u re 32 e x p e rim e n ts . presents th e The s e p a ra tio n f a c t o r in c re a s e s as th e column le n g th in c re a s e s . F ig u re 33 tw e n ty -o n e of pre se nts experim ents s e p a r a tio n in c r e a s in g w ith as in c re a se s s e p a r a tio n p ast work. le n g th th e is exten t of s e p a ra tio n a f u n c tio n o f l e n g th . w ith w ith in c re a s in g d a ta from the The maximum e x t e n t l e n g th . The tre n d of in c re a s in g column le n g th i s in agreement The maximum e x t e n t o f s e p a ra tio n pe r m eter o f column 0 .2 , 0 .0 1 5 and 0 .0 1 5 5 f o r th e 0 . 5 , 2 .2 5 and 6 .7 5 meter columns r e s p e c t i v e l y . F ig u re 34 pre se nts fu n c t io n o f len g th . are same th e in c re a s e 0 .0 0 8 4 as th e in c re a s e in product enrichment as a The tre n d s using th e product enrichm ent in c re a se those using exten t of s e p a r a t io n . The maximum in product enrichment pe r meter o f column le n g th is 0 .0 0 6 , and 0 .0 0 8 8 6 fo r th e 0 .5 , 2 .2 5 and 6 .7 5 meter columns re s p e c tiv e ly . The enrichm ent u n i t le n g th and th e column le n g th is in o p p o s itio n to pe r th a t of th a t ze ro s e p a r a tio n can occur a t any column le n g t h . in th e th e la c k o f a d e cre a sin g tre n d between th e change in h is to ric a l d a ta given in F ig u re 9. It should be noted The v a r i a b i l i t y d a ta f o r a g iven column le n g th is a r e s u l t o f th e f r a c t i o n o f I .4 - - Experiment T itle s Given 1 .3 5 - I . 3 G - SEPARATION FACTOR m I .2 5 - m I .2 - A 1 .1 5 CO 1.1 - I .0 5 - I — O 1 I 2 I 4 COLUMN LENGTH (M ) Figure 32. E ffe c t o f Length I I 6 I----------------------------- 8 0 .1I 0.1 - 0 .0 9 - EXTENT OF SEPARATION 0 .0 8 0 .0 7 0 .0 6 0 .0 5 0 .0 4 0 .0 3 - □ 0.02 - n 0.01 - O — O m -S 2 T T 4 6 COLUMN LENGTH (M) Figure 33. Extent o f Separation as a Function o f Length S 0.06 □ CHANGE IN ENRICHMENT 0 .0 5 - 0 .0 4 - E3 o LU , 0 .0 3 - [] 4LU 0.02 - I S TGCmD 0.01 U - [] E3 n 0 1 - - 0 2 JL_ ® I I I-------------------r 4 6 COLUMN LENGTH (M) Figure 34. Increase in Product Enrichment as a Function o f Length S 81 ' boron recovered in th e p roduc t. E f f e c t Of Resin Type F ig u re near 35 equal fo r IRA-67 th a t th e re p re se n ts a c o n d itio n s . and S, is a comparison o f r e s i n IRA-67 and IR A -93 f o r The comparison uses experim ents A, B and C T and U f o r IR A -93. d iffe re n c e in th e It is d i f f i c u l t to conclude s e p a r a tio n power between the re s in s . E f f e c t Of Temperature H is to ric a lly , in v e s tig a te d . in c old 20°C The tem p e ratu re s of be s e r v ic e s in p u rify in g could 40°C has been th e range o f tem peratures The low er l i m i t was due to decreased boron s o l u b i l i t y w ater. used to upper re s in s . steam. up lim it was due to maximum o p e ra tin g Both A m b e r lite re s in s used in t h i s work can to IOO0C. IRA-93 i s sometimes used in The o p e ra tio n o f th e column a t a high tem perature g r e a t l y improve throughput because o f th e h ig h e r c o n c e n tra tio n s a llow ed by increased s o l u b i l i t y . Experiment change H were e q u a l. P was conducted using th e IR A -67 r e s i n a t SO0C. in enrichm ent was d e te c te d in any f r a c t i o n . conducted Both No Experiments G and a t room te m p e ratu re w ith th e o th e r c o n d itio n s near experim ents re s u lte d in a d e t e c t a b l e s e p a r a tio n . No 0.05 EXTENT OF SEPARATI 0 .0 4 0.03 0.02 0.01 60 IRA-67 70 so 90 IRA-93 RESIN TYPE Figure 35. Extent o f Separation as a Function o f Resin ioo 83 s e p a r a tio n at e q u ilib riu m SO0C e nforc es c o n stan t fo r K a k ih a n a 's enrichm ent t h e o r y 21 in re s in th a t the decreases w ith in c r e a s in g te m p e ra tu re . E f f e c t Of Feed C o n c e n tra tio n Experiment in to 2 4 .4 a room grams of c o n c e n tra te d experim ent in d ic a te product D c o n s is te d te m p e ratu re boron than D o f th e i n t r o d u c t i o n o f hot feed s o lu tio n column. per lite r ty p ic a l fe e d . ( 2 4 .4 g /L ) to The which feed is c o n c e n tr a tio n was an Order magnitude more Fig u re 36 compares th e r e s u l t s o f experim ent A (2 .4 g / L ) . The r e s u l t s t h a t an in c re a s e in feed c o n c e n tr a tio n decreases the maximum enric h m e n t. This re s u lt is in agreement w ith Kakihana21 and d is a g re e s w ith U r g e l l . 2^ E f f e c t Of Feed Volume F ig u re of b o r ic experim ents 37 a c id pre se nts s o lu tio n a comparison o f th e s e p a r a tio n t o the volume added to th e column. 0 ( 1 . 0 ml) and J ( 1 0 .0 m l ) . The comparison uses The r e s u l t s i n d i c a t e t h a t an in c re a s e in fe^ed volume decreases th e s e p a r a tio n . E f f e c t Of F lo w rate F ig u re 38 pre se nts a comparison o f th e s e p a r a tio n t o the column 0.04 Experiment T itle s Given 0 .0 3 5 - A EXTENT OF SEPARATION 0 .0 3 - 0 .0 2 5 - 0.02 - CD 0 .0 1 5 - 0.01 - [] 0 .0 0 5 - O - - O T* 4 i 8 n I 12 i I 16 I I 20 FEED CONCENTRATION ( g / L ) Figure 36. E ffe c t o f Feed Concentration I H 24 I---------- r~ 28 0.12 Experiment T itle s Given 0.1 I 0.1 O n - EXTENT OF SEPARATION 0 .0 9 - n 0 .0 8 0 .0 7 0 .0 6 - Cl 0 .0 5 CO 0 .0 4 - in CD 0 .0 3 0.02 - 0.01 - O - - O I 2 I 4 I 6 I I I 8 VOLUME OF FEED ( m l) Figure 37. E ffe c t o f Feed Volume I 10 I 12 I 14 0.08 K Experiment T itle s Given I 0 .0 7 - EXTENT OF SEPARATION 0 .0 6 - 0 .0 5 - 0 .0 4 - G □ 0 .0 3 - 0.02 - 0.01 - Cl O 14 d 18 I 26 22 I I I 30 FLOWRATE ( c c / h r ) Figure 38. E ffe c t o f Flowrate I 34 I I- 38 42 87 flo w ra te . G (42 Experiments J c c /h r) s e p a r a tio n were occurs (16 c c / h r ) , compared. w ith a I (19 c c / h r ) , The re s u lts flo w ra te K (25 c c / h r ) in d ic a te o f 25 c c / h r . and th e optimum T h is r e s u l t is in agreement w ith K a k ih a n a .21 E f f e c t Of I n i t i a l F ig u re 39 enrichm ent and A Enrichment pre se nts a comparison o f th e s e p a r a tio n to the i n i t i a l o f th e b o r ic a cid feed s o l u t i o n . (18% B -10) were compared. Experiments B (53% B-10) The r e s u l t s i n d i c a t e the i n i t i a l enrichm ent d id not a f f e c t th e s e p a r a tio n . E f f e c t Of I n t e r a c t i o n s The d a ta was review ed seven param eters e x i s t e d . to d e term ine i f i n t e r a c t i o n s between the Two i n t e r a c t i o n s were found. E f f e c t Of Feed Q u a n tity Feed volume. as a q u a n tity is F ig u re fu n c t i o n product of feed c o n c e n tr a tio n and feed 40 pre se nts th e d a ta f o r the in c re a s e in enrichment of experim ent w ith enrichm ent decreases in c re a s e s . th e a product y ie ld . connecting l i n e . as th e The data p o in ts are grouped by In g e n e r a l , th e maximum product q u a n tity of boron feed to the column For feed q u a n t i t i e s o f le s s than 0 .0 0 1 5 moles o f boron-10 0.04 Experiment T itle s Given 0 .0 3 5 - A EXTENT OF SEPARATION B n 0 .0 3 - 0 .0 2 5 - 0.02 - [] 0 .0 1 5 - 0.01 - [] 0 .0 0 5 - O - - O 0 .2 0 .4 B - I O ATOM FRACTION IN FEED SOLUTION Figure 39. E ffe c t o f I n i t i a l Enrichment 0 .6 0.06 INCREASE IN PRODUCT ENRICHMENT 0 .0 5 0 .0 4 0 .0 3 0.02 0 .0 1 0.001 0.002 0 .0 0 3 MOLES OF B - I 0 IN PRODUCT Figure 40. Increase in Product Enrichment as a Function o f Feed Quantity 90 th e re is and ty p ic a lly product product ure y ie ld y ie ld . y ie ld 41. a l i n e a r r e l a t i o n s h i p between product enrichment The change in product enrichm ent p e r change in is p lo tte d as a f u n c tio n o f product y ie ld in F i g ­ C l e a r l y th e slope o f th e product enrichm ent versus product lin e s inc re a s e s d ra m a tic a lly as feed q u a n t i t y to the column decreases. E f f e c t Of Cycle Time Cycle tim e s e p a r a tio n The fa c to r exten t F ig u re of 43. a fu n c tio n s e p a r a tio n th e of flo w ra te ^ a n d column le n g th . The as a fu n c tio n o f c y c le tim e is shown in Figure 42. The de cre a se s , th a t is as experim ents s e p a r a tio n a fu n c tio n o f c y c le tim e is shown in ty p ic a lly improves. show t h a t as th e f l o w r a t e More im p o r t a n t l y , i t appears as c y c le tim e in c re a s e s , e i t h e r by decreasing th e f l o w r a t e or by in c r e a s in g th e column l e n g th , th e s e p a r a tio n in c re a s e s . C o n d u c tiv ity Results A ll h is to ric de te rm in e in itia l to ta l work experim ents boron w ith th e c a lib ra tio n curve using in -lin e th e te m p e r a tu re . A used c o n c e n tr a tio n A m b e r lite c o n d u c tiv ity in the r e s in s measurements column e f f l u e n t . attem pted to r e l a t i n g c o n d u c t i v i t y to c o n c e n t r a t io n . m o nitor m ajor was concern dependent was on both to The id e n tify a The curve flo w ra te and discovered when th e 6 .7 5 meter ENRICHMENT CHANGE/CHANGE IN YIELD 0 .0 0 0 4 0 .0 0 0 8 0.001 2 0.001 6 0.002 0 .0 0 2 4 0 .0 0 2 8 0 .0 0 3 2 B-IO YIELD (moles) Figure 41 Product Enrichment Slope as a Function o f Feed Quantity I .6 Experiment T itle s Given O g 1.5 - m □ SEPARATION FACTOR u J i □ I .4 - L a G I .3 F □ Q I .2 A 1. 1 - N Q M □ Cl cP [ 40 60 80 100 CYCLE TIME (HOURS) Figure 42. Separation Factor as a Function o f Cycle Time 120 0.1 I IT Experiment T itle s Given 0.1 n - 0 .0 9 EXTENT OF SEPARATION o.os 0 .0 7 0 .0 6 100 CYCLE TIME (HOURS) Figure 43. Extent o f Separation as a Function o f Cycle Time I 20 94 column was ure For s e v e ra l 4 4. than th e used. A ty p ic a l c o n d u c tiv ity t r a c e is shown in F ig ­ hours the e f f l u e n t w a te r had a lo w er c o n d u c t i v i t y feed w ater. determ ined th e re g io n A n a ly tic a l a tte m pts The of to use th e of an tra c e id e n tify o ff-lin e where th e a n a l y t i c a l method boron was th e e f f l u e n t . compounds in th e o th e r peaks fa ile d . One p o s s ib le a nonadsorbed ty p ic a lly im p u r ity r e a c t i o n are assumes B(OH)^ and OH'. found in could be e x p la in e d . a c id feed re s id e n c e p e r io d ty p ic a lly im p u ritie s trace in th e b o r ic occurred a t one boron l i t e r a t u r e s lig h t e x p la n a tio n o f th e outp u t is t h a t th e f i r s t The o f e f f l u e n t volume. t h a t th e anions I f th e th e s o lu tio n . peak is peak The in v o lv e d in the r e a c t i o n is based on B(OH)^ and r e s i n such as Cl" th e c o n d u c t i v i t y The r i s e in c o n d u c t i v i t y a f t e r th e i n i t i a l peak would be th e d is lo d g e d anions. The adsorbed anions in B(OH)^ th e feed would be d is lo d g e d w ater. c o n d u c t i v i t y below th e i n i t i a l The used c onclus ion T h is would due to s l i g h t e x p la in th e tr a c e s o f drop in b a s e lin e . o f t h i s work is t h a t e f f l u e n t c o n d u c t i v i t y can be as an i n d i c a t o r o f th e e n r ic h in g c y c le but should not be used as a d i r e c t measure o f boron c o n c e n tr a tio n . RELATIVE CONDUCTI Zone Containing Boron -10 -20 -3 0 -4 0 -5 0 -6 0 -7 0 -8 0 -9 0 - I 00 TIME (HOURS) Figure 44. C onductivity Results 96 SYSTEM MODELING The re s u lts developed in to p re s e n te d . The and models The second dis cu s s io n of firs t w ill a w ill th e address th e o v e r a l l v a rio u s to compared th e th e o r y o f th e s e p a r a t io n . w ill enrichment th e c o n trib u tio n to new experim ents p r e d i c t i v e n a tu r e . e v a lu a te th e of process. can Two models w i l l be be enrichm ent process. param eters and These models w i l l th e ir then be F i n a l l y an economic model be presented to examine both a s in g le stage and a m u l t i p l e stage process. General Model Of The New Experiments F ig u re graph th e and 45 pre se n ts th e product d a ta f o r the new exp e rim en ts. p lo ts a ll re c o v e re d . re p re s e n ts 50% of of to ta l when ze ro t o t a l when th e The th e f r a c t i o n o f boron-10 in the product as a fu n c tio n o f fra c tio n e x p e c t, . th e In th e boron recovered in the p ro d u c t. boron is recovered zero boron-10 is recovered to ta l Fig u re boron 45 th e is x recovered = y lin e a ll is recovered in th e boron-10 is is drawn. case in which no s e p a r a tio n occurs. boron-10 As one would This l i n e For example when 50% o f th e t o t a l boron, the product enrichm ent is i d e n t i c a l to th e enrichment o f th e fe e d . The fo rm a t o f F ig u re 45 is somewhat analogous to th e p r e s e n ta tio n FRACTION OF B - I O IN PRODUCT (No Separation) FRACTION OF TOTAL BORON IN PRODUCT Figure 45. B-IO Yield as a Function o f Total Boron Yield 98 of e q u i l i b r i u m d a ta in thermodynamics. d e fin e s a p o r t io n of lin e a r re la tio n s h ip th e d a ta range. th a t In thermodynamics Henry's law models e q u i l i b r i u m d a ta f o r a A pplying th e same concept to th e d a ta in F ig u re 40 l i n e a r f u n c tio n was c a l c u l a t e d . f B-IO Here and Fg_10 Fg_y e q u a tio n to ta l is is is th e lin e fo r a r e p r e s e n tin g tio n boron over F ig u re dim en sionless r e p r e s e n tin g to ta l v a lid th e c o e ffic ie n t (18) th e f r a c t i o n o f th e boron-10 recovered in th e product boron. in c lu d e a = I - 0789 Fb -T th e 46 recovered expands th e by p e rfe ct no f i t . fit A to of d a ta equation e quation 18 is 0 .9 9 8 . used p ro d u c t. This shown in Figure 40 to 18. The re g re s s io n The r e g re s s io n c o e f f i c i e n t is determ ine g o o d n e s s - o f - f i t w i t h ,1 .0 th e fu n c tio n c o e ffic ie n t of to th e d a ta and 0 .0 0 .9 9 8 i n d i c a t e s t h a t equa­ 18 pro v id es a v e ry good model f o r th e exp e rim en tal model. Model Based On Experim ental Equation Because a ll c o n d itio n , of th e range o f 0 . 0 to 0 . 8 o f th e f r a c t i o n o f generated number in th e 18 p ro v id es of th e th e unique view of th e new e xperim ents. e xperim ental r e s u l t s are near th e n o -s e p a ra tio n re g r e s s io n e x p e rim en tal a Parameters c o e f f i c i e n t is near u n i t y and independent p aram eters. p re vio u s a n a ly s is o f th e in d i v i d u a l T h is is not in agreement w ith the param eters. FRACTION OF B - I O IN PRODUCT (No Separation) frB-IO = 1.0789Fb_t FRACTION OF TOTAL BORON IN PRODUCT Figure 46. Yield Data Including a Linear Model 100 To understand param eters maximum a th e re la tiv e importance second model was developed. of th e in d iv id u a l This model can p r e d i c t the e x t e n t o f s e p a r a tio n f o r an experim ent g iven th e experim ental param e te rs. Equation p a ram e te r. The 19 r e s u l t s from using a l i n e a r model f o r each param eters t h a t d id not s i g n i f i c a n t l y c o n t r i b u t e to th e g o o d n e s s - o f - f i t were excluded. Vm x Here = 0.0 0 88 L - 0.0 0 09 2 T + 0.00038R L i s th e column le n g th in in degrees C e ls iu s and fo r IR A -9 3 ). model th e model in d ic a te s in c re a s e s . fu n c t i o n of th a t c c /h r. 300 c c / h r . IRA-67 or 93 not experiments model behave th e in creases o f th e The not in s ig h t in to as is lin e a rly . s e p a r a tio n . The column le n g th g o o d n e s s -o f-fit i s based on the a ls o th a t i n d ic a te s A d d itio n a lly , th e s e p a ra tio n modeling i d e n t i f i e d c o n c e n t r a t io n , feed volume, and not s i g n i f i c a n t l y 66 67 f o r te m p e ratu re in c re a s e s and t h a t IRA-93 is a b e t t e r IR A -67. d id param eters do s e p a r a tio n len g th . feed F lo w ra te t h a t th e does pro v id e decreases as column in itia l (e ith e r The r e g re s s io n c o e f f i c i e n t f o r t h i s model E ig h ty p e rc e n t r e s i n than th e column tem perature The p r e d ic te d and a c tu a l r e s u l t s o f th e new which i n d i c a t e s However, m e te rs , T is R is r e s in ty p e are shown in F ig u re 47. 0 .5 3 (19) a f f e c t th e a ffe c t However, no the in itia l s e p a r a tio n w i t h i n s e p a r a tio n s e p a r a tio n in occurred th e th e w ith t h a t the enrichment d id te s te d range a ranges. of 10 to flo w ra te of 0 .0 9 a Actual MAXIMUM EXTENT OF SEPARATI 0 .0 8 0 .0 7 0 .0 6 Predicted Results 0 .0 5 0 .0 4 0 .0 3 0.02 0.01 - 0.01 EXPERIMENT Figure 47. Results o f the Linear Model Dealing with Parameters 102 T h is la rg e modeling im p lie s q u a n titie s of th a t boron a in to l a r g e s c a le system should i n j e c t a long column c o n ta in in g IR A -93 a t room te m p e ra tu re and a t a r e l a t i v e l y high f l o w r a t e . Comparison Of The Model To Thenrv The model i n d i c a t e s t h a t th e most s i g n i f i c a n t param eter is column len g th . From d iffe re n tia l in c re a s e by e q u a t io n s . By by th e in c r e a s in g ba sis th e development is based on column l e n g th . in c r e a s in g determ ined s te p s . th e o re tic a l e quations d iffe re n tia l is a column le n g th From a s t a t i s t i c a l based of p a rtia l S e p a ra tio n should on the p a rtia l v ie w p o in t, th e s e p a ra tio n d i f f e r e n c e in number o f a d s o r p t io n /d e s o r p tio n column le n g t h , s ta tis tic a l th e o r y in d ic a te s t h a t product enrichm ent should in c re a s e . Thermodynamic in c re a s e s u n ity . has in d ic a t e d t h a t as th e r e s i n tem perature e q u ilib riu m c o n stan t fo r th e iso to p e s approaches The model agrees w ith th e d e cre a sin g t r e n d . The Each th e th e o r y model th e o r y in d i c a t e s has e ith e r th a t IRA-93 is a b e t t e r r e s i n than IRA-67. a d i r e c t o r i n d i r e c t param eter t h a t d e fin e s th e e f f e c t o f r e s i n ty p e . P r e v io u s ly th eo ry. The two firs t p re d ic tio n s were drawn based on th e s t a t i s t i c a l p r e d i c t i o n was t h a t a p e r f e c t s e p a r a tio n is not 103 p o s s ib le . The new experim ents supports t h i s c o n c lu s io n . p re d ic tio n is o to p e was t h a t th e s e p a ra tio n in c re a se s as th e tim e the boron-10 is fu n c t i o n The second adsorbed of in c re a s e s . F ig u re 48 p lo ts th e s e p a ra tio n as a adsorbed tim e f o r th e new e xpe rim ents. The tre n d in th e d a ta supports th e th e o r y . S cale Up Of A S in g le Stage System T h is have work looked shown in at not th e F ig u re magnitude, remains d id v ary s c a le 49. th e As re la tio n s h ip lin e a r. The column d ia m e te r . up o f columns. th e S everal s t u d i e s 50 The work o f Bowmati50 is d ia m e te r in c re a se s by an o rd e r o f between outp u t and column cross s e c tio n te x tb o o k method of s c a le up confirm s t h i s re la tio n s h ip . F ig u re per 50 hour. The experim ents a p l o t s th e change in enrichment as a fu n c t i o n o f y i e l d w ith fig u re a 50 c o n ta in s cm long colum n.28 column of these le n g th s To enrichm ent on per e x p e rim e n ts , Kakihana's It is obvious t h a t th e use o f a s in g le could in c re a s e enrichm ent by a maximum o f d e term ine an e s tim a te o f process economics a 4% s in g le pass was chosen f o r th e Japanese work and a 3% enrichment based Appendix T a b le 15. c ubic new cm long column21 and A id a 's experim ents w ith 410 7%. th e m e te r. a p p ro x im a te ly $ 0 .0 7 The cost o f th e re s in s are a p p ro x im a te ly $7000 The cost to eva p o ra te room te m p e ra tu re w ater is per lite r. Sample c a l c u l a t i o n s are shown in 0.1 I MAXIMUM EXTENT OF SEPARATI 0 .0 9 0 .0 8 0 .0 7 0 .0 6 0 .0 5 0 .0 4 0 .0 3 0.02 0.01 HOURS THAT BORON IS ADSORBED Figure 48. Extent o f Separation as a Function o f Time Adsorbed OUTPUT ( k g / h r ) o cn O 0.2 0 .4 0.6 (T h o u s a n d s ) COLUMN AREA (sq c m ) Figure 49. 0.8 Scale Up o f a Column 1.2 0.07 Kakihana CHANGE IN ENRICHMENT 0 .0 6 0 .0 5 0 .0 4 0 .0 3 0.02 This Work o.oi 0 .0 0 0 2 0 .0 0 0 4 MOLES OF B - I O Figure 50. 0 .0 0 0 6 0 .0 0 0 8 IN PRODUCT PER HOUR Enrichment, as a Function o f Yield per Hour 0.001 107 Appendix B. cost e v a p o ra tin g of d ilu tio n The of th e re s u lts are shown in Table 7. w a te r b o r ic For each case th e d r iv e s th e economics o f th e system. a c id w ith in th e column The makes t h i s system uneconom ical. The d iffe re n c e s between A i d a 's column and K a k ih a n a 's column is in te re s tin g . K a k ih a n a 's 0 .5 m eter column produced 22% boron-10 w ith a o f n in e hours and produced about 0 .2 l i t e r s c y c le tim e w ater. tim e in A i d a 's 4 .2 o f process meter column produced 22% boron-10 w ith a c y c le o f 237 hours and produced about 18 l i t e r s o f process w a te r . th e because than s c a le th e th a t c a lc u la tio n A i d a 's column was s u p e r i o r . This is in p u t o f boron per c y c le was orders o f magnitude g r e a t e r of param eters up Yet K a k ih a n a 's . The c onclusion is t h a t th e s i g n i f i c a n t f o r th e system are in p u t q u a n t i t y , c y c le tim e and e f f l u e n t volume. S cale Up Of A M u l t i - S t a g e System A m u l t i - s t a g e model computer and Lotus dim ensional m a trix . la b e le d numbers. by stage model F ig u re 51, was developed 1 -2 -3 s o ftw a r e . Columns Fig u re operated f o r are using a The la b e le d 46 is a f i v e c y c le s . Z e n ith 386 personal spreadsheet by le tte rs . s i m p l i f i e d example For th e example is a two Rows are o f a nine given in a feed q u a n t i t y o f one u n i t is placed in stage f i v e in the TABLE 7. COMPARISON OF ECONOMICS FOR A SINGLE COLUMN SYSTEM Output (kg B - 1 0 / y r ) Product Enrichment A id a 's Work Kakihana's Work This Work 500 500 500 23% 23% 22% Column Length (cm) 420 50 675 Column D iam eter (cm) 180 396 829 Volume o f Water (L) 1 .8 X IO 7 1 .9 6 X IO7 5 .4 X IO8 Cost o f Resin $75500 $43190 $2562900 Cost o f E vaporation Per Year $ 1 .3 X IO6 $ 3 .9 5 X IO6 $ 3 .8 6 X 10 Cost o f E vaporation Per Gram B-IO $ 2 .6 $ 3.3 5 $ 76.98 u u u u o u u u Cj u M n n rj a u —u —^ ^ Spreadsheet Row Numbers STAGE STAGE STAGE STAGE STAGE STAGE ,STAGE STAGE STAGE I 2 3 NUMBER=I NUMBER=Z NUMBER=S NUMBER=T NUMBER=B NUMBER=B NUMBER=? NUMBER=B NUMBER=S 4 5 6 7 8 9 Figure 51. A 0 .0 0 0 .0 0 0 .0 0 0 .0 0 1 .0 0 0 .0 0 0 .0 0 0 .0 0 0 .0 0 Spreadsheet Columns U L B 0 .0 0 0 .0 0 0 .0 0 0 .5 0 1 .0 0 0 .5 0 0 .0 0 0 .0 0 0 .0 0 0 .0 0 0 .0 0 0 .2 5 0 .5 0 1 .50 0 .5 0 0 .2 5 0 .0 0 0 .0 0 0 .0 0 0 .1 3 0 .2 5 0 .8 8 1 .50 0 .8 8 0 .2 5 0 .1 3 0 .0 0 S iiiipiifiG d Example o f a Multi-Stage Model ; E 0 .0 6 0.1 3 0 .5 0 0 .8 8 1 .88 0 .8 8 0 .5 0 0 .1 3 0 .0 6 I—1 O KO no f i r s t c y c le . moved up to stage column placed th e 0 .0 6 q u a n tity would of be cascade 50% i s moved o f th e s tage down to q u a n t i t y is s tage stage f i v e . feed fo u r. In of c yc les u n its both 0 .0 3 are and th e p re se n t in number o f s ta g e s . 52 A fte r fiv e both stages one and n in e . The product and r a f f i n a t e c o l l e c t e d in th e s ix t h c y c le u n its . system. The s o ftw a re a llow s r a p id expansion o f A id a 's w o r k ^ was used t o design a s i m i l a r The r e s u l t s from a Japanese experim ent was converted a p l o t o f enrichm ent versus y i e l d as shown in F ig u re 52. F ig u re each stage of Based on th e cascade model assumed t h a t 10% o f the stream was e n ric h e d 5%; 10% was enric he d 1%; 20% remained a t the enrichm ent in te g e r of th e values v a lu e . The in number c y c le s , to s i x and example 50% B, which is th e second c y c l e , th e feed q u a n t i t y o f one u n i t is again both A gain, f o r t h i s The a llow ed case ra ffin a te T h irty -th re e fe e d ; was m a te ria l p r e s e n t. boron-10 stage was of d e p le te d by 1%. each stage The use o f t o be an i n t e g e r and modeled th e product was 50% boron-10. w ith a ll stages s t a r t i n g w ith o u t The program m a in tain e d a c o n stan t feed to the 18% and c y c le s . F ig u re 53 id e n tifie s c a lc u la te d feed boron-10 were of steady 60% most concern in v o lv e d feed a t 18% enrichm ent. 17% number approach th e of stages and developed Fig u re s ta te . th a t p ro file s 53 fo r each increm ent in the p l o t s th e development o f a p r o f i l e . a p p ro x im a te ly 400 c y c le s a re re q u ire d to For each and i s shown in Figure 54. stage a column d ia m e te r was The cascade can be viewed as a 0.08 0 .0 7 0 .0 6 CHANGE IN ENRICHMENT 0 .0 5 0 .0 4 0 .0 3 0.02 0.01 0.01 - 0.02 -0 .0 3 FRACTION OF BORON RECOVERED Figure 52. Result of Aida's Experiment APPROACH TO STEADY STATE O 0 .2 0 .4 0 .6 0 .8 (T h o u s a n d s ) NUMBER OF CYCLES Figure 53. Approach to Steady State w ith the Multi-Stage Model 6 COLUMN DIAMETER (m ) 5 4 3 2 I 25 35 STAGE NUMBER (ALSO ENRICHMENT) Figure 54. Column Diameters fo r a Multi-Stage System 45 114 set of 136 len g th . The from to B-IO 0 .7 meters in d ia m e te r and 4 .1 meters in each stage r e q u ir e s th e 50% The p ro d u c tio n o f 500 kg enrichm ent r e q u ir e s th e processing o f 6 1 3 ,5 0 0 kg boron. e v a p o ra tio n produced. The c o n c e n tr a tio n o f the boron i n t r o d u c t i o n i n t o th e n ext s ta g e . at than each The d i s t r i b u t i o n o f th e columns is shown in F ig u re 55. e fflu e n t p rio r columns c ost of th e w a te r is $734 per gram o f 50% B-10 This c ost is a p p ro x im a te ly two orders o f magnitude g r e a t e r th e current market p ric e . In a d d i t i o n , th e o p e ra tio n would r e q u i r e te n y ea rs o f continuous o p e r a tio n to reach s t e a d y - s t a t e . The m ajor e n ric h e d F ig u re boron 56 product issue is w ith th e use of chromatography th e l a r g e amounts o f w a t e r produced. enrichm ent in creases de cre a se s . as th e to produce As shown in boron c o n c e n tr a tio n in the To in c re a se enrichm ent th e column produces more d i l u t e p ro d u c t. At le a s t la rg e th re e s c a le p ro d u c tio n chromatography. F irs t, re s e a rc h in g a b o r ic w ith o u t use a c id of fra c tio n s . in a p o t e n t i a l s e x i s t f o r improving th e economics f o r r e v e rs e strong of KLM e n ric h e d In d u s trie s boron of by Walnut ion-exchange Creek, CA are osmosis membrane system f o r r e c o v e rin g d i l u t e e v a p o r a tio n . base B a c kflu s h in g r e s in A second method would in v o lv e the to adsorb the v a r io u s enrichment w ith a s tr o n g e r a cid in a batch mode would e f f e c t produce a co n ce n tra te d p ro d u c t. A t h i r d method would be to l o c a t e an enrichm ent f a c i l i t y near a source o f waste h e a t. NUMBER OF .7m COLUMNS 10 76 r - 5 Z 4 —Z 3 n I n - Z Z Z Z Z Z Z Z Z Z I Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z i i F l Z Z Z Z Z Z Z Z Z Z Z Z i Z Z Z Z Z Z Z F l Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z F l Z Z Z Z Z Z Z Z Z Z Z Z F l Z Z Z Z Z Z Z Z Z Z Z Z i i i i i F l Z Z Z Z Z F l Z Z Z Z Z Z Z Z Z Z Z Z i pnpnpn F l Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z i i Z Z Z Z Z Z Z Z Z Z Z Z i Z Z Z Z Z Z Z Z Z Z Z Z i Z Z Z Z Z Z Z Z Z Z i Z Z Z Z Z Z Z Z Z Z i Z Z Z Z Z Z Z / Z Z Z Z Z Z Z Z Z Z Z Z i i i Z Z Z Z Z Z Z Z Z Z i Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z I i pn F l pn pn pnFn Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z I i i r Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z 17 18 1920 21 2223 24 25 2627 28 2930 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 STAGE NUMBER (ALSO ENRICHMENT) Figure 55. Number of Columns fo r a Multi-Stage System MAXIMUM CHANGE IN PRODUCT ENRICHMENT 0.08 0.07 0.06 x 0.05 - to E u? M- l^j B 0.04 -I 0.03 0.02 - 0.01 - O -B - cP I 0.2 I 0.4 I I 0.6 i I---------1---------r 0.8 I GRAMS OF BORON PER LITER OF PRODUCT Figure 56. Enrichment versus Product Concentration I .2 117 CONCLUSIONS In 1943 e n ric h e d D is tilla tio n and d is tilla tio n of novel boron gaseous was r e q u ir e d f o r th e Manhatten P r o j e c t . d iffu s io n were considered process remains th e process used to d a y . s e p a r a tio n methods, a new and the With th e advent process has th e p o t e n t i a l fo r reducing th e market p r i c e and c r e a t i n g new uses f o r e n ric h e d boron. T h is work could be was to determ ine i f l a r g e q u a n t i t i e s o f enriched boron produced chromatography. eco n o m ic a lly using e lu tio n ion-exchange The scope was broken down in t o s i x o b j e c t i v e s . The f o l l o w i n g is a summary o f r e s u l t s in l i g h t o f the o b j e c t i v e s . I. Twenty-one fa c to r fo r p u b lish e d Demonstrate The Enrichment Of Boron experim ents th e experim ents maximum c a lc u la te d to be maximum of in itia l enrichm ent p e r c e n t. 0 .0 7 . It e n ric h e d boron. were of was 1 .6 . 0 .1 0 4 of The as Using 1 8 .4 perform ed. 1 .5 4 as compared w ith a p r e v io u s ly maximum compared a 6 .7 5 atom The maximum s e p a ra tio n w ith e x t e n t o f s e p a ra tio n was a p r e v i o u s l y published meter column, b o r ic a cid w ith an p e rc e n t was e n ric h e d to 2 4.2 atom is obvious t h a t ion-exchange chromatography can produce 118 2. A ll work boron-10 to Compare V arious Theories d a te is based on an iso tope e q u i l i b r i u m in which p r e f e r e n t i a l l y remains as an anio n . s e p a r a tio n process have based on e i t h e r p a r t i a l been isotherm s of th e boron iso topes in a chromatography column or p l a t e th e o r y . enrichm ent as a T h e o rie s d e s c r ib in g th e fu n c tio n d iffe re n tia l e q u a tio n s , a d sorption Most t h e o r i e s r e s u l t in an expression f o r of tim e . No t h e o r i e s t o d a te d e fin e an e xpression f o r c o n c e n tr a tio n as a f u n c tio n o f tim e . 3. For F fi-io to = tw e nty -one I .0 7 8 9 F g _ j, fo r Fg_y T h is is th e 0 .8 and Develop A S im u la tio n Model For Enrichment provides F g _ j. is model th e experim ents a good model th e exp re s sio n , over th e range o f 0 .0 . F g .jo is th e f r a c t i o n o f th e boron-10 recovered fra c tio n of to ta l boron recovered in th e p roduc t. b a s i c a l l y d e fin e s t h a t th e f r a c t i o n o f boron-10 recovered ty p ic a lly 7 .8 9 p e rc e n t more than th e fra c tio n of to ta l boron recovered up t o 80 p e rc e n t o f product r e c o v e ry . 4. A second importance th e of model th e experim ents Perform A P a ra m e tric Study was developed to understand expe rim ental param e te rs. was le n g t h . As column th e re la tiv e The m ajor param eter f o r le n g th increased the 119 s e p a r a tio n in c re a s e d . decreased re s in not model a ls o in d ic a t e d t h a t s e p a ra tio n as column te m p e ratu re increased and t h a t IRA-93 is a b e t t e r than in itia l The IR A -67. feed c o n c e n t r a t io n , s ig n ific a n tly L ik e w is e , A d d itio n a lly , e ffe c t flo w ra te d id feed th e th e modeling i d e n t i f i e d t h a t the volume and i n i t i a l s e p a r a tio n w ith in enrichm ent d id th e t e s te d range. not a f f e c t th e s e p a r a tio n in th e range o f 10 to 66 c c / h r . 5. The modeling discussed p la te re s u lts p a rtia l were p re d ic ta b le d iffe re n tia l th e o ry . chromatography Comparison To Theory The was e q u a tio n s , concept expanded of Both a modeled. s p e c ifie d amounts d is p o s a l th e stage m u lti-s ta g e enric h m e n t. of is re c o v e ry w a te r based of s ta tis tic a l th e o ry to in c lu d e boron e n ric h m e n t. of The tr e n d th e o r y . Determine The S cale Uo Economics s in g le A a d s o rp tio n isotherms and th e in th e d a ta a ls o supported th e s t a t i s t i c a l 6. based on th e p r e v io u s ly system system d ilu te could a m u lti-s ta g e produce a system product were o f any The m ajor issue w ith th e model was the l a r g e produced. on and The model e v a p o r a tio n . is not economical when w a te r However, a d d i t i o n a l research in b o r ic a c id in c o n ju n c tio n w ith ion-exchange chromatography has th e p o t e n t i a l f o r economical o p e r a t io n . 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C h e m istry . Volume 56, 1968. 124 APPENDICES APPENDIX A EXPERIMENTAL RESULTS TABLE 8 . R e s in : C olum n L e n g th : IR A -6 7 T ime 2 .2 5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : F lo w r a te : B /L Peak o f Im p u r it y 1 0 ml B e g in n in g 55 c c /h r End o f B o ro n o f B oron B -T T o ta l In p u t F irs t F r a c tio n S eco n d F r a c t i o n T h ir d F o u rth T o ta l F r a c tio n F r a c tio n O u tp u t P r o d u c t M o le s C u tp o in t B -1 0 B -Il R e s id e n c e P e r io d s 1 .3 .9 4 .8 3 .4 11 At F ra c t. mg B -IO 24 .1 8 3 5 7 .8 Wt F r a c t . • B -1 0 B -Il B -IO mg mg — — — 1 .7 .1 7 8 5 .1 6 4 9 .3 1 .5 1 3 .5 .1 9 2 7 .1 7 8 3 2 .4 1 1 .1 7 .8 .2 0 6 7 .1 9 1 5 1 .5 6 .3 4 .2 .2 1 7 .2 0 1 2 .9 3 .4 2 7 .2 P e r c e n t R e c o v e re d EXPERIMENT A 113% — — — — — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n W a s te M o le s B -1 0 B -Il E n r ic h m e n t F irs t .0 0 0 0 9 .0 0 0 3 1 .0 0 0 4 2 .0 0 1 7 1 .2 0 1 0 1 .1 5 8 .0 0 8 Second .0 0 0 2 4 .0 0 0 8 8 .0 0 0 2 7 .0 0 1 1 4 .2 1 0 3 1 .1 2 8 .0 3 0 T h ir d .0 0 0 4 8 .0 0 1 8 9 .0 0 0 0 3 .0 0 0 1 3 .2 1 7 1 .1 3 4 .0 1 7 TABLE 9 . R e s in : C olum n L e n g th : IR A -6 7 Tim e 2 .2 5 m H o u rs P e r io d s 1 .8 1 .0 5 .3 3 .0 Co Iu m n "I e m p e r a t u r e : Room Feed C o n c e n tr a tio n : 4 .9 5 g F e e d V o lu m e : 10 m l B e g in n in g o f B oron 44 c c /h r End o f B oron F lo w ra te : B /L Peak o f Im p u r ity B -T In p u t F irs t F r a c tio n S eco n d F r a c t i o n T h ir d F r a c tio n F o u rth B -IO 4 9 .5 .5 2 6 7 .4 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — 5 .5 .4 7 5 .4 5 1 2 .5 3 .0 7 .8 .5 0 6 .4 8 2 3 .8 4 .0 1 1 .1 .5 1 8 .4 9 4 5 .5 5 .6 1 9 .5 .5 3 5 .5 1 1 1 0 .0 9 .6 T o t a l O u tp u t 4 3 .9 — — — — P e r c e n t R e c o v e re d 89% — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n P ro d u t : t C u tp o in t F r a c tio n R e s id e n c e 13 A t F ra c t. mg T o ta l EXPERIMENT B B -1 0 M o le s B -Il W a s te M o le s B -1 0 B -Il E n r ic h m e n t Fi rs t .0 0 1 0 .0 0 0 9 .0 0 1 1 .0 0 1 1 .5 3 5 1 .2 1 .0 2 1 S eco nd .0 0 1 5 .0 0 1 4 .0 0 0 6 .0 0 0 6 .5 2 8 1 .1 5 .0 3 0 T h ir d .0 0 1 9 .0 0 1 7 .0 0 0 2 .0 0 0 3 .5 2 3 1 .1 3 .0 3 0 TABLE 10. R e s in : C olum n L e n g th : C olum n T e m p e r a tu r e : IR A -6 7 T im e 2 .2 5 m H o u rs 2 .4 g F e e d V o lu m e : F lo w r a te : B /L Peak o f Im p u r ity P e r io d s B e g in n in g o f B oron 66 c c / h r End o f B oron B -T T o ta l .7 1 0 ml In p u t F irs t B -1 0 2 4 .0 F r a c tio n .1 8 3 5 .9 4 3 .4 10 8 .5 At F ra c t. mg Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — - _ 1 8 .6 .1 9 5 .1 8 0 3 .4 1 5 .2 S eco nd F r a c t i o n 5 .0 .2 1 6 .2 0 0 1 .0 4 .0 T h ir d — — — — ——— — — — — — — — — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n F r a c tio n F o u rth F r a c tio n T o t a l O u tp u t 2 3 .6 P e r c e n t R ec o v e re d 98% Produc ; t F irs t R e s id e n c e Room Feed C o n c e n tr a tio n : C u tp o in t EXPERIMENT C M o le s W a s te M o le s B -1 0 B -Il B -1 0 B -Il .0 0 0 1 0 .0 0 0 3 6 .0 0 0 3 4 .0 0 1 3 9 E n r ic h m e n t .2 1 5 6 — 1 .1 3 5 .0 2 1 -V LJ LJ U U U U CJ LJ ( 3 i > ( ) c L_J_ _LJ— LA TABLE 11. R e s in : C olum n L e n g th : C olum n T e m p e r a tu r e : IR A -6 7 T ime 2 .2 5 m H o u rs R e s id e n c e P e r io d s Room Feed C o n c e n tr a tio n : F e e d V o lu m e : F lo w r a te : 2 4 . 4 g B /L Peak o f 9 ml B e g in n in g o f B oron 44 c c /h r End o f Im p u r it y B oron B -T T o ta l In p u t F irs t F r a c tio n S eco n d F r a c t i o n T h ir d F o u rth T o ta l F r a c tio n F r a c tio n O u tp u t P e r c e n t R e c o v e re d P r o d u c t M o le s B -1 0 B -IO 1 9 .6 B -Il 2 .5 1 .4 8 .5 4 .8 20 At F ra c t. mg C u tp o in t EXPERIMENT D .1 8 3 5 1 1 .3 Wt F r a c t . B -IO B -Il B -IO mg mg — — — 4 .4 .1 7 8 .1 6 4 .7 3 .7 6 .9 .1 8 5 .1 7 1 1 .2 5 .7 1 4 .7 .1 8 9 .1 7 4 2 .6 1 2 .2 1 6 4 .9 .1 9 6 .1 8 2 2 9 .9 1 3 5 .0 1 9 0 .9 — — — — 87% — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n W a s te M o le s B -1 0 B -Il E n r ic h m e n t F irs t .0 0 3 0 .0 1 2 3 .0 0 0 4 5 .0 0 1 9 6 .1 9 6 2 1 .0 7 .0 0 8 Second .0 0 3 2 .0 1 3 4 .0 0 0 1 9 .0 0 0 8 5 7 .1 9 5 5 1 .0 9 .0 0 5 T h ir d .0 0 3 4 .0 1 3 9 .0 0 0 0 7 .0 0 0 3 3 5 .1 9 5 1 1 .1 2 .0 0 2 5 J U U U U U O O P n n m r~i q_ o—o — q—^ TABLE 12. R e s in : C olum n L e n g th : IR A -6 7 T ime 6 .7 5 m H ou rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : F lo w ra te : B /L Peak o f — Im p u r it y 39 4 .0 24 c c /h r End o f B oron 70 7 .2 In p u t At F ra c t. F irs t T h ir d F o u rth B -IO 3 6 .0 F r a c tio n S eco n d F r a c t i o n F r a c tio n F r a c tio n T o t a l O u tp u t P e r c e n t R e c o v e re d P r o d u c t M o le s B -1 0 P e r io d s B e g in n in g o f B oron B -T C u tp o in t R e s id e n c e 15 m l mg T o ta l EXPERIMENT F .1 8 3 5 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — 2 .1 .1 9 3 8 .1 7 9 3 .4 1 .7 6 .8 .1 6 3 3 .1 5 0 7 1 .0 5 .8 1 9 .8 .1 9 1 2 .1 7 6 9 3 .5 1 6 .3 1 8 .3 .2 3 2 9 .2 1 6 3 4 .0 1 4 .3 47 — — — —- 130% — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n W a s te M o le s B -Il B -1 0 B -Il E n r ic h m e n t Fi rs t .0 0 0 4 .0 0 1 3 .0 0 0 4 9 .0 0 2 1 6 .2 3 3 1 .3 3 .0 7 1 S eco nd .0 0 0 7 .0 0 2 8 .0 0 0 1 4 .0 0 0 6 8 • 211 1 .3 0 .0 3 8 T h ir d .0 0 0 8 .0 0 3 3 .0 0 0 0 3 7 .0 0 0 1 6 .2 0 4 1 .0 6 .0 0 3 j u u u u U O o o n n n n_Q__a__^ >- q—^ ^ TABLE 13. R e s in : C olum n L e n g th : IR A -6 7 T ime 6 .7 5 m H ours C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : B /L Peak o f 10 ml F lo w ra te : 4 2 .3 c c /h r Im p u r it y F irs t F r a c tio n T h ir d T o ta l F r a c tio n O u tp u t P r o d u c t M o le s C u tp o in t B -1 0 B -Il .6 End o f B o ro n 34 6 .2 At F ra c t. B -IO .1 8 3 5 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — .7 .1 7 0 4 .1 5 7 3 .1 3 .8 .1 6 6 6 .1 5 3 7 .6 3 .2 2 1 .7 .2 0 5 5 .1 9 0 4 4 .1 1 7 .5 2 6 .2 P e rc e n t R ec o v e re d 3 .5 4 .0 2 4 .0 ■ S eco nd F r a c t i o n P e r io d s 21 B -T In p u t R e s id e n c e B e g in n in g o f B oron mg T o ta l EXPERIMENT G 109% — — — — — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n W a s te M o le s B -1 0 .6 B -Il E n r ic h m e n t F irs t .0 0 0 4 1 .0 0 1 5 9 .0 0 0 0 6 9 .0 0 0 3 5 .2 0 5 5 1 .2 8 8 0 .0 3 4 S econd .0 0 0 4 7 .0 0 1 8 9 .0 0 0 0 1 1 .0 0 0 0 5 6 .1 9 9 7 1 .2 1 5 0 .0 0 5 . TABLE 14. R e s in : C olum n L e n g th : IR A -6 7 T im e 2 .2 5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : B /L Peak o f 10 ml F lo w r a te : 3 3 .9 Im p u r it y B e g in n in g o f c c /h r B -T T o ta l In p u t F irs t 3 .5 19 8 .3 At F ra c t. B -IO 2 4 .0 .1 8 3 5 .7 8 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — • 1 .7 .1 9 2 5 .1 7 8 1 .3 1 .7 .1 7 7 9 .1 6 4 4 .3 1 .5 T h ir d 4 .8 .1 8 9 5 .1 7 5 3 .8 4 .0 1 4 .0 .2 0 8 6 .1 9 3 3 2 .7 1 1 .3 T o ta l F r a c tio n F r a c tio n O u tp u t P e r c e n t R e c o v e re d P r o d u c t M o le s C u tp o in t P e r io d s S eco n d F r a c t i o n F o u rth F r a c tio n R e s id e n c e 1 .6 B oron End o f B oron mg EXPERIMENT H B -1 0 B -Il 1 .4 2 2 .4 — — — — 93% — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n W a s te M o le s B -1 0 B -Il E n r ic h m e n t F irs t .0 0 0 2 8 .0 0 1 0 4 .0 0 0 1 4 .0 0 0 6 2 .2 0 8 6 1 .1 4 .0 3 0 S eco nd .0 0 0 3 6 .0 0 1 4 0 .0 0 0 0 5 5 .0 0 0 2 6 .2 0 3 8 1 .1 2 .0 1 5 T h ir d .0 0 0 3 9 .0 0 1 5 3 .0 0 0 0 2 5 .0 0 0 1 2 .2 0 1 6 1 .0 6 .0 0 4 TABLE 15. R e s in : C olum n L e n g th : IR A -6 7 T im e 6 .7 5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : B /L Peak o f 10 ml F lo w r a te : 1 8 .9 c c /h r Im p u r it y In p u t F r a c tio n S eco n d F r a c t i o n T h ir d T o ta l F r a c tio n O u tp u t 5 .4 .4 3 1 .5 2 .6 End o f B oron 57 4 .6 P r o d u c t M o le s C u tp o in t B -1 0 At F ra c t. mg B -IO 24 .1 8 3 5 B -Il Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — 1 .8 .1 5 2 .1 4 0 8 .3 1 .6 2 1 .0 .2 0 1 .1 8 6 2 5 .8 1 .4 .2 3 2 .2 1 5 0 .4 1 .3 2 4 .2 P e r c e n t R e c o v e re d P e r io d s CO F irs t R e s id e n c e B e g in n in g o f Boron B -T T o ta l EXPERIMENT I 100% — — — — — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n W a s te M o le s B -1 0 B -Il E n r ic h m e n t F irs t .0 0 0 0 4 .0 0 0 1 2 .0 0 0 1 6 .0 0 0 6 7 .2 3 1 5 1 .2 7 .0 3 4 S eco nd .0 0 0 1 7 .0 0 0 6 5 .0 0 0 0 2 6 .0 0 0 1 4 .2 0 7 0 1 .4 4 .0 4 9 TABLE 16. R e s in : C olum n L e n g th : IR A -6 7 T im e 6 .7 5 m H ou rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : B /L Peak o f 1 0 ml F lo w r a te : 1 5 .5 Im p u r it y B e g in n in g o f c c /h r End o f B oron B -T T o ta l In p u t F irs t F r a c tio n S eco n d F r a c t i o n T h ir d T o ta l F r a c tio n O u tp u t P r o d u c t M o le s B -1 0 At F ra c t. mg B - IO 24 .1 8 3 5 B -Il R e s id e n c e P e r io d s 10 .7 60 4 .0 HO 7 .3 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg ----- — — 5 .4 .1 6 0 .1 4 8 .7 4 .7 1 5 .4 .2 0 4 .1 8 9 2 .7 1 2 .7 2 .5 .2 5 8 .2 4 0 .6 1 .9 2 3 .3 P e r c e n t R e c o v e re d C u tp o in t B oron EXPERIMENT J — 9 7 .1 % W a s te M o le s B -1 0 B -Il ' — — — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n E n r ic h m e n t Fi rs t .0 0 0 0 6 .0 0 0 1 7 .0 0 0 3 7 .0 0 1 5 5 .2 5 7 7 1 .4 5 5 .0 3 9 Second .0 0 0 3 5 .0 0 1 3 1 .0 0 0 0 7 9 .0 0 0 4 2 .2 1 1 5 1 .4 0 8 .0 5 7 O O O O n n s~ ) n _o—o—o O O fj o TABLE 17. R e s in : C olum n L e n g th : IR A -6 7 T im e 6 .7 5 m H o u rs C olum n T e m p e r a tu r e : Room F e e d C o n c e n t r a t io n : 2 .4 g F e e d V o lu m e : B /L Peak o f 10 ml F lo w r a te : 2 5 .1 Im p u r it y End o f B oron B -T T o ta l In p u t F irs t P e r io d s 5 .3 100 1 0 .7 At F ra c t. mg B -IO 24 .1 8 3 5 .3 50 Wt F r a c t . B -IO B -Il B -IO mg mg — — — 9 .8 .1 7 0 .1 5 7 1 .5 Second F r a c t io n .3 .1 9 2 .1 7 7 .1 .2 T h ir d .7 .2 0 2 .1 8 7 .1 .6 F o u rth F ifth T o ta l F r a c tio n R e s id e n c e 3 .2 B e g in n in g o f B oron c c /h r EXPERIMENT K F r a c tio n F r a c tio n F r a c tio n O u tp u t .4 .2 1 0 .1 9 5 .1 .3 1 2 .4 .2 2 1 .2 0 5 2 .5 9 .8 — — — 2 3 .6 P e r c e n t R e c o v e re d 8 .3 — 1007. — . P r o d u c t M o le s C u tp o in t B -IO B -Il W a s te M o le s B -1 0 B -Il P ro d u c t E n r ic h m e n t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n F irs t .0 0 0 2 5 4 .0 0 0 8 9 6 .0 0 0 8 5 .0 0 0 8 5 .2 2 1 1 .3 4 6 .0 7 3 4 Second .0 0 0 2 6 1 .0 0 0 9 2 3 .0 0 0 8 3 .0 0 0 8 3 .2 2 1 1 .3 5 6 .0 7 4 6 T h ir d .0 0 0 2 7 5 .0 0 0 9 7 7 .0 0 0 7 7 ,0 0 0 7 7 .2 1 9 6 1 .3 6 8 .0 7 5 2 F o u r th .0 0 0 2 8 0 .0 0 1 0 0 0 .0 0 0 7 5 .0 0 0 7 5 .2 1 9 1 1 .3 6 9 .0 7 4 7 TABLE 18. R e s in : C olum n L e n g th : C olum n T e m p e r a tu r e : IR A -6 7 T ime 6 .7 5 m H ou rs EXPERIMENT L R e s id e n c e P e r io d s Room F e e d C o n c e n t r a t io n : 2 .4 g F e e d V o lu m e : F lo w r a te : B /L Peak o f Im p u r ity 36 4 .8 31 c c /h r End o f B oron 50 6 .6 In p u t F irs t F r a c tio n S eco n d F r a c t i o n T h ir d F o u rth T o ta l F r a c tio n F r a c tio n O u tp u t P r o d u c t M o le s B -1 0 At F ra c t. B -Il Wt F r a c t . mg B -IO B -IO 60 .1 8 3 5 — B -1 0 B -Il mg mg — — 2 .4 .1 6 2 .1 4 9 .4 2 .0 8 .1 .1 7 3 .1 5 9 1 .3 6 .8 4 2 .1 .1 9 6 .1 8 2 7 .6 3 4 .4 1 3 .8 .2 3 5 .2 1 8 3 .0 1 0 .8 6 6 .4 P e rc e n t R e c o v e re d C u tp o in t .6 B e g in n in g o f B oron B -T T o ta l 4 .8 25 ml 110% — — — — — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n W a s te M o le s B -1 0 . B -Il E n r ic h m e n t F irs t .0 0 0 3 .0 0 1 0 .0 0 0 9 .0 0 3 9 .2 3 4 6 1 .2 9 8 S econd .0 0 1 1 .0 0 4 1 .0 0 0 2 .0 0 0 8 0 .2 0 5 7 1 .2 6 1 .0 2 9 T h ir d .0 0 1 2 .0 0 4 7 .0 0 0 0 4 .0 0 0 1 8 .2 0 1 6 1 .3 0 7 .0 8 5 .0 4 5 O O O O Q O O O O n n o - TABLE 19. R e s in : C olum n L e n g th : IR A -6 7 T ime 6 .7 5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : B /L Peak o f 1 5 ml F lo w r a te : 1 1 .4 Im p u r it y B e g in n in g o f B oron c c /h r End o f B oron B -T T o ta l In p u t F irs t F r a c tio n S eco n d F r a c t i o n T o ta l O u tp u t P e r c e n t R e c o v e re d Produc : t C u tp o in t F irs t ■ B -IO .0 0 0 6 5 At F ra c t. mg B -IO 36 .1 8 3 5 .0 0 2 6 R e s id e n c e P e r io d s 16 .8 94 4 .5 12 5 6 .1 Wt F r a c t . B -IO B -Il B -IO mg mg — — — 0 .3 .1 7 8 4 .1 6 4 9 3 5 .5 8 .1 7 2 8 .1 8 4 .0 0 4 6 .5 4 .0 2 2 9 .0 3 — — — — — — — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n M o le s B -Il EXPERIMENT M W a s te M o le s B -IO 0 B -Il .0 0 0 0 0 1 E n r ic h m e n t .1 9 8 7 1 .1 4 2 .0 0 0 0 9 TABLE 20. IR A -6 7 T im e C olum n L e n g th : R e s in : 0 .5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : B /L Peak o f 10 ml F lo w r a te : 1 1 .7 c c /h r P e r io d s — Im p u r it y — 4 2 .3 End o f 8 4 .7 In p u t B oron At F ra c t. mg B -1 0 24 .1 8 3 5 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — F r a c tio n * .2 .1 8 8 .1 7 4 S eco nd F r a c t i o n 1 0 .0 .1 9 7 .1 8 2 1 .8 8 .1 8 .2 .2 0 2 .1 8 7 1 .5 6 .7 F irs t T h ir d T o ta l F r a c tio n O u tp u t P e r c e n t R e c o v e re d P r o d u c t M o le s C u tp o in t R e s id e n c e B e g in n in g o f B oron B -T T o ta l EXPERIMENT N B -1 0 B -Il ' .0 3 .1 4 1 8 .4 — . . . — — 77% — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n W a s te M o le s B -1 0 B -Il E n r ic h m e n t F irs t .0 0 0 1 5 .0 0 0 6 1 .0 0 0 1 8 .0 0 0 7 5 .2 0 2 1 .0 3 .0 0 8 S econd .0 0 0 3 3 ,0 0 1 3 5 .0 0 0 0 0 2 .0 0 0 0 1 2 .1 9 9 2 1 .0 7 .0 0 0 6 U U U U U U D U U U U--Q_ _L TABLE 21. R e s in : C olum n L e n g th : IR A -6 7 T im e 6 .7 5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : I F lo w r a te : B /L Peak o f ml Im p u r it y B e g in n in g o f B oron 1 1 .6 c c /h r End o f B oron B -T At F ra c t. mg T o ta l In p u t F irs t 2 .4 F r a c tio n .1 8 3 5 R e s id e n c e P e r io d s 18 .9 90 4 .5 125 6 .2 Wt F r a c t . B -IO B -Il B -IO mg mg — — — .2 .1 5 3 .1 4 2 .0 2 8 .1 6 7 S eco n d F r a c t i o n .1 .1 4 9 .1 3 8 .0 1 6 .1 0 0 T h ir d .2 .1 5 5 .1 4 3 .0 2 3 .1 3 8 .2 .1 7 6 .1 6 2 .0 3 8 .1 9 5 .9 .2 2 8 .2 1 2 .1 9 4 .7 2 4 F r a c tio n F o u rth F ifth T o ta l F r a c tio n F r a c tio n O u tp u t 1 .6 P e r c e n t R ec o v e re d P ro d u t ; t C u tp o in t B - IO EXPERIMENT O B -1 0 M o le s B -Il 67% — — — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n W a s te M o le s B -1 0 B -Il E n r ic h m e n t — F irs t .0 0 0 0 2 .0 0 0 0 7 .0 0 0 0 1 .0 0 0 0 5 4 .2 2 8 1 .5 4 .1 0 4 Second .0 0 0 0 2 .0 0 0 0 8 .0 0 0 0 0 6 .0 0 0 0 3 6 .2 1 7 1 .5 3 .0 8 3 T h ir d .0 0 0 0 3 .0 0 0 1 0 .0 0 0 0 0 4 .0 0 0 0 2 4 .2 1 0 1 .4 8 .0 5 6 F o u r th .0 0 0 0 3 .0 0 0 1 1 .0 0 0 0 0 2 .0 0 0 0 1 5 .2 0 5 0 1 .4 1 .0 3 3 8 ) O o o O O o n n n n r, _o> TABLE 22. R e s in : Colum n L e n g th : IR A -9 3 T im e 2 .2 5 m H o u rs C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : F lo w r a te : B /L Peak o f Im p u r it y 15 ml B e g in n in g o f 41 c c / h r End o f B oron B -T T o ta l ' In p u t F irs t F r a c tio n P e r io d s A t F ra c t. B -IO 36 .1 8 3 5 3 .7 2 .0 6 .1 3 .3 Wt F r a c t . B -1 0 • B -Il B -IO mg mg — — — .1 9 1 .1 7 6 7 .5 2 .4 S eco n d F r a c t i o n 1 9 .9 .1 9 6 5 .1 8 1 9 3 .6 1 6 .3 T h ir d 1 0 .3 .2 0 2 5 .1 8 7 5 1 .9 .4 T o ta l F r a c tio n O u tp u t P e r c e n t R e c o v e re d P r o d u c t M o le s C u tp o in t R e s id e n c e NA B oron mg 2 .9 EXPERIMENT S B -1 0 B -Il 3 3 .1 — — 92% — — W a s te M o le s B -1 0 B -Il — — — P ro d u c t E n r ic h m e n t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n F irs t .0 0 0 1 9 .0 0 0 7 6 .0 0 0 4 1 .0 0 1 7 0 .2 0 2 5 1 .0 4 .0 0 9 Second .0 0 0 5 6 .0 0 2 2 4 .0 0 0 0 5 1 .0 0 0 2 2 .1 9 8 5 1 .0 4 9 .0 0 4 TABLE 23. R e s in : C olum n L e n g th : IR A -9 3 T ime 2 .2 5 m H o u rs EXPERIMENT T R e s id e n c e P e r io d s C olum n T e m p e r a tu r e : Room Feed C o n c e n tr a tio n : 5 . Og B /L Peak o f 2 .7 18 ml B e g in n in g o f B oron 4 1 .3 25 c c /h r End o f B oron 6 .5 2 .1 F e e d V o lu m e : F lo w r a te : Im p u r it y B -T A t F ra c t. mg T o ta l In p u t F irs t 90 F r a c tio n B -1 0 B -Il mg mg .5 2 6 --- — 1 8 .7 .4 8 2 .4 5 8 8 .6 Second F r a c t io n 1 3 .9 .5 1 4 .4 9 0 6 .8 T h ir d 59 .5 2 8 .5 0 4 2 9 .8 T o ta l F r a c tio n O u tp u t 9 1 .5 P e r c e n t R e c o v e re d P r o d u c t M o le s C u tp o in t Wt F r a c t . B -IO B -IO B -1 0 B -Il 102% 2 9 .3 — — — — — — — — P ro d u c t S e p a r a t io n E x te n t Of F a c to r S e p a r a t io n W a s te M o le s B -1 0 1 0 .1 B -Il E n r ic h m e n t F irs t .0 0 3 0 .0 0 2 7 .0 0 1 5 .0 0 1 5 .5 2 8 1 .1 3 8 .0 3 0 Second .0 0 3 7 .0 0 3 3 .0 0 0 8 6 .0 0 0 9 ,5 2 5 1 .1 8 9 .0 2 8 o o Q O o f) n n ^ ^ TABLE 24. R e s in : C olum n L e n g th : C olum n T e m p e r a tu r e : EXPERIMENT U IR A -9 3 T im e 2 .2 5 m H o u rs P e r io d s ——— ——— R e s id e n c e Room Feed C o n c e n tr a tio n : 2 .4 g F e e d V o lu m e : F lo w r a te : B /L Peak o f Im p u r it y 30 ml B e g in n in g o f B oron 20 c c /h r End o f B oron B -T T o ta l In p u t F irs t F r a c tio n S eco n d F r a c t i o n T o ta l O u tp u t P e r c e n t R e c o v e re d P ro d u t : t M o le s 2 .5 10 2 .6 A t F ra c t. mg B -1 0 72 .1 8 3 5 Wt F r a c t . B -1 0 B -Il B -1 0 mg mg — — — 7 0 .6 .1 9 8 .1 8 3 1 2 .9 5 7 .7 1 .4 .2 2 5 .2 0 9 .3 1 .1 72 — -----T 100% — W a s te M o le s C u tp o in t B -1 0 ' B -Il B -1 0 B -Il F irs t .0 0 0 0 3 .0 0 0 1 0 .0 0 1 2 9 .0 0 5 2 — — — — — P ro d u c t S e p a r a t io n E x te n t O f F a c to r S e p a r a t io n - E n r ic h m e n t .2 2 5 1 .1 7 6 .0 0 3 3 143 k APPENDIX B 1 SAMPLE CALCULATION ( ( ( ( r V V C C C C O O O O n U r , ---------------------------------= ----- n -------------------------,--------------- ---------------------------- ---------------- 144 To dem onstrate K a k ih a n a 's th e method used experim ents is used. to s c a le th e system one o f T able 25 ite m iz e s th e im p o rta n t data from th e 19 m l/hrocm2 exp e rim en t. TABLE 25. DATA FROM KAKI KAMA'S EXPERIMENT21 BORIC ACID FEED: C o n c e n tra tio n : 0.497M Volume: 10 ml Amount: 0 .0 0 5 moles B-T COLUMN INFORMATION: D ia m eter: I cm Length: 50 cm Cross S e c tio n a l Area: 0 .7 8 5 cm2 F lo w ra te : 19 ml/hrocm2 IN IT IA L DETECTION OF BORON: E f f l u e n t Volume: 50 ml Time: 2 .1 hr DETECTION OF FINAL BORON: E f f l u e n t Volume: 140 ml Time: 5 . 8 hr For th e a 4% in c re a s e in th e boron-10 f r a c t i o n boron fed to th e column would in th e p ro d u c t, 20% o f be recovered as p ro d u c t. The l i n e a r s c a le up o f th e system r e s u l t s in equation 20. Output = a (AREA) For K a k ih a n a 's la rg e r e q u ir e d h o u rly s c a le outp u t o u tp u t work, p la n t is r e q u ir e s (20) th e constant a equals 0 .0 0 13 moles/cm2 . to produce 2 7 .6 a 90% moles 500 kg B-10 b o r o n -t o ta l o n - l i n e tim e . per For a per y e a r , hour. the This Using e quation 20, an 145 area o f 1 23 ,40 0 cm2 is r e q u i r e d . The column volume is 6170 l i t e r s . is $ 4 3 ,1 9 0 . of w ater. From T a b le 25 To produce 1 .9 6 X IO 7 l i t e r s . 500 The column d ia m e te r At $ 7 .0 0 per l i t e r is 396 cm. th e r e s in cost 0 .0 0 1 moles boron-10 produced 0 .0 9 l i t e r s kg b o ro n -1 0 , the system would produce