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
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________________
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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121
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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