Fluid calcination of soda ash
by Jerry Dean Mason
A THESIS Submitted to the Graduate Faculty In partial fulfillment of the requirements for the degree
of Doctor of Philosophy in Chemical Engineering at Montana State College
Montana State University
© Copyright by Jerry Dean Mason (1959)
Abstract:
The problem as undertaken here at Montana State College was to develop a process which could
remove trace organic matter from a commercially produced soda ash as well as generally maintain or
improve other quality features of this ash.
To accomplish this , it was decided to use a fluid calciner using a gas-fired furnace as a heat source and
a compressed air system for the fluidizing air stream. Analysis of the calcined ash was made at Green
River, Wyoming by the Intermountain Chemical Company, producer of the soda ash. The study
involved treatment of both light ash and sodium carbonate monohydrate. Results of the study indicate
that a process which meets the objectives is possible.
It was found that the manner of removal of the contaminants in the various types of ash studied was
that of mass transfer rather than that of oxidation. Therefore, the variables that affect mass transfer
(temperature, stagnant air film, and treatment time) must be considered in determining conditions most
favorable for removing the contaminants.
The data indicate that for a given type of ash calcined under similar conditions, an equilibrium level of
contaminants is reached after sufficient time, regardless of starting level of the ash.
In general, it was found that the organic contaminant level could be reduced from 60 to 80 per cent
depending upon treatment conditions. Further, it was found that the bulk density of the treated light ash
was increased some 15 per cent by the fluid treating.
Addition of sodium nitrate in small amounts (2.3 pounds of sodium nitrate per ton of ash) was found to
be very effective in maintaining a high reflectance (a quality check) on the treated ash for temperatures
above 400°C. Steam mixed, with the air-fluidizing stream has the effect of lowering the contaminant
level of the calcined ash.
The economic considerations of setting up operating conditions are not discussed in this paper. These
data, along with the necessary economic considerations, however, should be an aid in determining the
conditions for manufacture of many grades of high quality soda ash. FLUID CALCINATION OF SODA ASH
by
JERRY D. MASON.
I
A. THESIS
S u b m itte d .to th e G raduate F a c u lty
.
in
■p a r t i a l , f u l f i l l m e n t of th e re q u ire m e n ts
f o r th e d eg ree of
D octor o f P h ilo so p h y i n Chemical E n g in ee rin g
'
a /
Montana S ta te C o lleg e
Approved:
Heady Major D e p a rtm g a ^
Chairman^ Examining Committee
b e a n , - G raduate D iv is io n
Bozeman, Montana
A u g u st, 1959
S> 3 I i
Nv 5 / 1 +
-2 -
TABLE of CONTENTS
Page
ABSTRACT ........................................
3
A BRIEF HISTORY OF SODA ASH
4
MANUFACTURE OF WESTVACO ASH
6
PROPERTIES OF WESTVACO ASH .
8
USES OF SODA ASH
8
.
.
.
PURPOSE OF THE PROJECT
.
.
.
EQUIPMENT USED IN THE PROJECT
COLLECTION OF DATA
ANALYSIS OF ASH
.
ANALYSIS OF RESULTS
.
.
.
.
.
.
.
8
9
13
18
.
.
19
DISCUSSION AND SUMMARY .
.
35
ACKNOWLEDGMENT ...........................
39
APPENDIX ........................................
40
LITERATURE CONSULTED •
•
V I T A ..............................................
•
107
108
133178
-3 ABSTRACT
"The problem as u n d e rta k e n h e re a t Montana S ta te C o lleg e was to
develop a p ro c e ss which could.rem ove tr a c e o rg a n ic m a tte r from a com­
m e r c i a l l y p ro d u ced soda ash as w e ll as g e n e r a lly m ain tain , d r improve
o th e r q u a l i t y f e a tu r e s of t h i s a s h .
<
To accom plish t h i s y i t was d e cid e d to u se a f l u i d c a l c i n e r u sin g a
g a s - f i r e d fu rn a c e as a h e a t so u rce and a com pressed a i r system f o r th e
f l u i d i z i n g a i r s tre a m . A n aly sis, of th e c a lc in e d .a s h was made a t •Green
R iy e r,. Wyoming by th e In te rm o u n ta in Chemical Company ,.p ro d u c e r of th e
soda a s h . The s tu d y .in v o lv e d tr e a tm e n t■of b o th l i g h t a sh and sodium
c a rb o n a te m onohydrate. R e s u lts o f th e s tu d y in d ic a te t h a t a p ro c e ss
which m eets th e o b je c tiv e s i s p o s s ib le .
I t was found t h a t th e manner of rem o v al. of th e co n tam in an ts in th e
v a rio u s ty p es of ash s tu d ie d was t h a t of mass t r a n s f e r r a t h e r th an t h a t
o f o x id a tio n . •T h e re fo re , th e .v a r ia b l e s th a t- a f f e c t.m a s s .tr a n s f e r (tem­
p e ra tu re ., s ta g n a n t a i r f i l m , and tre a tm e n t tim e) must be c o n sid e re d in
d e te rm in in g c o n d itio n s m ost fa v o ra b le f o r removing th e c o n ta m in a n ts .
■The d a ta in d ic a te t h a t f o r a g iv e n ty p e o f ash c a lc in e d u n d er s im ila r
c o n d itio n s , an e q u ilib riu m l e v e l o f co n tam in an ts is re a ch e d a f t e r . s u f . f i c i e n t tim e , r e g a r d le s s of s t a r t i n g l e v e l o f th e a s h .
In g e n e ra l., i t was found t h a t th e o rg a n ic ..contam inant le v e l could
be reduced from 60 to 80 p e r .c e n t depending upon tre a tm e n t c o n d itio n s i
F u r t h e r , i t was found t h a t th e b u lk d e n s ity o f th e t r e a t e d l i g h t a sh
was in c re a s e d some 15 p e r c e n t by th e f l u i d t r e a t i n g .
A d d itio n of sodium n i t r a t e in s m a ll UmourIts (2 .3 pounds o f sodium
n i t r a t e p e r to n of a sh ) was found to be v ery e f f e c t iv e i n m a in ta in in g
a h ig h r e f l e c t a n c e (a q u a lity check) on th e tr e a t e d .a s h f o r te m p e ratu res
above 400°'C. Steam m ixed w ith th e a i r - f l u i d i z i n g stre am has th e e f f e c t
of lo w erin g th e co ntam inant le v e l of th e c a lc in e d a s h .
■ The economic c o n s id e ra tio n s o f s e t t i n g up o p e ra tin g c o n d itio n s a re
n o t d is c u s s e d i n t h i s p a p e r. These d a t a , alo n g w ith th e n e c e ssa ry
economic c o n s id e ra tio n s ,.h o w e v e r, sh o u ld be a n a i d i n d e te rm in in g th e
c o n d itio n s f o r m an u factu re of many g rad es of h ig h q u a l i t y soda a sh .
.—4'-^
I.
A B rie f H is to r y .o f Soda Ash
Soda ash i s th e common name’ for te c h n i c a l g rad es o f sodium car-j
bo n ate .(Ha2CO3 ) .
P r e p a r a tio n ,and. u ses of soda, ash in one _or a n o th e r
o f i t s s e v e r a l forms were w e ll known in e a r ly h i s t o r i c tim e s .
This
'compound i s Qne o f th e few c u r r e n tly im p o rta n t chem icals .which has
been known and used, f o r t h i s le n g th .:of tim e .
ErQm th e tim e b e fo re
C h r is t to th e end o f th e 18th c e n tu ry soda ash was made' from d e p o s its
o f a l k a l i n e la k e s of th e a r i d re g io n s o f Egyp.t and Armenia and from
t h e ash es of p l a n t s , .T h e p ro d u c t was a v ery impure m ix tu re of sodium
and p o ta ssiu m .c a rb o n a te s.
1
A$ t h a t tim e , soda was d e c id e d ly th e le s s im p o rta n t and. th e more ■
ex p en siv e..o f th e two a lk a l ie s ..
P o ta sh was re a d ily ! o b ta in e d by. le a c h ­
in g wood, ashes, which, were a v a i l a b l e ,n e a r l y everyw here'.
A lk a li r ic h e r
in soda was p re p a re d from th e ash es ;o f . c e r t a i n -seashore p l a n t s . - The
p ro d u c t of th e N orth A fric a n la k e s c o n ta in e d p r i n c i p a l l y , c a rb o n a te of
so d a. ■Soda was n o t p r a c t i c a l l y d is tin g u is h e d from p o ta s h u n t i l some
decades p r i o r to L e b la n c 's ach ie v e m en t, and a l l a l k a l i e s were m ix tu res
o f r e l a t i v e l y low q u a l i t y .
The b e s t g rad es from th e .a s h e s of sea sh o re
p l a n t s , such as S pan ish B a r i l l a > c o n ta in e d an a l k a l i e q u iv a le n t of ab o u t
30$ .sodium c a rb o n a te and had. n e a r ly 3 $ .in s o lu b le m a te r ia l.
The p ro ­
d u c t o f th e d e s e r t la k e .beds seldom exceeded a sodium c a rb o n a te .con*
t e n t of 45$.
N ico las L eblanc (17421-1806) was t h e - f i r s t to su c c e e d in changing
•common s a l t . t o s o d a .a s h w ith sodium s u l f a t e as an in te rm e d ia te p ro d u c t.
The . f i r s t com m ercial soda works employing, t h i s new so u rc e o f soda ash
was b u i l t in France- i n YJS-L-.
By l8 l0 .y th e p ro d u c tio n -of L eblanc soda
ash was s u f f i c i e n t f o r th e n a tio n a l re q u ire m e n ts so im p o rta tio n of
f o r e ig n a l k a l i was p r o h ib i te d .
Commercial .p ro d u ctio n in England s t a r t e d
in 1823 b u t th e L eblanc p ro c e ss was n e v e r u sed com m ercially in America.
T hus, in a very s h o r t tim e , an e n t i r e l y .new so u rce .of a l k a l i had
been developed and th e p r im itiv e o r crude methods which h a d been used
f o r some 1800.y e a rs were re p la c e d by t h i s r e v o lu tio n a r y p r o c e s s .
This
n o t.o n ly made soda a sh ch eap er th a n p o ta sh b u t a ls o of a. q u a lity f a r
s u rp a s s in g h i t h e r t o ..known a l k a l i e s and much.more r e a d i l y a v a ila b le from
abundant common s a l t .
This pro d u ct,- Leblanc soda a s h , .c o n ta in e d 9 6 , 5$
sedium c a r b o n a te , ab o u t Lfo in s o lu b le m a t e r i a l , and th e rem ain d er about
e q u al p a r t s of sodium c h lo r id e and sodium s u l f a t e ,
■In ' th e s e few s h o r t y e a rs g r e a t p ro g re s s had. been made b u t th is
p ro c e ss had s e v e r a l u n d e s i r a b l e .p o i n t s .
High consum ption o f f u e l and
l a b o r , .u n d e s ira b le .b y -p ro d u cts , and d is a g r e e a b le w a s te ,m a te r ia ls were
c h a r a c t e r i s t i c s of th e L eblanc p r o c e s s .
I f . t h i s p ro c e ss d id n o th in g
e l s e , i t d id encourage th e se a rc h f o r s im p le r m ethods. - I t was n o t u n t i l
1863y how eyer, t h a t th e conversion, of common s a l t in to .th e c arb o n ate by
a .p ro c e s s u s in g low er te m p e ra tu re s th a n th o s e .used by L eblanc and w ith ­
o u t in te rm e d ia te fo rm a tio n o f s u l f a t e was s u c c e s s f u lly a c h ie v e d .
In
t h a t y e a r , E rn e s t and A lfre d Solyay e r e c te d th e .ir f i r s t so d a ash works
in C o u i l l e t , Belgium f o r th e .m a n u fa c tu re o f soda ash th ro u g h t h e i r
ammonia soda p ro c e s s .
. —6*^
In about 1915 th e .Leblanc p ro c e ss c o m p letely succumbed to th e
ammonia, soda p ro cess' and in i t s l a s t y e a rs was s u s ta in e d .only by i t s
b y -p ro d u c t, h y d r o c h lo r ic - a c id , which was used as a so u rc e f o r c h lo rin e
gas d u rin g th e e a r ly p a r t o f th e f i r s t W orld War.
The ammonia soda p ro c e ss was s u c c e s s f u lly in tro d u c e d i n t o England
in 18Y1I and in. th e U n ite d S ta te s th e f i r s t ammonia soda ash p la n t was
e r e c te d n e a r S y ra c u s e , New York in l 8 8 l.
In more r e c e n t tim e s ¥ d e p o s its o f a n a t u r a l l y o c cu rin g m in e ra l,
tr o n a , have been found i n the- U n ited S t a t e s . • Trona i s an impure form
o f th e chem ical .sodium se sq U ic a rb p n a te (Na2CO3 • NaHCO3 ,* SH2O).
One
o f th e m ajor d e p o s its of i n t e r e s t i s an e x te n s iv e d e p o s it n e a r Green
RiYer,. Wyoming which was d is c o v e re d in th e s e a rc h f o r o i l in th a t a r e a .
The tro n a bed extends o y er s e v e r a l sq u are m iles and i s lo p a te d a p p ro x l.m ateIy 1500 f e e t below th e s u rfa c e betw een two la y e r s o f o i l s h a le .
This d e p o s it i s c u r r e n tly b e in g mined .and c o n v e rte d to h ig h g rad e soda
ash by th e W estvaco Chem ical Company,, and t h i s r e p o r t in v o lv e s c e rta in ,
^ stu d ie s made w ith t h i s ash.
II
M anufacture o f W estvaco Ash
Because of th e type of raw .m a te ria l a v a i l a b l e in th e p ro d u c tio n
of W estvaco Soda Ash, th e p ro c e ss i s q u ite sim ple c o n s id e rin g th e p u r it y
of th e f i n a l p r o d u c t.
To i l l u s t r a t e t h i s .m anufacturing schem e. F ig u re I
(see appendix) i s p re se n te d .sh o w in g th e b a s ic elem ents in th e p ro c e s s .
The m ining i s done in a modern manner making f u l l u se of b e l t con­
v e y o r s ,m e c h a n ic a l lo a d e r s , d r i l l e r s , e t c .
Because of th e s t r u c t u r a l
•—7
s tr e n g th o f th e overburden^ alm ost ho tim b e rin g is r e q u ir e d .
A f te r .th e
'Ore,, is removed from th e tro n a b e d y .it i s conveyed to a c e n t r a l ore
s h a f t .where i t . i s
s to r a g e .
ta k en to th e s u rfa c e i n a sk ip h o i s t an d p la c e d in o re
From h e re * th e o re i s p u t th ro u g h a s c re e n in g .q n d c ru sh in g
.o p e ra tio n , and ch arg ed to t h e .d i s s o l v e r ,
At t h i s p o i n t y . a l l - o f th e s o l­
u b le m a te r ia l i s ta k e n in to s o lu tio n w ith h o t w a te r.
The r e s u l t i n g
s l u r r y from th e d is s o lv e r i s th en ch arg ed to th e c l a r i f i e r w here.m ost of
th e in s o lu b le m a tte r i s removed,,.as a heayy. slu d g e .
o f t h i s c l a r i f i e r i s s e n t" to a s u r g e .ta n k /
L iq u o r from th e top
th e n to a f i l t e r o p e ra tio n
f o r th e rem o v al-o f th e r e s id u a l s o lid s f. and th e n .to a s to ra g e ’ .ta n k .
From th e s t o r a g e . ta n k y th e ,f e e d liq u o r is . charged, to a c r y s t a l l i z e r
w h e re.w a te r i s removed and.sodium , s e s q u ic a rb o n a te c r y s t a l s a re form ed.
P a r t i c l e s i z e ,is in flu e n c e d by. th e a d d itio n o f D - 4 ,0 a s y n th e tic d e te r .SO3Na
.g e n t f y
L J ,c
,c
r
c
c . . c - .q v ..q .q -..q - .c , and q a r e f u lly m easured amounts
a re added to o b ta in th e d e sire d , p a r t i c l e s i z e from, th e - c r y s t a l l i z e r .
• F ollow ing th e c r y s t a l l i z a t i o n , th e s e s q u ic a rb o n a te and liq u o r a re se p ­
a r a te d by. s e t t l i n g ,,and. by a c e n t r i f u g a l s e p a r a to r .
The .s o lid s from t h i s
o p e ra tio n a re f e d .t o a steam h e ate d , c a lq f n e r and. th e liq u o r i s re c y c le d
.to th e d is s o lv e r ., .,In .the c a lc in e r th e -c h a rg e ,is d r ie d a n d .c o n v e rte d
in to , so d a .ash i
The re a c tio n ! h e re can b e g iv en -b y th e equation,:
- 2 [NagCO3 . - ■NaHCO3 ■• - 2Hg^-S> JNa2CO3 ;+ ' JH2O + CO2 ;
The d is c h a rg e .fro m th e . c a lc in e r i s . a t a .te m p e ra tu re , of 240°C.
From
h e r e y .th e soda, ash i s c o o le d .b y w a te r ja c k e te d .conv.eyors and s e n t to
>-8'—
■
p ro d u c t s to r a g e as l i g h t ash o r to re-treatm en t, in th e p ro d u c tio n o f dense
ash..
Ill
P r o p e r tie s o f W estvaco Soda- Ash
T able I (see appendix) giv es.a.su m m ary of some of th e b a s ic chem ical
a n d .p h y s ic a l d a ta on g rad e 100 l i g h t ash a s p u b lis h e d by. th e Westyaco-■Chlor--A lk a li D iv is io n of th e Westya.co Chemical Company.
IV
U ses. o f Soda Ash
Soda ..ash i s one o f th e .most im p o rta n t chem icals and th e most w id ely ,
used fix e d , ,a lk a li in th e manufacture o f o th e r .a l k a l i p ro d u c ts
sodium
- s a lts , g la s s , .Soap, .p p lp and paper.,, ir o n and . s t e e l , aluminum.,, clean in g ,
compounds., w a ter s o fte n in g compounds, . t e x t i l e s , d ru g s , c la y and b r i c k ,
b e e t sugar.,;, and, many, o th e r s .
F ig u re 2 (see appendix) shows th e d i s t r i b -
t i o n o f .u s e of soda ash f o r th e y e a r 1950. ■T o ta l consum ption in. 1950
was a lm o s t 4 .5 m illio n to n s o f soda a sh .
Y F u rp o se '.of the- P r o je c t
As m entioned aboyd>- th e tr o n a .d e p o s it .used in th e m an u factu re of
"Westvaco Ash" i s .-located .between two la y e r s of o il- b e a r in g s h a l e .
Be­
cause of i t s p ro x im ity to th e s h a le ,, th e 1t r o n a .c o n ta in s sm all-am ounts
of o r g a n ic .m a te r ia l.
Some, of th e s e .m a te r ia ls a r e w ater s o lu b le and,
b e ca u se of th e.m eth o d o f.m a n u fa c tu re o f soda a s h , fin d , t h e i r way in to
th e f i n a l .p r o d u c t .
-The chem ical oxygen, demand-. (C0D)> i n d i c a t i v e of
o rg a n ic co n ten t,- w i l l ru n from 5QQ to 500 ppm f o r a t y p i c a l a sh made in
th e ,manner d e s c rib e d e a r l i e r i n / t h i s r e p o r t . - For many of W estyacp's
-~9CUStomers ,,.th is tr a c e o f o rg a n ic m a te r ia l i s o b je c tio n a b le .
In a d d i­
t i o n , . th e foam ing .-c h a ra c te ris tic 's of W estyacp Ash was i n some cases
found o b je c tio n a b le .
P pr t h i s re a s o n th e p r o je c t was .undertaken h p re ;
. a t Montana S tu te C ollege to d e v is e a .method, o f re d u c in g th e o rg an ic
c o n te n t o f th e a sh and,- in g e n e r a l, im prove th e q u a lity o f th e .a s h .
To,...accomplish th e .re d u c tio n -of fh e o rg a n ic m a te r ia l,, i t was d e. e ld e d .t p . c a l c i h e . s o d a .a s h i n a f I u id ia e d ..s t a t e a n d .stu d y th e e f f e c t s of
re s id e n c e tim e , te m p e ra tu re , bed. d e n s it y , and - s ta r tin g m a te r ia l.
-In
a d d i t i o n to th e e f f e c t s qf th e s e v a r ia b le s on re d u c tio n o f o rg a n ic .c o n ­
t e n t , a s tu d y was a ls o made .to .determ in e th e e f f e c t s o f th e s e v a ria b le s
,on o th e r p h y s ic a l and. chem ical .c h a r a c t e r i s t i c s -of so d a a s h .
Thebe'
- c h a r a c te r is tic s .a r e :
I . CQD (an in d i c a t i o n o f o rg a n ic .co n ten t).
-2 . Bulk d e n s ity
3. Iro n c o n te n t
- 4 . • Foam h e ig h t
5. ; D-4 O c o n te n t
6. Ash r e f l e c t a n c e .
As t h e .p r o j e c t p ro g r e s s e d , s e v e r a l . d i f f e r e n t ty p es o f soda ash were
charged, t o .th e f lu id , c a l c i n e r .
These .-can be d iv id e d i n t o .th re e , m ajor
I
groups : I ) sodium c a rb o n a te (grade 100 .l i g h t ash) , 2) ,-sodium carb o n ate
.monohydrate-, . and 3) sodium c a rb o n a te monohydrate w ith t r a c e amounts of
sodium n i t r a t e added to th e c a r b o n a te .
•VI
Sbnipmont Used i n th e P r o je c t
As o r i g i n a l l y c o n c e iv e d , .th e f l u i d c a lc in e r was to u se a . n a t u r a l
gas h e a t s o u rc e and th e p ro d u c ts of com bustion as th e f l u i d i z i n g medium..
In th e e v en t t h a t th e p ro c e ss developed in to a p r a c tic a l .s itu a tio n * , th e
-1 0
c h o ic e of n a tu r a l gas f o r h e a tin g was lo g i c a l s in c e . i t i s an abundant and
Cheap h e a t so u rc e in th e Wyoming a r e a .
ed w ith t h i s i n m ind.
The f i r s t c a l c i n e r was c o n s tr u c t­
B ecause t h e Lproducts of com bustion were to be u sed
as th e f l u i d i z i n g m e d i u m i t was n e c e s s a ry to c o n s tr u c t a fu rn a c e th a t •
co u ld o p e ra te u n d er a .s m a ll p o s i t i v e p r e s s u r e .
F ig u re 3 (s e e appendix)
shows th e flow diagram of th e f i r s t c a lc in in g u n i t .
The fu rn a c e was
b u i l t o f f i r e b r i c k i n s i d e .a S te e l framework and s u p p lie d w ith, com pressed
a i r and n a t u r a l g a s .
A gas d u c t from th e fu rn a c e to th e r e a c to r
c a r r i e d th e com bustion g ases and p ic k e d up th e f r e s h c h a r g e .o f soda a sh .
This charge was re g u la te d by use -of a .gate ,v a lv e .
The com bustion g ases
and c h arg e e n te re d th e bottom of th e r e a c t o r where th e f l u i d bed was
h e ld .
As f r e s h c h a rg e e n te r e d th e bottom of th e r e a c t o r , some of th e
f lu id iz e d .b e d .w a s f o r c e d .to s p i l l over i n t o th e d is c h a rg e tu b e alo n g
w ith th e f l u i d i z i n g medium.
The h o t g ases s e p a r a te d from th e b u lk of
th e ash i n th e d u s t e lim in a to r a n d .were th e n .v e n te d to an o ff -g a s s ta c k
thro u g h a c y c lo n e .
A w a ter c o o le r was p la c e d .a ro u n d th e d is c h a rg e tube
to co o l the' e x i t c a lc in e d a s h .
The fu r n a c e t h a t was c o n s tr u c te d was
c u b ic a l in shape * about 20 . in c h es .o n a s i d e .
A .hole was p la c e d on th e
top to p e rm it l i g h t i n g . o f th e b u rn e r and was f i t t e d w ith a h ig h tem pera*
tu r e ceram ic p lu g to- p ro v id e a p r e s s u r e s e a l .
Both th e h e a t d u ct -and
c h arg e tu b e were I - in c h s ta n d a rd b la c k ir o n p ip e .
The r e a c t o r was f a b -
. r i c a t e d from type 316 s t a i n l e s s s t e e l . a n d was c o n ic a l in sh ap e.
Its
o v e r a ll h e ig h t was 36 in c h es and m easured I in c h a t th e bottom o r e n try
p o in t.
A cross th e top y i t m easured 6 in c h es and a t th e d is c h a rg e p o in t..
-'.11-
2 f e e t from th e .b o tto m y th e d ia m e te r was alm o st 4 . in c h e s .
The d is c h a rg e
tu b e slo p e d down 45° from th e h o r iz o n ta l and em ptied i n t o th e d u st e lim i­
n a to r .
This l a t t e r u n ity t h e dust elim inator y was a pyram id I f o o t
s q u a re a t th e top and ta p e r e d down to f i t a 2-in c h d is c h a rg e p ip e a t th e
bottom .
From th e top of th e d u s t e l i m i n a t o r , l - l / 2 - i n c h pipe' was used
to v e n t th e o ff -g a s i n t o th e cyC lone.
A 6-in c h s t e e l p ip e was used as
th e o u te r s h e l l . o f th e c y c lo n e a n d .th e r i s e r in s id e th e c y clo n e w as>
a g a in , a 1 -1 /2 -in c h p ip e .
W herever p o ssib le ,,, .th e u n i t was co v ered w ith
a 1 -in c h th ic k n e s s of m agnesia mud i n s u l a t i o n .
A fte r s e v e r a l t e s t o p e ra ­
tio n s y i t was d e cid e d to a l t e r th e sy ste m .b e ca u se o f - d i f f i c u l t y in
m a in ta in in g th e n e c e s s a ry p r e s s u r e , an d b ecau se of o p e r a tio n a l h a z a rd .
I t was d e c id e d to ru n s t e e l p ip e s th ro u g h th e fu rn a c e and h e a t
com pressed a i r .
-This h o t com pressed a i r was u sed a s th e f l u i d i z i n g
medium r a t h e r .t h a n th e com bustion p ro d u c ts from th e fu r n a c e .
t h i s c h an g e, th e flow was th e same a s b e f o r e .
O ther th a n
The c a lc u la tio n s in d ic a te d
t h a t th e r a th p r sm a ll q u a n t i t i e s of a i r r e q u ire d f o r f l u i d i z i n g would
have to. be in th e n e ig h b o rh o o d .o f 20000C i n o rd e r to m a in ta in a 1000gram bed o f a sh a t 400°C.
S ince i t was im p o s s ib le to p r e h e a t th e a i r
to t h i s te m p e ra tu re , a d d itio n a l h e a t was o b ta in e d by b u ild in g , a ja c k e t
around th e r e a c t o r th ro u g h which .th e h o t com bustion g ases co u ld be p a s s e d
b e fo re v e n tin g .
To f a c i l i t a t e r e p a i r s to th e u n it., which were o c c a s io n a lly n e ce s­
sary ,
th e m agnesia was e v e n tu a lly re p la c e d by a 3-in c h la y e r .o f ro ck
wool b a t t i n g which c o u ld be removed .and a p p lie d w ith much le s s d i f f i c u l t y .,
■- 1 2 -
The ro c k wool was In tu r n wrapped, w ith s h e e ts o f aluminum, f o i l to m in i. mize- h e a t lo s e by r a d i a t i o n , ■This co m b in atio n p ro v id e d e f f e c tiv e ' In ­
s u l a t i o n and te m p e ra tu re s in th e re g io n -of 560°"C c o u ld b e a t t a i n e d w ith ­
i n th e bed.
■F u r th e r tro u b le s showed up in t h e flow p a t t e r n y .h o w e v e r a s fre q u e n t
c lo g g in g o c c u rre d a t th e p o in t where th e f r e s h c h arg e e n te r e d th e h o t
f l u i d i z i n g .g a s s tre a m .
t h i s o b s tr u c tio n ,
This o f te n caused shutdown o f th e u n i t to c le a r
A f u r t h e r change i n flow p a t t e r n had to b e made to
to a v o id .th is p o in t o f f r e q u e n t clogging..
The .fr e s h c h arg e was. added
d i r e c t l y to th e top s u r f a c e o f th e f l u i d bed and a much sm oother opera­
tio n re s u lte d .
One a d d i t i o n a l .d if f ic u lty .c a m e as a r e s u l t of tu b e f a i l u r e in th e
fu r n a c e .
Tb c o r r e c t t h i s p o in ty s t a i n l e s s s t e e l p ip e s w ere u se d in th e
fu rn a c e ,
This was found to be .very e f f e c t i v e as only, one rep lacem en t
of th e s t a i n l e s s s t e e l p ip e s was r e q u ir e d i n two y e a r s . o f s e r v ic e .
One
fu r th e r .c h a n g e was made on th e u n i t and t h i s was done b e ca u se th e a i r
com pressor in th e la b o r a to r y d id n o t h av e s u f f i c i e n t c a p a c ity to su p p ly
th e re q u ire m e n ts of b o th th e f lu i d .b e d and th e n a t u r a l gas b u r n e r .
Spencer f o u r ^ s ta g e blow er was u sed a s .a n a i r su p p ly f o r .th e b u rn e r.
A
The
.c a p a c ity of t h i s blow er was 12 OPM .a t 35 o u n c es.
•F ig u re 4 (s e e appendix) shows th e f lo w .p a tte r n of th e c a lc in in g
u n i t as i t f i n a l l y d ev elo p ed .
q u i t e s im p le .
The soda ash flow th ro u g h th e u n it i s
From th e hopper la b e le d >c h a rg e 1 in. F ig u re 4 i t is. dropped
by g r a v ity onto th e s u r f a c e .of th e f l u i d i z e d bed.
H ere, b e c a u s e .o f th e
bed movement * th e f r e s h charge i s im m e d iately .d rag g ed downward .and mixed
th ro u g h o u t th e bed.
The p ro d u c t o r o v e rflo w .fro m th e r e a c t o r i s d is ­
charged in to p o r c e l a i n - l i n e d b u c k e ts . ■The flo w o f th e .f lu i d iz in g medium
thro u g h th e u n i t s t a r t s a t th e fu rn a c e where i t i s h e a te d to ab o u t 800
o r 900°‘C.
From, th e f u r n a c e , . i t e n te r s th e bottom of th e r e a c t o r where
i t mixes w ith th e bed.
The h o t com bustion g ases e x itin g from th e fu rn a c e
a f t e r p a s s in g th ro u g h th e ja c k e t su rro u n d in g th e r e a c t o r a r e ex h au sted
to th e s ta c k .
The e x ch a n g e r, of c o u rse * s e rv e s a d u a l p u rp o se * I ) i t
makes u se of i4hat o th e rw is e m ight go as w aste h e a t * and 2) i t co o ls th e
com bustion p ro d u c ts from th e fu r n a c e a n d .a llo w s th e h a n d lin g o f a much
c o o le r o ff -g a s stre a m .
The d u s t e lim in a to r was found to be s u f f i c i e n t and th e cy clo n e was
seldom u s e d ," a s th e d u s t problem was n o t s e r io u s a t t h i s p o i n t ;
Regu-*
l a t i o n o f th e r a t e a t which new..ash was added to th e bed was dene .by
use of a s ta n d a rd g lass, s to p c o c k .
W ith t h i s arrangem ent th e f e e d .r a t e
co u ld be v a r ie d from ab o u t 25 grams p e r m inute to over 100 grams p e r
m inute and by c o n tr o llin g th e bed d e n s ity a t th e p ro p e r le y e l., a r e s i —
dence o r r e t e n t i o n tim e o f from I to 35 m in u tes c o u ld b e a t t a i n e d .
By
c o n tr o llin g th e amount o f gas and a ir . f e d to th e furnace*, th e tem pera­
tu r e •c o u ld b e c o n t r o l l e d .
V II
C o lle c tio n of Data
In g e n e r a l, th r e e ty p es of s t a r t i n g m a te r ia l haye been used in t h i s
s tu d y . • These h av e been m entioned above b u t f o r review th e y a r e , I) l i g h t
a s h , 2) m onohydrate, and 3) m onohydrate w ith abided amounts o f sodium
n itra te .
AltJaough p ro c e d u re was s i m i l a r f o r a l l .ty p es o f m a te r ia ls c a l­
c in e d , the' .m onohydrates r e q u ir e d a p re d ry in g s te p b e fo re th e a c t u a l c a l ^
■c in in g was c a r r i e d .o u t .
The d ry in g ste p , was e f f e c t e d in th e c a lc in e r a t te m p e ra tu re s in th e
range o f 100 to 1500C.
B ecause th e s t a r t i n g m a te r ia l i s a m onohydrate,
tre a tm e n t a t t h i s te m p e ra tu re r e s u l t s in .the d is c h a rg e .of steam .
U su a lly
th e bed was fe d a t r a t e s o f oyer 100 grams of th e .monohydrate p e r m in u te ,
r e s u l t i n g i n th e fo r m a tio n of a b o u t. 15 grams, of steam p e r m in u te.
For
t h i s r e a s o n , th e norm al f e e d in g mechanism co u ld n o t be u sed ,as th e steam
d is c h a rg e caused c ak in g of th e c o ld a sh a t th e fe e d e n tra n c e .
The ash
was p o u red by hand thro u g h th e top of th e r e a c to r onto th e s u r f a c e of
th e f l u i d bed a t such a r a t e t h a t th e te m p e ra tu re c o u ld b e m a in ta in ed
.somewhere betw een th e l i m i t s o f 100 to 150°C.
This p ro c e s s was c a r r ie d
o u t u n t i l enough .o f th e d r ie d m onohydrate was c o lle c te d to su p p ly s u f ­
f i c i e n t f e e d f o r th e r e q u i r e d .runs i n th e s tu d y and a n e c e s s a ry sam ple
f o r a n a ly s is .
This, same p ro c e d u re was c a r r i e d out on a l l o f th e . mono-
h y d ra te s in v e s t ig a te d in. t h i s work.
• T em perature measurement was made by u se o f an I r o n -c o n sta n ta n
therm ocouple in c o n ju n c tio n w ith a p o te n tio m e te r.
The therm ocouple was
lo c a te d in th e .c e n te r o f th e bed a lo n g th e v e r t i c a l a x is o f th e r e a c t o r .
The su rro u n d in g therm ow ell was a .p i e c e o f pyrex- g la s s tu b in g .
tu r e g r a d ie n t o f le s s th a n
A tem pera­
from to p to bottom of th e r e a c t o r was n o r­
m al u n d e r.o p e ra tin g c o n d itio n s .
Feed r a t e s wefe d eterm in ed and .kept
w ith in l i m i t s by m easuring th e r a t e o f d is c h a rg e from th e u n i t .
.»*15-
The p ro c e d u re f o r c a lc in in g d r i e d .monohydrate p r l i g h t ash was th e
same,
A h e a t ^up tim e o f a b o u t 90 m inutes was r e q u ir e d b e fo re any s te a d y
s t a t e c o n d itio n s c o u ld b e a c h ie v e d .
This h e a t-u p p e r io d p ro v id e d tim e
to g e t th e f u r n a c e , com bustion gases ,, gas d u c ts , and th e r e a c to r a t h ig h
enough te m p e ra tu re to in s u r e t h a t th e f l u i d bed co u ld be .m aintained, a t
th e d e s ir e d .te m p e r a tu r e l e v e l ,
F o llo w in g th e h e a tin g p e r io d , a sh was f e d
to th e f l u i d bed and th e a i r r a t e was a d ju s te d .b y a n e e d le v a lv e i n o rd e r
to o b ta in a d e sire d , l e v e l o f ash in. th e b e d .
Next* th e fe e d r a t e was
.re g u la te d to g iv e a. p re d e te rm in e d r e te n tio n , tim e .
F in a lly * th e gas fe e d
to th e fu r n a c e w as. a d ju s te d , to g iv e th e p ro p e r . te m p e ra tu re ,
.ment was q 'u ite . c r i t i c a l and f r e q u e n tly r e q u ir e d ad ju stm en t*
This adjust?-,
W ith th e s e
a d ju stm e n ts m ade*.a p e rio d o f lin e ^ o u t fo llo w e d .in . which .steady, s t a t e
■conditions were m a in ta in e d w ith in as narrow, lim it s as p o s s ib le ,
This
c o n d itio n was m a in ta in e d th ro u g h a p e rio d of n o t le s s th a n th e a n t i c i ­
p a te d r e t e n t i o n tim e p r i o r to s t a r t i n g th e ru n pro p er*
A t .th e e n d .o f
t h i s p e rio d th e run was c o n tin u e d u n t i l a sample of 8 0 0 .to 1000 grams of
c a lc in e d a sh was c o lle c te d .
At th is , tim e th e run was co m p leted .
Opera­
t i n g ,d a ta was re c o rd e d ev ery th re e .m in u te s through .th e p e r io d i n which
a..sam ple was b e in g c o lle c te d .
I*
Z.
3«
4.
T h e s e .d a ta c o n s is te d of.:
E lap sed tim e
G ro ss.w eig h t o f a sh c o lle c te d
P r e s s u r e drop a c ro ss th e b e d
Tem perature w ith in th e f l u i d bed*
By way o f i l l u s t r a t i o n * assume t h a t i t w a s ,d e s ire d to make a ,r u n
a t th e fo llo w in g c o n d itio n s :
,
.- 1 6 -
TBBiperature - 350 °C
R e te n tio n tim e •- 20 m inutes
Red w eight — ^OO gram s.
Knowing th e d e s ir e d bed w eight and r e t e n t i o n tim e allo w ed th e c a lc u la tio n
Of th e p ro p e r fe e d r a t e .
This was done by d iv id in g th e bed w eight by
th e r e t e n t i o n tim e,; g iv in g a v a lu e of 4^ grams of a sh p e r m in u te. ■Be­
f o r e such a ru n was s t a r t e d * t h e r e a c t o r te m p e ratu re was b ro u g h t to a
l i t t l e over 600°C.
F ig u re 5 (see app en d ix ) shows a t y p i c a l he a t ^up curve
w here the- te m p e ra tu re i s t h a t m easured in th e empty r e a c t o r .
th e n ad d ed to th e bed to b r in g th e w eight up to gOO g ram s.
Ash was
This was
accom plished by using, .a monometer to i n d i c a t e th e p r e s s u r e drop a c ro ss
the' b e d .
This manometer was co n n ected to. th e .f lu i d iz in g ,a i r stream a t a.
p o in t j u s t o u ts id e th e f u r n a c e .
In t h i s way th e t o t a l p r e s s u r e d i f ­
f e r e n t i a l was in d ic a te d .on th e ,manometer and t h i s * in t u r n .,. in d ic a te d
th e approxim ate ..amount o f a s h p r e s e n t a t any i n s t a n t i n th e bed*
T able
I I (see appendix) shows v a lu e s of c o rre sp o n d in g bed .w eights and mano.m eter
re a d in g s .
From. Table I I i t can be see n t h a t th e b ed s h o u ld be
ru n w ith a.m anom eter re a d in g o f about 1% to .1.7.5 in ch es of w a ter i n
o rd e r to ,m a in ta in a bed w eight o f 900 g ram s.
To acco m p lish th is * th e
p ro p e r a i r r a t e was s e le c te d and. th e fe e d r a t e a d ju s te d to b e -45 grams
p e r m in u te .
Once th e s e a d ju stm e n ts w ere com pleted* .th e f i n a l -adjustm ent
on th e fu rn a c e was made and th e te m p e ra tu re b ro u g h t to th e '.d e s ir e d l e v e l .
■Follow ing t h i s s te p * c o n tin u o u s m easurem ents a n d a d ju stm en ts, were made
th ro u g h o u t th e ru n t ° m a in ta in th e d e s ir e d o p e ra tin g c o n d itio n s ,.
A fte r
a s u f f i c i e n t p e r io d o f s te a d y s t a t e c o n d itio n * .w h ic h in t h i s example was
c o n sid e re d to b e .a minimum o f 20 minutes.* th e ru n was c o n tin u e d ..u n til a
■sample^ .of .800 t&.lQOO grams had. been c o lle c te d .
co rd ed e v ery th r e e m in u te s.
O p eratin g d a ta was re-^
Table I I I (gee appendix) . i s a copy of th e
o p e ra tin g .d a ta as ta k e n Ju n e 24* 1957 on a. ru n s im ila r to t h a t j u s t
d e s c rib e d .
Once a. sam ple wag c o l l e c t e d as i l l u s t r a t e d in T able I I I , i t was
s to r e d i n a p o ly e th y le n e f r e e z e r bag* p la c e d in s id e a sealed * , h a rd p la s ­
t i c c o n ta in e r* and s t o r e d p r i o r to a n a l y s i s .
When a group o f samples ,r:say
8 tQ 10 sam p les* . h ad been c o lle c te d .,, th ey , were packaged and m ailed, to
Green R iver* Wyoming f o r a n a ly s is .
As m entioned p re v io u s ly * th e s ta r t i n g , m a te r ia ls f o r th e v a rio u s
ru n s c o n s is te d e s s e n t i a l l y . o f monohydrates a n d l i g h t a s h .
T a b le IV
(s e e appendix) l i s t s th e manner i n which th e s o u r c e .o f t h e v a rio u s
s t a r t i n g m a te r ia ls a r e r e f e r r e d to i n . t h e ta b u la te d d a ta .
•In essence* each s t a r t i n g . m a t e r i a l was used to make a s e r i e s , o f ru n s
in which r e t e n t i o n tim e and te m p e ra tu re were v a rie d .
F o r l i g h t ash
a s e r i e s was a ls o made .in which th e b e d .d e n s ity of th e a s h was v a rie d .
A l l .runs made w ith l i g h t ash a r e d e s ig n a te d sim ply by number. ■Runs
made w ith Drum. I (m onohydrate) c o n ta in a p r e f i x "M" b e f o r e th e number.
Runs made to ,determ ine t h e . e f f e c t o f WaNO3 .a d d itio n s .a r e d e s ig n a te d
"MN-11.
One o th e r b r i e f s tu d y was .made to o b serv e th e e f f e c t s of steam
■i n th e f l u i d i z i n g s tre a m .
These s e r i e s w ere accom plished by adding
w a te r to the' h o t a i r (c a ll e d s te a m .s e r ie s "S-^") .
T ab le V .and VI (see
appendix) p r e s e n t th e o p e ra tin g , d a ta an d a n a l y t i c a l ..data .C o lle c te d f o r
th is .w o r k .
In a d d i t i o n , some c ro s s -in d e x ta b le s a r e in c lu d e d t ° show
th e Varl-ous ,rims made u s in g ,.s im ila r , re te n tio n , tim e s .o r s im ila r tem pera^
tu re s y e t c .
•V III
A n a ly sis o f Ash
The a n a ly s e s of th e .a s h were .made a t G reen,R iv e r>. Wyoming, by th e
In te rm o u n ta in Chemical -Company.
I t was f e l t th a t.b e c a u s e some of th e s e
b e s ts w e r e .e m p lr ic a lx .it would be b e s t i f th e a n a l y t i c a l work were' done by
. those,.people- who were b e s t .tr a in e d to p e rfo rm .the t e s t s . .
more c o n s is te n t s e t . o f d a ta m ig h t b e o b ta in e d .
In. t h i s way* a
In th e ap p en d ix are' c o p ies
.o f t h e .i n s t r u c t i o n s f o r p e rfo rm in g . some o f th e v a rio u s a n a l y t i c a l s te p s .
Three b e s ts perform ed.on. th e .p ro d u c t Qf th e f lu id , c a lc in e r a r e n o t
o u tlin e d , in. th e s e i n s t r u c t i o n s . • These t e s t s a re sta n d a rd , i n th e a n a ly s is
of a soda ash sam ple b u t a r e . e m p iric a l,
D e term in atio n o f b u lk .d e n s ity
i s made by dropping a ch arg e o f ash from a s p rin g -lo a d e d ..s p lit, .d ish in to
a v e s s e l -Cf known w eight and volume!
The charge .is p la c e d .on th e s p l i t
■ m etal-dish a n d .th e v e s s e l i s p la c e d in p o s i t i o n b e n ea th th e .charge.
Upon
tr i g g e r i n g the. mechanism* th e two h a lv e s of th e s p l i t . d i s h a r e p u lle d
q u ic k ly ap art* , .causing, th e charge ,to, f a l l into- th e ,c o lle c tin g - v e s s e l.
A .s t r a ig h t e d g e .is used to smooth th e top s u r f a c e of th e ash a n d .sc ra p e
away th e excess m a t e r i a l .
The. v e s s e l and ash a re th e n weighed an d th e
.r e s u lts a re r e p o r te d as ,bulk, d e n s i t y . .
■loam, h e ig h t * a ls o a n e m p iric a l t e s t * i s a ,measure of th e f oaming
c h a r a c t e r i s t i c s of th e ash ,.
This d e te rm in a tio n is . made th ro u g h use o f
a . IOOaoentimeber g la s s column and. some p ro p e r tu b in g ,n e ar .th e ,bottom -of
. th e g l a s s , column.
A charge of soda.ash- i s p la c e d i n th e . v e r t i c a l column.
19*
and. .phosphoric a c id i s ru n in to th e column th ro u g h th e tu M n g a t th e
bottom o f th e column.
In each.C ase th e same amount o f a c id i s a d d e d .a t
th e same r a t e and th e h ig h e s t column of foam is re c o rd e d a s foam h e i g h t .
The t h i r d d e te r m in a tio n ,, t h a t of r e f le c ta n c e o r sodium trip o ly p h o s ­
p h a te r e f l e c t a n c e , i s made )?y cpm paring th e r e f l e c t a n c e .o f l i g h t from a
w h ite b lo c k (s ta n d a rd a n d .a c c e p te d as 100$ r e f le c ta n c e ) and. a sam ple of ■
f i n e l y ground so d a a s h .
This r e s u l t i s r e p o r te d .a s p e r c e n t r e f le c ta n c e
e i t h e r .from th e so d a ash o r from sodium, trip o ly p h o s p h a te p re p a red , from
th e c a lc in e d a s h .
The r e f l e c t a n c e and foam h e ig h ts a r e in d ic a tio n s o f th e chem ical
d u a lity o f .the ash where h ig h r e f le c ta n c e and low foam h e ig h ts a re th e
m o s t-d e s ira b le in a s a le a b le p r o d u c t.
A h ig h b u lk d e n s ity i s a ls o
d e s ir a b le .
I
■IX A n aly sis o f R e s u lts
Two d i s t i n c t mechanisms of rem oval o f th e o rg a n ic m a te r ia l from th e
ash seem f e a s i b l e .
F i r s t , th e m a te r ia l c o u ld b e o x id iz e d in th e f l u i d bed
and removed .a s .CO2 and H2O. -This would be a mechanism o f chem ical re~a c ti o n and,, b ecau se .of th e low., le v e ls of o rg a n ic m a tte r in th e ash and th e
am ount,of a i r n e e d e d .to f l u i d i z e t h e b e d , a sim ple a ssu m p tio n of f i r s t
o rd e r r e a c tio n would seem reasonab le-.
In d i f f e r e n t i a l form a f i r s t o rd e r
r e a c tio n can be expressed..by
- . dC.= bC
d&
or
--dC = bd&
C
(I)
(
2)
-iSO-1
zCF
or
or
where
.dC = b
c
d@
(3 )
.In (G 0Zcp ) .= W
(4)
C is . th e .c o n c e n tra tio n o f contam inants
. 0 ..is tim e
b .is a c o n s ta n t
Srom e q u a tio n 4 i t can h e seen t h a t a p,lo t of th e ,log o f th e r a t i o
•of th e S t a r t i n g to th e r e s u l t i n g c o n c e n tra tio n of o rg a n ic .m a te ria l p l o t t e d
a g a in s t tim e sh o u ld g iv e . a s t r a i g h t - l i n e of slo p e K.
I t m ight be remem­
b e re d t h a t th e r e a c tio n r a t e c o n s ta n t, K,. is a .fu n c tio n o f te m p e ratu re so .^
runs must be p ic k e d .fo r t h i s p l o t where te m p e ra tu re i s .not a v a r i a b l e .
•T able -V III (see appendix), i s a summary, o f c a lc u la tio n s , f o r t h i s k i n e t i c
P lo tl
■T.able V III p e r ta in s to l i g h t ash from Drum I, c o n ta in in g . 562 ppm COD.
l e v e l as a . s t a r t i n g m a t e r i a l .
By u s in g th e r a t i o CODq/COD^ , no need .of
f u r t h e r c o n v e rsio n to c o n c e n tr a tio n i s n e c e s s a ry s in c e th e r a t i o would pe
th e sa m e .in any o th e r u n its .a s i t i s i n term s, of COD l e v e l .
F ig u res 6,.
7 x and 8 (see appendix.) p r e s e n t th e d a ta of Table V III as a p l o t .of
log(C0Do/C 0D f) a g a in s t tim e ( r e te n tio n .time .of th e psh w ith in th e b e d ) .
W ith t h i s type' of p l o t i t sh o u ld be remembered, th a t th e f u n c tio n
log(C0Do/C0Df ) v e rsu s tim e goes th ro u g h th e . o r ig i n . - I t i s q u ite c le a r
t h a t very p o o r c o r r e l a t i o n can be .fo u n d .u n d er th e mechanism o f chem ical
r e a c tio n c o n cern in g th e l i g h t ash. fro m Drum I .
P ic k in g a group of runs
made from Drum 3 and a te m p e ra tu re n e a r ■475°C, t h i s same p o o r c o r r e l a t i o n
.-2 1
.can. .bg -shown c o n ce rn in g chem ical r e a c tio n .
F ig u re 9 (see appendix) shows th e d a ta of T ab le IX (k irie tic -data
f o r Drum 5 l i g h t ash) p lo tte d , as Iog(COD0ZCOpf ) y ergus tim e and h e r e ^
a g ain ^ no c o r r e l a t i o n can be found f o r t h i s d a ta where th e mechanism is
one o f ch em ical r e a c t i o n .
This same s o r t of c a lc u la tio n and p,lQt could
b e u sed to .show t h a t a chem ical ,re a c tio n , mechanism, i s n o t th e p ro p e r
mechanism, to c o rre la te - th e rem oval o f o rg a n ic m a te r ia l from th e mono-,
h y d ra te a s h .
T able -X (s e e ap p en d ix ) p r e s e n ts d a t a .s i m i l a r to Tables
■VIII and IX; however.* t h i s t a b l e p e r t a i n s to m onohydrate w ith some.added
n itra te .
■ F ig u re 10 (se e appendix), shows a p l o t o f th e d a ta p re s e n te d in
T ab le X where log(C0Do/C0Df ) i s p l o t t e d a g a in s t r e t e n t i o n tim e* and
..again, no l i n e a r c o r r e l a t i o n seems .in d ic a te d ;
A second.m echanism t h a t . Co,uld a c c o u n t.f o r th e rem oval o f „org an ic
..m a te ria l from t h e soda ash .is mass t r a n s f e r .
The sim p le mass t r a n s f e r
e q u a tio n is g iy en as
N-=JKi a (P1 - P 1J)
where
(5)
N i s th e r a t e o f t r a n s f e r
K1 i s th e maSs t r a n s f e r .c o e f f ic ie n t
a i s th e a r e a .a v a i l a b l e f o r t r a n s f e r of mass
P 1 -Is the' p r e s s u r e o f th e o rg an ic m a te r ia l
a t th e .in te r f a c e of th e t r a n s f e r a re a
P. ,is th e p re s s u re of th e o rg a n ic m a te r ia l
i n th e b u lk a i r stream.
B ecause o f th e low. c o n c e n tra tio n o f th e o rg a n ic m a te r ia l* - th e pres?s u re of th e o rg a n ic ,m a te r ia l i n th e b u l k - a i r stream . (Pfei) ,can be. cons I b e r w
-ed z e r o .
U sing t h i s assum ption we g e t
-2 2 -
N.=. Ki a (I^i )
(5 b )
To. make' use' of t h i s equation , we m ust g e t -an e s tim a te of how, P1
-changes .w ith temperature-,.
This can be done, by making some s i m p l i f i ­
c a tio n s i n th e C lausius--C lapeyrqn e q u a tio n
dP/dT = AHP/RT2 .'
where
P
T
A
R
(6)
i s yapor p re s s u re
i s a b s o l u t e •te m p e ra tu re
h i s m o lar h e a t .of v a p o riz a tio n
.is th e gas c o n s ta n t
Qn re a rra n g in g ,- we g e t
■dP/P = (A H / r ) dT/T2 .
.( 7 ),
Qn in te g ra tio n .,, we ge&
I n P = (-AH/R) l / T + C.
.(8).
At th e n o rm a l b o ilin g p r i n t (Tfi) th e yapor p re s s u re o f a . l i q u i d
i s one a tm o sp h ere .
This is used to e v a lu a te th e c o n s ta n t o f in te g r a tio n
.In (I) ..= 0 -
(^A H /R) 1/Tfi + .C
,C-= A V R T fi
th e r e f o r e
(9)
- (10)
InP 1 = ^H /R T .+ 'AH/RTfi
' ( I l)
The e x p o n e n tia l form of e q u a tio n 11 is
P1 = e ( A.H/RTfi
AH/RT) ,= ,g AH/RTfi
.- ^ H /R T
(12)
Sinqe th e q u a n tity AH/RT^ i s - a c o n s ta n t, -eq u atio n 12 .can be r e w r i t t e n
as
P1 = Z 2B ^ a h Zrt
Where
-
. (13)
K2 =
H sing th e r e l a t i o n o f e q u a tio n 13,, e q u a tio n ^b can b e .r e w r itte n as
.N -= K ]aK2e " AHZRT
= K3O^ ah Zrt
'. ( 5c)
-2 3 T h 'e -q u a n tity
H .is th e h e a t of y a p e r iz a tip n of th e o rg a n ic m a te ria l,h 'e -
.. in g tr a n s f e r r e d .f r o m th e s o d a .a s h .
W hile i t does v ary w ith te m p e ra tu re ,
t h i s v a r i a t i o n i s .s m a l l. in . th e te m p e ra tu re ra n g e In y o Iy ed a n d .so th e
.la te n t h e a t o f v a p o r iz a tio n w i l l be c o n sid e re d a c o n s ta n t h e r e .
I f th e
lo g .,o f e q u a tio n 5-c i s ta k e n , a n e q u a tio n i n two a r b i t r a r y c o n sta n ts
re s u lts .
lo g W = lo g ,K3 -H- (- A'H/RT) lo g e
or
l o g .N -= .lo g K3 -f
KfZT,
(it)
.By use .of a l e a s t sq u a re s p ro c e ss th e s e c o n s ta n ts K3 and K1 can be
e v a lu a te d .
B ince K3 .has in c o rp o ra te d i n i t as a, m u ltip ly in g f a c to r th e
,mass t r a n s f e r c o e f f i c i e n t (K1),- p r o v is io n m ust be made f o r th e rem oval
. o f the e ffe c t of te m p e ra tu re and the degree' of f l u i d i t y of th e bed.
Q .
• Mass t r a n s f e r c o e f f i c i e n t s as d e fin e d by T reybal a re
K1 M daB/ r .t zg
where
(15)
K1 is. th e mass t r a n s f e r c o e f f i c i e n t
D . i s th e :d i f f u s I v i t y of component A
in to com ponent-B
R i s th e .u n iv e rs a l gas -co n stan t
T i s th e a b s o lu te te m p e ra tu re
Z i s a f i c t i t i o u s o r e f f e c tiv e , la m in a r
film , th ic k n e s s whose r e s ! s t a n c e to
m o le c u lar d i f f u s io n is. th e same as
t h a t o ff e re d to mass t r a n s f e r by a
r e a l .la m in a r film ,,- b u f f e r z o n e , an d
tu r b u le n t r e g io n , all.C o m b in ed .
F u r th e r , T rey b a l - s ta te s t h a t ,d if f u S ly ity v a r ie s w ith -T
U sing t h i s s ta te m e n t (Dab =o(.T3^ 2 ) we co u ld , r e w r ite e q u a tio n 1 5 .
K1 = 4 t 3//2A t.zq = '< tV rzg
. (16).
W ritin g two o f these' e q u a tio n s each a t ,a .d i f f e r e n t .te m p e ra tu re and
724-*
ta k in g t h e i r . r a tio , re 's,a lts in
(Ki)TjZ(Ki)Tg = < T & R Z y ^ T ^ / R Z g
Qn re a rra n g in g , and. canceling,, e q u a tio n 17 r e s u l t s .
(K i)T1 = " / V rT l
(K1 ) t2
(17)
E q u a tio n 17 gives a r e l a t i o n betw een mass t r a n s f e r c o e f f i c i e n t s f o r
d i f f e r e n t te m p e ra tu re s , a l l e ls e b e in g e q u a l.
l u s t as te m p e ra tu re was used .as an o p e ra tin g v a r i a b l e ,in .the c e l*
l e c t i q n o f d a t a , so was b e d .d e n s ity o r bed w e ig h t.
S in ce th e same re v
a c tio n v e s s e l was u sed i n a l l th e r u n s , b e d d e n s ity i s d ir e c tly .p ro p o r­
t i o n a l tb th e .bed w e ig h t.
In th e c o l l e c t i o n o f - d a ta th e bed w eig h t was
.m e asu re d ..a fte r each ,run and as. p re s e n te d e a r l i e r i n Table .11,. th e bed,
w eight i s a l i n e a r f u n c tio n q f th e p r e s s u r e .drop a c r q s s th e bed,.
T h is
d a ta i s i l l u s t r a t e d , in .F ig u re 11 (see appendix) where th e p r e s s u r e drop
.a c ro s s th e b e d ,is p l o t t e d a g a i n s t bed w e ig h t.
I n o rd e r to g e t a r e l a t i o n
betw een th e mass -t r a n s f e r c o e f f i c i e n t and. th e v a riq u s bed w eights used
in th e .v ario u s runs a s h o r t review must be made of some work, done by
5
5
M illik a n and r e p o r te d by Knudsen and K atz
- The s ta g n a n t, boundary
la y e r about a p a r t i c l e depending upon i t s . shape can be- d eterm in ed by th e
e q u a tio n
2
■ ?ZQ. A 0V = K4
, where
■ ■¥ ,is th e v e lo c ity qf th e f l u i d stre am .
Z q i s th e th ic k n e s s of th e s ta g n a n t la y e r
r'p i s a c h a r a c t e r i s t i c m easure -of th e
dim ension -of th e p a r t i c l e
v. i s th e k in e m a tic y ls c o s ity , of th e
moving f l u i d
K4 is a c o n s ta n t depending upon th e shape
o f th e p a r t i c l e .
(18).
-2 5 P-Qr th e p u rp o se s here, v Q> J i .-and K4 may he c o n sid e re d in v a r ia n t
g iv in g th e r e l a t i o n
Zg2 = ^ / y
VfhQre
(ip )
Kc -encompasses K4jr r Qy .and y .
Op re a rra n g in g t h i s r e l a t i o n , e q u a tio n 20 was o b ta in e d .
2G = ^6
(20)
Qn'e .r e l a t i o n s t i l l rem ains to be d iscu ssed ..a n d th a t i s th e .r e la tio n
betw een bed w eight and v e lo c ity of th e f l u i d th ro u g h t h e bed.
Under
norm al c o n d itio n s a p r e s s u r e drop Versus v e l o c i t y . p l o t f o r a f l u i d bed
s i t u a t i o n such as t h i s .h a s th e g e n e r a l p r o p e r tie s t h a t th e p r e s s u r e drop
a c r o s s th e bed r i s e s w ith in c r e a s in g .v e lo c ity to th e p o in t Qf f l u i d i -n a tio n .
At t h i s p o in t th e tr e n d re v e rs e s a n d th e p r e s s u r e drop d e c lin e s
as. th e v e lo c ity , o f th e f l u i d medium i s in c re a s e d , -This i s .an in v e r s e
r e l a t i o n and co u ld be e x p re sse d i n th e re g io n yrhere th e f l u i d v e lo c ity
i s .a t l e a s t s u f f i c i e n t for. f l u i d i z a t i o n o f th e _ash a s
^ P = K7/ u .
(21)
/Prom F ig u re 11 (se e appendix) we hav e th e r e l a t i o n t h a t
-BW..= K8 A P
(22)
S u b s titu ti n g t h i s (22) in to equatio n . 2 1 , .-we o b ta in
BW = K9A
(25)
U sing e q u a tio n 23 in e q u a tio n 20., we can o b ta in
zQ = K10 Y bT
,P u ttin g t h i s
(24)
( 2 4 ) .in to e q u a tio n 1 5 , a r e l a t i o n was ,o b tain ed .b etw een
mass ,tr a n s f e r c o e f f i c i e n t s and th e b e d w eight a t which t h i s t r a n s f e r
-2 6 -
ta k e s .place..
(25)
K11 = 1W rtk IOV™~
A r a tio .o .f two .of th e s e e q u a tio n s (25) a t d i f f e r e n t b ed w e ig h ts w ill
r e s u l t i n th e d e s ir e d r e l a t i o n
(ltIl)BW1 ■= / W
m
(26)
T (K11)a i2 .
Combining t h i s r e l a t i o n w ith th e r e l a t i o n o u tlin e d in. e q u a tio n I? ^ a
c o r r e c tin g f a c t o r .c a n be .o b ta in e d f o r a n y .ru n made i n th e so d a ash
s e r i e s which w i l l r e f e r i t to a re f e r e n c e c o n d itio n .
This r e l a t i o n
would be
K12 = Z t 1BW2Zt2BWi
K15
(2?)
U sing t h i s c o r r e c t io n f a c t o r f o r th e e f f e c t s ,of te m p e ra tu re .a s w e ll as
bed w e ig h t, th e fundam ental mass t r a n s f e r e q u a tio n can now be w r itt e n as
N = K / T 1BW2ZT2B ri'
eK' / T
(2 8 )
-This form of th e e q u a tio n has a c o r r e c tio n f a c t o r i n i t to reduce th e
e f f e c t s o f any ru n to .th o se a t a r e f e r e n c e . s t a t e .
F o r t h i s re a so n th e
r e f e r e n c e s t a t e w i l l be c o n sid e re d as a te m p e ratu re of 4lO°C and a bed
w eight o f 900 gram s.
These y a lu es were p ic k e d p r im a r i ly .a s re fe re n c e
b ecause c o n s id e ra b le d a ta haye been g a th e re d a t o r n e a r th e s e c o n d itio n s .
I n a manner s im ila r to f in d in g A quation 14 b u t w ith th e c o r r e c tio n f o r
bed w eight and. te m p e ra tu re , we c an o b ta in e q u a tio n 29 by ta k in g th e lo g
of e q u a tio n 28
lo g N = lo g .K + lo g / T 1BW2ZT2BW1 + A 34 K '/T
(29)
and on r e d e f in in g some term s we can w r ite
n = k + lo g / T 1BW2Zt 2BW1 + k ' t
(30)
■27-
where
n =
k =
k '=
T=
lo g N
lo g K
.434' Ki
l/T °K
Table XI p re s e n ts , d a ta p e r ta in in g to mass t r a n s f e r a t a. r e te n tio n ,
tim e of 19 to 21 m in u te s .
From th e s e d a ta a l e a s t sq u a re s a n a ly s is can.
be made to f in d th e b e s t ap p ro x im atio n f o r K and Kt in e q u a tio n 29.
E q u a tio n 30 can be r e w r itte n as
n - r k - l o g T]_BW2/ T2BW1
- k 't = 0
(31)
and f o r th e method of l e a s t sq u are’s
X ( n - k - lo g TZt 1BW^T2BW11 - k ' t ) 2 = R
(32)
Taking th e p a r t i a l d i f f e r e n t i a l o f R w ith r e s p e c t t o .k and k ' and s e t ­
tin g each t o z e ro th e norm al e q u a tio n s a r e o b ta in e d f o r e v a lu a tin g k
and k ' ,
M y z6Pk = 0 •= 2 JStn-A^lpg /T 1BW2ZT2BW11 ^ k 't ) .
5 R/
k i = 0 -= 2 S (n-k-ilog -/T^BW2ZT2BW1' - k ' t ) t
. (33)
( 34)
.R e a rra n g in g e q u a tio n 33 g iv e s
n - 2 k ^ H log Vt 1BW2ZT2BW1' - k ' t = 0
3.23256 -H, 3k - .0.05803 «. . 0041988k ' = 0.
(33)
. S im ila r ly r w ith e q u a tio n 34 th e fo llo w in g r e s u l t s
S .n t ^ Z k t
S t lo g YT1BWaZT2BW1' - X k ' t 2 .=' 0
0 . 0 0 4 5 2 9 1 0 . 0041988k - 0.000079745
(34)
0 . 0000058836k '= 0
The s o lu tio n of th e s e two, e q u a tio n s g iv e s th e fo llo w in g v alu es
K-I = -Z 99.3
K =
I 7 .6
•To ru n an a d d itio n a l check on th e c a lc u la tio n s p re s e n te d above*, th e
v a lu e of K1 was u se d .a n d v a lu es of K were c a lc u la te d from ra w .d a ta w ith
-2 8
- th e u s e of th e e q u a tio n
W = K y TaBWSZT2BWi
(28 )
: R e f e r rin g t o e q u a tio n ' 14 i t can be se e n t h a t / \ E / R has been r e ­
p la c e d . by .K1-.
Hpweyer y t h i s sh o u ld ,not be .consiirued, to mean, th a t A H
Can be approxim ated from K1 s in c e N as u sed in th e s e e q u a tio n s .is th e
r a t e o f COD r e d u c tio n f a t h e r th a n th e m olar r a t e . o f o r g a n ic . rem o v al.
K' i s r e l a t e d to th e ra te .-o f COD r e d u c tio n i n th e same manner as
<
i
1
A H/R i s r e l a t e d to t h e .m o l a r .t r a n s f e r o f o r g a n ic .m a tte r .
This v a lu e
o f K1 sh o u ld be a c o n s ta n t th ro u g h any one l o t o f ash and W ill be c one
• s id e r e d c o n s ta n t f o r Drums I , 2> and. 3. of lig h t, ash..
■s t a n t f o r a p a r t i c u l a r r e t e n t i o n tim e .
K-i s only con-
Table X II p r e s e n ts Ks f o r runs
made a t r e t e n t i o n tim es o f 1$ to 21 m inutes .C alculated, from .th e raw
. d a ta u s in g a v a lu e Qf-K1 as c a lc u la te d .above.
Two a d d itio n a l.r u n s n o t
.u sed f o r .the l e a s t sq u a re s C a lc u la tio n have been in tro d u ce d , f o r a check a n d .show re a so n a b le a g re e m e n t.
Tables X I I I f -XIV,- ,and' XV p r e s e n t mass
t r a n s f e r d a ta f o r ru n s made a t v a rio u s r e t e n t i o n tim e s .
Again-,;. th e
a d ju s te d -Ks f o r runs o f s im ila r r e t e n t i o n tim e rem ain q u ite Constant .
■ I n iP ig u re .12 th e s e d a ta a re p l o t t e d w h e re.K i s shown as a fu n c tio n .
-of retention tim e .
.T h is-c u rv e in d ic a te s , t h a t a: m echanism '.is .one of mass
t r a n s f e r . - R e fe rrin g ;.to T able -XVI (Run 3 2 ) , an a d ju s te d v a lu e -o f K of
17.7 was o b ta in e d a t a r e t e n t i o n tim e o f 19 ,5 .minutes when W2 was u sed
_a s th e f l u i d i z i n g medium in s te a d ,o f a i r .
. This v a lu e i s in d ic a te d by
(W)yOn F ig u re 12 an d f a l l s -very c lo s e to th e cu ry e,
■
■■
T h i s .i s f u r t h e r
-
,
su p p o rt t h a t th e mechanism i s .one o f mass t r a n s f e r f a t h e r th a n o x id a tio n .
Table XYII p r e s e n ts m ass, t r a n s f e r d a ta f o r s e v e r a l runs made a t tem pera­
tu r e s .below .400°C .
In each c a s e th e a d ju s te d v alu es o f K a re co n sid er--
a b ly lower th a n th o se I n d ic a te d b y .th e cu rv e.O f F ig u re 12 which was
p l o t t e d from th e d a ta .o f runs a l l of which were made a t te m p e ratu res
above 400°C .
This in d ic a te s t h a t th e te m p e ra tu re r e l a t i o n s h i p y r^ /T g
as used in e q u a tio n 28 i s n o t v a lid , f o r te m p e ratu res below 400°C'.
• The d a ta p re s e n te d th u s, f a r have been f o r runs made W ith a l i g h t
L
■ash h av in g .an, i n i t i a l -COD value, o f 562 ppm.
T able X V III.p re s e n ts mass
tr a n s f e r - d a ta f o r runs made w ith ,a l i g h t ash h av in g a n i n i t i a l COD v alu e
o f 485 ppm.
These d a ta a re p l o t t e d in F ig u re 15...
A lthough a .s i m i l a r
c o r r e l a t i o n r e s u l t s th e mass t r a n s f e r c o e f f ic ie n ts :.in c r e a s e w ith in ­
c re a s e d COD l e y e l .
■Table XIX p r e s e n ts mass t r a n s f e r d a ta on. runs made w ith ash h av in g
a startin g .C O D l e v e l of 517 ppm.
The a d ju s te d Ks a re a l l low er a t a
g iv e n r e t e n t i o n tim e th a n th o se f o r co rre sp o n d in g runs of higher-COD
le v e l.
Runs .5 8 , 39 r and. 40- i n t h i s group were a l l made w ith low. bed
w eight (below 500 ,gms)'!. and th e .r e s u ltin g . Ks f o r th e se th r e e runs when
p l o t t e d a g a in s t .r e t e n t i o n tim e show..the ex p ected , c o r r e l a t i o n , a lth o u g h
th e curye does n o t f i t th e v alu e f o r K o b ta in e d from Run 43 which was
made .a t a .bed,..weight o f. 1060 gms.
I f Run 43 is c o n sid e re d alo n g w ith
Runs 4 5 , 4 6 , and 4% from th e N1Itr o g e n s e r i e s
(Table XYT) which were made
w ith th e same s t a r t i n g . a s h and bed w eig h ts betw een 900 and 1200 gram s,
a c o r r e la tio n , i s in d ic a te d f o r t h i s g ro u p .
of fo u r runs a re a ls o p l o t t e d in F ig u re 1 3 .
A d ju sted Ks fo p t h i s group
I f t h i s curve i s v a lid ,, i t
—JO
a c ts as a d d itio n a l s u p p o rt .fo r th e .mass t r a n s f e r mechanism.
The f a c t
t h a t two d i s t i n c t curves were p l o t t e d f o r . t h i s .ash would in d ic a te th a t
th e bed. w eight r e l a t i o n s h i p --/BW2ZBWi as used , in e q u a tio n 28 i s n o t v a,lid
f o r bed w eights below JOO o r 600 gram s.
seems to h o ld .
Above 600 grams th e r e la tio n s h ip
The K f o r Run 4-2 p l o t s .b e lo w .e ith e r o f th e two curves m en-
- tio n e d .because .of th e in v a lid .te m p e ratu re ,r e l a t i o n s h i p .
■Once a g a in .i t should, be p o in te d o u t .th a t w h ile re fe re n c e i s made
th ro u g h o u t t h i s p a p e r to bed w eight as one o f th e v a r i a b l e s a more
u n i v e r s a l .term m ight be bed .d e n sity o r as ap p ears in some l i t e r a t u r e >
bed d e f ic ie n c y .
Only, becau se th e r e a c t o r .volume rem ains c o n s ta n t.f o r
a l l . r u n s , can com parison be made on th e b a s is of bed w e ig h t. ■The volume
.of th e f l u i d bed used to make th e runs a p p e a rin g in t h i s stu d y was Q.O77
cu b ic ..f e e t.
A JOO^gm bed would th e n co rresp o n d to a bed d e n s ity , of - 2 J .8
pounds p e r cubic f o o t . • F ig u re 14- shows thfe .r e la tio n s h ip betw een bed
w eight and bed d e n s ity .
R e fe rrin g a g a in to F ig u re I-J, i f Es a re p ic k e d from t h i s curve a t
r e t e n t i o n tim es o f 5 , 7 , 8-#, IOy .and 20 ,minutes f o r each of th e th re e
l i g h t •ash sam ples s tu d ie d , f i n a l COD le v e ls can be .c a lc u la te d ,from th e s e
v a lu e s .
-These d a ta a re p re s e n te d in F ig u re -I-J. -This f ig u r e in d ic a te s
t h a t f o r a given, tem perature- and bed w eight y. e q u ilib riu m .is reached
■a f t e r s u f f i c i e n t .r e te n tio n tim e .a t th e same COD le v e l r e g a r d le s s of th e
startin g .C O D l e v e l . ■F or l i g h t ash w ith COD v alu es in th e .range of JOO
to J00 ppmy 10 m inuses seems to be s u f f i c i e n t f o r reaching,, e q u ilib riu m .
U n til now th e ash c o n sid e re d in t h i s r e p o r t has been, g ra d e •100
•l i g h t soda ash w ith v a rio u s s t a r t i n g .le v e ls of organic, m a te r ia l.
.As
m entioned e a r l i e r . a n o t h e r ty p e of ash was tr e a te d i n t h i s s tu d y .
was .monohydrate w ith - c o n tr o ll e d •am ounts. o f sodium, n i t r a t e added.
This
A l-.
though th e i n v e s t ig a ti o n on m onohydrate was more l i m i t e d . i n scope and
-was co n cern ed p r im a r ily w ith ,r e ta in in g h ig h r e f l e c t a n c e y ,an ,attem p t was
„ made w ith th e lim ite d d a ta a v a ila b le to show t h a t mass t r a n s f e r was
again, th e c o n tr o llin g .,mechanism.
A ll of th e s e m onohydrates have a much
h ig h e r COD s t a r t i n g l e v e l th a n the. l i g h t a sh used in t h i s .in v e s tig a tio n .
an d a ls o had .a d i f f e r e n t c r y s t a l l i n e fo rm .
Because o f th e s e d if f e r e n c e s y
,e q u a tio n s 53 and 34- were a g a in used to .c a lc u la te new v a lu e s o f K and- K1
by th e l e a s t sq u ares p r o c e s s . .Again;,- s ta n d a rd c o n d itio n s f o r tem pera­
tu r e and bed w eight were s e t a t -UlO0C an d 900 grams-, .r e s p e c tiv e ly ,
Table XX p r e s e n ts th e .-d a ta .used f o r th e s e ,c a lc u la tio n s ..
,00 67 3 37
4.91242
3k - ..0 6 5 2 1 . 0041172k ' = 0
. 0041172k - .900086,328
.0000956973k' = 0
(33)
(34)
.The. s o lu tio n of th e above e q u a tio n s g iv e s r e s u l t s , o f
K'- =--243
K .=
5 7 ,6
A g ain , u sin g th e above v a lu e f o r K' , Ks w ire c a lc u la te d f o r s e v e r a l
I
runs.m ade w ith .m onohydrates which had no ad d ed , n i t r a t e . These v alu es
I
a p p ea r in T able XXI and a r e p l o t t e d as -a f u n c tio n of retention tim e i n
■F ig u re 1 6 .
A lthough th e d a ta a r e lim ite d , and coyer a v e ry .narrow ..range
•of r e t e n t i o n tim es,, th e .same te n d e n c ie s and ty p es of cu rv es r e s u l t .
Ks
d e c re a se w ith in c re a s e d .r e te n tio n tim e and. in c re a s e w ith in c re a s e d cpp.-
-3 2 -
.cen tratiO H of o rg a n ic m a t e r i a l . -The in d ic a tio n , i s t h a t e q u ilib riu m i s
r e a c h e d .a t a h ig h e r COD le v e l th a n w ith l i g h t ash f o r the-sam e p ro c e s ­
s in g c o n d itio n s .
■From th e shape of th e curve's and th e f a c t t h a t mass t r a n s f e r co­
e f f i c i e n t s a re :a f u n c tio n of th e s t a r t i n g .le y e i of o rg a n ic .m a te r ia l,
s o m e .s p e c u la tio n can be made a s . t o th e d is tr ib u tio n , o f t h i s o rg an ic
.m a te r ia l w ith in , th e s o d a .a s h c r y s t a l .
I f th e .c o n ta m in a n t were on th e
.:o u te r s u r f a c e o n ly , mass t r a n s f e r . c o e f f i c i e n t s would rem ain r e l a t i v e l y
."constant to a p o in t of d e p le tio n . • This .does n o t ap p ear to .be th e c ase
s in c e no ev id en ce of a c o n s ta n t re g io n was found in. th e s e c o e f f i c i e n t s .
For l i g h t ash th e COD le v e l d e c re a se d a t p r o g r e s s iv e ly slo w er rates', from
•0 to . 10 ..m inutes, a t which tim e -e q u ilib r iu m was re a c h e d .
I f th e con­
ta m in a n t were d i s t r i b u t e d through th e p a r t i c l e , the- r a te ..o f d if f u s io n
thro u g h th e p o re s of th e c r y s t a l -would c o n tr o l th e r a t e o f d e p le tio n .
■ C oncentration w o u ld ..a ls o -a ffe c t t h i s r a t e and. r e s u l t s s im ila r , to th o s e
o b ta in e d i n t h i s s tu d y would be ..expected.
.a ls o be e x p e c te d .
An 'e q u ilib riu m l e v e l would
F u r th e r evidence is ,o b ta in e d .b y observing-R uns MN-34
and M - 35 which were made b sing. a s t a r t i n g ,m a te ria l t h a t had,, in one case-,
a l l th e m a te r ia l above- 20 mesh .removed and in th e second .,case ,- - a ll . of
th e m a te ria l.a b o v e 28 mesh removed.
The s c re e n in g a lo n e did. n o t a f f e c t
th e COD le v e l which, m ight .be- expected, .if th e -contam ination were prim ­
a r i l y . On th e s u r f a c e . • By. com paring th e s e .r u n s w ith Runs M -4+, -13., -1 4 ,
and .,-15., . i t d id a f f e c t th e r a t e . o f rem oval and th e f i n a l (equilibrium .)
. COD l e v e l which i s what wpuld be ex p ected i f th e co n tam in an t had to
-3 3 -
■d iffu se to the surface from Within the p a r tic le .
■In th e s tu d y in v o lv in g l i g h t ash no m arked e f f e c t on th e r e f le c ta n c e
o f th e ash was in d ic a te d .
W ith th e m o n o h y d ra te h o w e v e r, th e a sh r e ­
f le c ta n c e was s e r io u s ly lo w e re d .Ipy th e c a lc in in g tr e a tm e n t.
In an
a tte m p t to r e t a i n h ig h ash r e f l e c t a n c e , a stu d y was. made' to d eterm ine
th e e f f e c t o f adding .sm all - q u a n titie s o f sodium n i t r a t e to th e h y d ra tin g
l i q u o r . from which ,the monohydrate was made.
Four b a tc h e s of m onohydrate
were p re p a re d c o n ta in in g -c o n tro lle d amounts o f sodium n i t r a t e v a ry in g
from 0 .0 to 9-95 pounds p e r to n o f a sh .
t h i s ash ap p ear in T a b le .V.
in t h i s t a b l e .
The d a ta from ru n s made w ith
These r u n s .a re la b e le d , w ith th e p r e f ix rMN1
F ig u re 17 p r e s e n ts a p l o t of .ash r e f le c ta n c e -versus
te m p e ra tu re w ith p a ra m e te rs of pounds of NaNO3 p e r to n o f a s h .
f ig u r e two m ajor f a c t s s ta n d o u t.
From t h i s
F i r s t , w ith o u t a d d itio n of n i t r a t e
th e r e f le c ta n c e f a l l s o f f w ith in c r e a s in g c a lc in in g tem p eratu r.e.
Second,
th e a d d itio n of n i t r a t e does have a b e n e f i c i a l e f f e c t tow ard r e ta in in g
h ig h r e f le c ta n c e le y e ls when th e c a lc in in g te m p e ra tu re i s above 1IOO0C.
A d d itio n s o f n i t r a t e aboye th e 2 .3 pounds p e r to n l e v e l does n o t have
an a p p re c ia b le e f f e c t .
Ta)?I e .V a ls o .in c lu d e s d a ta on th e r e f le c ta n c e
.of sodium trip o ly p h o s p h a te (.STPP) made from th e a sh .
In o rd e r f o r th e
chem ical q u a lity of th e so d a ash to be a c c e p ta b le , th e r e f l e c t a n c e .o f
STPP made fro m th e a sh should, be 93 p e r c e n t o r h ig h e r .
A lthough h ig h
te m p e ra tu re tr e a tm e n t.o f th e a s h .b e fo re m aking phosphate, improves th e
STPP r e f l e c t a n c e , i t r e q u ir e s h ig h e r te m p e ra tu re s w ith o u t NaNO3 to a t t a i n
th e .-d e s ire d v a lu e . ; High te m p e ratu re - c a lc in a tio n of soda .ash in com-
-3 4
..bI n a t io n w ith s m a ll a.mo,unts o f s o d iu m .n itr a te .produces . an ash which*
under a l l c o n d itio n s stu d ie d * w i l l p ro d u c e an ash which can b e ,u se d
■"as i s " fo r,m a k in g .a c c e p ta b le sodium tripo.lyphosp.hatp.*
■S o d iu m .n itra te a ls o SdemS' to have Jiad,.some e f f e c t on lo w erin g th e
f i n a l -CQD l e v e l . ■T able XXII. p r e s e n ts d a ta from s e v e r a l s im ila r..ru n s
w ith and w ithout-added., n i t r a t e .
D uring th e c a lc in in g .of th e ash w ith
added n i t r a t e , , n i t r i t e s a re .fo rm e d which sh o u ld in c re a s e th e COD v alu e
.o b tain ed .u p o n a n a ly z in g th e p r o d u c t. . However * even though a b s o lu te COD
v a lu e s .a r e th e r e f o r e m isleading*, i t a p p ea rs as though, th e r e i s a s l i g h t
lo w erin g o f .th e f i n a l COD l e v e l ,a t t r i b u t e d , to o rg an ic co n tam in an ts.
In. Table V* b u lk ,d e n s ity was re p o rte d , o n ly , on. th d l i g h t a s h and n o t
on t h e .m onohydrate a s h .
As. m entioned b e fo re and p re se n te d , in T a b le .V I I y
th e p e was no s i g n i f i c a n t -change.i n p a r t i c l e s iz e d is trib u tio n - b e tw e e n th e
t r e a t e d and u n tr e a te d a s h ; however* th e r e w a s.an e f f e c t upon th e b u lk
d e n s it y .o f th e ash when t r e a t e d in th e f l u i d , s t a t e .
-In F ig u re l 8 th e
r e s u l t s of some'.runs a r e .p lo tte d w ith te m p e ra tu re as th e param eter*
showing ,th a t -a t any te m p e ra tu re th e .bulk d e n s ity in c re a s e s w ith r e s i ­
dence tim e and a t c o n s ta n t re s id e n c e tim e * .h ig h e r-d e n s ity r e s u l t s from
h ig h e r te m p e ra tu re .
. No -c o r r e l a t i o n betw een th e .o p e r a tin g v a r ia b le s and foam h e ig h t
- c o u ld .b e fo und; ,h o w e v e r* .it should, be n o te d t h a t a; s ig n if ic a n t- d e crea se
in th e foam h e ig h t r e s u l t e d fro m ,th e f l u i d c a lc in a tio n .
In th e c a s e of
t h e ■ash from Drum 2 * .a r e d u c tio n in foam h e ig h t as much as 75 p e r c e n t
-Of th e o r i g i n a l was noted*
-3 5 -
. .D isc.uss.ion and Summary
AS thn' program was .s e t up * ,th e o.bject was to. d e c re a se th e o rg an ic
:c o n te n t ,... in c r e a s e th e .b u lk . d e n s i t y . low er th e foam h e i g h t ,. and m a in ta in
-Cr improve th e .re fle c ta n c e ., o f th e ,.ash and sodium trip o ly p h o s p h a te made
frq m - th e a s h . ■F lu id , c a lc in a tio n , o f soda ,ash. w ,ill do each of th e s e th in g s
.,and,, o p e ra tio n of th e p ro c e ss i s C o n tin u o u s.
- A n aly sis ,of th e r e s u l t s . IndiIp at'e t h a t rem o v al. o f -organics JLs ..a
m a tte r p r im a r ily of mass t r a n s f e r and t h e . v a r ia b le s t h a t a f f e c t mass
tr a n s f e r - (te m p e ra tu re , bed w eight* ,and, r e t e n t i o n time') m ust be consId ^
e rp d .
For a g iv e n ty p e .o f as,h c a lc in e d a t se t. te m p e ra tu re and bed
. d e n s ity * a n e q u ilib riu m l e v e l i s reached-, , a f t e r s u f f i c i e n t . tim e., which
i s in d ep en d en t of t h e s t a r t i n g .le v e l.,
F ig u r e 15. i l l u s t r a t e s t h i s p QiI n t ,
E xtending th e s e d a ta a l i t t l e , f a r t h e r f o r l i g h t ash y .c o e f f ic ie n ts
ta k e n from F ig u re 12 p e rm it p e r c e n t COD r e d u c tio n to., be c a lc u la te d ■
f o r ,a. v a r ie ty , o f. o p e ra tin g ,c o n d itio n s .w ith th e a id of e q u a tio n 28.,
This
in fo rm atio n , i s p re s e n te d , in. th e fo llo w in g f ig u res.:
F ig u re 19
P e rc e n t GOD. R ed u c tio n vs R e te n tio n Time ■ (,T.= I lO 0C), •
■F ig u re 20
P e rc e n t C©P ,Reduction
■F ig u re 21
■P e rc e n t COD R ed u ctio n Vs -Tem perature
(R e te n tio n Time
2,0. m in u te s ) '
/F ig u re 22
P e rc e n t COD Reduction vs Tem perature
(BW., = 900 gms)
,F ig u re .23
P e rc e n t COD. R edu ctio n vs Bed W eight
, F ig u re 24
v s .R e te n tio n Time
(BW. = 9QQ gms)
(T^_ 4 l0 °C )
P e rc e n t COD R e d u c tio n .vs Bed W eight
(R e te n tio n Time = 2 0 .m inutes)
■K36-F ig u re s 19 a n d -20 a g a in b rin g o u t th e p o in t t h a t f o r a g iv en
te m p e ra tu re and bed w eight th e r e i s a p r a c t i c a l l i m i t to th e rem oval
of any f u r t h e r o rg a n ic m a te r ia l. - The e f f e c t of bed w eig h t and tem pera*
tu r e can a ls o be o b serv ed .
F ig u re s 21 .and 22 g iv e a somewhat c le a r e r
p i c t u r e of th e e f f e c t .o f te m p e ra tu re -o n th e o rg a n ic rem oval and lik e *
w ise F ig u re s 25 and 24 a r e aimed a t showing more c l e a r l y t h e e f f e c t
o f bed w e ig h t.
From th e s e f ig u r e s % then,-, th r e e g e n e r a l f a c t s can be .-summarized.
I.
L i t t l e i s g a in e d by in c r e a s in g r e t e n t i o n tim e above 10 m in u te s.
■2.
A d e c re a se in bed w eight ( f l u i d b e d -d e n s ity ) b rin g s ab o u t a '
5.
marked r e d u c tio n in COD l e y e l .
X
Only about 6 to .8 p e r c e n t a d d itio n a l r e d u c tio n i n COD le y e l
i s r e a l i z e d by in c r e a s in g th e te m p e ratu re from 400 to $00*0 .
Although, th e s e d a ta were p re s e n te d f o r th e l i g h t a s h w ith -a s t a r t i n g
COD le y e l o f 562 ppm, s im ila r - c u r v e s would r e s u l t f o r . t h e o th e r l i g h t
ash s to c k and f i n a l COD le v e ls co u ld be e stim a te d from t h i s d a ta f o r
l i g h t -ash of v a ry in g i n i t i a l COD l e v e l .
A f u r t h e r w ord.m ight be s a id a b o u t b ad w e ig h t.
S in ce th e lower
b ed d e n s it ie s in v o lv e h ig h e r r a te s of f l u i d i z i n g a i r th ro u g h th e u n it*
th e .more e f f i c i e n t rem.oval .th a t r e s u l t s m ight b e a t t r i b u t e d to th e a i r
f i l m . e f f e c t around th e p a r t i c l e .
Less r e s i s t a n c e w i l l p e rm it g r e a te r
rem oval, -This in c re a s e d rem oyal ,w ith d e c re a se d f l u i d bed d e n s itie s
b rin g s up one f u r t h e r .c o n s id e r a tio n .
Depending upon th e eco n o m ics.o f
p ro v id in g th e a d d itio n a l a i r and a d d itio n a l h e a t an d .d ep en d in g upon
-57
■what i s ■c o n sid e re d .a s . a s a t i s f a c t o r y maximum COD l e v e l y ,co n sid e ra tio n
m ig h t be' g iv e n to d e c re a s in g th e bed w eig h ts w h ile a t th e same tim e d e.e ie a s in g r e te n tio n tim e i n o r d e r .to .keep up th e th ro u g h p u t.
The fo llo w -
.ing data.* a lth o u g h .sp arse* i l l u s t r a t e what m ight .be d o n e .
Run
HT
. min
56
ko
1$
4 .7 7
- 2 .4
11.5
Temp
0C1
415
409
■411
■BW
650
264
802
Throughput
gms/min
■158.
HO
8 2 .5
CODo
5-62
517
562
COD.
158
■ 18-5
.158
I f th e .a d d itio n a l th ro u g h p u t o f s im ila r q u a lity p ro d u c t can o f f s e t
th e added o p e ra tin g c o s t , t h i s ty p e o f approach must .a lso .be .c o n sid e re d .
■C oncerning th e r e f l e c t a n c e p f th e t r e a t e d ,m onohydrate, th e a d d itio n
of. NaNO3 in amounts above 2 ,5 pounds .p er to n of. ash h o ld s th e r e f le c ta n c e
a t h ig h l e v e l (90^ r e f le c ta n c e * o r b e t t e r ) i n t h e te m p e ra tu re ran g e above
UOO0C.
The same .is t r u e of th e STPP r e f l e c t a n c e .
Again,* .c o n sid e ra tio n ,
m ight be g iv e n to u s in g low f l u i d bed d e n s it ie s i n c o n ju n c tio n w ith low
, r e t e n t i o n tim e s .
R e f e r rin g t o Run, M-7 i n T able -V* i t w i l l be n o te d
t h a t a lo w .bed d e n s it y in c o n ju n c tio n w ith a low r e te n tio n , tim e r e s u lte d
i n re m o v a l.o f o r g a n ic .m a te r ia l com parable to some of th e b e t t e r runs
w ith o u t lo w erin g th e ash r e f l e c t a n c e . • This was acco m p lish ed w ith o u t
th e .use of sodium n i t r a t e as a n a d d i t i o n .
e v e r , .was n o t im proved.
The SlPP r e f le c ta n c e * how­
High STPP r e f le c ta n c e .is a p p a r e n tly more de­
p e n d en t on h ig h te m p e ra tu re .
In th e c o u rse of t h i s work a group o f runs.w as made i n which w a te r
vapor was in tro d u c e d w ith t h e . a i r f lu i d i z i n g .s t r e a m .
Runs o f com parable
n a tu re were p ic k e d from T a b le -V .and p re s e n te d in T able X X III.
Rrbm t h i s
-58
. c o l l e c t i o n of d a ta i t c a n .b e see n t h a t f o r l i g h t ash n o t a. g r e a t d e a l
. i s g a in e d i n a s f a r as th e r e s u l t i n g . COD le y e l i s concerned by th e a d d itio n
o f s team to th e f l u i d i z i n g stre a m .
In th e Case o f th e p r e d r ie d mono­
h y d ra te runs % however* .a. ,s ig n if ic a n t r e d u c tio n in r e s u l t i n g COD le y e l
can b e .n o te d .
C oncerning .,any y f th e ■o th e r p h y sica l.m e a su re m e n ts made
on th e a sh sam ples > th e a d d itio n of steam made no d i f f e r e n c e ,
F lu id ,c a lc in in g a f f e c t s th e b u lk d e n s ity f a v o r a b ly .
As shown in
F ig u re 18* r e s u l t i n g b u lk d e n s ity i s a f u n c tio n o f both, te m p e ra tu re and
r e t e n t i o n tim e .
■I t i s beyond ,the scope of t h i s s tu d y to go in to .th e economics o f
a com m ercial o p e ra tio n .
However* .alo n g w ith th e n e c e s s a ry c o s t data.,
p ro d u c t s p e c i f i c a t i o n s * h e a t t r a n s f e r d a ta , e tc..* th e c o r r e la tio n s d e v e l­
oped in t h i s r e p o r t sh o u ld h e lp i n s e t t i n g up th e m ost ..fa y o ra b le .condirtio n s f o r a f l u i d c a l c i n a t i o n u n i t to t r e a t and im prove th e q u a lity
o f a s im ila r a sh .
ACKNOWLEDGMENT
The a u th o r wishes, to e x p re ss h is s in c e r e a p p r e c ia tio n to E ro fe ss p r
H. A, Saner,. ■His c o n s tr u c tiv e c r i t i c i s m and many ho u rs of h ard ,: h o t
work made t h i s p a p e r p o s s ib le .
A lso* th e a u th o r w ishes to th an k Food
•Machinery and- Chemical. C o rp o ra tio n f o r t h e i r sp o n so rsh ip , of - t h i s
p r o j e c t -..and. t h e i r h e l p . i n making th e a n a ly se s . Of th e many a sh sam p les,,
*40-.
APPENDIX '
TABLES',;. '
. Page'-
I P roductfcQ uallty and .S p e c ific a tio n s • •
............. ..
. 42
.11 . C orresponding. Bed VJeights and Manometer R eadings ..
. .. 43
■I I I . O p e ratin g .D ata .Taken June 24 , .1957 • ■ - • . . . . . . . . .44
i y •S t a r t i n g M a te ria ls . . •
...... ......
...
. .
. 44
V A n a ly tic a l a n d O p eratin g .Data
................. .. . . . . .
.' . 4$
VI ': Cios s -Index: o f O p eratin g D ata . ........................... 52
y i l T y p ic a l S creen A n a ly sis . . . .
.- . . . . . . . . . . . . . . ... 58
V I li .E i r s t O rder R e a c tio n D ata (Drum I).., .. . . . . . . . .
59
, IX. Chem ical R e a c tio n D a ta '. (Drum 3)
. ... . . . . . .
60
-X, Chem ical R e a c tio n D a ta -..-.(Monohydrate .Ash).
. . 6.0
-XI -Masd -T ra n s fe r D ata f o r L ig h t Ash . -. . »
., . / ' . . . 'I 61
X II - Mass T r a n s fe r.D a ta f o r L ig h t Ash (19*21.m in.)
■. . . . 61
. :X III Mass. T ra n s fe r D ata f o r L ig h t Ash - (l4 .-l6 m i n .) . .. . . . . .6 2
' XIY ,Mass -T ra n sfe r D ata f o r L ig h t Ash (10*12'm in .j . .
. . . . . 62
Xy . Mags T ra n s fe r Data, f o r L ig h t Ash (Below 10 and
■ • * ■• 63
above 21 m in .)
' - XVI Mass T ran sfe r- D ata f o r N itro g e n Runs . . . . . . . . . . . . . . . . . .
63
■Xyil .Mass T ra n s fe r f a t a . f o r L ig h t Ash
6.4
• (T em p eratu res■Below '40O°O.). •
-XVIII
M ass-T ran sfer D afa f o r
L ig h t Ash (Drum 3)
•
64
-XIX
M a ss.T ra n sfe r Data, f o r L ig h t Ash (Drum 2)
••
...
.,. . . 65
XX ..Mass ■T ra n s fe r Data, ,for- M pnohydrates ■ . . <
....................................... ..65
XXI
Mass T r a n s fe r C o e f f ic ie n ts f o r Mpnohydrates- • •
• •
• 66
• 'XXII P in a l - COD Y alues f o r Monphydrates . a t .......................... ....
67
Y arious T em p eratu res. and Amounts of
Added .N itr a te (C orrected, to 900 gms BW).
XXIII Gomparispn o f Steam -RUns to . Normal. C a lc in a tio n s . . . .
-. 68
FIG-ORES
1 M anufacture of West veep Eioda Ash.
. . . .....
.
2 Soda Ash D i s t r ib u tio n
................... . . < « .
3 .F i r s t - F l u i d G a lc in e r . . . . . .
......
. . . . .
. . . . .
4 Schem atic Flow-Diagram p f F in a l F lu id -C a lc in e r- • . . . .
5 ■E e a t*.up •Curve f o r E n it
. . . •. . - . .
6 Log COD0/CODp vs.. -Retention.-Tim e (T = 4 li° C )
.. .. - .
7 Log C0Do/C0Dp ys- R e te n tio n Time (T ..= 440°C). . . . . . . .
,8
Log ,C0Do/C0Df VS R e te n tio n Time (T. = 475°C) ■• ■
»: ■.
9 . Log COD0/CODf ys . R e te n tio n ■T im e. .. . . . . . .
. . ....
(Drum 3 , T = 475°C)
69
70
. 71
; 72
73
Y4.
75
76
77
-4 1 APPENDIX (c o n tin u e d j
FIGURES
Page
.10 Log CQDq/COD^. y S 'R e te n tio n Time' (Monohydrate Ash.). 11' P r e s s u r e Dpop vs Bed W eight
..............................................
12 Mass T ra n s fe r C o e f f ic ie n ts vs R e te n tio n Time .. - .
(Drum !>_ L ig h t Ash)
’ .
13 Mass T ra n s fe r C o e f f ic ie n ts ys R e te n tio n Time. . . . . .
(L ig h t Ash).
14 F lu id -B ed D e n s ity . VS-Be’d. W eight
. .. . . . .
15 R e s u ltin g COD’V alues vs . R e te n tio n Tim e................- .
(L ig h t Ash)
16 Mass T ra n s fe r C o e f f ic ie n ts ys .R e te n tio n Time . . . .
(M onohydrates)
I f - R e fle c ta n c e VS T em perature (MOnohydrates) . . . . .
Ip. Bulk D e n sity , ys. R etentio n -T im e
. ., . . . . . . . . . . .
.19 P e rc e n ta g e R e d u c tio n ,in COD L e v e l,v s R e te n tio n Time
(T..= 4 1,0°C)
20 -P ercentage. R e d u c tio n in COD L ey el vs R e te n tio n Time
(BW = 900 g'fnS\)
21 P e rc e n ta g e R ed u ctio n i n COD L ev el vs Tem perature . .
(R e te n tio n .= 20 m in .)
22 P e rc e n ta g e R ed u ctio n i n COD-Leyel ;ys T em perature . .
(BW. = 900- gms)
23 P e rc e n ta g e R ed u c tio n .in COD. L ev el ys Bed WeiS^4 . . .
(T em perature .= 4 10'°C)
. 24 P e rc e n ta g e R ed u ctio n in COD,L ey el ys Bed W e ig h t.
(R etention = 20 m in .)
ANALYTICAL .-PROCEDURES
LITERATURE CONSULTED
......................................... . . . . . . . . . .
. - .-TP
. ... 79
.. . . Po
...
Pl
..
.8 2
.. .. 83
. t .. 84
. .. . 85
. ..
87
..
8p.
.
'
.!
89
.
90
■.
91
.
92.
93
I .07
.-4 2 -
TABLE I
.PRODUCT QUALITY AND;SPECIFICATIONS
T y p ic a l A n aly sis
T y p ica l S creen A n aly sis
i
■Through 14 m esh, %
N&^O > %
58.44
-N&gCO^j ^
99.88
NaCI , %
0 .0 2
Through .40 mesh,y
Through .100 m esh, %
93
.16
Na2S04> %
0 .0 2
, Through. 200 meshy ■%
2
Pe2O3 r ppm
8,
Through 16 m esh, %
- Through 2 0 ,mesh* %
■ Through 50 mesh, ■%
,S p e c ific a tio n s
Na2O,
(as t o t a l a l k a l i )
58 -0 min.
NcLgCOjg y
•9 9 .■2 ' min.
N3.01 y %
0 .2 max.
P e2O3y, ppm
30
W ater i n s o lu b le ,.%
. 0 .0 5 max.
max.
—
100
-43
TABLE I I
.CORRESPONDING BED WEIGHTS AND ^ANpMETER READINGS
P re s s u re
(in c h es o f w ater)
. Bed W eight
(grams)
4
.107
7
'264
11
.472
13,5.
.570
17.5
995
18
980
=44-
TABLE. : I I I
-Time
E lap sed
- ,(min)
.
.
OPERATING .DATA TAKEN June 24 y 1957
Tem perature
°C
■Amount
C o lle c te d
(gram s)
■Pressure
Drop Across
Bed .(in ch es H2O).
O
342
0
.18
3
340
.-130
17
6
340
270
17
■9 .
343
415
17
12
.341
550
18
15
337
725
17
l8
342
845
17.5
'
Source - Drupi I L ig h t Ash
Bed W eight - $40 grams
•Feed R ate 4-5.9 gram s/m ln.
R e te n tio n Time - 2 0 .5 min.
Average Tem perature
^ l 0C.
• TABLE IV
STARTING MATERIALS
L ig h t Ash
Drum I
Drum, 2
Drum 3
Monohydrate
Drum I (mono)
9 .95# NaNO3/ to n
5 .5 # NaN03/ t o n
• 2 .3 # NaNO3Z ton
0 .0 # NaNO3/ to n
Chamber P roduct
of
of
Of
of
Ash
Ash
Ash
Ash
O I) LJ O O O O O O O O
-4 5 TABLE V ANALYTICAL .AND OPERATING.DATA
•Run
-No.
Drum I
13
14
15
16
17
,18
19
20
21
22
*23
24
25
26
27
' 28
29
30
31
32
33
34
35
36
37
R e te n „ Ave.
Temp.
Time
(min) ( 0C)
Bed Wt.
(gram s)
37
16.2
19.9
10.8
439
439
443
450
903
893
910
935
29.1
14.6
19-7
■ n .5
31.2
15.2
2 0 .5
ll.l
28.5
. 16.0
19.6
2 2 .1
12.1
19.1
22.3
19.5
2 0 .5
11.6
4.78
4 .7 2
8 .3 9
411
411
412
411
478
475
472
478
513
513
514
332
503
556
333
510
341
443
349
413
413
740
802
865:
950
765
850
830
865
720
825
855
900
690
690
1080
1084
940
945
875
650
965
f
F lu id
A P
Medium ■ Bed
: A
A
A
A
A
A
A
A
A
A
A
A
•A
A
A
A
A
A
N
-N
A
A
A
A
A
10
16.5
.16
.16.5
Remarks
Source
Bulk Den.
# /ft3
Fe
ppm
Foam
H eight
(cm)
Drum I
50.0
54.3
53.7
53.9
4
10
9
8
48 +
22
■ 22
34
——
52-1
51.4
52.5
51.6
53.7
53.5
53.9
53.7
56.9
54.8
55.3
8
9
9
9
10
13
21
18
21
23.
17
8
9
8
9
28
25
30
24
24
54.6
58.0
51.0
55.2
50.7
52.9
50.3
4 9 .9
50.0
12
12
11
10
12
8
10
12
6
31
I!
I!
I!
Broken
See 34
16
16
16
17
16.5
Broken
.17
15.5
16
15
17
17
Broken; See 33
16
13
15
21
19
17.5
16.5
15
12
17
I!
I!
»
I!
II
II
It
II
II
II
U
II
.
— —-
D-40
ppm
COD Ash
ppm R e f l .
362
117
130
■ 120
97
88
91
88
•—-*
142
'19
15 ■ .150
16
139
158
17
21
118
—
127
14
108
127
25
100
15
14
105
122
3
90
92
92
95
89
91
92
90
92
89
4
116
4
100
4l
305
26
132
3 - 237
134
9
30
267
158
9
8
159
80
80
92
80
90
92
90
89
89
69
12
16
26
"
II
Il
II
II
II
II
Il
Il
Il
-> »
48+
24
28
32
23
24
30
STPP
R e fl.
NaCl
i%)
O O LJ O O O O U O O I
-.46TABLE V ANALYTICAL AND OPERATING DATA (co n tin u ed )
Run
No.
Reten..
Time
(min)
Ave. . Bed -Wt.
Temp. ■ (grams)
( 0Q)
F lu id
Medium
r _
Drum 2
10.7 ' 412
472
’ 58
4 l4
247
59
11.7
264
409
40
2 .4
107
0 .9 4
4l
415
546 ■ 1025
42
5.7
415
1060
8 .6
45
1005
544
44
16.7
1190
22.5
405
45
451
970
46
15;2
1020
47
512
16.5
A
A
A
A
A
A
N
.N
N
■N
■
905
980
990
890
990
970
960
945
940
w.
A
A
A
A
A
A
A.
A
A
Drum 5 .
48
8 .5
11
49
• 17.1
50
5224.5
10.6
55
54
15.9
18.9
55
24.7
56
57
19.9
eeT *
478.
.477
476
■477
40 6
420
4 ll
4 l4
476
Remarks
S aurce
Drum 2
11
7 .7
7
4
14
14
15.5
1 5.5
16.0
16.5
•— lhfc.
17.5
18
17.5
18.0
17.5
18
18
.18.
.18
U
Il
H
11
Il
. 11
Il
H
II
Il
Drum 5
Il
II
H
I!
II
Il
II
Il
Mono
Drum I
Mono
Drum I
P redried
Feed
AP
Bed.
.100
150
—
A
. II
Bulk Den.
# /ft3
Fe
ppm
Foam
H eight
(cm)
- D-40
ppm
4 9 .7
52.2
52.2
50.4
51.2
—-t'
52.5
51.7
52.0
51.8
52 .1
5
6
5
5
11.2
9.8
8 .5
9 .6
10.4
8
8
88
20
22
26
50
40
25
42
50
19
59
71
■ 17
.16
20
29
12
' 16
26
25
0
0
517
149
148
185
550
274
.161
286
207
155
. 128
^ w '— '
485
.111
145
18
15
15
15
20
82
.1
2
I
I
9
10
7
7
2
" 95
176
270
149
.235
174
98
87
90
90
88
95
92
94
94
.8 5
100
64
571
94
69
80
58
■459
91
64
4 9 .4
54,8
54.5
55.5
55/5
51.9
52,9
52.6
52.7
55.7
.
19
21
25
20
22
24
24
29
22
25
--------
57.4
8 .5
17
16
21
1 9
COD Ash
ppm Ref I .
; 9 . 5
95
95
95
97
95
96
94
96
95.5
88
85
STPP
R e fl
65
76
86
85
79
NaCl
W
C; O ( j O O O O IJ
u
O O C
-4 .7 TABLE. .V ANALYTICAL AMD OPERATING DATA (co n tin u ed )
Run
No
.
R e te n i
Time
(min)
"
M-I
M-2
M-j
Bed Wt . F lu id
Ave
Tetip. ■ (grams) Medium
(0C)
.
,
A P
Bed
Remarks
Source
Bulk Den,
dVW
.Fe Foam
ppm H eight
(cm)
p-40
ppm
COD Ash
ppm R e f l.
STPP
R e f l.
NaCl
W
-■
1 5 .8.
10.5
14.2
410
450
478
P r e d r ie d
Feed
M-4
12.0
M-5
13.1
14.0
M-6
• 96
M-T
m-8
18.3
100
150
509
478
354
4 l6
433
P r e d r ie d
Feed
16.2
M-9
668
455
(500)
A
A
A
Mono
Drum I
14
12
.1 2 .5
Il
11
■
59.8
59.0
59,6
9 ,8
9-2
20.4
50
20
30
50
52
31
318
■256
256
.83
75 .
72
74
77
82
59,5
57,0
58.5
56.9
52.5
58.8
20.4 .84
2 6 .1 • 25
1 1 .2
31
24
1 3 .2
9.8 •45
42
13
68
28
22
45
11
8
640
238
254
352
-I81
174
92
65
72
97
95
81
63
92 .5
84
..
510
510
555
HO
1080
A
A
A
A
A
A
11.2
1 2 .0
15.5
5,0.
19.0
100
150
■465
9.60
A
A
i4
22
33
100+
43
.161
59
1260
45
.89
90
Q.29
0 .3 1
P re d rie d
Feed
M-IO
13.7
100
.150
y-68
780
A
A
■13
9
14
100+
27
118
17
539
48
77
82
0.0 7
0,07
P re d rie d
Feed
M -Il
18.0
100
.150
463
.87
70
O.52
0.51
D ried
Sample
MN-I
1 7 ,2
MN-5 , 14,8
100
.150
479
390
.
•«-< * • -
.
. H
.u —
M
Il
II
■
I!
67
77
-
.
&90
A
A
.1100
■975
A
A
•A
-W
-
14
■Monoh y d ra te
. 14.5
.14.5
9.9 5 NaNO3
.
,
.64
66.
59
30
331
108
.8
100+
.98
1004
95
93
.19
10
24
10
5Q5
84
97 .5
.22
-1655
125 ■
Il
11
J
O
O
O
O
O
O
O
O
O
O
O
*48.TABLE .V ANALYTICAL AND OPERATING DATA, (co n tin u ed )
Run
No.
R e te n , Atfe. . Bed Wt.
■Temp. ..(grams)
Time
(min) ■( 0C).
F lu id
.Medium
A P
Bed.
Remarks
Source
Bulk Den.
# /ft3
Fe Foam
D-40
H
eight
•
ppm
' PPm
(cm)
11.0
15.8
433
546
935
830
A
A
14.5
14,5
9 .9 5 -NaNO3
11
D ried
Sample
MN*2
15.3
MNrS' 18.0
MN-9
12,9
■MN-.10 10.3
100
150
478
3.90
■436.
550
980
.1000
985
775
A
A
A
A
A
14.0 .
14 ■
14
14.7
5 .5 NaNO3
11
Il
11
. 11
12
11
8
10
12.
100+
2,3
23
1T .
19
Dried.
Sample —
MN-J
11,3
MN*11 13.6
MN-^12’ 13.5
MN-16 12,5
100
.150
474
291
439
56.0
880
895
1050
.1050
A
A
A
A
A
1414.5
15
15
2 .3 NaNO3
II
11
11
Il
13
11
11
26
13
D ried
Sample —
MN*4
15.4
MN-13 l l . l
MN-14 • 10.8
MN-^15 n . 9
■V100
.1.50
478
393
135
558
1212
855
815
950
A
A
A
A.
A
.
14
15
14.5
16
' -0.0 NaNO3
. 11
II
Tl
11
20
18
20
21
, £l
D ried
Sample - *
MN-I? 26.0
MN-18
7 ,0
MN-19
9-0
MN-20
2.74
• 10Q
.1.50
4-35
442
433
430
. 1140
810
690
290
.5 .5 NaNQ3
I!
Il
. 11
II
9
1-2
14
13
12
mn-6
ffl-7
M M ,
A
A
A
•A
A
13.5 .
10,5
8.
.7-5
430:
20
,7
7.
.
COD Ash
STPP
.PPm R e f l. - R e f l.
NaCl
(#
.12
• 10
-480
318
89
90
101 . .121
9 6 .5 • -23
58
12
11
10
. 10
831
.3 3 5
.421
. 415
222
94
'93
91
92.
95
86
• .19
9 2 .5 .18
,1 2
/98
.21
,8 7
97
-17
85
30
. 18
20
19
62
46
11
13
11
949
389
406
354
314
94
90
.89
92
91
7 7 .5 .21
93
-19
.9 4 .5 •17
9 3 .5 . .18
-91.5 .18
40
17
32
34
53
58
24
. 20
11
7
.
.
910
389
46l
.436
362
94
6.9 .
86
74
66
65
88
87
.85
95
.16
•17
.15
.17
,17
31
6
22
Ig 18
928
359
46l
4.19
46l
95
92
8,9.5
§5
8 3 .5
98
93
97
97
95
•17
■ ,18
- .16
. .16
-15
100+
22
28
19
12-
J O O O O O O O O O O O
»4 9 *
T lB L E y
Run R eten . Avef.
•TeAip,
No. Time
(min),. , ( 0C).
B eE W t. F lu id
(grams.) ■Medium
D ried
Sample •--MN-21 •12.9
MN-22 12.6MN-23 11.7
100
150
48.1
391
.441
975
860
1010
A
-N
-N
..N
D ried
Sample
MN-24 13.9
MN-25 13.6
MN-26 13.3
100
159
391
448
4-12
920
950
890
A
N
N
A
Dried.
Sample
MN-27 15.8
-MN-iSS 1 5 .3
-100
.150
386
442
805
870
A
A
910
1050
E
A
D ried
Sample. ^
MN-29 1 6 .5
■MN-30 I 6 . 8.
100 •
19.O
394
485
Dried.
Sample
MN-31 12.5
MN-32 12,5
MN-33 I S ,0
100
15Q
396
427
477
AP
Bed
INALYTICAL. MD OPERATING.DATA (co n tin u ed )
.Remarks
Source
9 .9 5 NaNO3
13.0
. 12.0
. 13.5
M
I!
II
' 0 .0 NaNO3
15
15.5
12.5
II
II
-I!
2 ,3 MelNO^
9 .3
13
ii
it
5 .5 - NaNO3
15
.14
II
9.95 NaNO3
860
840
990
A
A
A
13
13
13.5
II
Il
II
B qlk Den.
# /ft3
Fe Foam
ppm . H eight
• (cm)
P-40
ppm
.COD Ash
ppm R e f l ,
STPP
R e fl.
NaCl
W
9 8 ,5
9 7 .5
.94
93
. 16
. .16
.17
. *17
100+
.38
22
20
24
7
9
7
.933
513
534
525
7 .0
18
16
16.
70
75
58
35
61
.48
■24
16
793
383
233
217
92
67
61
79
6.6
67
72
77
9
10 ■
1.1
86
20
.14
62
8
0
638
117
84
93
8.6
.88
85
93
94
20
24
13
100+
29
15
74
48
41
8.12
213
„58
94
84
89
85
92
97
15
10
11
8
.100+
32
-19
16
81
40
52
5
„38
10
17
10
94,5
.86.
71
83 '
.847
95
. 174
8 3 .5
161 .89
■20 ■.84
.8.9
94
99
96
■.24
) O
O O O O O u u U O O
-^o*TABLE.V
Run L. vReten.
No.
Time
(min.)
Ave.
Temp.
;(°C)
.Bed M t.
(grams)
F lu id
Medium
AP
Bed
■Remarks
_______
- 2.0 mesh
D ried
Sample
20.8
MN-34
D ried
Sample
16
MNO 5
457
1000
4.54
755
A
13
S -I
24.5
43.5
785
A
11
S-2
12.4
587
570
A
11
D ried
Sample
15.8
8-3
S-4
13.3
13,1
8-5
100
150
•46.0
.427
402
D ried
Sample
SO
S-T
Sr8
8-9
S—1C'
F -Il
100
150
437
412
475
:4 l2
"510
450
15.7
11.5
12.1
13.7
13.3
1 0 ,1
ANALYTICAL AND .OPERATING DATA (continued.)
A
15.5
M
—28 mesh
Il
Steam
A
A
A
11.5
1 2 .5
13.5
A
A
A
A
A
A
Bulk Den.
Fe
Foam
# /ft3
ppm H eight
. .. .
____ _
(cm) .
0 .0
NaNO3
II
Il
11
II
907
88
65
.19
12
10
64
100+
7
' 66
125
898
74
91
79
85
.19
.20
10
38
9
106
77
82
.19
52.5
12.6
28.
2,6
129
96
96
52.2
12.6
23-
10
.8 2
89
9 2 .5
- -x
7
100+
63
846
94
92.
.22
10
9
9
25
24
32
8
6
5
69
106
173
92
89
88
92
96
96
.24
.23
.23
11
94
56
829
92
87
.19
14
14
7
.11
10
' 13
38
56
68
47
75
70
6
6
•4
5
3
7
101
128
65
113
56
40
89
89
91
92
87
90
9293
84
83
84
88
.20
.20
.03
.03
. .03
.05
'
5-5
NaNO3
11
,11.5
14
•15
15
13.5
It
II
II-
II
Il
II
Drum 2
L ig h t
II
II
II
.11
NaCl
{%)
72
ii
II
COD Ash
STPP
ppm R e f l. . R e f l.
100+
.11
9 .9 5
NaNO3
It
D-40
ppm
____
7
it
M
A
880
770
750
860
785
758
..
Drum 2
L ig h t
.ti
A
870
830
83O
Source
52.9
51.7
53.0
52.8
o
o
o
o
o
o
o
o
o
o
o
t 51-<
.TABLE 7
Run. -Reten.,
No. ■Time
(min)
,Bed- Wt. F lu id
(grams) .Medium
AP
Bed
11.9
11.4
401
459
-Remarks
Source
. 0 .0
NelNO3
100
150
D ried
■Sample
S*12
S^-13-
Aye.
■ Temp.
( 0C)
ANALYTICAL .AND OPERATING. DATA, (c o n tlim ed)
740
660
A'
A
■14.5
12.5
U
11
Bulk Den.
Fe ■Foam
ppm H eight
. (cm)
D-40
ppm
COD Ash ... STPP
ppm R e f l . ■Ref I .
NaCl
(#)
.14
100+
58
8.51
86
55
.18
16
17
53
-67
27
13
265
147
81
77
79
76
.19
)
-5 2 r
•TABLE VI
CROSS INDEX OF OPERATING. DATA
Grade 100 Ash R eten tion Time Index ± 2 min.
idex
Run No.
R eten tion .>
Temperature
2
40
'4 1
2 .4
0.9 4
.40.9
415
6
35
36
42
4 .7 8
-4 .7 2
5.7
349
413
346
IO
16
• 20
24
34
37
38
39
43
48
49
53
10.8
11.5
1 1 .1
1 1 . 6.
8 .3 9
10.7
11.7
8 .6
8 .5
. 11,-0
1 0.6
450
4 ll
478
443
413
412
4 l4
415
478
477
406
.14
18
■22
26
29
46
54
1 4.6
1 5 .2
. 16.0
12-. I
1 5 ,2
15 .9
4 ll
475
513
503
4.51 (N)
420
l8
1.4 •
15
19
27
30
32
44
47
50
' 55'
.57
1&.2
19 .9
. 19.7
19.6
. 19 .1
1 9 .5
16 .7
16.3
1711
18.9
19 .9
439
443
412
514
556
512 (N)
344 (N)
512 (N)
476
411
476
"I
j
i
Ii
-■53
.TABLE -YI
CROSS INDEX.. OP OPERATING-DATA (.Continued)
■Index
..Run No.
R eten tion
. 22
. 23
28.
31
33
45
52
5.6
2 0 .5
2 2 .1
22 .3
2 0 .5
22 .3
. 2 4 .5
■24.7
28 +
13
17
2.1
25
'
Temperature
• 472
332
333 (N)
341 '
403 (N)
.477
4 l4
439
.411
-478.
513
37
2 9 .1
31-.2
2 8 ,5
R eten tio n
S'
Grade 100 Ash Temperature Index +
■ Temperature
Index
Run. No.
390"
' 28 '
31
33
35
42
44
2 2 ,1
2 2 .3
20 .5
4 .7 8
5 .7
16.7
332
3 3 3 -(N)
,3.41
349
346
344 (N)
17
18
19
20
36
37
38
39
■40
4l
43
45
53
54
55.
56
■29.1 '
i4 .6
19,7
.1 1 .5
4 ,7 2
8 .3 9
10.7
11.7
2 .4
0 .9 4
8 .6
22.3
1 0 .6
13 .9
1 8 .9
24 .7
4n
411
■41.2
.411
413
412
412
■4l4
409
415
415
403 (N)
4p6
420
411
4 l4
4 l0
TABLE :VI
CROSS. INDEX QF OPERATING DATA. (co n tin u ed )
• Index
■Rjm. No,
450
15
14
. 15
16
3446
37-0
1 6 .2
19 .9
10.8
1 1.6
.15*2
4-70
" 21
22
23
24
48
49
• 59
52
57
3 1 .2
1 5 .2
2 0 .5
1 1 .1
8 .5
.. 11.0
17 .1
2 4 .5
19 .9
510
25
26
27
29
32
47
39
2 8 .5
16.0
1 9 .6
.12 .1
1 9 .5
16.3
• 19.1
■R e te n tio n
Tem perature
439
439
443
4.50
443
451 (N)
478.
475
472
47-8
478
4-77
476
■477
476
513
513
5i4
5&3
510 ' (N)
512 (N)
. 556
Monohydrate and. Added NaNO3
g -P -
O
. S
0
Run No.
M r - I
M-2
M^-3
M-4
-M-5
M -4 6
M-7
MrS
Mr-9
M-IO
M -Il
MN-4
MN-13
MN--14
R e te n tio n
.15,8
.10.5
1 4 .2
12.0
1 3.1
14.0
.0 .9 6
18 r3
. 1 6 .2
1-3.7
.18.0
15 .4
.1 1 .1
.10.8
T em perature
410
450
478
509
478
354-4i6
433
465
468
463
478.
393
435
-55^
TABLE J I
.CROSS INDEX CF' OPERATING- DATA (co n tin u ed )
-Monohydrate and Added NaNO3
#NaNO V to n
O
Rtm No.,
R e te n tio n
Temp-Brature1
-MN'*! 5
MN^
MN■*25
MN^26
MN-34
m -3 5
1 1.9
1 3 .9
-IJ.. 6
.13.3
20.8
.16.0
558
391 (N)
448 (N)
412
457
454
.2.3
.MN-3
■MNwll MNr-12
MN-16
MNw27
• MNw-28
11.3
.13.6
13 .5
1 2 .5
15,8
-15.3
4.74
394
-439
560
386
.442
5.-5
MN-2
MN-S
MN-;9
MNwlO
MNwlT
- MNwlS
MNwl9
,MN-EO
MN.-29
MNwJQ
1 5,3
18.0
1 3.9
.10.3
2 6 .0
7 .o
.9 ,0
• 2 .74
1 6 .5
16.8
478
390
4J6
550
435
442
433
430
394
48 5
9 .9 5
MNwl
MN-5
MNw6
MN-?
MNwgl
,MN-EZ
,MNwZJ
MNwJl
MNwJZ
MNwJJ
.17 ;.2
l4 .8
11.0
■1.5 .8
12.9
1 2 .6
.1 1 .7
12 .5
1 8 .O
.12,5
479
390
433
546
4 8 I (N)
391 (N)
441 (N)
394
477
427
TABLE VI
.CROSS INDEX CE OPERATING DATA (c o n tin u e d )
N itro g e n u s e d a s - .F lu id iz in g Medium
LA = L ig h t ^sh
MNrX.= Monohydrate +'X Pounds NaXOs a d d e d /to n
Run No.
31
3?
44
45
46
■47
MNrtZl
MN-22
MN-23
MN-24
■MN»25
.R e te n tio n
Tem perature
22.3
. 1 9-5
1 6 ,7
.2 2 .3
1 5 ;2
16.5
1 2 .9
1 2 ., 6
.1 1 ,7
13.9 ,
.1 3 ,6
333
510
344
403
451
512
48.1
■391
44l
391
448
M a te ria l
LA
,L A
L A
L A
L A
.L A
-MNr9 .9 5
-MNr9,9 5
MN.-9.95
.MN-O
MN-O
■Runs Made U sing .,a M ixture o f L igh Ash and ■Monohydrate
L ig h t Ash from Drum 2
Monohydrate, from Dpum I
Run No.
■R e te n tio n
Tem perature
RM-L-I
RM-L^2'
RM--L-5
13.4
19.4
12.7
438
,451
432
.'Gms Monohydrefe
Gms' L ig h t Ash
I / 2
1 /1
-2 / I
Runs ,Made U sing L ig h t Ash o r Monohydratei and-Steam ,
InR theu-Fluii^i.zifctg A ir
Run. No.
S rl
8-2
S—3
Sr4
S-5
S—6
S.-7
8-8
S-9
_.R e te n tio n
2 4 .5
1 2 .4
1 5 .8
13.3
13.1
1 5 ,7
11.5
1 2 .1
13,7
.Tem perature
F in d . p,f Ash
435
387
-460427
4oz
437
412
475
412
L A
L A
JOT-9.95
MN-9.95
■MN-9 .9 5
MN-5 .5
-MN-5 . 5
L A
L A
.-"57“
. ■TABLE, JX
CROSS. INDEX OF OPERATING .DATA (.ddntlnue'd.)
■Runs .Made U sing B ig h t Ash o r MonOhydrate .in th e
F lu id iz in g A ir
Rpn .Np,.
R e te n tio n
Sxio
S x ll
SxlZ
Syl3
Run -No-V
.
.Kind o f Ash
510
450
4oi
459
15.5
1 0 .1
1 1 .9
11.4
- ■
Cxl
CB2
.0x5
Tem perature
-L..A
-L A
MNxQ
-MN-1Q
-Chamber P ro d u ct
I,, I;,. , .R eten tio n
„14.4
I? ..6
1 9 .5
T em perature
501
522
555
-5 9 - TABLE, y11
TYPICAL .SCREEN ANALYSIS
,C um ulative P e rc e n t-R e ta in e d on IJ. S. S creen
S creen
Run
'48
Run
49
Run
50
Run
52
Run ■ Run
54
53
Run
55
Rim
. 56
■Run
57
1 .5 .
2 .1
3 .9
• +30
3 .7
■1.5
1 .9
1 .7
' 2-7
1 .4 . 3.0
440
l ? .2
a .8
1 1 .1
10.9
1 3 .9
•9.4
16.3
1 2 .1
12 .1
16,8
+100
79.8
7 2 .1
7 3 .6
74 <2
7 8 ,8
7 1.7
7 8 .8
7 6 .1
7 6 .1
7 9.1
.+140
92.7
.8 9 .5
8 9 .8
90.2
9 2 .)
8 8 .7
91.4
9 0 .6
9 0 .6
9 1 .5
' +200
9 8 .1
. 97.3
97.-0.
97.3
9 8 .1
9 6 .9
97 .2
9 7 .0
97.0
9 7 .2
+325
9 9 .6
99.8
9 9 .7
9 9 .6
99 .9 .9 9 .4
9 9 .5
9 9 .7
99.7
99 .4
-325
0 .4
0 .2
0 .3
0 .4
0 ,5
-0.3.
0 .3
0 .6
' .0 . 1 .
0 ,6
■-‘59TABLE V III
• Run Ho.
FIRST ORDER REACTIOH DATA
(Drum I)
CODf
lo g C0Do/C0Df
R eten tion
Temp.■0C
13
3 6 2
117
.490
.37
4)9
14
U
130
. .444
1 6 .2
439
1.5
M
120
.480
1 9 .9
■443
134
.432
11.6
443
.407
2 9 .1
4 ll
.14.6
411
34
17
II
142
.18
II
150
19
a
ro
COD0
. .416
19.7
412
.360
1 1 .5
411
413
413
20
II
158'
36
II
158
O
MD
KA
139
.4 .7 2
159
.257
8 .3 9
37
21
11
118
A 87
3 1 .2
478.
22
II
127
.455
1 5 .2
475
108
• 525
2 0 .5
472
127
.455
11.1
478
23
24
It
- 6 0 -*
TABLE.. IX
CHEMICAL. REACTION. DATA
(Drvmi 5.)
Run. No.
COD0
CODjr.
48
483
111
.638
a .5
■49
.H
145
- .525
, 1 1 .0
477
95
/707
1 7 .1
476
50
lo g COD0/CODj,
R eten tio n .
• Tempt. 0C.
. 478 '
52
II
95
.715
2 4 ,5
477
57
II
174
.444
1 9 .9
476
\
■ TABLE .X .•CHEMICAL REATTON DATA
.Run NO.
NaNO3ZtOn
COD0,
• _=_--J
CODf
-< .
(■Monohydrate Ash)-
lo g -CODq/CODf
‘
R e te n .
.. '
I T
928
559
.412
26
- MNr l 8
5 .5
.928
461
■ .504
7
/MN-19. '
5-5
928
419 '
5 .5
928
4 61
MN*17
MN-20
"
. .546
.504
9
'2 *.74
Temp. .0C.
455 ■
442
455
430
•"61 -
■Run
No.
-"Reten.
• Temp.
- 0K
19
.1 9 .7
68.5
15
-1 9 .9
■23
2 0 .5
. B-.W.
.
MD*
MASS .TRANSFER .DATA FOR- LIGHT..ASH
-CGDj,
V'i
-N
lo g N
, 1
865
362
139
,1 1 .3 2
726
910
362
120
12.17
' 7^5
,830
362
108
'12,. 40
.Re-ten.
■Temp.
BiN.
.COD
• 0
-CQDf
1
log-7/9OO T
/ 683 BW
1.05385 - ,0014599
1.027
.01157
1.08529
.0013966
1,021
...OO903
1.09342
,D013423
1.090
TABLE X II .MASS TRANSFER. DATA. FOR ' LfGHT . ASH.
Run.
Mh.
g #
Vl -O
XI
table
.03743 ,
(19-21 m in .)
■N
- JSOQ-JS-.
if $ 5 BW
•e ^ / T
K
19
19.7
685
865
362
139
11,32
1,027
.646
1 7.1
1.5
19-9
716.
910
382
120
12.17
1.021 '
,658
18.1
2:3
20.5
745
,8,3.0.
262
108
12,40.
1.090
-.669
1 7 .0
27
19. 6.
787
855
31^2
122
1 2 .2
1 .1 1
-.684
16,1
829
690
362
.100.
13.7
li2 6
-t697
15.-7
30
.1 9 ,1
- 62-TABLE X lII ..MASS TRAMSFER DATA
-Run. Mo.
• Re te n .
■B.W.
16.-2
(14-16 .m in.)
COD,
CODf
N■
342
130-
14.3
712
.657
1.03
2 1 .1
Temp..°K
e^ '/T
-_./ 500: T
'
683 DW
..K
.18.
1U-.6
# 2
362
150
.1 4 .5
684
. . 645
.1.06.
2 1 .2
26
1 6 .0
825
- 362
105
1 6.0
786.
.684
.1 .1 2
2 0 ,9
TABLE. :XIV MASS TRANSFER DATA
(.10-12. m in .)
-Reten.
B.-W.
COD,
• CODf
.20
.11.5
950
3.62
. 1.58
1 7 ,7 4
684
,. 645
24
1 1 .1
.865
36.2
127
21.17
751
- .671
29
12.1
690
.362
.116 .
20,33
776
.. 6,80
1.218
24.8
34
. I l .6
945
362
134
1 9.66
716.
,658
..999
.29,8
Run. Np. ■
N
Temp. °K
eK'/T
-,/.9Q 0 -T
V 683 BW
.974
-1 .
07
■
K
28 .3
29 ,4
- 63TABLE -XV MASS TRANSFER DATA ABOVE .21 MINRTES AND BELOW 10 MINUTER.
,B.W.
O
■R eten ,
I ;
Run
No,
COD^,
' N
Temp.
.0K
/9OO T ' e %
T 683 BW
K
15
3 7 .0
903
362
117
6: 62
712
1 .0 2
.656
9 .9
17
2 9 .1
740
362
142
7 .5 6
684
1 .1 1
. .645
1 0 .6
.21
3 1 .2
76§
362
118
7 .8 5
75i
1 .1 4
-.671
.1 0 .2
:25
2 8 .5
720
3.62
100
- 9 .1 9
786
1 .2 0
.684
11.2.
36
%.72
650
362
15.8
4 3 .2 2
686
I .I 9
• . 647
56 .0
37
8 .3 9
969
362
159
24.20
686
. 0 .9 7
..647
37.4
MASS TRANSFER DATA FOR iNITROGEN RIJNS
•R eten.
B.W.
C O D o
32
.1 9 .5
1084
45
2 2 .3
46
47
-CODf '
.N
362
132
11.8
.1190
317
■207
1 5 .2
970
317
153
16.3
1020
317
.128
Temp.
. 0K
/ 900 T
. eVT
T 683 BW
E
783
.980
- .682
676
CO
•
O
Run
No.
.642
8 .8
10.8.
724
.995
. 66l
1 6 .5
11 .6
785
.68.2
1 6 .9
4 .9 3
-r>l
■TABLE XVI
1 .0 1
1 7 ,7 .
-r64—■
.. TABLE- XVII
Run
•Reten.,
No. •
Temp.
. °K
- B.W,
4 ,7 8
622
,875
-table; x v i i i
■Reten.
Temp.
0K :
362
. 237
267
CO
35
362 '
H
94&
I—
I
6-14
'N
OV
2 0 ,5 -
CODf
VO
33
Run
■No..
MASS -,TRANSFER DATA FOR LIGHT ASH
(Temp era tu res Below 400 0C)
- ,/- 9 0 0 T
/ 6 8 3 . BW
48
9 .5
751
905.
483 ,
49'
11.0
.750
980
50
' 1 7 .1
' 749
52
.2 4 ,5
53
CODf
N
-K
.0,933
,.6 1 3
.1 0 ,6
0 .9 7
.6 1 8
-3 .3 .1
MASS TRANSFER DATA FOR LIGHT ASH
'..BiW. . ■C0D.o
, e K/T
(Drum 3)
./9 0 0 T ■ e %
7 -6 8 3 BW
K
ill
4 3 .7 6
1.0-5
. , 671
56.7
483
,145
30.7
1 .0 1
.671
45.-3-
990
': 48-3
95
' 2 2 .6
1.00
,670
3 3 ,8
.750
890
48.3.
.93
1 .0 1
.671
•23.5
IOi .6
679
990
483
.176
28 .9
,955
.643
4 7 .1
54
.15,9
749
970
483
.270
13 .4
.971
.. 650
2 1 .2
55
18.9
684
960
483
.149
17.7
.973
.645
28 .3
56
2 4 .7
687
949
48-3
233
1.0.12
• 98
.64?
1 6 .1
.57
19.9
749
940
483
174
15.5
1.03
.670
2 2 ,5
15.92
r.65-^
-TABLE. XIX
COD^
Temp.
°K
_N
.149
68$
15.7
317
148
687
14.4
264
317
183
682
55.83
5 .7
1025
317
274
619
8 .6
io 6o
-317
161
688
■ B.'W.
10.7
472
317
39
11-7
247
40
• 2 .4
42
43
38
'
GODo
.
V 900 T
/ 683 BW
■ .646
■K
1.39
17.6
I
-R eten.
Rmi
No.
MASS,.TRMSPER BATA .FOR LIGHT, ASH ,(Drum 2)
1 .9 2
11..6
.644
1 .8,5
46.8
7 .5 4
.616
.89
13.8
.18 »14
■ .647
. .92
30.2
TABLE XX MASS .TRANSFER -DATA FOR MQNQHYDRATES
.R eten.
- Temp.
• 0K
B.-W.
. OODo
CODf
MN^-13
1 1 .1
. 6.66
8.55
910
4 6l
I .60692
.0015015
.00604
MN-14
10.8
708
.815
910
436
1 . 64227
.0014124
.02898
MN^-15
11.9
831
950
91Q
362
1.66323
. .0012033
.03019
Run -No . '
'
‘ .nT
t
lo g )/90Q T
f 683 BW
'TES­
TABLE ZX I
.HASS, TRANSFER .COEFFICIENTS FOR HONOHYDRATES
TSmp.
-0K
ByW.
GODg
CQDf
' -N
Rete n .
M-I
68 J
688
459
318
8 .9 3
15.8
1.15
. .701
.11,1
•M-2
72J
4:55
459
- 256
19.3
1 0 .5
1.45
' .715
. 1 8 .6
M-3
751
JOO
459 ■
2J 6
.14.3
' l4 i2
1 .4 l
.724
14 .0
H-4
792
510
640
ZJ8
33 .5
.12.0
1 .4 J
.733
3 2 .2
M-5
751
■ . 510.
640
254
29,4
1 3 .1
1.41
.724
2 8 .9
M-6
627
555
64p
352
20 .6
14.0
I i 22
,679
24.9
• M^t
.689
HO
640
181
4 7 .9
2,88
.703
237.0
'MN-4
751
1-212
910
389
33.8
MN-13
666
855
910
46l
MN-IfJ-
.708
815
910
MN-15
831
550
730
72-6.
Run
No.
M -jJ J
0 .9 6
\Z900 -T
( 68 j BW
.=K>
-K
15.4
0.905
. .724
51.7
.40.45
.1 1 .1
.1.014
.694
57-6
4J6 .
4 J.8 8
10,8
-I.O 69
.709
58.0
910
362
4 6 .0 5
11.9
1.072
.747
57.6
1000
907
125
57.7
20.8.
0.98
.716
53.8
755
' 8.98
106
4 9 .5
16.0
1.13
.715
61.4
-
■^67*
-TABLE XXII
■Run•No.
PINAL . COD VALtES FOR MONQHYDRATES AT VARIOUS TEMPERATURES' • '
AND- AMOUNTS' OF ADDED NITRATE CORRECTED TO 900g BW.
...
■.
NaNO3
# / ton.'Of. Ash
: , °J
Temp.. 0C
,
CODf
„ Corrected
'MN-h-IJ
.0
595
475
MN-Il
2;. 5
594
405
MN-8
5 .5
59Q
.45,8
MN-14
O
455
462
MNr 1 2
. a>5
459
308
MNr-9
5 .5
45.6.
396
0
558
548.
MNrtl 5
.
.
MN-1.6.
2.5.
5$0.
Z$4
MNrlO
5.5
550
268
. r68
- TABLE .XXIII
•Run No. .Temp.
- 0C
COMPARISON OF STEAM RUNS TO NORMAL-CALCINATION.
R eten. .Bed Wt. COD1 COD1
(min)
,(gm s.) .ppm ■ ppm
$ Red.
COD
$ Red. COD COD1
co rrected
co rrected .
,.to BW
. to BW
900 gms.
900 grams
412
435
450
475
510
412
439
445
478
513
13.7
2 4 .5
10.1
12.1
13.3
19.7
16.2
11.6
ll.l
16.0
860
783
758
750
785
.865
893
945
865
825
317
317
317
317
317
362
362
362
362.
362
113
129
40
65
56
139
. 130
134
127
105
64.4
59.3
8 7 .5
7 9 .5
,8 2 .3
61,7
64.1
63.0
65.O
7 1 .2
62.9
55.5
8 0 .4
7 2 .5
76.8
60.5
64a
64.5
63.7
68.0
,117
141
62
.87
74
143
139
129
131
116 -
S-12
8*13
MN-13
.MN-=l4
■401
459
393
455
11.9
11.4
1 1 .1
10.8
740
660
855
815
851
851
910
910
263
147
. 461
456
69.1
.8 2 .6
4 9 .4
5 2.1
62.7
70.8
4 8 .0
4 9 .6
318
248
■473
459
• 8-7
' 8-6
ffl-8
MN-9
412
437
390
456
11.5
15.7
18.0
■13.9
770
.880
1000
985
.829
#29
831
831
128
. 101
421
415
8 4 .6
8 7 ,8
4 9 .4
50.1
78 .3
8 7 .0
52.0
52..5
180
108
400
395
8-5
8-4
MN-5
- MW'^6.
402
427
390
433
13.1
13.3
14.8
11.0
83.01
830
973
933
846
846
1004
1004
173
106
505
-480
7 9 .5
8 7 .5
■49.6
5 2 .1
7 6 .3
8 4 .0
51.7
53.1
201
135
■487
471
Sr9
"f.St:!
S -II
S-8
S-IO
'■'•'19
.14
34
24
■26
. Screening
and
.Crushing
Storage
C la r ifie r
S.urge
F i lt e r
D isso lv e r
J Feed Liqdor
I
Storage
C entrifu ge
CooJer
C alciner
Skip
Hoist.
Mining
Figure I .
Manufacture of Westvaco Soda Ash,..
100,000 Tons Soda Ash
-7 0 -
9
1
2
5
4
5
6
Uses of Soda
7
Glass
8
Other Chemicals
9
C austic & Bicarbonate
10
Non-ferrous Metals
11
Pulp & Paper
12
M iscellaneous
Figure 2 .
10
11
12
Ash
Cleansers & M odified Sodas
Soap
Water S often ers
T e x tile s
Exports
Petroleum R efin in g
Soda Ash D is tr ib u tio n .
I
-7 1 r e a c to r
charge
d is c h a rg e
tube
w a ter
to s ta c k
charge tube
p re s s u re
r e le a s e
w a ter
v
V X X
XXN.
\
d u st
e lim in a to r
p ro d u c t
F igu re 3.
F i r s t F lu id C a lc in e r .
p re s s u re
' fu rn ac e
-7 2 -
charge
thermocouple
rea cto r
stack
discharge
tube
bed le v e l
to stack
cyclone
.heat exchanger
heat duct
furnace
comp. a ir
comp. a ir
o r ' N;
dust elim in a to r
product
vent
Figure 4 .
Schematic Flow Diagram of F in a l F lu id C a lcin er.
lower
-73700
I
I
I
>
I
133
6oo
500
0
Temperat
Temperature
O
VJ
O
O
I
1
200
-
100
/
/
0J-------------3^
/
/
^7
Time (hours)
F igu re 5«
H eat-up Curve f o r U n it.
Log(COD0/CODf )
- 711-
R eten tion Time (minutes)
F ig u re 6.
Log(COD0ZCODf ) v s . R eten tio n Time.
”7 5 “
I
I
.50 _
R eten tion Time (m inutes)
F igu re 7 .
Log(GOD0ZCODf ) v s . Time.
"76 -
l
.5 5
i
l
t
-
o
5
10
15
20
R e te n tio n Time (m inutes)
F igu re 8 .
Log(COD0ZCODf ) v s . Time.
25
-7 7 -
R eten tion Time (m inutes)
F ig u re 9 .
Log(COD0ZCODf ) v s . Time.
(Drum 5)
-7 8 -
l
l
l
Log(COD0ZCODf )
I
0
L
5
i
10
- I -------------------1------------------ 1------------------ 1
15
20
25
50
R e te n tio n Time (m inutes)
F igu re 10.
Log(COD0ZCODf ) v s . Time.
--79-
Bed W eight ( grams)
F ig u re 11.
P re s s u re Drop v s. Bed W eight.
.8 0 -
_________ I
0
5
F ig u re 12.
I
i
'
10
15
20
R e te n tio n Time (m in u tes).
)
25
■
50
Mass T ra n s fe r C o e f fic ie n ts v s. R e te n tio n Time
f o r Drum I L ig h t Ash.
■61-
•> Drum I O Drum 2 x Drum 3 -
cod
362 ppm
COD 483 ppm -
R e te n tio n Time (m in u te s).
F ig u re 13.
Mass T ra n s fe r C o e f f ic ie n ts v s. R e te n tio n Time.
F lu id Bed D e n sity ( l b s / f t 3 )
-8 2 “
Bed W eight (grams)
F igu re 1 4 .
F lu id Bed D e n sity v s . Bed W eight.
-8 3 -
COD 483 ppm
COD 362 ppm
2*5
5
7 «5
10
12.5
R e te n tio n Time (m inutes)
F igu re 15•
R e s u ltin g COD V alues v s . R eten tio n Time For L ig h t Ash.
-8 4 -
70 r
I
I
6o -
Mass T ra n s fe r C o e f fic ie n ts
50 -
40 -
\
50 -
0
\
O
\
20 _
0
\
X
0
10 -
0 L
0
» - COD
0 -COD
X - COD
c-COD
459 ppm
x
640 ppm
910 ppm
900 ppm (screen ed )
I
5
F ig u re 16.
^
1
10
19
R e te n tio n Time (m in u tes)
1
20
*
25
Mass T ra n s fe r C o e f f ic ie n ts v s . R e te n tio n Time
F o r M onohydrates.
-8 5 95
I
I
I
90
85
80
75
9 .9 5 # /to n
5-5 # /to n
2 .5 # / to n
0 .0 # /to n
70
65
60
_I__________ i__________ I__________ L
_1_
350
550
400
450
500
Temperature ( 0C)
F ig u r e
17.
R e f l e c t a n c e v s . T e m p e r a tu r e .
-86-
R e te n tio n Time (m inutes)
F ig u re l 8 .
Bulk D en sity v s . R e te n tio n Time.
•-87it
<u 50
R e te n tio n Time (m inutes)
F ig u re 19.
P e r c e n t a g e R e d u c tio n i n COD L e v e l v s .
R e t e n t i o n Time (T = 4 1 0 ) .
-88-
R e te n tio n Time (m inutes)
F ig u re 20.
P e r c e n t a g e R e d u c tio n in COD L e v e l v s .
R e t e n t i o n Time (BW = 9 0 0 ) .
-8 9 -
400
450
T em perature ( 0C)
F ig u r e 2 1 .
P e r c e n t a g e R e d u c tio n i n COD L e v e l v s .
T em p era tu re ( R e t e n t i o n Time = 20 m i n . ) .
-9 0 -
Tem perature ( 0C)
F ig u re 22.
P e rc e n tag e R ed u ctio n in COD L evel v s.
Tem perature (BW = 900).
-9 1 -
1000
Bed Weight (grains)
F ig u re 25.
P e rc e n ta g e R eduction in COD Level v s. Bed Weight (Tem perature = 410)
-9 2 -
8oo
900
1000
Bed W eight (grams)
F ig u r e 2 4 .
P e r c e n t a g e R e d u c tio n i n COD L e v e l v s .
Bed W eig h t ( R e t e n t i o n Time = 20 m i n . ) .
DETERMINATION OF SODIUM CHLORIDE .IN REFINED SODA ASH
P r in c ip le
A. w eighed sam ple o f soda ash Is a c i d i f i e d a n d .th e c h lo rid e is
d eterm in ed .by a d d in g a known amount o f s i l v e r n i t r a t e and back t i t r a t i n g
w ith ammonium th io c y a n a te to th e f e r r i c alum e n d -p o in t.
The sample is
b o ile d a f t e r a c i d i f i c a t i o n to remove th e hydrogen s u l f i d e .
P rocedure
1.
Weigh 20 ± 0 ,0 1 gram sam p le.an d .tr a n s f e r to a 5^0 ml E rlenm eyer
fla s k .
2.
Add
Add. about $0 ml of d i s t i l l e d w a te r.
.m l.o f .1 :1 n i t r i c a c id w ith s w ir lin g to a v o id foaming
o u t of th e .f la s k .
3.
B o il f o r 15 .minutes.* and c o o l.
Add b y .p i p e t t e 5«00 m l.o f 0 .1 N s i l v e r n i t r a t e and 2 ml of
f e r r i c alum s o lu tio n ,
4.
'U sing a 5 *ov 10 ml b u re t* back t i t r a t e w ith Q.1.N ammonium
th io c y a n a te to a f a i n t perm anent p in k ( s ta b le f o r 3 0 -seco n d s).
5. • T i t r a t e a blank, c o n ta in in g 100 ml w ater* 5 Ail ,o f 1 :1 n i t r i c
a c id .and 3 .00 ml of 0 .1 N s i l v e r n i t r a t e s o lu tio n .
C a lc u la tio n
(ml b la n k - m l sam ple) X 0.293 x N = NaCl^
.-94'DEiERMINATIOW OF. TOTAL..IRON. IN SODA ASH OR TRONA
P r in c ip le ■
The soda a s h .o r tro n a i s fu s e d to s o l u b i l i z e th e iro n , compounds and
. a c id ifie d .
A fte r a p p ro p ria te d ilu tio n ,/ .,an'.aliquot i s a c i d i f i e d , , reduced
w ith hydroxyl-amine h y d ro c h lo rid e I o c o n v e rt th e ir o n to th e fe rro u s s t a t e . .
- Q rth o ^ p h e n a n th ro lin e i s added and. th e s o lu tio n b u f f e r e d w ith ammonium,
■ acetate. -The volume o f th e s o lu tio n i s b ro u g h t to- 100 ml and o p tic a l
d e n s ity determ ined, p h o to m e tr ic a lly .
T h e .iro n c o n te n t i s re a d frpm a
c a l i b r a t i o n curve o r c h a r t .
P rocedure
1.
Weigh 5 ..PO- g . of s o d a .a s h o r tr o n a a n d ..tra n s f e r .to a c le a n
p la tin u m c r u c ib le .
2.
I g n it e I n a .m u ffle fu rn a c e 9-t -87.5 ± 25 C f o r 5 m in u te s.
5. • C ool, p la c e C rucible in a 250-m l.b eak er* add 40 ml of 1:1 HCl
I
-and. s w i r l to. co m p letely d is s o lv e .
4 . . R inse and. remove th e p la tin u m c r u c i b l e , make th e volume to 2.50
I
ml .in a 2 , 5 0 g r a d u a te d .c y lin d e r , and mix by in v e r tin g ,
5. ■F i l t e r 25 to 50 ml of th e d i l u t i o n through a Whatman.No. 5
f i l t e r p a p e r . C ap tu rin g th e f i l t r a t e in a c le a n -d r y b e ak e r.
6.
P ip e tte 10.00 ,ml in to a 250^ml E rlenm eyer f l a s k , add 4 m l,o f
Iil-H C ly 2 m l.o f hydroxylam ine .h y d ro c h lo rid e s o lu tio n and I ml
of o rth o ^ p h e n a n th ro lin e s o lu tio n .
Add. 10. ml o f 6N ammonium
a c e t a t e and make to 100 ml .in a lOO.-ml .g ra d u a te d c y lin d e r^
m ixing by p o u rin g back and f o r t h betw een th e f l a s k and. c y lin d e r .
-
95-
Let s ta n d .15 minutes but no longbr than two h o u rs.
7* •Read th e o p t ic a l .d en sity u sin g the :Fisher electroph otom eter
and th e g re e n (525) f i l t e r ..comparing .to d i s t i l l e d w a ter a t z ero
• o p t i c a l d e n s ity .
8 . -Read the. micrograms . of Pe2O3 from the' c a lib r a tio n curve, or c h a r t.
.C a lc u la tio n s :
m icrogram s .Pea03 x d i l u t i o n x 100 _ ^ Pe2O3
sample .Wt.. x -.a llq d o t x .IyOOO 3-OOO .
■Ror Routine Procedure:
micrograms Fe2O3 =
2000
^e2Q3
“96-DETERMINATION QF D-.40. IN REFINED SODA. ASHP r in c ip le
The sample Is "weighed, and the Dw40 I s titr a te d - w ith standardized
r e p e a l- s o lu tio n p n t il .the in d ic a to r moves to the chloroform layer..
A
blank i s run a t the s t a r t of a s e r ie s o f D-4-0 d eterm in ation s.
Procedure:
1.
Weigh 20 + 0 .1 g . o f soda ash, and add approxim ately 60 ml of
water to th e sample in an 8 o z ..g l a s s stoppered b o t t l e .
Add
I scoop * about 0 .3 g . o f anhydrous Na2SO4y. -approximately 2 ml
o f bromophenol .blue in d ic a to r arid $0 m l.o f chloroform .
2.
-T itrate w ith ..rdccal u n t il a lig h t b lu e c o lo r forms in the chloro^
.form la.yer.
One or two drops should make. a. d e f in it e change in
c o lo r .
- 3.
A blank i s run by w eighing 0 .5 g . ,of C .P ..Na2QO3 fo llo w in g the
aboye procedure.
C a lc u la tio n s i
ppm D-4Q '= (T ltre Blank), x Factor
Sample Weight
‘
97' *
PROCEDURE EOR DETERMINING NITRATE. IN SODA ASH
,P r in c i p le :
The sample' ,is .weigh'ed -and a c i d i f i e d w ith -con, s u l f u r i c a c id , • P e r*
r o u s . s u l f a t e s o l u t i o n i s added to be -o x id ize d .b y th e . n i t r a t e p re s e n t i n
th e .s a m p le .
Tne excess f e r r o u s s u l f a t e i s t i t r a t e d w ith 0 . 1 ,N p o tassiu m
d ic h ro m a te .using, o '-p h e n a n th ro lin e f e r r o u s s u l f a t e i n d i c a t o r .
.The b lan k
minus sam ple t i t r 'e i s th e amount of f e r r o u s . s u l f a t e consumed by th e
n itra te .
P ro c e d u re :I.*457
I.
-Weigh a 20.0 ± 0 .1 gram, sam ple a n d .p la c e in. a 500'^ml-B rlenm eyer
fla s k .
•2.
Add ab o u t 50 m l - d i s t i l l e d w a te r .
Add con. s u l f u r i c a c id to a ph o f I u s in g ,ph p a p e r.
■5.. • P ip e tte 25 m l .of 0 .2 N f e r r o u s s u l f a t e s o l u t i o n an d 20 ml.-con.
s u l f u r i c a c id -sh a k in g , f r e q u e n tly .
4.
.Heat to b o ilin g on th e h o t p l a t e and b o i l f o r 3 m inutes *
• 5» - C ool.by s w ir lin g under ta p u n t i l -lukewarm.?, add 50 .ml-O ist i l l e d ,
.w ater a n d .I , ml i n d i c a t o r ,
,
5. ■ T i t r a t e w ith ,0.1 .N p o ta ssiu m dichrom ate>• u n t i l t h e c o lo r changes
from orange oyer brown to b lu e g re e n .
The e n d -p o in t is Very
sh arp and may be re c o g n iz e d w ith in a few- h u n d re d th s of a
m illilite r.
7.
Run a .b l a n k .i n th e above p ro c e d u re ^ ,o m ittin g th e sam ple.
■.Calculations :
Blank :-■■ sample x 0 .1 x ,02835 x 100
Sample w eight
_ f0 as NaNO3
■R ea g en ts:12*456
1.
S tandard. NaNO3 -1.5.000 gm C .P. . NaNO3 d is s o lv e d i n one l i t e r
• d i s t i l l e d w a te r .
2.
One ml = 5-000. mg NaNO3 ,
F e rro u s s u l f a t e s o ln . - Q-.2 N p la c e 77-6 gm fe r r o u s ammonium
s u l f a t e and 20 gm NaCl in a l i t e r v o lu m e tric f l a s k .
Add 10 0 .ml
d i s t i l l e d w a ter an d -a few .d ro p s d i l u t e s u l f u r i c a c id .
u n t i l d is s o lv e d .
ShaJcp
F i l l up to volume w ith 50% v /v s u l f u r i c a c id .
S o ln . m ust be ,made f r e s h d a ily .
5.
C o n .■s u l f u r i c a c id .
4.
50% v /v s u l f u r i c a c id
add 500 jn l con. s u l f u r i c a c id to 500 ml
d i s t i l l e d w a te r, .(.caution),
5.
P o tassiu m d lc h ro m a te -s o ln .
0 . 1.■N 4-9055 gm C .P. p o tassiu m
dichrom ate d is s o lv e d in I l i t e r d i s t i l l e d w a te r.
6 . • 0 -p h e n a n th ro lin e fe r r o u s s u l f a t e in d i c a t o r .
D isso lv e 1.485 gm,
. o-phenanthroline' and . 6 9 5 gm ferro u s s u lf a t e in 100 ml
d i s t i l l e d w a te r.
-
9-9-
DETERMINATION OF SODIUM SULFATE. IN SODA ASH
P r in c ip le :
A w eighed sam ple -of soda .ash is a c i d i f i e d and th e s u l f a t e d e t e r ­
m ined from th e t u r b i d i t y form ed w ith Barium c h lo r id e . - The sample must
be f i l t e r e d - a f t e r a c id if y in g and b o ilin g to remoye, s u l f u r t u r b i d i t y .
The
tim es and .te m p e ra tu re s m ust be -v igorously ..adhered t o . . I f o th e r th an
5 -g .o f soda ash ,is u s e d / s ta n d a rd Na2CO3 o r NaHCO3 .must be added to
g iv e th e t o t a l e q u iv a le n t of 5 g. .of' so d a ,a sh .
.P rocedure';
1«
Weigh a 5 i 0 .0 1 gram sam ple and t r a n s f e r to a 250wm l-E rlenm eyer
fla s k .
Add 50 ml d is tille d - w a te r .? 3 , drops of p -n itro p h e n o l
i n d i c a t o r ? n e u t r a l i s e w ith 1 :1 HGI^ and add 2 m l.e x c e ss a p id ,
■ 2.
B o il th e s o lu tib n f o r one m in u te , co o l and d i l u t e w ith w ater
to 100 .ml in. a g r a d u a te d .c y lin d e r . - F i l t e r th ro u g h a d ry What­
man No, 5 f i l t e r p a p e r,
3 . - -R eturn most of th e sample f i l t r a t e to i t s f l a s k , h e a t to 50-60
- C u s in g ,a therm om eter.
4-.
Add. one scoop ( 0 . 5 -- 0 .7 g) of 20^3 0 .mesh BaCl2 c r y s t a l s .
Allow
to s ta n d .10 m in u te s , s w ir l f o r 5 seconds and l e t s ta n d 5 m in u te s.
5.
S w irl .and re a d th e o p t i c a l d e n s ity on th e F is h e r E lec b ro p h o to - ■
m e te r, u s in g "A" s e t t i n g and t h e , r e d ( 650) f i l t e r a g a in s t
d i s t i l l e d w a te r a t z ero o p t i c a l d e n s ity .
Na2SO^ from th e - c a lib r a tio n c u rv e .
• C a l c u la tio n :
mg Na2SO4
~ 50
= % Na2SO4
Read th e mg. of
»100DETERMIMTIQW OF TOTAL ALKALINITY OF SODA ASH
P r in c ip le :
An. a c c u r a te ly , w eighed sam ple o f soda, a sh Is .d is s o lv e d in w ater and
t i t r a t e d ..to a. pH -of 3 .9 •
The .method d eterm in es a l l su b sta n c e s which r e ­
a c t down to t h i s pH> t h e r e f o r e , when t i t r a t i n g n a t u r a l soda ash samples
w a te r^ lris o lu b le c a rb o n a te s w i l l - r e a c t slow ly, w ith th e ..acid.
The t i ­
t r a tio n . must b e .s to p p e d when a pH of 3 ;9 i s re a c h e d , even though th e
e n d -p o in t may te n d t o . d r i f t .
.Na s u c h - d r i f t sh o u ld o ccu r w ith r e f in e d
soda a s h .
■.P ro ced u re ;■
1. ■A c c u ra te ly weigh oh th e a n a l y t i c a l b a l a n c e a 1 ,0 . to 1 .2 gram
s ample,-of soda ash and t r a n s f e r .to a ,c le a n , 250-m l.b e a k e r.
2.
S ta n d a rd iz e th e pH..meter a t pH -4.0 w ith 4 .0 b u f f e r .
3.
P o s itio n b e a k e r and sample, in. t i t r a t i o n , a ssem b ly , add a p p ro x i.m ately .100. ml o f d i s t i l l e d w a te r and s t i r to d is s o lv e .
.4 ,
Add 3 to 4 drops o f.m o d ifie d m eth y l-o ran g e .in d ic a to r and
t i t r a t e - c a r e f u l ly t 0 pH 3 .9 /, .checking c o lo r o f in d ic a to r as. .
■ v e rific a tio n , o f p ro p e r O p e ratio n o f pH m e te r.
I f - e n d - p o in t
d r i f t s when a n a ly s in g n a tu r a l .ash-,, s to p t i t r a t i o n when pH. of
3 .9 i s f i r s t re a c h e d .
5.
Read volum e-of t i t r a t i o n and. a p p ly B u re tte and te m p e ra tu re
c o rre c tio n s .
T lO l-
■C a l c u la tio n :
. G eneral
■C o rre c te d ml x n o rm a lity ,x ,053 x IOO- = .<f0 t o t a l 'alk a *J
'
g',' Sample
'
U n i t y ,as Na2COs
.For above r o u tin e p ro c e d u re :
f a c to r *
g sam ple
_ (g t o t a l a l k a l i n i t y as Na2CO3
^ fa p tp r . = n o rm a lity k .053 x, 100
■ 3,02.-
O.OD ANALYSIS
•Liquor Samples
The sample Is ta k e n In a ta r e d M--Ozi b o t t l e . - The w eig h t .of th e
sample Is d e te rm in e d arid, i s th e n d i lu te d w ith an e q u a l w eig h t of w a te r.
-This I r I s o lu tio n does n o t s e t up and i s e a s i l y h a n d le d .
-The u s u a l
p r a c t i c e h e re i s to f i l t e r th e d i l u t e d sam ple through 4'1-H Whatman p a p e r
to., remove any. f o r e ig n m a tte r . ■S lh e e a l l o f. pur liq u o r sam ples c o n ta in
sodium s u l f i d e a n d ..th io s u lf a te th e s e .m a te ria ls must be a n a ly z e d for-*
• s in c e b o th c o n tr ib u te to th e g ro ss COB.
This i s a ls o tr u e f o r P h ld r id e .
Into- a 50Q-rml w ide mouth E rlenm eyer i s p la c e d 20 .ml . of cadmium c h lo rid e
s o lu tio n (1 2 ,5 g / l i t e r of CdCI2 .- 2 -1 /2 H2O ).
O btain t a r e w eight and
th e n p i p e t t e .5P.0- ml o f th e 1 :1 d ilu te d sample in to th e f l a s k .
.to determ in e .sa m p le .w e ig h t.
Reweigh
Now ru n th e u s u a l s u l f i d e and. th io a n a ly s is
G alp u laflo n . of th e b la n k due to s u l f i d e and th io to be s u b tr a c te d from
th e g ro ss COD.is as ,fo llo w s :
. Net ,,ml th io x n x .059 x /52
.
-
= grams O2- to o x id iz e Na2S
Net m l.th io x n x 52 = grams O2 t.p- o x id iz e th io
' IQOO
• The sum. o f th e aboye .r e s u l t s .g iv e s th e t o t a l grams o f O2 needed to
.o x id iz e a l l th e s u l f i d e and. th io p r e s e n t in 2-5 U l .of th e 1:1 d ilu te d
sam ple.
This, i s .as d e s ir e d , s in c e 25 ml of. sample is u s e d f o r th e COD
,d e te rm in a tio n .
To r e l a t e a l l . r e s u l t s back to th e o r i g i n a l s o lu tio n *
one q u a r te r of th e w eight ,of .th e 50. ml o f .1:1 d i l u t i o n i s ta k e n as th e
sam ple w e ig h t.
T h erefore:
Y t o t a l gOg (from above) x IO^
sairip'le w eight
= ppm COD b lan k
A c h lo rid e a n a ly s e s i s n e x t ru n on 25 g . .of th e 1 :1 d i l u t e d .m a te ria l
and th e p e rc e n t c h lo rid e i s c a lc u la te d , on th e o r i g i n a l s o lu tio n (12«5 g ,
sam ple w e ig h t).
From .thes-fe d a ta y . th e COD b la n k due to c h lo r id e i s th e n
c a lc u la te d as f o llo w s t
■% NaCl x 13.60 = ppm COD duo to NaCl
This f ig u r e .is added to th e COD blank, f o r Na2S and th io and th e sum i s
th e t o t a l b la n k to be s u b tr a c te d fro m .th e g ro ss COD.
- I n to a 50O-jfflI E rlenm eyer .f la s k w ith ST 2N/1+0 j o i n t p la c e .by means
of a p i p e t t e o r .b u r e tte e x a c tly 25 fflI o f .0.500 N K2 Cr2 O^.
This s o lu ­
t i o n i s made up by d i l u t i n g 24.5175 g. K 2 . C R 2 O y to one l i t e r w ith 20°C
w a te r.
Now p i p e t t e 25.0 ,ml-of th e 1 :1 d i lu te d sample in to th e f l a s k .
Allow, th e m ix tu re to s ta n d f o r a few m inutes and th e n by means of a b u r ­
e t t e add e x a c tly 68 ml o f c o n c e n tra te d s u l f u r i c a c id .
tu b e ( to be d e s c rib e d l a t e r ) and. r e f l u x one h o u r.
I n s e r t a b o ilin g
Now add one. p e l l e t
of Ag2SO4 w eighing. O.7 to 1 ,0 gram by d ro p p in g .down th e co n d en ser.
C ontinue th e r e f l u x f o r an. a d d itio n a l two h o u rs .
R aise th e f l a s k from
th e h o t p l a t e and a f t e r a few. m inutes wash down th e co n d en ser w ith a
sm all am ount. o f w a te r (use c a re h e r e ) .
-Remove th e fla sk * , remove and
r i n s e -off .the b o i l i n g tp b e w ith a minimum of w a te r.
w a te r.
Cool th e f l a s k c o n te n ts to room tem p eratu re'.
Then add l80 ml. of
Now add 6-8 drops
o f f e r r o i n i n d i c a t o r and back t i t r a t e th e ex cess chrom ate w ith s ta n d a rd
f e r r o u s ammonium s u l f a t e .
The e n d -p o in t i s v e ry sh arp and goes from
g re e n to b lu e to b r ig h t re d .
-Record th e t i t r a t i o n .
At th e same tim e
-1 0 4 -
■t h a t th-e sam ple i s b e in g run., a b la n k sh o u ld a ls o be .run. • I t i s p r e -1
p a re d as f o ll o w s ;
'• .25 ,ml 0.500 N-K2Cr2P7
30 .ml c o n c e n tra te d
H2SO4
1 .0 g . Ag2S04
R eflux, f o r th r e e h o u rs th e same as th e sam p le.
A fte r w ashing o f f th e
b o ilin g tu b e add. 86. ml w a te r and t i t r a t e as ab o v e.
The b la n k sh o u ld be
ru n a t l e a s t o n c e.e a ch day. ■The f e r r o u s ammonium s u l f a t e i s about 0 .1
•It .and i s made up as f o llo w s :
■42.8 g Re-"(NH4 )-S (SO4 ) 2 - . 6H20
20.0 ml c o n c e n tra te d H2SO4
D ilu te to I l i t e r w ith 200C w a te r.
The f e r r o l n in d i c a t o r i s made up a s f o ll o w s :
1.485 g ,0-phenan th ro l i n e
0.. 695 g FeSQ4 * JH 2O
D ilu te to 100 m i w ith w ater
C a lc u la tio n o f CQD
25 x ,.50 = n o rm a lity o f f e r r o u s . ammonium s u l f a t e
B lank T i t r a t i o n
Nx 8000 = K
Sam pleW eight
Kx (Bug) ,= Gross COD
Gross COD .-^(N a2S / th io and NaCl COD b lan k ) ■= n e t COD
The b o ilin g tu b e s r e f e r r e d to e a r l i e r are' made by s e a lin g about 2
in c h es of 8-mm g la s s tu b in g to a p ie c e of s m a lle r g la s s ro d of such a
le n g th (about 6 in c h e s) t h a t when th e e n t i r e assem bly i s p la c e d v e r t i c a l l y
i n t o a 500rmil f l a s k y th e tu b e w i l l p ro tr u d e s l i g h t l y above th e neck .of
,
- 105 • th e f l a s k .
The open end o f th e tube Is p la c e d down in to th e f l a s k and
c o n tr o ls th e b o ilin g c h a r a c t e r i s t i c s v ery w e ll.
. The volumes .of s u l f u r i c a c id .and w a ter which have been c i t e d a re
b ased on th e fo llo w in g :
D uring th e r e f lu x p e r io d , 55 volume p e rc e n t ex-
. c e ss s u l f u r i c aqi-d sh o u ld be p r e s e n t.
D uring th e . t i t r a t i o n , a t o t a l of
2 1 .5 volume p e rc e n t a c id sh o u ld .b e p r e s e n t.
■I f f o r any re a so n i t becomes
n e c e s sa ry to change sam ple s iz e s th e new volumes can be e a s i l y c a l ­
c u la te d by th e .u s e ■of two sim ple s im u lta n e o u s . e q u a tio n s :
1.
2.
V + x -= y
X ■= .55 y
S u b ra c tin g 2 from I
V = .45 y
Solve f o r y and s u b s t i t u t i n g b a ck , s o lv e f o r x
V ■= .volume of chrom ate + volum e.of sample +
volume o f a c id n e c e s s a ry to n e u t r a l i z e th e sample
x .= volume of ex cess a c id to be added
y. = to ta l.v o lu m e d u rin g r e f lu x
When x i s o b ta in e d , add to i t th e volume of a c id n e c e s s a ry to
n e u t r a l i z e sam ple.
This g iv e s t o t a l volume of a c id to be added.
To
determ in e th e volume of w a ter to add b e fo re th e t i t r a t i o n , y x 55
2 1.5
volume V2 to which th e sample sho u ld be d il u t e d . T h e re fo re ,
=
V2 - y = volume o f w a ter to be added.
As f a r as th e a n a ly se s of s o l i d sam ples i s c o n ce rn e d , no s u lf id e o r
th io a n a ly s e s a re r u n , s in c e th e se .tw o m a te r ia ls a re Very low.
c a s e .o f a r e f in e d ash sam ple, a 20 g sam ple i s u sed .
In th e
The chrom ate is
0 .0 5 N (,2.4-518 g .K2C r 2 O y d ilu te d to o n e ,l i t e r w ith 20°C w a te r).
ml o f th is reagen t is u sed .w ith lo w . OOD ashed.
F ifty
The ferrou s ammonium
S u lfa te i s about 0.025 N (9.800 g .Fe (NH4 ) 2 w i l l n e u tr a liz e 20 g .ash.
• In th e case of h ig h COD ashes such a s e v a p o ra te d f i l t r a t e o r w e ll
b r i b e , i t i s a d v is a b le to use 5 g sam ples w ith 25 ml o f th e s tro n g e r
( 0 .5 - N) chrom ate.
In th e s e sam ples th e c h lo r id e becom es. an im p o rtan t
f a c t o r and m u st.b e c o r r e c te d f o r .
The .blank f o r th e weak .chromate is
ru n as f o llo w s :
50 ml chrom ate
6 l m l'H2SO4
1 .0 g -Ag2SO4
R eflux f o r th r e e h o u rs and add 175 ml w a te r b e fo re t i t r a t i o n .
LITERATURE .CONSULTED
■1.
w
G i l l i l a n d , E . -R ., and Mason,. E . A. 1951.
FLUIDIZED SOLIDS.
. I & EC. 4 4 , .No. I , J a n . 2; 18-24.
GAS MIXING ,IN BEDS OF
■2 . .• K ite a n d -R o b e rts. 1947. ■APPLICATION. .TQ LIME .CALCINATION. .Chem.
-E n g r.' $4, No. 12, D?c. 1 1 :-2 ^ 1 5 .
,5. , Knudsen, J . G ., a n d -K atzy D. L. 1958. FLUID DYNAMICS AND ,HEAT
TRANSFER.
•■3,10 p p . , - MgGraw. Book Co. , I n c . , ,New Y ork, London, T oronto.
:4 , ■L eva, M ., and Grummer, M- 1952. CORRELATIONS OF SOLIDS. TURNOVER
' IN FLUIDIZED SYSTEMSITS RELATION TO .HEAT TRANSFER. '
,Chem .-Engr. P ro g re ss 4 8 , No. . 6 , - J u n e : '5.07-13.
5.
6..
M illic a n ,, C .-B .
1954. -T ran s. ASME..AMP 3995-2\
Osberg-, G. L. , and C h a rle sw o rth ,■ D. H. -1951. . ELUTRATION. IN
■ FLUIDIZED .BEDS'.
, Chem,. E n g r. P ro g re ss 47_, ,No. l l , Nov. :, ,556.
7 . - Thomas, C. L. 1943.. - CRACKING WITH CATALYSTS PROCEEDINGS,.
Amer. P e t r . ■I n s t . 2 4 , Sec. 3: .75-82.
8 . - Toomeyy--R. ■D..-, and .J o h n sto n , H. F. 1952. ■GASEOUS,FLUIDIZATION
OF SOLID PARTICLES,.
, Chem. - E n g r. P ro g re ss 48_,, No. 5,, May: -220^26.
9. - T re y b a ly-R. E,. 1955. MASS TRANSFER OPERATIONS.
,38 'pp.,, McGraw-Hill Bpok Co. , I n c . , ,New. Y ork, L ondon,, T o ro n to .
10. -CONFERENCE,OF FLUIDIZATION TECHNOLOGY, 1952.
Soc, Chem .--'In d u stry , No. 39#. Sept., 10: .15-31.
- 108-
■VITA
J e r r y Dean Mason was b orn June I l y 1929 a t Sidney* ..Montana* th e
s. on -of Mr. & M rs. - C arl -Mason. .He a tte n d e d .elem entary and h ig h sch o o ls
in S id n ey , g ra d u a tin g from h ig h sch o o l i n J u n e y .19^7• He e n te re d
Montana S ta te C o lleg e In Septem ber 19^7 an d .b eg an h is s tu d ie s in th e
C hem istry D ep artm en t.
A v e te ra n o f th e Korean Wary he e n te r e d th e army in 1948 and
was h o n o rab ly d is c h a r g e d .in 1952.
R e -e n te rin g .Montana S ta te C ollege in th e D epartm ent of Chemical
E n g in e e rin g i n Septem ber 1952y he was th e r e c i p i e n t of advanced s c h o la r ­
s h ip s in 1953-^1956. He became a member of e n g in e e rin g h o n o ra rie s Tau
B eta P i and P/hi Kappa P h i and was g ra d u a te d w ith honors in June 1956
w ith th e degree .of B ach elo r of S cien ce in Chemical E n g in e e rin g .
Im m ediately f o llo w in g .h is g ra d u a tio n * he .began work on th e
d o c to r of p h ilo so p h y degree i n th e D epartm ent of Chemical E n g in ee rin g
a t Montana S ta te C o lle g e . Mr. Mason was e le c te d to Sigma Xi ( a s s o c ia te
member) in 1957 and advanced t o . f u l l membership in 1959• He com pleted
re q u ire m e n ts f o r .t h e .d e g r e e .of D octor of P h ilo so p h y in Chem ical E n g in eer­
in g in Septem ber 1959 and took employment w ith S tan d ard .o f ' C a lif o r n ia
a t Richmond* C a l if o r n ia .
MONTANA STATE UNIVERSITY LIBRARIES
139178
F lu id c a lc in a tio n o f soda ash