Louisiana State University

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LSU Historical Dissertations and Theses Graduate School

1950

A Fluidization Process for Making Sodium

Sulphate From Sodium Chloride.
Roger Foster Detman
Louisiana State University and Agricultural & Mechanical College

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Recommended Citation
Detman, Roger Foster, "A Fluidization Process for Making Sodium Sulphate From Sodium Chloride." (1950). LSU Historical
Dissertations and Theses. 7948.
https://digitalcommons.lsu.edu/gradschool_disstheses/7948

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 MANUSCRIPT THESES

U n p u b lish ed t h e s e s s u b m itte d f o r th e m a s te r* s and d o c to r * s

d e g re e s and d e p o s ite d i n th e L o u is ia n a S t a t e U n iv e r s ity L ib r a r y

a r e a v a i l a b l e f o r in s p e c tio n * Use o f a n y t h e s i s i s l i m i t e d b y th e

r i g h t s o f th e a u th o r* B i b l i o g r a p h i c a l r e f e r e n c e s may be n o te d , b u t

p a ssa g e s may n o t b e c o p ie d u n le s s th e a u th o r h a s g iv e n p e rm iss io n *

C r e d it m ust b e g iv e n i n s u b s e q u e n t w r i t t e n o r p u b lis h e d work*

A l i b r a r y w hich borrow s t h i s t h e s i s f o r u se b y i t s c l i e n t e l e

i s e x p e c te d t o make s u r e t h a t th e b o rro w e r i s aw are o f th e above

re s tr ie tio n s *

LOUISIANA. STATE UNIVERSITY LIBRARY

119- a
 A FLUIDIZATIGH PROCESS FOB MAKim

SODIUM SULPHATE FROM SODIUM CHLORIDE

A D is s e rta tio n

S u b m itte d t o t h e G ra d u a te F a c u l t y o f t h e
L o u is ia n a S t a t e U n i v e r s i ty a n d
A g r i c u l t u r a l a n d M e c h a n ica l C o lle g e
in p a r t i a l f u lf illm e n t o f th e
re q u ire m e n ts f o r th e d e g re e o f
D o c to r o f P h ilo s o p h y

in

The D epartm ent o f C hem ical E n g in e e rin g

by
R o g er F o s t e r Batman
B#S * , L o u is ia n a S t a t e U n i v e r s i ty , 1939
M .S ., L o u is ia n a S t a t e U n i v e r s i ty , 19U8
A u g u s t, 19U9
 UMI Number: DP69326

All rights reserved

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UM I
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The a u th o r w ish e s t o e x p re s s h i s s i n c e r e a p p r e c i a ti o n t o Dr* J e s s e

C o a te s u n d e r whose d i r e c t i o n t h i s w ork was c a r r i e d o u t , f o r h i s a d v ic e

a n d g u id a n c e , a n d a l s o t o Dr* ? • H* H o rto n f o r h i s i n t e r e s t a n d many

h e l p f u l su g g e s tio n s *

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 TABLE OF c o m m a s

liXST Oft FlOuRES I * * * " * # ! ! * # # * * * * # # * - ! # * - * * ! * * # * * *

LLS^1 Ql' JIX&STRATIUNS yr

ABSTRACT- — «* *» *» -n. mm VX
BJTROBoOTIOM------------------------------------------- ----------------------- . . . . . 1

CHiPIEKS

I* DESCRIPTION CFCOMKEKCIU,PROCESSES- . . . . . . . . . 7

II. FIIfJLDIZATlON RXPKRT 12

III. DESCRIPTION OF REACTION^mSKGdaiTS* 25

XV. 0XSCUwSXOIi OF rUSUlIS^ ^ h» « 1|||

¥. THEORETICAL ASPECTS OF THE REACTION-* ~ ~ ^ - ~ 5ll

V I. SlUmftBX* 62
SELECTED BIBLXOOH4PHX 68
APPMHEX - ---------- ~-----.--------- 70

BIOGRAPHX - - -------- - * -------- - - *. .. xo6

111
 LIST OF FIGURES

F ig u re 1 P r e s s u r e Drop T hrough S a l t - - - - - - - - - - - - - - 17

F ig u re 2 L a b o r a to r y F lu id is s a tio n U n it - - - - - - - - - - - - - 18

F ig u re 3 Com m ercial F l u i d i s a t i o n U n it - - - - - - - - - - - - - 19

F ig u r e h C o n tin u o u s R e a c to r F lew R a te s— - - 20

F ig u re 5 Design, f o r C om m ercial R e a c to r - - - - - - - - - - - - - 2k
F ig u r e 6 R e a c tio n R a te s - - - - - - - - - - - - - - - - - - - - UB

F ig u r e 7 B q u ilih x iu ia C onstants-* - - - - - - - - - - - - - - - - 55

F ig u re 8 P a r t i a l P r e s s u r e o f S u lp h u r ic A c id - - - - - - - - - - 60

F ig u r e 9 P r o c e s s F low S h e e t - - - - - - - - - - - - - - - - - - 61*

iv
 LIST OF ILLUSTRATIONS

Illu s tra tio n X P h o to m icro g rap h s o f S a l t U sed 13

T it u s t w r t io n XX R e a c to r Number 8» — 21

I I l a s t f a t i f l B XXX R e a c to r Number 9s— — — —— — —— - — —— — — — 22

I l l u s t r a t i o n IV L a b o ra to ry A p p a ra tu s - ~ * 26

D iM tw tlo n V F u rn a c e Tubes — — — 27

I l l u s t r a t i o n VX R e a c to r Number 2— 30

X llttslr& tic ffi V II R e a c to r Number 7** — — ******* • » • * « * <•<*«■« 37

I l l u s t r a t i o n VIXI P h o to m icro g rap h s o f P r o d u c ts - - - - — - - * ** 50

H l n 8 t r a t i o n XX Fho to rn ic ro g ra p lis o f P r o d u c ts - - - - - - - - - - 51

Illu s tra tio n X P h o to m icro g rap h s o f Products** —— — 52

U l u s t r a t i o n XX P h o to m ic ro g ra p h s o f P ro d u c ts — - — — 58

v
 ABSTRACT

The p ro b lem u n d e rta k e n w&s t h e a p p l i c a t i o n o f t h e te c h n iq u e o f f l u i d *

i s a t i o n t o t h e H a rg re a v e s p r o c e s s f o r m aking sodium s u lp h a te fro m sodium

c h lo r id e * T he more im p o r ta n t com m ercial m ethods o f im m f a c tu r in g sodium

s u l p h a te a r e d e s c r i b e d t o g e t h e r w i t h t h e i r a d v a n ta g e s an d d is a d v a n ta g e s

i n o r d e r t o p r o v id e a b a s i s f o r e v a lu a tio n o f t h e p r o c e s s developed#

The p ro b lem was d iv id e d i n t o tw o p a r t s %t h e f i r s t p a r t in v o lv e d

d e te r m in a tio n o f t h e f l u i d i z a t i o n p r o p e r t i e s o f sodium c h l o r i d e a n d t h e

d e s ig n o f e q u ip m en t i n w h ic h a flui&Ls&ed s o l i d c o u ld be c o n ta c te d w ith a

g a s i n c o u n te r c u r r e n t flo w ? t h e seco n d p a r t was t o f i n d th© n e c e s s a r y

c o n d itio n s u n d e r w h ich sodium c h lo r i d e i n a i l u i d l z e d s t a t e c o u ld b e

con v e r t e d t o sodium s u lp h a te #

3h f l u i d i s a t i a n e x p e rim e n ts w ith s a l t o f v a r i o u s p a r t i c l e s iz e s *

t h e sm o o th e st o p e r a tio n was o b ta in e d w ith t a b l e s a l t * The p r e s s u r e d ro p

th r o u g h a b e d o f t a b l e s a l t f o r v a r i o u s g a s r a t e s i s p re s e n te d * S e v e ra l

l a b o r a t o r y u n i t s w ere b u i l t a n d o p e r a te d u s in g t a b l e s a l t t o show t h a t

s o l i d s and g a s e s c o u ld be c o n ta c te d c o u n t e r c a r r e n t l y i n a s e r i e s o f f l u i d *

i z e d beds* D raw ings o r p h o to g ra p h s o f th e s e u n i t s a n d t h e i r g a s a n d s o l i d

f lo w r a t e s a r e p re s e n te d #

The e x p e r i r n n ta c o n d u c te d t o f i n d o u t i f sodium c h lo r id e c o u ld b e

c o n v e r te d t o sodium s u lp h a te in. a f l u i d ! z e d bed w ere s t a r t e d u s in g t h e

c o n d itio n s em ployed i n t h e H a rg re a v e s p ro c e ss # C o n s id e ra b le d i f f i c u l t y

w as e n c o u n te re d due t o t h e f o rm a tio n o f p r o d u c ts w hich c a u se d s o l i d i f i c a t i o n

vi
o f t h e f l u i d ! a e d bed* Iiowsr te m p e ra tu re and more v i o l e n t a g i t a t i o n o f

t h e s a l t p e rn & tte d l o n g e r p e r i o d s o f o p e r a t io n a n d g r e a t e r , th o u g h l n ^

c o m p le te , c o n v e rs io n o f t h e s a l t * As t h e te m p e ra tu re was lo w e re d s t i l l

f u r t h e r , u n s a t d s f a c t o r y o p e r a tio n m s o b ta in e d a s a r e s u l t o f condensa­

t i o n o f a l i q u i d th o u g h t t o b e s u lp h u r ic a c id # C o n se q u e n tly t h e fo rm a tio n

o f a p p r e c i a b le am ounts o f s u l p h u r i c a c i d was p r e v e n te d b y in tr o d u c in g t h e

s u l p h u r d io x id e i n t o t h e a i r s tre a m a t t h e r e a c t o r i n s t e a d o f a t t h e f u r ­

nace in le t* A l l su b s e q u e n t r u n s u s in g t h i s a rra n g e m e n t w ere c a r r i e d o u t

w ith o u t s o l i d i f i c a t i o n o f t h e b e d , b u t a t v e r y lo w c o n v e rs io n r a t e s * fh©

f o r m a tio n o f s u l p h u r i c a c i d v a p o r i n t h e g a s b e f o r e e n t e r i n g t h e s a l t b e d

was t h e n c o n s id e r e d o f p r im a r y im p o rta n c e i n t h e r e a c t i o n an d c o n d itio n s

f a v o r a b l e t o i t s f o rm a tio n w e re b e li e v e d n e c e s s a r y t o g iv e s a t i s f a c t o r y

re a c tio n ra te s *

F u r t h e r e x p e rim e n ts w ere c o n d u c te d I n w hich s u lp h u r ic a d d v a p o rs

w are p ro d u c e d b y th e a d d i t i o n o f a c a t a l y s t cham ber i n t h e fu rn a c e * In

t h e s e r u n s t h e c o n d itio n s f o r s a t i s f a c t o r y o p e r a tio n w ere d isc o v e re d * A

r e d u c t io n i n c o n c e n tr a tio n o f w a te r v a p o r a s w e l l a s s u lp h u r d io x id e was

fo u n d t o e li m in a te s t i c k i n e s s a n d r e s u l t e d i n a u n ifo rm p ro d u c t o f com­

m e r c ia l g rade#

From t h e o b s e rv e d b e h a v io r end t h e o r e t i c a l c o n s id e r a tio n s a m echanism

i l l u s t r a t e d b y th e f o llo w in g s e r i e s o f e q u a tio n s was p o s t u l a t e d !

2 S02 <e) / 02 Cg) — 2 so 3 (g )

2 SO3 (g ) / 2 H2O (g ) 2HgSOj^ (g )

2 HgSQij (g ) / 2 MaCl ( s ) — 2 HaHSO^ (X) / 2 HCl (g )

2 NaHSOjj (X) NagSgO? (X) / HgO (X)

v ii
 SBjjSgC^ (1 ) y£ 1^0 (1 ) / 2 HaCl ( s ) 2 N agSt^ ( s ) / 2 HCl (g )

* SOg ( g ) J (fc <g) ,< 2 HgO (g ) / U KaCX ( e ) 2 NagSOj^ ( a ) / It HCl <g)

Photomicrographs of t h e salt p a r t i c l e s at d i f f e r e n t d e g re e s o f e o n -

v e r s i o n a s w e H as t h e e q u ilib r iu m d a t a f o r t h e g a se o u s r e a c t i o n s s u p p o rt

t h e a rg u m en ts i n f a v o r o f t h e p ro p o se d mechanism* The U n i t i n g c o n d itio n s

o f te m p e r a tu re a n d g a s c o n c e n tr a tio n a r e d e te rm in e d by th e f o r m a tio n o f

l i q u i d w h ich c a u s e s f l u i d i z a t i o n t o cease* H igh te m p e r a tu re s o f a b o u t

UOO°G c a u s e t h e f o r m a tio n o f l i q u i d in te r m e d i a t e s i n s u f f i c i e n t q u a n t i t y

t o m e lt t h e b e d a n d fo rm a cake* Low te m p e r a tu re s o f a b o u t 2U0°C p e r ­

m it c o n d e n s a tio n o f s u l p h u r i c a c i d v a p o r w ith a t t e n d a n t s t i c k i n e s s an d

poor flu id iz a tic n * H igh c o n c e n tr a tio n s o f w a te r v a p o r a n d s u lp h u r d i­

o x id e r e s u l t i n h ig h r e a c t i o n r a t e s a n d e x c e s s iv e r a t e s o f f o r m a tio n

o f l i q u i d i n te r m e d i a t e s a s w e l l a s c o n c e n tr a tio n s o f s u l p h u r i c a c i d v a p o r

w h ic h r e s u l t i n l i q u i d c o n d en sa tio n # R e a c tio n r a t e d a ta a t v a r io u s tem ­

p e r a t u r e s a r e p re s e n te d * th e h ig h e r tem p era tu re © g iv in g t h e h i g h e r r a te s *

A t a te m p e ra tu re o f 3U0°C* w ith a w a te r v a p o r c o n c e n tr a tio n o f 3*0$ an d

s u lp h u r d io x id e c o n c e n tr a tio n o f l u 7$ s a t i s f a c t o r y o p e r a t io n was o b ta in e d *

A p r e l i m i n a r y p r o c e s s f lo w d ia g ra m i s p r e s e n te d an d t h e econom ic
f e a s i b i l i t y o f t h e p r o c e s s p ro p o se d i s i n d i c a t e d ms f a v o r a b l e b y a com**

p a r i so n w ith a s i m i l a r p ro c e s s * th e m a n u fa c tu re o f s u l p h u r i c a d d *

v iii
 w m o m w im
The t r a n s p o r t a t i o n o f s o l i d s b y a e r a t i o n o r p n su u m tic convoying i s
f a i r l y m i l known a t t h e p r e s e n t tim e* I t i s o o m p a r a tir e iy new , how ever,

a n d new a p p l i c a t i o n s o f t h e p r i n c i p l e a r e c o n t i n u a l l y b e in g found# Con­

t r a s t e d w ith o l d e r m th o d s o f movement o f s o l i d s , i n many c a s e s , a e r a t i o n

h a s many d i s t i n c t a d v a n ta g e s among w hich a r e lo w e r pow er co n su m p tio n , l e s s

e x p a n s iv e e q u ip m en t, lo w e r m ain ten a n ce c o s t , g r e a t e r c o n v e n ie n c e , and

lo w e r l a b o r c o s t f o r o p e ra tio n # Of c o u rs e a l l p ro b lem s o f movement o f

s o l i d s a r e n o t am enable t o s o l u t io n b y a e r a tio n # t h e s o l i d m ust f i r s t

have & s u ita b le p a r t i c l e s iz e d is trib u tio n # The r e d u c tio n o f s o l i d s t o

s u i t a b l e s i z e s a n d movement b y a e r a t i o n may i n some c a s e s p ro v e more e c o -

ncasLcal o r c o n v e n ie n t th a n movement by o t h e r means#

T h is d i s c u s s i o n o f t h e a d v a n ta g e s o f a e r a t i o n , v& ich i s c o u ^ a r a t iv e l y

w e l l known, i s in te n d e d t o in tr o d u c e a n d i n d i c a t e s i m i l a r a d v a n ta g e s f o r

l u i d i s a t i o n * a new er companion p r o c e s s t o be more f u l l y d isc u sse d #

S ta n d a rd f l u l d i z a t i o n n o m e n c la tu re an d d e f i n i t i o n s have r e c e n t l y

b e e n p ro p o s e d (It) a n d a r e p r e s e n te d i n p a r t t o d e s c r i b e t h e p r o c e s s a n d

c l a r i f y l a t e r d is c u s s io n * The f o llo w in g i s q u o te d from r e f e r e n c e (li) s

ttHhen th e v e l o c i t y o f a g a s o r l i q u i d flo w in g up th ro u g h a m ass o f

s o l i d p a r t i c l e s i s s u f f i c i e n t t o s u p p o rt a n y o f th e s o l i d , t h e m s s i s c a l l e d

a f i x e d b e d o r moving b e d dep en d in g on w h e th e r th e s o l i d i® s t a t i o n a r y o r

m oving w ith r e s p e c t t o t h e c o n ta in in g v e s s e l* W ith i n c r e a s i n g f l u i d v e lo ­

c i t i e s i n t h e a b se n c e o f c h a n n e lin g , th e p r e s s u r e d ro p th ro u g h t h e b ed

r i s e s u n t i l i t a p p ro a c h e s t h e n e t e f f e c t i v e w e ig h t o f th e s o l i d p e r

1
 2

u n i t a r e a , when t h e p ack in g arrangement o f t h e p a r t i c l e s becomes more

open s o t h a t th e bed e x p a n d s; w ith s l i g h t f u r t h e r i n c r e a s e s i n v e l o c i t y

t h e p a r t i c l e s a re f u l l y s u p p o rte d and t h e expanding bed becom es f l u i d i z e d #

J u s t a t t h e p o i n t o f f l u i d i z a t i o n th e m ass may form a q u ie s c e n t f l u i d i z e d

b e d # W ith l i q u i d - s o l i d s y s te m s , f u r t h e r i n c r e a s e s in f l u i d v e l o c i t y g iv e

a p r o g r e s s iv e s e p a r a t io n o f t h e p a r t i c l e s w hich re m a in i n d i v i d u a l l y and

u n ifo rm ly d is p e r s e d i n p a r t i c u l a t e f l u i d i z a t i o n ♦ W ith many g a s - s o l i d

System s t h e b e d expands o n ly to a l i m i t e d e x t e n t , and a p o r tio n o f t h e

g a s te n d s t o a c c u m u la te i n g a s p o c k e ts o r b u b b le s p a s s in g th ro u g h th e

f l u i d i z e d b ed i n a g g r e g a tiv e f l u i d i z a t i a a # I n s m a ll t u b e s , t h e s e b u b b le s

may grow t o a s i z e s u b s t a n t i a l l y f i l l i n g t h e c r o s s s e c t i o n o f t h e v e s s e l ,

r e s u l t i n g i n slu g g in g # N o rm ally , how ever, t h e bubble© re m a in s m a ll w ith

r e s p e c t t o t h e v e s s e l and t h e mass becomes a t u r b u l e n t f l u i d i z e d bed#

Such a t u r b u l e n t b ed can even b e m a in ta in e d above th e f r e e - f a l l i n g v e lo ­

c i t y f o r th e s o l i d p a r tic le © in a g a s - s o l i d sy stem i f th e r a t e a t w h ich

s o l i d s a r e f e d i s k e p t h ig h enough# F in a lly , i f th e f lu id v e lo c ity i s

s t i l l f u r t h e r in c r e a s e d o r i f th e s o l i d s f e e d r a t e i s to o lo w , t h e s u r f a c e

o f t h e f l u i d i z e d bed d is a p p e a r s and t h e w hole mas© becomes a d is p e r s e d

s u s p e n s io n #" The f o llo w in g d e f i n i t i o n s w ere p ro p o se d i n t h e same r e f e r e n c e !

"A f l u i d i z e d b e d i s a m ass o f s o l i d p a r t i c l e s w hich e x h i b i t s t h e

l i q u i d l i k e c h a r a c t e r i s t i c s o f m o b il i ty , h y d r o s t a ti c p r e s s u r e , and an ob­

s e r v a b le u p p e r f r e e s u r f a c e o f boundary zone a c r o s s w h ich a m arked change

i n c o n c e n tr a tio n o f p a r t i c l e s o c c u r s ."
 3

«A setims c a n t z m m r n * b e d I s a d e n se f l u i d i z e d b e d w hich e x h i b i t s

l i t t l e o r no m ix in g o f t h e s o l i d p a r t i c l e s * ”

*A t u r b u l e n t f l u i d i z e d b e d i s & f l u i d i z e d b e d i n w hich m ixing o f t h e

m s s o f s o l i d t a k e s p l a c e . 11

" C hanneling: i s t h e e s ta b lis h m e n t o f f l o e p a th s i n a b e d o f s o l i d

p a r t i c l e s th ro u g h w hich a d i s p r o p o r t io n a te q u a n t i t y o f t h e in tr o d u c e d

f l u i d p a s s e s *11

11S lu g g in g i s a c o n d itio n i n w hich p o c k e ts o r b u b b le s o f t h e support-*

in g f l u i d grow t o t h e d ia m e te r o f th e c o n ta in in g v e s s e l* a n d th e m ass o f

p a r t i c l e s tr a p p e d betw een a d ja c e n t p o c k e ts moires upw ard i n a p i s t o n l i k e

fa s h io n * *

F lu id L c a tio n i s a s t e p fo rw a rd fro m movement by a e r a t i o n s i n c e some

a d d i t i o n a l p u rp o se i s s e r v e d b e s id e s m ere movement* The i n t e r a c t i o n o f

t h e s o l i d a n d g a s t o p ro d u c e a d e s i r e d change i n one o r t h e o t h e r o f th e

m a t e r i a l s i s t h e im p o r ta n t developm ent* A t t h e p r e s e n t tim e many a p p lic a ­

t i o n s o f t h i s p r i n c i p l e a r e u n d e r i n v e s t i g a t i o n a n d many more a r e e n v isio n e d *

The w id e s t a p p l i c a t i o n o f f l u i d i z a t i o n t o - d a t e I s c a t a l y t i c c ra c k in g

o f p e tro le u m f r a c t i o n s in w hich t h e se c o n d p u rp o se i s p r e s e n t a t i o n o f new

c a t a l y t i c s u r f a c e f o r c h e m ic a l r e a c tio n # T here a r e o t h e r a d v a n ta g e s t h a t

m y be e n u m e rated f o r f l u i d i z e d sy stem s b e s id e s th o s e r e l a t e d t o movement

b y a e r a t i o n a n d t h e p r e s e n t a t i o n o f s u r f a c e f o r re a c tio n # The a b i l i t y o f

a f l u i d i z e d s o l i d t o o b ta in i n ti m a t e c o n ta c t w ith t h e a e r a t i n g g a s i s o f

im p o rta n c e i n many p r o c e s s e s su ch a s v a p o riz a tio n * h e a t t r a n s f e r * a d s o r p tio n *

d e s o r p tio n a n d c h e m ic a l r e a c t i o n s in v o lv in g g a se s o r v a p o rs* The a b i l i t y

o f a f l u i d i z e d s y s te m t o o b t a i n r a p i d h o m o g en eity i s o f g r e a t im p o rta n c e

w here h e a t i s b e in g e v o lv e d o r a b so rb e d b j t h e m a te r ia ls * T h is p r o p e r t y
V .

a llo w s r a p i d h e a t e q u a l i z a t i o n a n d p r e v e n ts l o c a l o v e rh e a tin g -which I s a

common f a u l t o f o t h e r sy stem s*

The te c h n iq u e o f f l u i d i z a t i o n i s b e in g u t i l i z e d i n many new dev elo p *

m eats* One o f t h e m ost im p o r ta n t i s t h e s y n t h e s i s o f h y d ro c a rb o n s from

c a rb o n m onoxide an d h y d ro g en u s in g a f l u i d i z e d c a t a l y s t * O th e r a p p l i c a ­

t i o n s o f t h e same te c h n iq u e a r e t h e g a s i f i c a t i o n o f c o a l* r e c o v e r y o f o i l

fro m s h a le * b u rn in g o f lim e* a n d th e E y p e re o rp tio n p r o c e s s f o r s e p a r a t i o n

o f l i g h t h y d ro c a rb o n s• T h ere a r e many a p p l i c a t i o n s o f t h e f l u i d i z a t i o n

p r i n c i p l e y e t t o come* s i n c e i t s i n h e r e n t a d v a n ta g e s i n d i c a t e i t s s u p e r ! *

o r i t y o v e r c e r t a i n m ethods o f o p e r a tio n now i n use# To c i t e a n example*

t h e d ry in g o f g r a n u l a r m a t e r i a l s i n r o t a r y equipm ent c o u ld v e r y w e ll be

h a n d le d t o a d v a n ta g e b y f l u i d i z a t i o n * H ig h e r c o e f f i c i e n t s o f h e a t t r a n s f e r

betw een s o l i d a n d g a s may b e e x p e c te d i n f l u i d i z e d sy ste m s s in c e more

i n t i m a t e m ix in g i s e f f e c t e d t h a n i n a r o t a r y c y lin d e r* A n o th e r a d v a n ta g e

o f f l u i d i z a t i o n i s t h a t r e a c t i o n s w hich a r e n o t e c o n o m ic a lly o r p h y s i c a l l y

p o s s i b l e b y m ethods p r e v i o u s ly a t t e s t e d due t o p r o c e s s in g d i f f i c u l t i e s o r

h ig h l a b o r a n d h a n d lin g cost© may be s u c c e s s f u l l y c a r r i e d o u t u s in g a

f l u i d i z a t i o n te c h n iq u e * The same a p p ro a c h may b e em ployed i n p r o c e s s e s

i n cosB nercial o p e r a tio n a s a means o f p ro d u c in g a c h e a p e r p ro d u c t*

A t p r e s e n t* p r o c e s s e s em ploying f l u i d i z a t i o n may v a r i o u s l y b e de©*»

c r i b e d a s f i x e d b e d o r moving bed* u p flo w o r downflow* © ingle b e d o r s i n g l e

 $

s t a g e u n i ts * T h is t o r a i n o lo g y r e f e r s t o t h e movement o f s o l i d m a te r ia l*

F l u i d i z e d b e d s i n com m ercial o p e r a tio n c o n s i s t m a in ly o f s i n g l e u n i t s i n

w h ich t h e g a seo u s p h a se m akes one p a s s th ro u g h one bed o f f l u id i Bed s o lid #

The s o l i d how ever may b e moved c o n tin u o u s ly betw een two f l u i d i s e d b e d s e ac h

u s in g a d i f f e r e n t ty p e g as o r vapor* The re a s o n f o r th e se c o n d bed i n t h i s

c a s e ±*j f o r r e g e n e r a tio n o f t h e s o lid * I n o p e r a tio n s w here th e s o l i d i s

m a t e r i a l l y a f f e c t e d by t h e r e a c tio n * a s happens i n c a t a l y t i c c ra c k in g * t h e

r e t e n t i o n tim e o f t h e s o l i d i n t h e p rim a ry o r r e a c t o r b ed i s o f g r e a t im­

p o r ta n c e a s i t l o s e s i t s a c t i v i t y a t a r a t e w h ich i s p r o p o r t io n a l t o i t s

tim e o f r e s i d e n c e i n t h e p rim a ry r e a c to r # The r a t e o f m ix in g i n a f l u i d ­

i z e d b e d o p e r a tin g u n d e r com m ercial c o n d itio n s i s v e ry g r e a t* so t h a t th e

c o m p o s itio n o f th e b e d i s q u i t e u n ifo rm th ro u g h o u t# I n view o f t h i s f a c t

i t i s e v id e n t t h a t o f t h e s o l i d b e in g removed i t may b e s a i d t h a t i t con­

t a i n s some s o l i d m a t e r i a l w hich had j u s t r e c e n t l y e n te r e d t h e b ed a s w e l l

a s some s o l i d w hich had b een i n th e bed f o r q u i te some tim e* The bed may

t h e r e f o r e c o n ta in a s u b s t a n t i a l amount o f s o l i d w hich had n o t f u l f i l l e d

i t s f u n c tio n o f c a t a l y s i s t o t h e optimum d e g re e b e f o r e b e in g removed a s

w e l l a s a s u b s t a n t i a l amount o f s o l i d w hich had lo n g s in c e c e a s e d to

f u n c tio n s a t i s f a c t o r i l y a s a c a t a l y s t *

I n v iew o f t h e s e c o n s id e r a tio n s i t a p p e a rs t h a t an a d v a n ta g e w ould

b e g a in e d i f t h e one l a r g e b ed w ere s u b d iv id e d i n t o a s e r i e s o f f l u i d i z e d

b e d s i n w hich t h e s o l i d i s moved c o n tin u o u s ly from one bed t o t h e n e x t i n

su c h a m anner a s t o move c o u n te r c u r r e n t t o th e flo w o f gas* T h is a p p l i ­

c a t i o n o f t h e p r i n c i p l e o f c o u n te r c u r r e n t flo w t o f l u i d i z e d system© i s
 6

e x p e c te d t o h a v e w ide a p p l i c a t i o n s h o u ld a u n i t b e d e s ig n e d t o p e rm it

s a t i s f a c t o r y o p e ra tio n #

Two e ac h d e s ig n s a r e p ro p o s e d w ith o p e r a tin g d a t a on g a s a n d s o l i d

flo w r a t e s g iv e n f o r l a b o r a t o r y m o d els. I t i s e v id e n t t h a t no s i n g l e

d e s ig n o f su c h a u n i t c o u ld be u n i v e r s a l l y a p p li e d t o a l l f l u i d l a e d system s#

F o r t h a t r e a s o n t h i s i n v e s t i g a t i o n was r e s t r i c t e d t o a s i n g l e p r o c e s s on

w h ich t h e d e s ig n s a r e based* The p r o c e s s chosen was t h e m a n u fa c tu re o f

sodium s u lp h a te o r s a l t cake from sodium c h lo r i d e o r s a l t # S e v e r a l com*

m e r e ia l p r o c e s s e s a r e d e s c r i b e d f o r com parison w ith th e one developed*

I n t h i s i n v e s t i g a t i o n t h e c o n d itio n s n e c e s s a r y f o r t h e s u c c e s s f u l

a p p l i c a t i o n o f f l u id i s s a t i o n t o t h e p r o d u c tio n o f s a l t c ak e a r e shown a n d

t h e p r o b a b i l i t y o f s u c c e s s f u l o p e r a tio n on a com m ercial s c a l e i s in d ic a te d *

 DESCRIPTION OF COISIERCIAL PROCESSES

A b r i e f d is c u s s io n o f t h e m ethods o f m a n u fa c tu re o f sodium s u lp h a te
i s o f v a lu e f o r com parison w ith t h e p r o c e s s p ro p o se d i n t h i s d i s s e r t a t i o n *

An a c t u a l econom ic co m p ariso n o f t h e p ro p o s e d p r o c e s s w ith p r e s e n t m ethods

m ust b e r e s t r i c t e d t o e s tim a te s b a se d on l a b o r a to r y equipm ent s in c e tim e

d id n o t p e rm it c o n s t r u c t io n and o p e r a tio n o f l a r g e r u n i t s . }
The m ost im p o rta n t m ethod o f m a n u fa c tu re o f s a l t cak e i s th e Mannheim

p r o c e s s i n w hich s a l t and s u lp h u r ic a c id a r e t h e r e a c ta n ts * The Mannheim

f u r n a c e i s an u p r i g h t c y l i n d e r e le v e n t o e ig h te e n f e e t i n d ia m e te r* w ith

a f i r e box i n t h e lo w e r p o rtio n * Above t h e f i r e form ing th e to p o f th e

f i r e box i s a c a s t ir o n p a n , d e p re s s e d i n t h e c e n te r * and h a v in g a s e r i e s

o f s c r a p e r s o r plow s w h ich move t h e r e a c t a n t s s lo w ly tow ard t h e o u t e r pe­

rip h e r y * The p an i s c o v e re d w ith a c a s t i r o n to p form in g a c lo s e d v e s s e l

o r m u ffle* The f l u e g a se s p a s s o v e r th e t o p o f t h e m u ffle a id i n g i n th e

h e a t in g p ro c e s s * A l a r g e u p ta k e f o r th e g as g e n e ra te d a sc e n d s v e r t i c a l l y

from t h e c e n t e r o f th e to p o f t h e m u ffle* th e r e a c t a n t s a r e b o th i n t r o ­

d u ced th ro u g h t h i s open in g and f a l l t o t h e c e n t e r o f t h e pan* The o v e r a l l

r e a c t i o n i s a s fo llo w s*

HgSO^ / HaCl — NflgSOi / 2 HCl

V a rio u s a u th o r s have d e s c r ib e d th e r e a c t i o n a s o c c u rrin g i n two s t e p s a s

fo llo w s s

HgSO^ / NaCl —*» Na2SOjt f- 2 HCl

Halloo^ / NaCl —*■ Na^SO. / HCl

7
 The f i r s t s t e p p ro c e e d s a t o r d in a r y te m p e ra tu re s * w h ile th e second

s t e p r e q u i r e s c o n s id e r a b le h e a t t o c o m p le te th e r e a c tio n * The s o l i d p ro ­

d u c t o v e rflo w s from t h e o u t e r edge o f t h e pan th ro u g h o p e n in g s p ro v id e d

f o r t h a t p u rp o se* The p ro d u c t i s a c a k e w hich may c o n ta in u n r e a c te d s u l ­

p h u r ic a c id and a l s o some b is u lp h a te * The g a se s p a s s in g o f f a r e p u re

h y d ro g en c h l o r i d e w hich may b e a b so rb e d i n w a te r o r u se d d i r e c t l y in some

o t h e r p ro c e s s * When t h e Mannheim p r o c e s s i s u se d t h e d e s i r e d p ro d u c t i s

u s u a l l y h y d ro g en c h lo r i d e and t h e s a l t cak e i s c o n s id e re d a by—p ro d u ct*

The p r o p e r t i e s o f t h e s o l i d p ro d u c t a r e c o n t r o l l e d by th e e f f i c i e n c y o f

t h e o p e ra tio n * b u t u s u a l l y a r e su c h a s t o make h a n d lin g and sh ip m en t d i f ­

f i c u l t and c o s tly *

The L aury f u r n a c e o f th e r o t a r y k i l n ty p e use© © a lt and b i s u l p h a t e

o r n i t r e c ak e and p ro d u c e s a m ore s a t i s f a c t o r y s o l i d p ro d u c t and d i l u t e

h y d ro g en c h lo r i d e gas*

The H a rg rea v es p r o c e s s u se d f o r many y e a r s i n Europe em ploys s a l t

and s u lp h u r a s t h e p rim a ry raw m a te r ia ls * T here i s o n ly one com m ercial

p l a n t i n t h i s c o u n try due t o th e f a c t t h a t th e p r o c e s s e n t a i l s h ig h l a b o r

and h a n d lin g c o s ts * T h is one p la n t* The Bay C hem ical Company a t Weeks

I s la n d * L o u isia n a * u t i l i z e © w a s te s a l t d u s t from n e a rb y s a l t m in in g o p e ra ­

t i o n s and s u lp h u r w h ich i s a ls o o b ta in e d from a l o c a l so u rc e* The p r o c e s s

i s co m m ercially s u c c e s s f u l due t o i t s p ro x im ity t o raw m a t e r i a l s o f v e ry

low c o s t*

The o v e r a l l r e a c t i o n i s a s fo llo w s*

2 NaCl / H20 / S02 / |s02 — NagSOj* / 2 HCl

 9

Th© s u lp h u r i s b u rn e d i n a n e x c e s s o f a i r t o fo rm s u lp h u r d io x id e w h ich

i s m ixed w ith ste a m t o fo rm t h e r e a c t i o n gas*

I r o n c h lo r i d e i s u s e d a s a c a t a l y s t t o t h e e x t e n t o f one h a l f o f one

p e r c e n t o f t h e w e d ^ it o f s a l t * The s a l t a n d c a t a l y s t a r e fo rm ed i n t o o v a l

sh a p e d b r i q u e t t e s a b o u t one b y t h r e e in c h e s i n sis© * The b r i q u e t t e s a r e

dnaped i n t o one o f e i g h t r e a c t i o n cham bers h a v in g a 9 $ t o n c a p a c ity * T hose

cham bers a r e l i n e d w ith f i r e b r i c k a n d a r e c u b ic i n sh ap e m easu rin g a b o u t

tw e n ty f e e t on a s id e * One o f th© e i g h t cham bers i s n o rm a lly o u t o f e e r *

v i c e f o r rem oval o f p r o d u c t a n d re c h a rg in g * The o t h e r se v e n a r e o p e r a te d

i n s e r i e s * t h e f r e s h g a s r a t e b e in g c o n t r o l l e d t o m a in ta in t h e r e a c t o r tern*

p e r a t u r e below 593o c * A r i s e i n te m p e ra tu re above 593°C c a u s e s f u s i o n o f

t h e m ix tu re w ith c m s e q u e n t r e d u c tio n i n p e r c e n t c o n v e rs io n » Any f u s e d

m a t e r i a l m ust b e b ro k e n up m a n u a lly a n d g ro u n d f o r re - p r o c e s s in g * When

t h e g a s a n a l y s i s i n d i c a t e s c o m p le tio n o f t h e r e a c t i o n a r e a c t o r i s r e ­

moved fro m t h e sy s te m a n d c o o le d by c i r c u l a t i n g a i r * The p ro d u c t i s

rem oved fro m t h e cham ber by a p n eu m atic sy ste m a n d ground* The im p u ri­

t i e s am ounting t o a b o u t t h r e e p e r c e n t c o n s i s t m a in ly o f s a l t * i r o n oxide*

c a lc iu m s a l t s * a n d s i l i c a * The e x h a u s t g a se s a r e s e n t t o a n a b s o rb in g

sy ste m td iic h p ro d u c e s com m ercial m u r ia tic a c id * Th© tim e f o r c o m p le tio n

o f t h e r e a c t i o n o f one chamber i s t h r e e days* One a d v a n ta g e o f t h i s p ro ­

c e s s o v e r th o s e p r e v i o u s ly m en tio n ed i s t h a t t h e e x o th e rm ic n a tu r e o f t h e

r e a c t i o n re d u c e s t h e f u e l c o st* how ever t h e n e c e s s i t y f o r l a r g e am ounts

o f h a n d l a b o r i n c h a rg in g a n d rem oval o f p r o d u c ts fro m t h e cham bers re d u c e s

 10

t o srnae e x t e n t t h e adhrantages o f a h i g h e r g ra d e p r o d u c t a n d lo w e r f u e l

re q u ire m e n ts *

T h e re a r e o t h e r s o u rc e s o f com m ercial s a l t c ak e b e s id e s th o s e men-

ti:n e d » The c h e m ic a l i n d u s t r i e s p ro d u c e s m a ll q u a n t i t i e s a s a b y -p ro d u c t

due t© t h e u s e o f c a u s t i c a s a n e u t r a l i s i n g a g e n t f o r s u lp h u r ic a c i d o r

su lp h a te s* , A s y n t h e t i c s a l t calce i s made b y s i n t e r i n g a m ix tu re o f suX*

p h u r a n d soda, ash* T h is m ix tu re i s th e n re d u c e d t o t h e s u lp h id e f o r u s e

i n k r s f l p a p e r m a n u fa c tu re . I t h a s b een a m a jo r c o m p e tito r f o r s a l t cak e

i n t h e S o u th , b u t h a s r e c e n t l y gone o u t o f p r o d u c tio n due t o c o js p e titio n

w ith m a n u fa c tu re d an d n a t u r a l s a l t cake*

f t a t u r a l s a l t cake r e c o v e r y I s i n c r e a s in g and p r o v id e s a cheap s o u rc e

o f t h e m a t e r i a l i n a r e a s a d j a c e n t t o i t s lo c a tio n * T h ese a r e a s a r e gen*

e r a l l y i n t h e a r i d r e g io n s o f th e W est a n d N orthw est* A v e r y l a r g e am ount

o f s a l t c ak e i s now b e in g re c o v e r e d i n Canada f o r sh ip m en t t o t h e U n ite d

S ta te s *

The S outh x s a n e x c e l l e n t l o c a t i o n f o r a com m ercial s a l t c ak e p l a n t

s i n c e t h e k r a f t i n d u s t r y t h e r e m ust im p o rt t h e c h em ic al fro m Canada o r

buy t h e r e l a t i v e l y h ig h p r i c e s p ro d u c t made i n t h e South* The p r e s e n t

p r i c e o f com m ercial s a l t cak e i n t h e S o u th ra n g e s fro m $ 1 8 .5 0 t o $22*00

p e r to n * The p rice v a r i e s somewhat -with t h e p u r i t y a n d t h e s o u rc e a n d

i s s u b j e c t t o sh ip p in g c h a rg es*

The p r i n c i p l e a d v a n ta g e o f a f l u i d i z a t i o n p r o c e s s o v e r t h e H a rg re a v e s

p r o c e s s I s lo w e r o p e r a tin g c o s t , lo w e r cost© a r e o b ta in a b le b y e li m in a t ­

in g th© f o rm a tio n o f b r i q u e t t e s , h e av y m ach in ery f o r solid© movement, th©

manual operation of of fused cake, end t h e g r in d in g o f b r i q u e t t e s
 r w m a ta im w m x m m s
R article S ize ^onsdderations
Thm l i t e r a t u r e c o n ta in s some d a ta fro m v& ich t h e f l u i d i z a t i o n p ro p ex'*

tie ® o f s o l i d s may b e p r e d i c t e d ( l ) * Any p a r t i c u l a r s o l i d may h a v e

p r o p e r t i e s vfcich make g e n e r a l c o r r e l a t i o n s u n r e l i a b l e a n d i n su c h e a s e s

t h e f l u i d i z a t i o n c h a r a c t e r i s t i c s m s t be d e te rm in e d e x p e rim e n ta lly * So*

d i u a c h l o r i d e m s c h o sen a s t h e s o l i d f o r t h e e x p e r im e n ta l s t u d i e s o f

f l u i d i s a t l o n a s I t w o u ld b e u s e d l a t e r a s t h e r e a c t i n g s o l i d i n t h e r e a o -

t i o a e x p e rim e n ts* I t b e h av e s i d e a l l y i n s i z e s l a r g e r th a n 6$ mesh M ilch

i s t h e s i z e o f f i n e t a b l e s a l t * S m a lle r s i z e s e s p e c i a l l y i f t h e y a r e
i
s h a r p r a t h e r th a n c u b ic c r y s t a l s have a te n d e n c y t o s l u g i n s m a ll d ia m e te r

v e s s e l s o r t o c h a n n e l i n l a r g e r v e s s e ls * The r e a s o n f o r t h i s b e h a v io r

a p p e a rs t o l i e i n t h e f a c t -th at sm a ll ja g g e d s a l t p a r t i c l e s do n o t p o s s e s s

a sy m m e tric a l e l e c t r o s t a t i c f i e l d an d th u s stig fc t o g e t h e r r e a d ily * In

m ix tu r e s o f g ro u n d s a l t “where t h e r e i s a l a r g e p r o p o r tio n o f l a r g e r s i z e s

o f a p p ro x im a te ly 3*8-65 mesh* f i n e s do n o t p r e v e n t s a t i s f a c t o r y f l u i d i s a *

tio n * T hey a p p e a r t o a d h e re t o th e l a r g e r p a r t i c l e s w hich do n o t th e m s e lv e s

s t i c k t o g e t h e r due t o t h e i r l a r g e r s iz e # Hock s a l t g ro u n d t o p a s s 35 mesh

was fo u n d t o h a v e s a t i s f a c t o r y f l u i d i z a t i o n c h a r a c t e r i s t i c s * Photomicr©**

g ra p h s o f t h e s a l t u s e d a r e shown i n I l l u s t r a t i o n I*

I n p r e p a r in g a s o l i d f o r a r e a c t i o n i t i s e x p e c te d t h a t t h e g r e a t e s t

a d v a n ta g e -would b e g a in e d i n r e a c t i o n tim e b y g r in d in g a s f i n e a s pos-*

s i b l e s o a s t o ex p o se t h e g r e a t e s t p o s s i b l e s u r f a c e f o r r e a c tio n * In th e

c a s e o f s a l t however* t h e l i m i t a s t o t h e s m a lln e s s o f t h e a v e ra g e p a r t i c l e

22
 33

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w i l l b e d e te rm in e d p r i m a r i l y b y t h e a b i l i t y t o d e s ig n equipm ent t o h a n d le

i t in th e flu id iz e d s ta te * Of c o u rs e th e c o s t o f g r in d in g may e n t e r t h e

econom ics o f t h e o p e r a t io n and l i m i t th e s i z e re d u c tio n * One a l t e r n a t i v e

s o l u t i o n may b e th e u s e o f & c a r r i e r s o l i d w h ich i s i n e r t and s e r v e s a s an

a i d t o f l u i d i z a t i o n , th u s a llo w in g h a n d lin g o f f i n e r p a r t i c l e s # The c a r ­

r i e r may b e a s u i t a b l y s i z e d f r a c t i o n o f th e p ro d u c t o f r e a c t i o n and th u s

m in im ise s t h e d i f f i c u l t i e s o f s e p a r a t io n o f t h e c a r r i e r from t h e p ro d u c t*

The optimum p a r t i c l e s i z e d i s t r i b u t i o n w i l l have t o be d e te rm in e d econom ic

c a l l y b a s e d upon c o n s id e r a tio n s o f r e a c t o r d e s ig n , r e a c t i o n tim e , and

g r in d in g c o s t* I t i s e x p e c te d t h a t t h e n o rm al pr o c ed u re w ould b e t o d e s ig n

a u n i t t o h a n d le a s o l i d w hich h a s a p a r t i c l e s i z e d i s t r i b u t i o n o b ta in a b le

on a s ta n d a r d com m ercial g rin d e r* The r e a c t i o n tim e and f l u i d i z a t i o n c h a r ­

a c t e r i s t i c s f o r a s o l i d o f such s i z e w ould be th e b a s i s f o r r e a c t o r d esig n *

A r e a c t o r c o n s tr u c te d on th e b a s i s o f th e s e c o n s id e r a tio n s sh o u ld b e t e s t e d

f o r t h e a c t u a l l i m i t s o f o p e r a b i l i t y a s t h e g r in d in g o p e r a tio n i s a d ju s te d

f o r f i n e r and f i n e r p a r t i c l e s iz e * The f i n e s t p a r t i c l e s i z e c o n s i s t e n t

w ith good o p e r a tio n and r e a s o n a b le g r in d in g c o s t sh o u ld g iv e t h e m ost

eco n o m ical o p e ra tio n * A s i m i l a r p ro c e d u re sh o u ld b e fo llo w e d i f Hie

s o u rc e o f s a l t i s b r i n e w hich m ust be c r y s t a l l i z e d and d r ie d b e f o r e use*

I t i s e x p e c te d t h a t , f o r e q u iv a le n t p a r t i c l e s i z e , a b e d o f s a l t c r y s t a l s

h a v in g u n ifo rm sh a p e w i l l e x h i b i t l e s s te n d e n c y t o c h a n n e l th a n a b e d o f

ground s a l t w h ich h a s p a r t i c l e s o f Ja g g e d and n o n -u n ifo rm shape*

 t h e © xothorm ie c h a r a c t e r o f t h e r e a c t i o n i n d i c a t e s some econom ic

a d v a n ta g e may b e g a in e d by o b ta in in g th e s a l t i n t h e fo rm o f b r i n e a n d

e v a p o r a tin g t h e b r i n e u s i n g t h e h e a t e v o lv e d i n t h e r e a c tio n * Th# sis©

o f t h e s a l t c r y s t a l s s a y t h u s be c o n t r o l l e d f o r m ost e f f i c i e n t p r o c e s s in g

t o t h e s u lp h a te * The p r e s e n t c o s t o f ro c k s a l t i n c a r l o a d l o t s a t t h e

m ine i s a b o u t #3*00 p e r t o n w h ile s a l t i n a 2$% s o l u t i o n i s $1 *1$ p e r to n

o f d r y s a l t w hich i s s l i g h t l y l e e s t h a n h a l f t h a t o f t h e ro c k s a l t *

The e:q > erim e n tal work was c a r r i e d o u t f o r th e m ost p a r t w ith o r d in a r y

t a b l e s a l t f o r tw o r e a s o n s . I t i s a c o n v e n ie n t u n ifo rm m a t e r i a l a n d i t

h a s e x c e l l e n t f l u i d i z a t i o n p r o p e r tie s * OoiEp&rable r e s u l t s w ere o b ta in e d

I n e x p e rim e n ts w ith t a b l e s a l t a n d r o c k s a l t o f e q u iv a le n t p a r t i c l e sisse*

Esqpexim ental Work

C o n s id e ra b le w ork h a s b een done r e c e n t l y on f l u i d i s s a t i o a o f v a r io u s

s o l i d s a n d c o r r e l a t i o n s h av e been made t o show t h e r e l a t i o n s h i p s betw een

t h e c h a r a c t e r ! s t i e s o f t h e m a t e r i a l sa d p r e s s u r e d ro p s th ro u g h i t a s a

f u n c t i o n o f g a s v e l o c i t y (2 )* A t h e o r e t i c a l e q u a tio n h a s been d e v e lo p e d

fro m w h ich t h e p r e s s u r e d ro p th ro u g h a f l u i d i s e d b e d may be c a l c u l a t e d ( 3 )*

The e q u a tio n in v o lv e s s e v e r a l p r o p e r t i e s w hich m a t be o b ta in e d b y measure**

m eat su c h a s "Vj*'# t h e dumped volum e o f t h e s o l i d ( c u b ic f e e t ) , <fA^w c r o s s

s e c t i o n a l a r e a o f t h e f lu i& L s a tio n v e s s e l (s q u a re f e e t ) , * 8 « f r a c t i o n a l

v o id s i n t h e b e d (n o d im e n s io n ), n / ° e n p a r t i c l e d e n s i t y (pounds p e r c u b ic

f o o t ) , an d fl/ 0 * f l u i d d e n s i t y (pounds p e r c u b ic f o o t ) * The p r e s s u r e d ro p

2® i s th en *
 t h e m easurem ents o f t h e v a r io u s tern ® i n t h e e q u a tio n i s s u b j e c t t o

e r r o r a n d s i n c e t h e s a l t was a v a i l a b l e th e p reso u r© d ro p w as d e te rm in e d

e x p e rim e n ta lly * t h e d a ta i s p r e s e n t e d i n t h e a p p e n d ix an d g r a p h i c a l l y

i n F ig u r e 1* t h e s c r e e n a n a l y s i s o f t h i s m a t e r i a l i s a l s o p r e s e n te d i n

t h e ap p en d ix*

From F ig u r e 1 i t i s se e n t h a t p r e s s u r e dro p i s v i r t u a l l y in d e p e n d e n t

o f m ass v e l o c i t y o f t h e g a s f o r t h e f l u i d i s e d bed* Any i n c r e a s e o f p r e s ­

s u r e d ro p w ith in c r e a s e i n m ass v e l o c i t y I s due t o f r i c t i o n betw een t h e

g a s s tr e a m a n d t h e r e t a i n i n g w a lls o f t h e v e s s e l a n d c o n n e c tin g p ip e s*

t h i s p r e s s u r e l o s s i s p r e d i c t a b l e b y c o n v e n tio n a l methods*

A t h r e e s t a g e c o u n te r c u r r e n t flo w r e a c t o r was d e s ig n e d and b u i l t

o f l a b o r a t o r y equipm ent t o t e s t th e o p e r a b i l i t y o f t h e d e sig n * A s k e tc h

o f t h e a p p a r a tu s i s shown i n F ig u re 2 * Flow r a t e s o b ta in a b le on t h i s

m odel a r e p r e s e n te d i n t h e appendix* t h i s m odel i s t h e b a s i s f o r a sug­

g e s te d d e s ig n o f a com m ercial s i z e c o u n te r c u r r e n t u n i t w h ich i s p r e s e n te d

i n F ig u r e

A se c o n d l a b o r a t o r y s i z e c o u n te r c u r r e n t flo w r e a c t o r ( r e a c t o r number

8) was b u i l t a n d t h e flo w r a t e s f o r i t a r e p r e s e n te d i n F ig u re U a n d a

p h o to g ra p h o f i t i s p r e s e n te d i n I l l u s t r a t i o n II* A t h i r d r e a c t o r w hich

i s a c o m b in atio n o f p a r a l l e l a n d c o u n te r c u r r e n t flo w ( r e a c t o r num ber 9 )

was b u i l t a n d t e s t e d f o r o p e r a b i li t y * D ata f o r i t a r e p r e s e n te d i n t h e

a p p e n d ix and a p h o to g ra p h o f i t i s p r e s e n te d i n I l l u s t r a t i o n I I I *

P a r a l l e l flo w le n d s I t s e l f more r e a d i l y t o d e s ig n th a n c o u n te r c u r r e n t

f lo w s in c e t h e s o l i d i n a c o u n te r c u r r e n t sy stem m ust be i n tr o d u c e d i n t o a
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FIG. 2
LABORATORY FLUID1ZATION UNIT
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FIG. 3 SOLID INLET GAS

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ILWJSTRATICM II
Reactor Buaaiber 8

I l l u s t r a t i o n I3A I l l u s t r a t i o n IIB
Hate c o n str ic tio n above fou r Jacketed w ith g la ss tube and
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m m s m x im h i
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■*

b e d a t h ig h e r p r e s s u r e th a n t h e on e i t i s le a v in g * In c o u n te rc u rre n t

u n i t e t h i s h e a d i s overcom e by a v e r t i c a l f e e d p ip e o f s o l i d h ig h e r th a n
*

th e b e d h e ig h t* The c o n tr o l o f s o l i d flo w m ust b e m a in ta in e d b y th e

p r e s s u r e d i f f e r e n t i a l o f t h i s v e r t i c a l colum n o f s o lid * T h is h a s been

a c c o m p lish e d i n co m m ercial u n i t s b y th e u s e o f d i f f e r e n t i a l p r e s s u r e

c o n tr o l o f f e e d v a lv e s* T h is m ethod i s im p r a c tic a l o r v e ry d i f f i c u l t

on la b o r a to r y s c a l e equipm ent n e c e s s ita tin g m anual c o n tr o l o f f e e d b y

g la s s s to p c o c k s ( r e a c t o r num ber 9 )* An a l t e r n a t e m ethod u s e d f o r c o n tr o l

o f downward flo w o f s o l i d w as b y in tr o d u c tio n o f a s u i t a b l e c o n s t r ic ti o n

a t th e b o tto m o f th e f l u i d i z e d b ed an d a d ju s tin g th e downward flo w r a t e

o f s o l i d th ro u g h t h e c o n s t r ic ti o n b y c o n tr o l o f th e g a s v e lo c ity ( r e a c t o r

num ber 8 )* ^ h e am ount o f s o l i d h e ld i n th e r e a c t o r a s w e ll a s th e s o l i d

flo w r a t e i s a f u n c tio n o f th e g as v e lo c ity * T h is r e la tio n s h ip i s shown

i n F ig u r e 1** T h is r e a c t o r fo rm s th e b a s is f o r th e d e s ig n o f a com m ercial

r e a c t o r s u g g e s te d i n F ig u re 5 *
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T he s t a r t i n g p o in t f o r e x p e rim e n ta l w otk m o th e d e s ig n o f a s in g le

s ta g e f l u i d i z a t i a n u n i t i n w hich th e r e a c tio n c o u ld h e s tu d ie d t o d e te r *

m in e, i f p o s s ib le * th e e f f e c t o f th e o p e ra tin g v a r ia b le s upon th e r e a c tio n

r a te * T he conditions w ere ch o sen t o a p p ro x im a te , a s c lo s e ly a s p o s s ib le *

th o s e en$& oyed i n th e H a rg re a v e s p ro c e s s * T he d e s ir e d te m p e ra tu re w as

S38°C a n d th e gas c o s p o s itlo n d e s ir e d was s to ic h io m e tr ic a l p r o p o r tio n s

a c c o rd in g t o t h e fo llo w in g 09®r a i l re a c tio n *

It S a C l / i SGfc £ 2 ^ 0 / Cfe «*+* 2 4 t BOX

I l l u s t r a t i o n 17 i s a p h o to g ra p h o f th e a p p a ra tu s * P ro v is io n s w ere

made t o r e g u la te a n d m easu re s u lp h u r d io x id e flo w fro m a c y lin d e r o f th e

gas*

C om pressed a i r m s h a n d le d by r e g u la to r a n d ro tam eter b e fo re passing

th ro u g h a s e ig h t f o o t h u m id ify in g to w e r p ack ed w ith h a lf in c h r e s c h ig

r in g s , T he te s a p e ra tu re o f th e w a te r u s e d i n t h e h u m id ify in g to w e r was

c o n tr o lle d b y a w a te r b le n d e r t o g iv e th e a i r th e d e s ir e d m o is tu re con­

te n t* The m o is t a i r an d s u lp h u r d io x id e m m m ixed a n d p a s s e d in to a

f o u r f o o t bank o f h a l f in c h p ip e s ( I l l u s t r a t i o n 7) h e a te d by two long­

i t u d i n a l g a s b u rn e rs *

The r e a c t o r w as lo c a te d a t th e e x i t o f th e bank o f fu rn a c e tu b e s ,

The w a ste g a s e s coming fro m th e r e a c t o r w ere p a s s e d th ro u g h a s c ru b b e r

to w e r made o f t h r e e le n g th s o f s i x in c h t e r r a c o tt a p ip e p a ck e d w ith

ceram ic b e r l s a d d le p ack in g *

25
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X* S u lp h u r d io x id e r e g u la to r 5* Steam ja c k e te d l i n e
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S h e f i r s t r e a c t o r { r e a c to r num ber X) c o n s is te d o f a one f o o t s e c tio n

o f p y re x g la s s tu b e f o u r in c h e s in d iam eter* t h e s a l t w as s u p p o rte d on a

s c r e e n a t th e b o tto m o f th e tu b e* ^h© e n t i r e r e a c to r w as s u p p o rte d on a n

ir o n b a s e w h ich c o n ta in e d a g a s d i s t r i b u t i o n p l a t e t o p ro v id e e q u a l d i s t r t *

b u tto n o f g a s th ro u g h th e b e d o f s o lid *

T he d e s c r ip tio n o f t h e e x p e rim e n ts t o g e th e r w ith a n a ly s is o f p ro d u c ts

a n d c o r r e c tiv e ch an g es made t o t h e a p p a ra tu s a r e p r e s e n te d l a c h ro n o lo g ic a l

o r d e r i n o r d e r t o show th e p a th o f th e d ev elo p m en t c le a r ly * The d i f f i c u l t

t i e s t h a t a r o s e a r e d is c u s s e d a n d th e m anner i n w hich th e y a r e r e s o lv e d i s

d e sc rib e d *

Run # 1

When th e a i r te m p e ra tu re ab o v e th e s c re e n re a c h e d 510OG w ith a b o u t

a o n e in c h s a l t b ed p r e s e n t th e s u lp h u r d io x id e w as in tro d u c e d a t a low

r a te * T h e p r e s s u r e d ro p w as f l u c t u a t i n g w id e ly fro m a b o u t t e n t o tw e n ty -

f i v e in c h e s o f w a te r* The m anom eter blew o u t a f t e r a b o u t t h i r t y m in u te s

o f o p e ra tio n when t h e te m p e ra tu re was *538°C* ^ h e b o tto m o f th e s a l t b ed

h a d s e v e r a l luag>8 o f c ry s ta lin © s o l i d a d h e rin g t o t h e s c re e n w h ich h a d

becom e b r i t t l e an d b ro k e v e ry e a s i l y when h an d led * T he a n a ly s is o f th e

b e d show ed a n e q u iv a le n t o f t e n gram s o f s a l t cak e b a se d on a s u lp h a te

d e te rm in a tio n o r a b o u t f i v e p e rc e n t c o n v e rsio n *

The c a u s e f o r t h e p r e s s u r e f l u c t u a t i o n s a n d p lu g g in g w as d is c o v e re d

t o b e due t o w a te r c o n d e n s a tio n In th e l i n e s p re c e d in g th e fu rn a c e * The

c o n d e n sa te a b s o rb e d s u lp h u r d io x id e t o fo rm su lp h u ro u s a c id w h ich d is s o lv e d .
 29

i r o n I n th e c o o le r p ip e s and d e p o s ite d th e s a l t s a t th e en tra n ce t o th e

f u r n a c e fo rm in g a h eav y s c a l e .

C hanges P r i o r t o Kim #2

A ste a m ja c k e t was i n s t a l l e d on ‘th e m o is t a i r l i n e t o p r e v e n t w a te r

c o n d e n s a tio n a n d a new b e d s u p p o rt w as o o n s tro c te d * The new s u p p o rt con­

s i s t e d o f tw o s t a i n l e s s s t e e l p l a t e s one e ig h th in c h a p a r t h a v in g © m il

h o le s f o r p a ssa g e o f th e g a s , th e h o le s i n e a c h p la te being o f f s e t t o

p r e v e n t dow nflow o f s o lid * T h is v a r i a ti o n o f th e f i r s t r e a c t o r was c a lle d

R e a c to r num ber 2 a n d i s shown i n I l l u s t r a t i o n V I.

Ron #2

The r a n m s s t a r t e d s i m il a r ly t o t h e f i r s t run * A f te r f i v e m in u te s

o p e ra tio n t h e b e d su d d e n ly s o l i d if i e d * Numerous e m a il c h a n n e ls fo rm ed

i n th e s a l t , e a c h ab o v e a h o le i n t h e s t e e l p la te * The o d o r o f s u lp h u r

d io x id e becam e s tr o n g a n d smoke is s u e d fro m t h e d is c h a rg e s id e o f th e

r e a c to r *

The c h a n n e ls w ere l a t e r exam ined a n d fo u n d t o h av e a pow dery w h ite

c o re Mash w h ite r th a n th e su rro u n d in g s a l t a n d m ore f ir m ly fu se d * The

b o tto m p l a t e c o n ta in e d a ro u n d a re a a b o u t th e c e n te r w hich a p p e a re d t o

h a v e b een w e t d u rin g th e run* I t c o n ta in e d h a rd e n e d p i l e s o f s a l t# The

cores w ere fo u n d t o c o n ta in much m ore s u lp h a te th a n th e su rro u n d in g bed*

N e ith e r w as fo u n d t o c o n ta in a n y m o istu re *

C hanges P r io r t o Run #3

A t r a p w as i n s t a l l e d i n th e m o is t a i r l i n e a t t h e fu rn a c e e n tr a n c e
t o c a tc h a n y c o n d e n sa te fo rm ed i n th e u n h e a te d p o r tio n o f t h e U n a *
 musri&tioH vx
R e a c to r num ber 2

I3GTS* Gas d is tr ib u tio n p la te on th e

l e f t f i t s in s id e th e iro n support*
 n

Ito #3
T he m m m s s t a r t e d s im ila r l y t o th e f i r s t tw o a n d a f t e r s i x m in u te s

t h e c e n te r p o r tio n o f th e b e d s to p p e d fln id i& in g * f h e u n i t w as op en ed a n d

th e b e d m s s t i r r e d , b u t th e h o le s seem ed t o b e p lu g g e d up# th e u n it m e

o p e ra te d f o r tw o m ore m in u te s when th e e n t i r e b e d sto p p e d f lu id is in g *

t h e sam e c e r e s w ere fo u n d a g a in a n d a ls o th e h o le s i n th e c e n te r pom*

t i o n o f th e to p p l a t e w ere c lo s e d w ith a r u s t y s c a le *

Change® P r i o r t o Bun #U

A Corrumdum p l a t e w as made t o c o v e r th e u p p e r s t e e l p l a t e a n d g la s s

w ool m s p la c e d i n th e sp a c e b etw een th e p la te ® ( r e a c t o r num ber 3 )#

Bun #1*

R e s u lts w ere th e sam e a s Rbn # 3 w ith th e e x c e p tio n t h a t th e h o le s

d id n o t p lu g up a n d th e o p e ra tio n l a s t e d te n m in u tes*

Change® P r io r t o Bun #§

A near r e a c t o r w as d e sig n e d ( r e a c t o r num ber h) t o p r o r id e g r e a t e r

a g i t a t i o n o f t h e b e d i n o r d e r t o p r e v e n t s o l i d if i c a t io n * I t c o n s is te d

o f a tw o a n d one h a l f in c h g la s s tu b e ta pf e r e d to w a rd th e b o tto m i n a

le n g th o f a b o u t tw e lv e in c h e s* !h© lo w e r d ia m e te r m s th r e e eig h th ©

in c h . A h a l f in c h p e r f o r a te d c e ra m ic d is k w as p la c e d i n th e lo w e r

p o r tio n t o s u p p o rt th e b ed o f s o lid #

Run 05
Im proved o p e r a tio n w as n o te d o v e r p re v io u s ru n s* te m p e ra tu re wa®

m a in ta in e d b etw een hOO a n d U20°C* A bout tw e n ty m in u te s o f s a t i s f a c t o r y

 3a

o p e r a tio n w as fo llo w e d b y a b o u t t h i r t y m in u te s o f p o o r o p e r a tio n when

th e b e d becam e in c r e a s in g ly m ore s t i c k y i n a p p e a ra n c e u n t i l i t w o uld n o

lo n g e r f l u i d i s e ev en when s t i r r e d * A cake h a d form ed on th e ceram ic

d is k w ith th e u s u a l c h a n n e ls le a d in g upward* The m ajo r p o r tio n o f th e

b e d w as lo o s e a f t e r c o o lin g an d a n a ly s e d a b o u t 60$ sodium s u lp h a te b a se d

on t h e s u lp h a te a n a ly s is * The cak e on th e d is k a n a ly z e d 9 8 . 5$ on th e same

b a s is *

Run #6

C o n d itio n s w ere i d e n t i c a l w ith Run #£ except f o r a lo w e r te m p e ra tu re

w h ich w as e x p e c te d t o re d u c e th e m e lte d cak e fo u n d p re v io u s ly * I t had

l i t t l e e f f e c t on cak e fo rm a tio n o r s tic k in e s s *

C hanges P r io r t o Run # 7

The c eram ic d is k w as rem oved c o m p le te ly an d a n in e ty d e g re e ben d

made a t th e b o tto m o f th e r e a c t o r t o e lim in a te th e d ead zone e x is ti n g

set th e p e r ip h e r y o f th e c e ra m ic d is k ( r e a c t o r number 5 )*

Run #7

Results were sim ilar to the previous runs5 the product was 39$ so­
dium sulphate and the run la sted fifte e n minutes before the s a lt stopped
fiuidizin g*
C hanges P r i o r t o Run # 8

A f l u i d i z a t i o n p ro m o te r was i n s t a l l e d i n th e b o tto m o f th e r e a c to r
s in c e i t w as n o tic e d t h a t th e g a s was c h a n n e lin g up th e s id e o p p o s ite th e

i n l e t ( r e a c t o r num ber 6 )* The p ro m o te r w as a sm a ll s p i r a l made o f g la s s

rod *
 33

Rian # 8

S tic k in e s s w as o b se rv e d a f t e r i i v e m in u te s a n d th e ru n w as te rm in a te d *

The p ro m o te r h a d become s tu c k I n th e b o tto m o f th e r e a c t o r a n d c a k e h ad

fo rm ed a ro u n d i t *

Run §9

The ru n d u p lic a te s ru n # 8 e x c e p t t h a t t h e p ro m o te r was n o t stu c k *

Cake fo rm ed i n b o th ru n s*

Run #10

The te m p e ra tu re w as re d u c e d t o a b o u t 220®C t o f i n d a lo w e r te m p e ra tu re

a t w h ich r e a c tio n p ro c e e d s w ith o u t fo rm a tio n o f cake* The o p e ra tio n w as

f a i r l y s u c c e s s f u l s in c e o n ly #23h gram s o f cake fo rm ed o f a 20 gram c h a rg e

i n a n h o u r o f o p e ra tio n # The p ro d u c t a n a ly s e d h9% sodium s u lp h a te b a se d on

s u lp h a te #

Run # 1 1

A h ig h e r te m p e ra tu re o f a b o u t 260°C was a tte m p te d to in c r e a s e th e r e ­

a c t io n r a t e , b u t f l u i d i z a t i o n c e a se d a f t e r tw e n ty -s e v e n m in u te s* The p ro d u c t

w as 5i# s a l t cake#

Run #12

A re d u c tio n i n s u lp h u r d io x id e c o n c e n tr a tio n was n e x t a tte m p te d a s a

m eans t o re d u c e th e s u r f a c e t e i ^ e r a t u r e o f t h e r e a c tin g p a r t i c l e a n d th u s

rem ove a p o s s ib le c a u se o f s tic k in e s s # T he r e a c tio n d id n o t p ro c e e d an d

I t w as assum ed t h a t n o s u lp h u r d io x id e re a c h e d th e s a l t * A lth o u g h th e

s u lp h u r d i 02d .de r o ta m e te r f l u c t u a t e d w id e ly i t m s fo u n d t o do so ev en
w ith th e s u p p ly s h u t o ff* T he f l u c t u a t i o n s w ere c a u se d b y th e p re s s u re

v a r i a t i o n a c r o s s th e f l u i d l a e d bed*

B aa #33

A g la s s w o o l p lu g i n t h e l i n e re d u c e d th e f l u c t u a t i o n s t o p e rm it

s a t i s f a c t o r y o p e ra tio n * C o n c e n tra tio n o f s u lp h u r d io x id e tnas re d u c e d

when th e © o lid becam e s t i c k y p e r m ittin g c o n tin u e d re a c tio n * T he ru n to®

e n d ed a f t e r f i f t y zain u tes a n d y ie ld e d a p ro d u c t o f Wf> ©odium s u lp h a te *

T he te m p e ra tu re re a c h e d 360°C a t th e en d o f th e ru n when th e s o l i d m s

b e g in n in g t o a p p e a r s tic k y *

Sun #3i*

T he tu r b u le n c e p ro m o te r w as b ro k en i n rem o v al fro m th e sc & e to r on

ru n #13 so i t s u s e to © d is c a rd e d f o r t h i s run* b u t e x c e s s iv e c a rry o v e r

p re v e n te d a s a t i s f a c t o r y o p e ra tio n *

C hanges i n O p e ra tio n P r i o r t o Bun #15

A t th e c o n c lu s io n o f ru n #31* l i q u i d to© n o tic e d co n d en sed on th e

m i l s o f th e r e a c t o r even th o u g h i t s te m p e ra tu re w as l £ 0®C. F or th is

re a s o n th e w a te r c o n c e n tr a tio n o f th e r e a c t o r g a s to® re d u c e d b y d e­

c r e a s in g th e h u m id if ie r to w e r te m p e ra tu re fro m 65*6c*C t o 32*2°C* A

tu r b u le n c e p ro m o te r m s a ls o u s e d a g a in *

Run #15
The te m p e ra tu re v a r ie d fro m 330- 3 70°C d u rin g a s e v e n ty m in u te ru n *

Sample© w ere ta k e n a t i n t e r v a l s u n t i l th e b e d to® n e a r ly d e p le te d * The

o p e ra tio n m s s a t i s f a c t o r y f o r o v e r an h o u r when a © lig h t s tic k in e a © w as

n o tic e a b le , b a t a u n ifo rm p ro d u c t w as o b ta in e d w hich a n a ly s e d 9 ® sodium

s u lp h a te b a se d on a c h lo r id e a n a ly s is # The l a s t sam p le rem oved a n a ly s e d

so d iu m s u lp h a te b a se d on s u lp h a te s a n d c o n ta in e d n e g li g i b le a c i d i t y

s in c e i t a p p e a re d b a s ic t o m e th y l o ra n g e in d ic a to r *

Bun #16

A lo w e r te m p e ra tu re m s u s e d t o o b ta in r a t e d a ta * T h is d a ta i s p re ­

s e n te d i n th e d is c u s s io n o f r e s u l t s # The te m p e m tu re m a h e ld a t 2hO°G

f o r o v e r f e w h o u rs y ie ld in g hS% c o n v e rsio n *

Hun #1 ?

A t a b o u t 2p£°C th e same c o n v e rsio n was o b ta in e d i n tw o h o u rs , how ever

t h e b e d becam e s t i c k y a t th e e n d o f th e r u n re d u c in g th e r e a c tio n r a t e eon-*

s id e r a b ly .

Hun # 1 8

A t a b o u t 335 °0 th e same c o n v e rsio n was o b ta in e d i n s e v e n ty - f iv e min­

u te s * T he ru n w as i n te r r u p te d b y a n in c r e a s e i n s u lp h u r d io x id e r a t e due

t o a f a u l t y v a lv e * T he sam e s t i c k i n e s s was n o te d n e a r th e e n d o f th e r u n ,

t h e s t i c k y p o r tio n b e g in n in g a t th e f l u i d i z a t i o n p ro m o te r fo rm in g a h o llo w

cone e n d th e n d is in te g r a tin g *

C hanges P r i o r t o Hun #19

An e x te n s io n o f one f o o t w as a d d e d t o t h e to p o f th e r e a c t o r t o e lim in a te

t h e f l n i d i a a t i o n p ro m o te r a n d a ls o t o p re v e n t c a rry o v e r ( r e a c t o r num ber 7,

shown i n I l l u s t r a t i o n V II)*
 36

Run #19

The t e j ^ e r a t u r e r o s e g r a d u a lly fro m 2 6 0 ° t o 33Q°C* th e m la s tin g

tw o h o u rs a n d tw e n ty w L nutes t o g iv e a p ro d u c t o f 8&$ sodium s u lp h a te *

S oae s t i c k i n e s s m s s t i l l n o te d *

Run #20

A c o n tin u o u s ty p e r e a c t o r m s s e t u p t o t e s t i t s o p e m b i l it y (re *

a c t o r num ber 8)* th e g a s r a t e s ^rere s e t b e fo re in tr o d u c tio n o f s a l t *

T h e f i r s t s a l t t o f l e a iim sed i& tely s tu c k t o th e g la s s v e s s e l a t w id e ly

s c a t t e r e d p o in ts * m a in ly a t t h e c o n s tr ic tio n s re d u c in g t h e i r d i s a s t e r

a n d p r e v e n tin g downward flo w *

Hun #21

The sam e c o n d itio n s w ere u s e d a s i n th e p re v io u s ru n e x c e p t th e s a l t

m s s t a r t e d b e fo r e th e s u lp h u r d io x id e * O p e ra tio n m s s a t i s f a c t o r y f o r

a b o u t f i v e m in u te s when s o l i d fo rm ed a b o u t th e lo w e r c o n s tr ic tio n * liq u id

w as n o tic e d c o n d en se d t o a s i n g l e d ro p a t th e b o tto m o f th e r e a c to r *

C hanges P r io r t o Run #22

The s u lp h u r d io x id e l i n e was c o n n e c te d t o th e f u r n a c e o u t l e t in s te a d

o f th e f u rn a c e i n l e t t o p r e v e n t f o rm a tio n o f liq u id *
Bun #22

R e a c to r # 8 w as o p e ra te d a t a v a ry law th ro u g h p u t f o r f i f t y m in u te s

a t a te a a p e ra tu re o f 385°C a t th e same g a s c o a ic e n tra tio n p r e v io u s ly u sed *

T he p ro d u c t c o n ta in e d no s u lp h a te *
 37
ILLUSTRATION V II

R e a c to r Number 7

VXXB a n d VXXC a r e f a s t a c t io n p h o to ­
g ra p h s show ing th e p o s itio n o f th e
s a l t p a r t i c l e s w h ile t h e b e d i s
f X a id ie ln g ,

rase
 38

Run #23
The tesperature was raised as much as p ossib le by increasing the
fu e l rate to th e furnace* After fifte e n minutes at U2X°C the product
contained & trace o f sulphate estimated at one or two percent*
Hun #21*
A ca ta ly st added to the s a lt (*2# Ferric chloride) had no noticeable
affect* A trace of sulphate was again produced*
Run #25
The sulphur dioxide rate was increased ten fo ld causing a slig h t
improvement in yield* About three percent conversion was obtain© d in
th irteen admites»
Run #26

The reactor was reinsulated and wound with heater wire to give more
even heating* R esults were no b etter| only a trace of sulphate was pro­
duced in eig h ty -six minutes at about U71°G*
Run #2?
Reactor number 2 was in sta lle d to permit higher gas rates* A one h alf
inch bed of s a lt was used and operated for th irty -eig h t minutes a t maximum
rotameter readings of a ir and sulphur dioxide* A trace of sulphate was
found in the product*
Run # 2 6

Reactor number 9 a two stage combination p ara llel counter flow re­
actor was operated for about ten minutes a t 51*3°C* The product showed a
trace of sulphate*
 39

Shm #29

Reactor number ? uninsulated m operated with red iron oxid© added

as a c a ta ly s t* The am lsm m temperature obtainable i n t h e s a l t bed w a s
2liO°C* Ho conversion -was noted*
San #30
R e a c to r num ber 7 w a n d w ith h e a te r w ire an d i n s u l a t e d m s o p e ra te d

w ith r e d i r o n o x id e a d d e d t o t h e s a l t a s a c a ta ly s t* T he r e a c t o r tem pera**

t u r e a t th e to p o f t h e b e d r e a d ie d hOO^C b y laeans o f th e h e a tin g w ire

a lo n e , With, s a l t p r e s e n t t h e te m p e ra tu re re a c h e d 380®C a t t h e m a x im a
g a s m te * The te n ^ e r a tu r e w as much h ig h e r a t th e r e a c t o r i n l e t s in c e

th e r e a c t o r b e n t downward due t o i t s crm w e ig h t d u rin g th e ra n * T he pro*

cfeiet show ed a h e av y t r a c e o f su lp h a te *

C hanges P ries? t o Bun # 3 1

The f u r n a c e w as r e d e s ig n e d t o p ro d u c e h o t t e r g a s a t a lo w e r r a t e b y

i n s t a l l i n g s m a lle r h e a te r tu b e s o f one e ig h th in c h p ip e * in s u la tio n m s

p la c e d b etw een th e h e a te r w ire a n d r e a c t o r t o re d u c e l o c a l o v e rh e a tin g *

Bun # 3 1

The r u n m e s t a r t e d a t a r e a c t o r teugje n a tu re o f *»20®C, A c h a rg e d

o f t h i r t y gram s o f s a l t w as u s e d t o w h ich a b o u t f i v e grains o f i r o n o x id e

re d u c e d fro m t h e s u lp h a te m » a d d e d . A f te r se v e n m in u te s th e te m p e ra tu re

h a d re a c h e d 6O0°C a n d f l u l d l s a t i a n ceased * A t a te m p e ra tu re o f 5Uo°0

som e sm oke w as n o te d e s c a p in g fro m th e r e a c t o r e x it# The e n t i r e b ed

h a d s o l i d i f i e d w ith a s m a ll h o le th ro u g h one s id e o f i t # A la r g e f u s e d
 ko

eafce h a d fo rm ed w h ich c o n ta in e d a p p r e c ia b le su lp h a te * t h e to p p o r tio n

o f t h e b e d h ad becom e d a rk g r a y i n c o lo r in d ic a tin g a chan ge i n fo rm o f

t h e i r o n o x id e*

Bun #32

A b la n k w as ru n w ith o u t c a t a l y s t f o r com parison* The sam e t r a c e o f

s u lp h a te w as fo u n d a s p re v io u s ly *

Run #33

A f o r t y gram c h a rg e o f s a l t w ith f i v e gram s o f a c tiv a te d ir o n o x id e

e& t& ly st w ere f l n i d i a e d a t p r o g r e s s iv e ly h ig h e r tem p eratu re® u n t i l r e a c tio n

w as n o te d b y a sam ple t e s t e d w ith b a riu m c h lo r id e s o lu tio n * R e a c tio n b eg an

a t a b o u t 1*90 °C a n d in c r e a s e d slo w ly w ith r i s e i n te m p e ra tu re u n t i l th e

aaadvBUB o b ta in a b le w as rea ch e d * A f te r p r o g re s s iv e in c r e a s e s th e tem p era*

t o r e w as m a in ta in e d a t 5 8 5 °c f o r tw e n ty -tw o m in u tes* The p ro d u c t o f t h i s

ru n c o n ta in e d %% s a l t cake*

Hun §3k

An u n s u c c e s s f u l a tte m p t w as made t o s w itc h fro m s u lp h u r d io x id e t o

tr lo x L d e b y h e a tin g oleum an d p a s s in g i t i n to th e system * The s u lp h u r ic

a c i d w as a ls o p a r t i a l l y v a p o riz e d a n d i n c o n d en sin g i n th e r o ta m e te r p re ~

v e n te d s a t i s f a c t o r y o p e r a tio n .

C hanges P r i o r t o Hun #35

The v e ry low r e a c tio n r a t e s n o te d i n th e r u n s w here s u lp h u r d io x id e

w as in tr o d u c e d a t t h e f u rn a c e o u t l e t l e d t o th e c o n c lu sio n t h a t f a s t e r

r e a c tio n w o u ld o c c u r i f th e s u lp h u r d io x id e w ere f i r s t o x id is e d t o th e
 la.

to d .o x id e a n d th e n com bined w ith t h e w a te r v a p o r t o p ro d u ce g a se o u s m&»

p h u r ic a c i d . C o n se q u e n tly a c a t a l y s t cham ber m s i n s t a l l e d i n th e fu rn a c e *

She c a t a l y s t c o n s is te d o f ir o n o x id e s u p p o rte d on a s b e s to s f i b r e c o n ta in e d

i n a f o u r f o o t s e c tio n o f h a l f in c h p ip e * The c a t a l y s t m e made an d a c t i ­

v a te d b y re d u c in g i r o n s u lp h a te i n a m u ffle fu rn a c e a t 650°C*

Hun #35
P r i o r t o in tr o d u c tio n o f s a l t an d f u e l t o t h e f u r n a c e th e r e a c tio n

g a s w as a n a ly s e d f o r s u lp h u r d io x id e b y a b s o r p tio n i n io d in e s o lu tio n

a n d a l s o b y a b s o r p tio n i n d i l u t e c a u s tic s o lu tio n * The g a s m s fo u n d

t o c o n ta in k*& s u lp h u r d io x id e * The f u r n a c e m s h e a te d a n d a se c o n d

a n a ly s is show ed s u lp h u r d io x id e t o b e X*d$ b a se d on a b s o r p tio n i n io d in e

s o l u t io n . The c a u s tic g av e th e p e r c e n t o f b o th s u lp h u r d io x id e an d t r i ­

o x id e a s 2.7%* The d e c re a s e w as assum ed t o be c a u se d b y a b s o r p tio n o f

g a s b y th e c a t a l y s t s in c e e q u ilib riu m w as p ro b a b ly n o t s e t up when th e

a n a l y s i s w as made* o r b y c o n d e n sa tio n o f s u lp h u r ic a c id gas i n t h e c o o l

s a i l i n g tu b e s . The a n a ly s is o f th e g a s le a v in g th e r e a c t o r a f t e r te n

m in u te s o f o p e r a tio n w ith s a l t i n th e r e a c t o r show ed *5£% s u lp h u r d io x id e

b a se d on a b s o r p tio n i n io d in e s o lu tio n a n d *53% o f b o th g a se s b a a e d on

c a u s tic s o lu tio n * I t i s b e lie v e d t h a t th e p e rc e n t o f s u lp h u r t r i o x i d e

p r e s e n t I n th e l a s t a n a l y s i s i s n e g lig ib le s in c e th e u s u a l smoke w h ich

i n d i c a t e s t h e p re s e n c e o f s u lp h u r t r io x i d e d is a p p e a rs c o m p le te ly when

s a l t i s p la c e d on th e r e a c to r * The d if f e r e n c e i n th e l a s t tw o v a lu e s

i s w ith in th e e x p e rim e n ta l e r r o r o f th e a n a ly s is . The ru n m s c o n tin u e d

 U2

f o r a n h o u r u n t i l th e f a u l t y o p e ra tio n o f th e s u lp h u r d io x id e ro ta m e te r

c a u se d i t s te r m in a tio n . The p ro d u c t a n a ly s e d 37$ sodium c h lo rid e # The

a v e ra g e te m p e ra tu re w as 3kO°G* A s l i g h t am ount o f cake w as fo u n d a t th e

b o tto m o f th e r e a c to r *

Run #36

A lo w e r te m p e ra tu re o f 230*C m s u s e d t o im p ro v e c o n v e rs io n o f © u l-

p h u r d io x id e , b u t th e s a l t becam e s t i c k y a f t e r o n ly te n m in u te s o p e ra tio n #

A c ak e h a d fo rm ed i n th e b o tto m o f th e r e a c to r # $

C hanges P r io r t o Run #37

T he h u m id ity o f th e a i r w as re d u c e d t o lo w e r t h e p a r t i a l p r e s s u r e

o f s u lp h u r ic a c id g a s a n d th u s p re v e n t i t s c o n d e n sa tio n # An e x te r n a l

h e a t e r m s ad d ed t o t h e u p p e r p o r tio n o f th e r e a c to r a n d th e v o lta g e

m s re d u c e d on th e in n e r h e a t e r s in c e e x c e e d in g ly h ig h te m p e ra tu re s w ere

fo u n d t o e x i s t i n t h e i n l e t tu b e a t th e b a se th u s e x p la in in g th e b en d in g

o f t h e g la s s i n ru n #31 a n d # 3 2 .

Run #37

T he a v e ra g e te m p e ra tu re w as 3fcOOC# The dew p o in t o f th e a i r a t

t h e s t a r t o f th e ru n w as 21*1*0 a n d a t th e end was 30*0# The r u n p ro ­

g r e s s e d sm o o th ly f o r t h r e e h o u rs w ith o u t a n y s ig n s o f s tic k in e s s # A

sam p le ta k e n fro m t h e b e d a n a ly z e d 96*5$ s a l t cak e b a s e d on a c h lo r id e

a n a ly s is o f 3 #5$ sodium c h lo rid e # The r e a c t o r show ed no s ig n s o f cak e

a n d th e p ro d u c t w as u n ifo rm i n a p p e a ra n c e e x c e p t f o r a few b a l l s t h a t

h a d fo rm e d fro m d ro p s o f a d d w hich h ad co n d en sed on th e e x i t tu b e a n d

d ro p p ed b a c k i n t o th e bed*

Ran #38
The o p e r a tio n w ith o u t c ak in g o r s t i c k in e s s m y h a w b een doe t o r©«*

d a c e d l o c a l o v e rh e a tin g o r re d u c e d h u m id ity * T h is ru n W e made a t a n

a i r dew p o in t o f 32*2°C w ith a m ix tu re o f g ro u n d ro c k © a lt f i n e r th a n

s i x t y - f i v e mesh* S tic k in e s s a n d c a k in g w as n o te d a f t e r t h i r t y m inute©

o p e ra tio n * The p ro d u c t a n a ly s e d H # sodium C h lo rid e#

Rim #3P

Run # 3 8 was r e p e a te d u s in g t a b l e s a l t , b u t p lu g g in g en d ed th e ru n

a f t e r s e v e n ty - th r e e m in u tes* I t w as c o n c lu d e d t h a t t h e dew p o in t was

to o h ig h *

Rim ih O

The a i r s tre a m was s p l i t , p a r t b e in g s e n t th ro u g h th e h u i^ d ify X n g

to w e r th e re m a in d e r was s e n t d i r e c t l y i p t h e fu rn a c e * T h is a rra n g e m e n t

p e r m itte d c o n tr o l o f th e a i r dew p o in t* R e a c to r num ber 6 w as ja c k e te d

w ith a g la s s tu b e upon w hich h e a te r w ire w as wound# The te m p e ra tu re o f

t h e r e a c t o r re a c h e d ZhO^O u t i l i s i n g th e h e a tin g w ire o nly* The u n i t was

o p e ra te d f o r a b o u t two h o u rs a t w ere r a t e o f s o l i d rem o v al s in c e th e

b o tto m o u t l e t c ak e d fro m l i q u i d c o n d e n sa tio n * No cak e fo rm ed d u rin g th e

o p e r a tio n i n th e u p p e r p a r t o f th e r e a c t o r , b u t a few p a r t i c l e s o f s a l t

s tu c k t o t h e g la s s in th e u p p erm o st s e c tio n s * T h is p ro b a b ly o c c u rre d

d u e t o t h e f a i l u r e o f th e ja c k e t h e a te r to p ro v id e s u f f i c i e n t h e a t i n

t h a t s e c tio n * The p ro d u c t a n a ly s e d sodium c h lo rid e *

 DISCUSSION CF BESUIM

O b s e rv a tio n o f th e b e h a v io r o f th e bed o f s o U d i n th e f i r s t ru n s

a t a te m p e ra tu re o f a b o u t S20©€ in d ic a te d t h a t a l i q u i d was b e in g fo rm ed

on th e s u r f a c e o f th e s a l t a s a r e s u l t o f th© r e a c t i o n , an d t h i s l i q u i d

c a u se d th e p a r t i c l e s t o s t i c k to g e th e r t o fo rm a s o l i d cake# The assum p­

t i o n w as made a t f i r s t t h a t sodium s u lp h a te m s p ro d u ce d on th e s a l t

s u r f a c e a n d th e h e a t o f r e a c tio n may h av e b een h ig h enough to r a i s e th e

s u r f a c e te m p e ra tu re t o th e m e ltin g p o in t o f th e e u te c t i c w hich i s 623°C#

I n a n a tte m p t t o overcom e t h i s c a k in g a c o n ic a l sh ap ed r e a c t o r w as ,

u s e d w hich p e r m itte d g r e a t e r a g it a t i o n o f th e s a l t ! L onger ru n s w ere

th e n o b ta in e d a t a lo w e r te m p e ra tu re o f a b o u t MjQOC b u t th e same c a k in g

c o n d itio n s w ere fo u n d t o e x is t# S e v e ra l ch an g es w ere made to e lim in a te

c o m p le te ly th e e x is te n c e o f a n y s a l t w hich m s n o t I n m otio n i n th e g as

stream * When t h i s w as acco m p lish ed * r e a c tio n w as e v id e n t a t a s t i l l

lo w er te n p e r a tu r e o f 220°C a n d th e w e ig h t o f cak e f orm ed w as re d u c e d t o

a b o u t one p e r c e n t o f th e ch arg e# A h ig h e r te m p e ra tu re o f 260°C w ith th e

im proved a p p a r a tu s , employed, to o b ta in a h ig h e r r e a c tio n r a t e , w as .un­

s a t i s f a c t o r y due t o a n in c r e a s e i n th e am ount o f cake#

A r e d u c tio n i n c o n c e n tra tio n o f s u lp h u r d io x id e was th e n c o n s id e re d

a s a m eans o f lo w e rin g th e r a t e o f c o n v e rsio n i n o rd e r to d e c re a s e s u r f a c e

temperature* The ru n was s t a r t e d a t th e u s u a l c o n c e n tra tio n and when th e

te n d e n c y o f th e s a l t p a r t i c l e s t o s t i c k to g e th e r was n o te d , a r e d u c tio n

i n th e s u lp h u r d io x id e flo w r a t e was fo u n d t o e lim in a te t h i s te n d e n c y

hh
m o m en tarily * C o n tin u e d re d u c tio n o f th e s u lp h u r d io x id e r a t e a t i n t e r ­

v a ls p e r m itte d th e r e a c tio n t o p ro c e e d to e ig h 1y**nine p e r c e n t co n v ersio n #

The a p p e a ra n c e o f co n d en sed l i q u i d on th e w a lls o f th e r e a c to r p ro m p ted

th e r e d u c tio n o f th e e a t e r v a p o r c o n c e n tr a tio n i n th e f o llo w in g ru n w hich

a c h ie v e d p r a c t i c a l l y co m p lete c o n v e rs io n , a lth o u g h © tickings© w as n o tic e a b le #

A t t h i s s ta g e i n th e dev elo p m ent s e v e r a l a ssu m p tio n s w efe made ba 'e d

on th e o b s e r v a tio n o f l i q u i d c o n d e n sa te w hich a p p e a re d d u rin g t h ^ r e a c t i o n

a t low te m p e ra tu re s * Some o th e r e x p la n a tio n o f s t ic k in e s s a n d cak e f orma­

t i o n w as so u g h t th a n th e o r i g in a l assu m p tio n o f h ig h s u r f a c e te is p ^ d tu r e #

The fo rm a tio n o f cak e a t lo w e r te m p e ra tu re s a s w e ll a s th e a p p e a ra n c e

o f c o n d en sed l i q u i d in d ic a te d t h a t th e r e m ig h t be a d i f f e r e n t e x p la n a tio n

f o r th e u n s a t is f a c to r y o p e ra tio n * The a p p e a ra n c e o f m is t a t th e sc ru b b e r

o u t l e t w h ich h a d th e o d o r o f s u lp h u r t r i o x i d e l e d t o th e s u p p o s itio n t h a t

s u lp h u r d io x id e w as b e in g p a r t i a l l y o x id iz e d i n th e fu rn a c e tu b e s t o fo rm

s u lp h u r t r i o x i d e w hich r e a c te d w ith th e w a te r v a p o r p r e s e n t t o fo rm s u l*

p h u r ic a c id gas* The c o n d e n sa tio n o f t h i s s u lp h u r ic a c id g a s on th e c o a le r

s u r f a c e s o f th e r e a c t o r w ould e x p la in th e a p p e a ra n c e o f th e liq u id #

To p re v e n t th e s e r e a c tio n s w hich form ed s u lp h u r ic a c id g as i n th e

f u r n a c e tu b e s th e s u lp h u r d io x id e w as in tr o d u c e d i n to th e a i r s tre a m a t

th e f u r n a c e e x i t r a t h e r t h a t th e f u rn a c e e n tra n c e * T h is ch an g e, b e s id e s

e lim in a tin g th e u n d e s ir a b le e f f e c t s a ls o re d u c e d c o n s id e ra b ly th e r a t e

o f c o n v e rs io n t o th e s u lp h a te * The r a t e w as p r a c t i c a l l y a e ro u n t i l th e

te n p e r& tu re w as r a i s e d t o a b o u t !i50 °C* A t $ 8£oc o n ly f i v e p e r c e n t

c o n v e rs io n w as o b ta in e d i n a b o u t tw e n ty - f iv e m in u tes* S t i l l h ig h e r tem ­

p e r a tu r e s w are em ployed b u t t h e b ed s o l i d i f i e d t o fo rm a h a rd cak e w h ich

m s assu m ed t o b e c a u se d b y th e fo rm a tio n o f th e l i q u i d e u te c tic * A c ti­

v a te d i r o n o x id e m ixed w ith th e s a l t m s u s e d a s a c a t a l y s t i n t h e s e h ig h

te m p e ra tu re ru n s* a n d s u lp h u r ic a c i d m is t m s n o te d is s u in g fro m th e re *

a c t o r a f t e r fo rm a tio n o f th e c a k e m en tio n ed i n th e p re v io u s se n te n c e #

The c o n c lu s io n w as th e n re a c h e d t h a t s u lp h u r t r i o x i d e m s fo rm ed i n th e

f u r n a c e tu b e s i n a l l o f t h e e a r l i e r ru n s a n d a l s o t o some e x te n t i n t h e

r e a c t o r i n th e l a t e r ru n s i n w hich t h e s u lp h u r d io x id e b y -p a s se d th e

fu rn a c e a n d e n te r e d th e s a l t b e d c o n ta in in g ir o n o x id e a s a c a ta ly s t*

On th e b a s is o f t h i s c o n c lu sio n * t h e e a r l y e x p e rim e n ts in d ic a te d ,

t h a t t h e p re s e n c e o f a p p r e c ia b le am ounts o f s u lp h u r t r io x i d e a t h ig h

te m p e ra tu re c a u se d r a p id fo rm a tio n o f s o l i d cake* L a te r h ig h e r te m p e ra ­

t u r e e x p e rim e n ts sh o v ed t h a t t h e in tr o d u c tio n o f s u lp h u r d io x id e d i r e c t l y

i n t o th e r e a c t o r w ith c o n se q u e n t lour s u lp h u r t r io x i d e c o n c e n tr a tio n p e r ­

m itte d s a t i s f a c t o r y o p e ra tio n b u t low r e a c tio n v e lo c ity * C om parison o f

th e s e tw o ty p e s o f o p e ra tio n a t h ig h te m p e ra tu re shone t h a t th e r e a c tio n

r a t e depend s on t h e s u lp h u r t r i o x i d e c o n c e n tra tio n * W ith a p p re c ia b le

am ounts o f s u lp h u r t r i o x i d e p re s e n t* lo w e r te m p e ra tu re s re d u c e d th e r a t e

o f r e a c tio n a s w e ll a s th e te n d e n c y to w a rd s tic k in e s s * The im m ed iate

c a u se f o r c a k in g o r s t i c k i n e s s m e assum ed t o b e th e fo rm a tio n o f l i q u i d

on t h e s u r f a c e o f t h e s a l t p a r t i c l e w hich r e s u l te d e i t h e r fro m th e a p ­

p e a ra n c e o f a m e lte d s o l i d on th e s u r f a c e o r from l i q u i d c o n d e n sa tio n *

 ky

H igh tc a p e im tu r a s o f a b o u t SOO°C w ere fo u n d t o f o m c a k e w h ich w as &&■»

sum ed t o r e s u l t fro m t h e fo rm a tio n o f a l i q u i d p ro d u c t m th e s o l i d

su rfa c e . L o se r te m p e ra tu re s o f a b o u t $1*Q°C w ere fo u n d t o c a u se stick !* *

n e s s w h ich w as assum ed t o r e s u l t fro m c o n d e n sa tio n o f s u lp h u r ic a d d

gas* A t in te r m e d ia te te m p e ra tu re s o f 300 t o 350°C b o th e f f e c t s w ere

n o tic e a b le u n t i l th e w a te r v a p o r c o n te n t o f th e a i r w as re d u c e d below

t h a t em ployed i n a n y o f th e p re v io u s ru n s* T h is w as a cc o m p lish e d i n

ru n # 3 7 . The p e rc e n ta g e c o m p o sitio n o f th e g a s u se d in ru n #37 i s shown

b e lo w ;

Mol %
A ir 92*3

u & te r T hpor 3*0

S u lp h u r Bio3d.d e Ju 7

13 q£5>

U nder th e s e c o n d itio n s a t a te m p e ra tu re o f 3hO°C n e i t h e r c a k in g n o r

s t i c k i n e s s w as n o te d th ro u g h o u t t h e o p e ra tio n *

B eg in n in g w ith ru n #15 a te c h n iq u e w as d e v e lo p e d f o r w ith d raw in g

sam p les fro m th e r e a c t o r d u rin g th e run* C hem ical a n a ly s is o f th e s e

sam p les fo rm t h e b a s is f o r r e a c tio n r a t e d ata* The v a r i a ti o n o f th e

f r a c t i o n r e a c te d w ith tim e f o r s e v e r a l ru n s i s shown in F ig u re 6 * The

s lo p e o f t h e l i n e i s i n d ic a t i v e o f t h e sp e e d o f re a c tio n * g r e a t e r © lope

in d ic a tin g h ig h e r r e a c tio n r a te # In o r d e r t o in c lu d e th e d a ta fro m th e

v a r io u s r u n s on a s in g le p l o t f o r co m p arison p u rp o se s* c o r r e c tio n s f o r

i n i t i a l tim e* w e ig h t o f s a l t c h a rg e d , an d w e ig h t o f sam p les w ith d raw n

 FIG.6 REACTION RATES
RUN .57

RIJN 1$

.8

F
.6
fraction
reacted
.4

.2

0
0 20 40 60 80 100 120 14 0

Time min.
 h9

h a v e b een a p p lie d * E q u iv a le n t g a s c o n c e n t r a t i ons w e re u se d w ith th e e x -

c e p tio n o f ru n #37 w hich h a s l e s s w a te r v a p o r th a n th e o th e r ru n s*

P h o to m icro g rap h s o f t h e p ro d u c ts o f r e a c tio n a t v a rio u s d e g re e s o f

c o n v e rs io n ( s e e I l l u s t r a t i o n s V III an d IX ) show t h a t t h e o r i g in a l sh a p e

o f th e p a r t i c l e i s m a in ta in e d th ro u g h o u t th e r e a c tio n w ith th e e x c e p tio n

o f th e c o m e rs ufolch become ro u n d ed , £&a r tic le s w hich w ere p a r t i a l l y con­

v e r te d w ere b ro k e n u n d e r th e m icro sco p e a n d w ere f ound t o c o n s is t o f c u b ic

sh a p e d s h e l ls o f gaaa.11 c r y s t a l s e n c lo s in g a sm ooth c o re o f tr a n s p a r e n t

s a lt, ( s e e I l l u s t r a t i o n X)» The th ic k n e s s o f th e s h e l l su rro u n d in g th e

s a l t v a r ie d i n p r o p o r tio n t o th e c o n v ersio n * in d ic a tin g p r o g r e s s iv e ly

d e e p e r p e n e tr a tio n o f th e r e a c tio n su rfa c e * The l i n e a r r e l a t i o n betw een

t h e f r a c t i o n r e a c te d an d th e tim e in d ic a te s t h a t th e e x p o su re o f s a l t

s u r f a c e t o th e g a s d o es n o t c o n tr o l th e r e a c tio n r o te u n t i l th e c o n v e r­

s io n i s n e a r co m p letio n *

The u t i l i s a t i o n o f s u lp h u r d io x id e m s n o te d t o v a ry w ith th e tem p era ­

tu r e ., t h e h ig h e r te m p e ra tu re s c a u s in g h ig h e r r e a c tio n m t e a n d co n su m p tio n o f

ho r e s u lp h u r d io x id e * In th e s in g le s ta g e r e a c t o r a t 3hO°C t h e s u lp h u r a p p e a r­

in g i n t h e p ro d u c t am ounted t o a b o u t t e n p e r c e n t o f th e s u lp h u r c h a rg e d a s

s u lp h u r d io x id e * l a r e a c t o r num ber 8 u se d i n ru n $ iQ a b o u t tw e n ty p e r c e n t o f

th e s u lp h u r c h a rg e d a s g a s a p p e a re d i n th e s o l i d p ro d u c t* S in c e r e a c t o r num ber 8

h a s a d e e p e r b e d f o r t h e same w e ig h t o f s a lt* th e d a ta i n d ic a t e s a n a d v a n ta g e n a y

be g a in e d by c o u n te r c u r r e n t o p e ra tio n * A m ore e f f i c i e n t c o n v e rs io n o f t h e

s u lp h u r d io x id e t o th e t r i o x i d e a n d o p e ra tio n o f a c o u n te r c u r r e n t ty p e
 50
m u s m T io H t t eii

VXXIA T a b le S&lb VXIIB $% C o n v ersio n

VHXC C o n v ersio n TOO® 3<& Conversion

 51
xum m aio® xx

IXC 9 2 , 3$ C onversion HD 96*7? Conversion

 52

imsTRmciii x

xi XB

P a r t i c l e s o f s a l t 8C$ c o n v e rte d
f r a c t u r e d u n d e r th e m icro sco p e# Mote
th e tr a n s p a r e n t c o re o f sodium c h lo ­
r i d e i n th e c e n te r o f I l l u s t r a t i o n M *
a n d t h e tw o la y e r s o f th e s h e l l below
th e c e n te r i n I l l u s t r a t i o n XB#
tta it a p p e a r to be th e in d ic a te d im provem ents n ecessary im p i l o t p l a n t
d e v elep fflsn t o f t h e p ro c e s s *
 THEORETICAL ASPECTS OS’ THE REACTION

T he o v e r a ll r e a c tio n i s shown b elo w l

2 NaCl (*) / % o Cg) / SQ^ Cg) / $Gfe (g) — ► SagSOjj (a) / 2 HCi (g) (i)
t h e r e a c tio n i s ex o th erx o ic a t 25 °C a s i n d ic a te d b y a v a lu e f o r

o f -*1*9*300 c a lo r ie s * th e p r o b a b i l it y t h a t i t w i l l p ro c e e d i n th e d ire o *

tn o n shown i s i n d ic a te d a s f a v o r a b le b y a v a lu e o f -3 7 * 2 0 0 c a l o r ie s fo r

a t 25oc*

I t i s re a s o n a b le t o assum e t h a t t h e r e a c tio n m ust o c c u r i n s te p s s in c e

t h e sim u lta n e o u s c o l l i s i o n o f t h e f o u r r e a c ta n ts i s h ig h ly iu p r o b a b ie a s

i s a l s o t h e sim u lta n e o u s a d s o r p tio n o f th e th r e e g a s e s on th e s u r f a c e o f

th e s a lt* T h ere a r e many p o s s ib le w ays th e r e a c tio n may be b ro k e n down

i n t o s h o r t e r s te p s * The m ost l o g ic a l p a th f o r a g iv e n s e t o f c o n d itio n s

o f te m p e ra tu re * p re s s u re * a n d c o n c e n tr a tio n s may b e ded uced fro m t h e prow

v io u s ly o b se rv e d b e h a v io r o f th e r e a c ta n ts *

Two r e a c tio n s c o n s id e re d t o b e in v o lv e d i n th e p ro c e s s a r e th e fo llo w in g *

ao^ (g) / itfc (g) • soj Cg) (2 )

so3 (g ) / % 0 Cg) « HgSOk (g ) (3 )

The e q u ilib riu m c o n s ta n ts f o r b o th a r e shown i n F ig u re 7 a s a f u n c tio n o f

te m p e ra tu re * X t i s n o te d t h a t a lo w te m p e ra tu re f a v o r s th e fo rm a tio n o f

b o th s u lp h u r tx io x id e a n d s u lp h u r ic a d d g a s an d h ig h te m p e ra tu re in c r e a s e s

th e r a t e o f a p p ro a ch t o e q u ilib riu m w ith h ig h e r c o n c e n tra tio n © o f th e r e ­

a c ta n ts * M e llo r (5 ) s t a t e s t h a t th e s te p s ta lc in g p la c e i n th e H a rg re a v e s

5k
 FIG 7 EQUILIBRIUM CONSTANTS
+2

loq K

-2

-33 -------- :----------1— 1— 1— 1— -------- — 1— --------------------------- ------------------ --------- --------- — 1—

0 200 400 600 800 1000 1 200 1400
TEMPERATURE *C
r e a c t i o n a t 500^6 a r e f i r s t th e r e a c tio n o f s a lt* s u lp h u r d io x id e * a n d

w a te r t o fo rm sodium s u lp h ite a n d h y d ro c h lo ric a c id an d seco n d th e rm>

a c t io n o f sodium s u l p h i te a n d oxygen t o fo rm sodium s u lp h a te # T hese

r e a c tio n s a r e shown below *

2 HaCX ( s ) / HjO (g ) / SOg (g ) Na^SOj ( s ) / 2 HBl (g ) (fa)

(Si
T h is d o e s n o t e x p la in th e f u n c tio n o f th e I r o n c a ta ly s t#

T he e x p e iim e n ta l r e s u l t s a s w e ll a s th e e q u ilib riu m d a ta p r e v io u s ly

m e n tio n e d i n d i c a t e a d i f f e r e n t m echanism fro m t h a t su g g e s te d b y M e llo r

a t a l o n e r te m p e ra tu re o f a b o u t 300°C . T h e re i s a ls o some d o u b t o f th e

m echanism m en tio n e d b y M e llo r a t th e h ig h e r te m p e ra tu re # The lo w e r tem ­

p e r a t u r e f a v o r s th e fo rm a tio n o f s u lp h u r ic a c id g as* a n d s u lp h u r ic a c id

r e a c t s r e a d i l y w ith s a l t t o fo rm th e b is u lp h a te an d h y d ro g en c h lo r id e

a c c o rd in g t o th e re a c tio n *
HjSO^ / NaCl —► UaHSOj^ / HC1 ( 6)
The e x is te n c e o f t h i s r e a c tio n i s in d ic a te d b y idle d is a p p e a ra n c e o f th e

f a m i l i a r s u lp h u r ic a c i d m is t fro m th e r e a c t o r o u t l e t when s a l t i s p la c e d

i n t h e r e a c to r #

The f i n a l s te p o f fo rm a tio n o f sodium s u lp h a te may o c c u r i n s e v e r a l

ways# I t i s p ro b a b le t h a t th e sodium b is u lp h a te fo rm ed fro m s a l t an d

s u lp h u r ic a d d g a s i s r a p id ly tra n s fo rm e d i n t o sodium p y ro s u lp h a te s in c e

th e b is u lp h a te decom poses r e a d i l y a t th e r e a c tio n te m p e ra tu re t o fo rm th e

p y ro s u lp h a te a n d m t e r a c c o rd in g t o th e f o llo w in g e q u a tio n i

2 NaHSO^ _ * » H a g S * ^ yf % 0 (7 )

The f i n a l s te p i n th e r e a c tio n n a y th e n he a s fo llo w s#

K*2$2°7 * 2 NaC1 / % 0 - * * 2 Na^SOu / 2 HC1 (8 )

(T he c o m b in a tio n o f e q u a tio n s ( ? ) an d (8 ) i s th e se co n d s t e p i n th e Mann*

h elm re a c tio n * ,}

T h e re a r e a f e e o b s e rv a tio n s i n f a v o r o f t h i s h y p o th e sis* One IS

t h e o b s e r v a tio n t h a t p u re sodium h i s u lp h a te when h e a te d , b e g in s t o de*

com pose a t a b o u t 150©C fo rm in g a s o lu tio n o f th e p y ro s u lp h a te an d th e

b is u lp h a te * C o n tin u e d h e a tin g c a u se s e v o lu tio n o f b u b b le s o f w a te r

v a p o r fro m & v is c o u s s o lu tio n w hich d oes n o t fo rm a d r y s o l i d a s th e

te s p e r a tu r e i s ra is e d * T he m e ltin g p o in t o f th e p y ro s u lp h a te i s hOG*9<>C*

T h is d e c o m p o sitio n o c c u rrin g on th e s u r f a c e o f th e s a l t w ould p ro v id e

s u i t a b l e c o n d itio n s f o r th e r e a c tio n p ro p o sed *

M ic ro sc o p ic e x a m in a tio n o f th e s u rfa c e s h e l l o f p a r t i c l e s h a s re-*

v e a le d th e e x is te n c e o f tw o d i s t i n c t la y e r s b e s id e s th e c o re o f s a lt*

( s e e I l l u s t r a t i o n XX) The in te r m e d ia te la y e r may be th e in te r m e d ia te

p ro d u c t* T h e re i s l i t t l e d o u b t t h a t one o r th e o th e r o f th e in te rm e ­

d i a t e p r o d u c ts e x i s t s i n s iz a b le p r o p o r tio n s d u rin g th e o p e r a tio n s in c e

th e h ig h a c i d i t y v a lu e s on some sam p les c a n n o t b e a c c o u n te d f o r b y coi>*

d e n sed s u lp h u r ic a d d a lo n e , e s p e c i a l l y s in c e th e sample© a p p e a r bone dry*

A n o th e r r e a c tio n w hich m ust be c o n s id e re d a lo n g w ith th e o th e r s p ro ­

p o se d i s th e fo llo w in g i

—a* KagSOii. / SOy (9 )

 XLLU3m.TI0K XX

XXB

A p a r t i c l e of s a l t converted
f r a c tu r e d under th e microscope • I l l u s ­
t r a t i o n XIA shews th e p a r t i c l e a f t e r
th e i n i t i a l fra c tu re * I l l u s t r a t i o n
XIB shows th e sane p a r t i c l e more com­
p l e t e l y broken* Mote th e co n c en tric
la y e r s o r s h e lls#
 59

A c c o rd in g t o Jo h n sto n e (6 ) t h i s occur© above 300°^* The c o n tr ib u tio n o f

t h i s r e a c t i o n t o th e am ount o f f i n a l p ro d u c t i s c o n s id e re d s l i g h t due

t o t h e slo w d e c o u p o sitio x i r a t e a t th e r e a c tio n te m p e ra tu re * The r e a c tio n t

2 N aCl / HgSO^ f 2 HG1 (1 0 )

may a c c o u n t f o r a p o r tio n o f th e p ro d u c t a ls o *

H ie m echanism o f th e r e a c tio n -was c o n s id e re d i n o r d e r t o e x p la in

0
a n d h e lp overcom e th e d i f f i c u l t i e s e n c o u n te re d i n a c c o m p lish in g th e pri«*

m ary aim o f th e in v e s tig a tio n * th e a p p lic a tio n o f th e f l u i d i c e d s o lid s

te c h n iq u e t o th e m a n u fa c tu re o f sodium s u lp h a te * The d i f f i c u l t i e s o f

c a k e fo rm a tio n e n c o u n te re d a t h ig h s u lp h u r d io x id e *r_d w a te r co ncentre-*

t i c n s a r e e x p la in e d b y th e m echanism p ro p o se d s in c e a t th e s e c o n c e n tra tio n s

a h ig h r a t e o f fo rm a tio n o f th e l i q u i d in te r m e d ia te s ( b is u lp h a te an d

p y r o s u lp h a te ) w ould occur* H ie r a t e o f rem ov al o f th e s e l i q u i d p ro d u c ts

by r e a c tio n t o fo rm sodium s u lp h a te an d h y d ro g en c h lo r id e i s in d e p e n d e n t

o f t h e c o n c e n tr a tio n o f th e g a se s s in c e t h e r e a c tio n o c c u rs i n th e l i q u i d

p h ase* As i n t h e Mannheim re a c tio n * h ig h te m p e ra tu re f a v o r s th e r a p id

c o u p le t! o n o f t h e f i n a l s te p * The d i f f i c u l t y e n c o u n te re d a t lo w te m p e r s

to r e * th e c o n d e n s a tio n o f th e s u lp h u r ic a c id on th e s a l t a n d on th e

r e a c t o r I t s e l f * i s d i r e c t l y c o n n e c te d t o th e c ak in g d i f f ic u lt y * Too

l a r g e a c o n c e n tr a tio n o f w a te r v a p o r a n d s u lp h u r d io x id e p e ir a lt th e

p a r t i a l p r e s s u r e o f s u lp h u r ic a d d g as t o re a c h th e dew p o in t* w ith re *

e o l t a a t s t i c k i n e s s an d cak in g * The p a x t i a l p r e s s u r e o f 99*%3$ a n d 9 &*&$(

s u lp h u r ic a d d a r e shown i n F ig u re 8* T h is s tic k y c o n d itio n i s n o tic e a b le

 FIG. 8
PARTIAL P R E S S U R E
of
SULPHURIC ACID
500

400

300

200
PARTIAL
PRESSURE

mm. Hq,

100

80

60

40

30
200 220 240 260 280 300

TEMPERATURE °C
 61

i n th o s e ru n s w here s a t i s f a c t o r y r e a c tio n r a t e s a n d o p e ra tio n w ere ob­

t a i n e d u n t i l h ig h c o n v e rs io n s w ere reach ed * A t t h i s p o in t s t i c k i n e s s

w as s e e n t o becom e m ore s e v e re a s c o m re rsic n in c re a s e d * u n t i l th e bed

o f s o l i d s to p p e d f l u i d i s i n g c o m p letely * A t low c o n v e rsio n s i n th e e a r ly

p a r t o f th e ru n th e s u lp h u r ic a c id g as m s rem oved r a p id ly enough by r e ­

a c tio n w ith th e s a l t t o p re v e n t i t s re a c h in g th e denar p o in t* As th e ra n

p ro g re s se d * t h e r a t e o f rem o v al o f s u lp h u r ic a c id g a s d e c re a se d p e rm it­

t i n g i t s p a r t i a l p r e s s u r e t o r i s e u n t i l c o n d e n sa tio n to o k p la c e * Ih is

d i f f i c u l t y w as overcom e b y th e r e d u c tio n o f th e c o n c e n tra tio n s o f s u lp h u r

d io x id e a n d w a te r v a p o r t o su ch an e x te n t t h a t th e p a r t i a l p r e s s u r e o f

s u lp h u r ic a c i d g a s rem ain ed below th e dew p o in t o f s u lp h u r ic a c id th ro u g h ­

o u t th e run*
 s u m ia

T he p ro b lem u n d e r i n v e s tig a tio n was th e a p p lic a tio n o f th e te c h n i­

q u e o f f lu id L a a tio n t o th e r e a c tio n ta k in g p la c e i n th e H a rg re a v e s p ro c e s s

f o r th e m a n u fa c tu re o f sodium su lp h a te * E x p erim en ts w ere c o n d u c te d t o

d etex m n © th e b e h a v io r o f s a l t o f v a rio u s a v e ra g e p a r t i c l e s iz e s when

su sp e n d e d an a stre a m o f a ir * The s i z e fo u n d t o be m ost s u i t a b l e was t h a t

o f common, t a b l e s a l t ; c o n s e q u e n tly th e r e s is ta n c e to th e flo w o f a i r Of

t h i s m a te r ia l i n a f l u id i z e d c o n d itio n w as d eterm in ed * In c o n s id e rin g th e

d e s ig n o f eq u ip m en t i n w hich th e r e a c tio n u n d e r s tu d y w as to be c a r r i e d o u t

i t w as th o u g h t h a t th e m ost e f f i c i e n t ty p e o f o p e ra tio n w ould in v o lv e th e

c o u n te r c u r r e n t flo w o f s o l i d an d gas* W ith t h i s p r i n c i p le in v iew s e v e r a l

laboratory u n i t s w ere d e s ig n e d , c o n s tr u c te d , a n d o p e ra te d t o show t h a t th e .

\
c o u n te r c u r r e n t p r i n c i p le c o u ld be s u c c e s s f u lly a p p lie d t o th e c o n ta c tin g

o f s o l i d w ith g a s e s i n a f l u i d i z e d system * D esig n s f o r tw o l a r g e r u n i t s ^

a r e p r e s e n te d b a se d on th e know ledge o b ta in e d fro m th e o p e ra tio n o f th e

la b o r a to r y u n ite *
\
E x p erim e n ts w ere c o n d u cted t o d e te rm in e w h e th e r th e r e a c tio n c o u ld be sue--

c e s s f u ll y c a r r i e d o u t in a f l u i d i z e d bed* liiuaerous d i f f i c u l t i e s w ere

e n c o u n te re d * The s o l i d i f i c a t i o n o f th e s a l t b ed l a th e c o u rse o f th e r e a c tio n

a t h ig h te m p e ra tu re le d to th e s u p o s itio u t h a t Ix rb erjaed iate p ro d u c ts w ere

fo rm ed i n a l i q u i d s ta te # From th e fo rm a tio n o f l i q u i d c o n d e n sa te a t low

te m p e ra tu re s and th e a p p e a ra n c e o f s u lp h u ric a c id r a is t, th e e x is te n c e o f s u l­

p h u r ic a c i d v a p o r i n th e g a s s tre a m was concluded* A mechanism, f o r th e r e a c tio n

w as th e n p ro p o se d w hich m ig h t e x p la in th e phenom ena o b se rv e d a t th e v a rio u s

62
o p e r a tin g c o n d i t i o n s * S a t is f a c to r y o p e ra tio n w as o b ta in e d when red u o *

t i o n s i n g a s c o n c e n tr a tio n s w ere made i n a c c o rd a n c e w ith c o n c lu s io n s

re a c h e d fro m c o n s id e r a tio n o f t h e p ro p o se d r e a c tio n mechanism*

T he n e c e s s a r y s te p s i n t h e p ro c e s s a s w e ll a s th e c o n d itio n s o f

O p e ra tio n su c h a s te m p e ra tu re a n d g as c o n c e n tr a tio n w ere d isc o v e re d *

The f i r s t s te p i n t h e a p p lic a tio n o f th e f l u i d i g a b io n te c h n iq u e t o a

c ommer c i a l p r o c e s s , s u c c e s s f u l o p e ra tio n on a la b o r a to r y s c a l e , w as

a c c o m p li shed*

O th e r in f o r m a tio n o f v a lu e t o f u r t h e r dev elop m ent on a p i l o t p l a n t

s c a le su c h a s r e a c tio n v e lo c it y , p r e s s u r e l o s s e s , g a s f lo w r a t e s , a n d

m a te r ia l l o s s e s w ere a ls o o b ta in e d * I n th e developm ent o f th e p ro c e s s

t h e d i f f i c u l t i e s w hich w ere e n c o u n te re d a n d overcom e in d ic a te th e p ro b ­

a b le te m p e ra tu re a n d c o n c e n tr a tio n l i m i t s f o r l a r g e r s c a le o p e ra tio n *

On t h e b a s i s o f th e s e c o n s id e r a tio n s a p ro c e s s flo w d iag ram m s d e v elo p ed

w h ich i s p re s e n te d *

I n th e a b se n c e o f s u f f i c i e n t d a ta fro m w hich th e pow er a n d o th e r

c o s ts s a y b e e s tim a te d , th e com m ercial f e a s i b i l i t y o f th e p ro p o se d p ro ­

c e s s may b e i n d ic a te d fro m a c o n p a riso n w ith th e m a n u fa c tu re o f s u lp h u r ic

a c i d b y th e c o n ta c t p r o c e s s . T h ese tw o p ro c e s s e s h av e many s i m il a r

f e a t u r e s f o r w h ich th e o p e r a tin g an d f ix e d c o s ts sh o u ld be a b o u t th e

©am * The c o n v e rs io n o f s u lp h u r t o th e t r i o x i d e i© a c c o m p lish e d i n

b o th # H e a t econom ies e f f e c t e d i n t h e c o n ta c t p ro c e s s may a ls o b e ob­

t a i n e d i n th e p ro c e s s su g g e ste d * I r o n o x id e , a much c h e a p e r c a t a l y s t
 sa IT
BRI NE salt wa ter
storage
evaporator

to

air

SULPHUR
42 95

reactor
centnfuqe
me I t e d
sulphur superheater
turbine

///////// um m
////////// ///////////
////////// im ttm
////////// iim im air

su lphur b lo w e r
b o il e r co n ve rt e rs a ci d
bu rn er p u mp
blow er 0

FIG. 9 PROCESS FLOW DIAGRAM

 <55

th a n V anadium oar P la tin u m may h e em ployed i n th e m a n u fa c tu re o f s a l t

c ak e s in c e lo w e r s u lp h u r d io x id e c o n c e n tr a tio n s a n d th e p re s e n c e o f

m t e r v a p o r a r e m ore f a v o r a b le t o c o n v e rsio n o f s u lp h u r d io x id e th a n

t h e c o n d itio n s em ployed i n th e c o n ta c t p ro c e ss*

Th© c o s t o f raw m a te r ia ls an d th e m ark e t v a lu e o f t h e p ro d u c ts

r e s u l t i n g fro m th e co n su m p tio n o f one to n o f s u lp h u r w i l l b e th e b a s is

f o r co m p ariso n o f th e tw o p ro c e s s e s * The c o s t o f a to n o f s u lp h u r a s

q u o te d b y t h e m anagem ent o f th e l o c a l s u lp h u r ic a d d p l a n t I s $20*00*

C om plete c o n v e rs io n o f one to n o f s u lp h u r t o s u lp h u r ic a c id w ould re-*

s u i t i n a n in c r e a s e i n v a lu e t o $l$ * 0 0 b a se d on a s e l l i n g p r ic e o f

$16 •0 0 p e r to n f o r p u re s u lp h u r ic a c id * The in c r e a s e i n v a lu e i s ob­

t a in e d b y c o n s id e r a tio n o f th e fo llo w in g w e ig h t b ala n ce #

S / laOg / HgO Ifesqk

1 Ton / 1*5 Tons / *56 Tons » 3*06 Tons

The c o s t o f th e oxygen an d w a te r a r e assum ed s m a ll i n cosqparison w ith

th e c o s t o f th e s u lp h u r a n d a r e th e r e f o r e n e g le c te d * T h is shows an a d ­

v a n ta g e o f $33*00 w hich r e p r e s e n ts th e com bined c o s t o f p ro c e s s in g a n d

p r o f i t fro m th e c o n v e rsio n o f one to n o f su lp h u r*

A c o s t o f $1*1*5 p e r to n o f d ry s a l t o b ta in e d a s a tw e n ty -fiv e p e r­

cent s o l u t io n , an d v a lu e s o f $18*00 p e r to n f o r s a l t cak e a n d $145*00 p e r

to n o f p u re h y d ro c h lo ric a c id a r e ta k e n a s r e p r e s e n ta tiv e f o r th e s e

materials* These v a lu e s w ere o b ta in e d fro m a l o c a l in d u s tr y w hich manu­

factures s a l t cake a n d h y d ro c h lo ric a c id * The v a lu e f o r s a l t cak e i s

 66

ta k e n a s a t t h e factory a n d does n o t in c lu d e sh ip p in g c h arg es# The v a lu e

f o r th e p u re a c id r e f e r s t o a n y q u a n tity o f w eak a d d w hich co ntain © th e

e q u iv a le n t o f one to n o f p u re h y d ro g en c h lo rid e # I t i s a ls o ta k e n a s

th e p r i c e a t t h e f a c t o r y a n d d o e s n o t in c lu d e s h ip p in g c h arg es# A w e ig h t

b a la n c e f o r th e p ro p o se d p ro c e s s s i m il a r t o th e one made f o r th e c o n ta c t

p r o c e s s i s show n b elo w i

8 / I 3O2 / HgO / 2 HaCl NagSO^ / 2 HC1

X Ton j£ 1*5 Tone / .5 6 T ons / 3*66 Tone * k*bh Tons / 2*28 Tone

A co m p ariso n o f p r i c e s o f raw m a te r ia ls a n d product© f o r th© p ro ­

posed p r o c e s s s im ila r t o th e one made f o r th e m an u fa ctu re o f s u lp h u ric

a d d shows an a d v a n ta g e o f o f p ro d u c t v a lu e o v e r raw m a te r ia l

cost per to n of s u lp h u r u t il i z e d * T h is f ig u r e i s m ore th a n f o u r tim e s

as la r g e a s th e c o rre e ro n d iiig one f o r th e m an u fa c tu re o f s u lp h u r ic a cid *

The m o n etary a d v a n ta g e may be c la im e d f o r th e H a rg re a v e s P ro ­

cess a s w e ll a s f o r a p ro c e s s c o n s is tin g o f a co m b in atio n s u lp h u r ic a c id

p l a n t a n d MpTm heim s a l t cak e p la n t* The u n d e s ir a b le f e a t u r e s o f h ig h

la b o r fmH pow er c o s t h av e p r e v io u s ly b een su g g e ste d a s th e re a so n f o r

th e l im i te d u s e o f th e H a rg re a v e s P ro c e s s , The com m ercial s u c c e s s o f

-the o n ly p la n t i n o p e ra tio n i n t h i s c o u n try i s due in p a r t to i t s lo ­

c a tio n a t a s o u rc e o f s u lp h u r a n d cheap s a lt* A co m b in atio n s u lp h u r ic

a d d a n d Mannheim s a l t cak e p l a n t w ould e n t a i l c o s ts w hich a r e e lim i­

n a te d b y th e f l u i d i z a t i o n p ro c e ss* I t e lim in a te © th e fo rm a tio n o f

l i q u i d s u lp h u r ic a c id a n d th e c o s ts a tte n d a n t t o i t s h a n d lin g an d s to ra g e #
 67

I t ftlim in a t e s th e h ig h i n i t i a l stud. m ain ten an ce c o o ts o f &. ip fur**

n ace* I t i s a ls o e x p e c te d to p ro d u ce a m ore u n ifo rm s o l i d p ro d u c t w hich

w i l l e n t a i l lo w e r h a n d lin g a n d sh ip p in g c o st*

The eq u ip m en t shown i n th e p ro c e s s flo w d iag ram w hich i s n o t p r e s e n t

i n a c o n ta c t s u lp h u r ic a c id p l a n t a r e th e s a l t e v a p o ra to r* c e n tr if u g a l,

d r y e r , s to r a g e v e s s e l , r e a c t o r an d s a l t cak e c o o le r* S in c e h e a t reo o v *

e r e d fro m t h e b u rn in g o f s u lp h u r i s t o be u t i l i s e d f o r e v a p o ra tio n an d

pow er g e n e r a tio n , th e o p e ra tin g c o s t o f m aking c ry s ta lin © s a l t s h o u ld be

low* T he m a jo r ite m o f ex p en se f o r w hich th e p ro c e s s i s c h a rg ea b le* i n

a d d itio n t o th o s e in v o lv e d i n a s u lp h u r ic a c id p l a n t , i s th e i n i t i a l c o s t

o f th e e q u ip m en t i n w h ich s a l t o r s a l t cak e i s h and led* W ith th e excep­

t i o n o f t h e r e a c t o r , su ch eq u ip m en t i s o f s ta n d a r d d e sig n an d i t s c o s t

s h o u ld n o t b e e x c e ssiv e * A t th e p r e s e n t s ta g e o f dev elo pm en t th e c o s t

o f a r e a c t o r c a n n o t b e p r e d ic te d w ith any d e g re e o f c e r ta in ! t y , b u t th e

Hggj gnn p r e v io u s ly s u g g e s te d a r e o f a ty p e c o n s tr u c tio n f o r w hich th e

c o s t s h o u ld be i n l i n e w ith th e o th e r e q u ip m en t.

The ccszgsarison o f th e p ro p o se d s a l t cak e p ro c e s s w ith th e c o n ta c t

p ro cress f o r t h e m a n u fa c tu re o f s u lp h u r ic a c id w as c o n s id e re d t o b e a

re a s o n a b le one a n d i t p ro v id e d a b a s is upon w hich an econom ic a p p r a is a l

m ig h t b e made*
A c o n s id e r a tio n o f th e s i m i l a r i t y o f th e tw o p ro c e s s e s and a com-

p a r is a n o f th e in c r e a s e in v a lu e o f p ro d u c ts r e s u ltin g from e q u iv a le n t

am ounts o f s u lp h u r p ro c e s s e d in d ic a t e t h a t th e econom ic f e a s i b i l i t y o f

th e f lu id iz & tio n p r o c e s s i s h ig h ly fa v o ra b le #
 68

SELECTED BIBLIOQB&PHT

(1 ) P a r e n t, J* D .$ X ag o l, H ,$ S te in e r , Gh&s. S . " F lu id iz a tio n P ro c e s s e s " *

C hssu & * g r., V o l. to # S o . 8, U29- t o 6 .

(2 ) L ev a, Max " P r e s s u r e Drop T hrough P ecked Tubes*1* Chem. Bhgr«, V o l. 10*

Mo* 1 0 , 510-55U * Mo. IX , 633-638* Mo. 12, 713-718*

(3 ) Leva., Max a t a l " I n tr o d u c tio n t o F iu id iz a td o n " 3 Chem* % g r« , F o l* l i t ,

S o . 7 , 5 H -6 2 0 * S o . 8, 6 1 9 -6 2 6 .

(I*) Iferp h y , S a l t e r J . , e d i t o r , " F lu id i a c tio n N o m en clatu re a n d Sym bols" j

2n d . a n d & ig r. C hem ., V o l. U l, No* 6$ 1210*

(5 ) M e llo r, M odem In o rg a n ic C h em jg try i Mew T o rk , Longmans, G reen en d

Ccaapany 1939, p 5 (XU

(6) Johnstone, H . F . " C h lo rin e P ro d u c tio n " * Chem* Efogr*, V o l. iUj., Mo* 9#

6 5 7 -6 6 8 .

(7) M oore, B* E . " S a l t Cake a S u rv e y o f th e I n d u s tr y " , a r e p o r t s u b m itte d

t o D r. A rth u r K e lle r , P r o f e s s o r o f C hem ical E n g in e e rin g , L o u is ia n a

S ta te U n iv e r s ity , 19U9*
( 8) S e h e x n ay d e r, M. J . " R e p o rt on t h e Bay C hem ical Company P la n t o f

Weeks I s la n d , L o u is ia n a " , A r e p o r t su b m itte d t o S r . A rth u r K e lle r ,

P r o f e s s o r o f C hem ical E n g in e e rin g , L o u is ia n a S ta te U n iv e r s ity , 19lv7 *

(9 ) H augen, 0 . A . a n d W atson, K. M. C hem ical P ro c e ss P r i n c ip l e s . P a r t Two,

T herm odynam ics, Sew Y o rk , John W iley & S o n s, I n c . , 19L 7, p 7 2 2 .

 69

(3J0) G lad ston e, S* Thermodarosjslca fo r C h em ists i se co n d p r i n t i n g , New T o rk ,

B. Von N ostrand Company, 19l& , p 508#
(ll) Ferry, H# Chemical Basineerg Handbook i se co n d e d it i o n , se c o n d im­

pression, New Tork, Book Company, 19l*l, p UOX

(3 2 ) In tern et!o n C r itic a l T ab les, M e ltin g P o in ts System Sodium C blorlde,

Sodium Sulphate,^V ol* IV, 68*
(3 3 ) B od en stein , M. a n d K a ta y a n a , M. "Bin© beguem© M ethods s u r ^ s s u n g
w Bampfdichteai H e A s s o c ia t io n von h y d r a tis h e r S c h w e fe lsa u re u n d
von S tie k s to f f d ia x y d " $ 2 e i t s o h r i f t f u r F h y sik a lisc h © Chen&e, V o l. 6 9 ,

2 6 , 1909*

(H i) Laurey, H. A . H ydrochloric A cid and Sodium Sulphate* New Tork,

Chemical C atalog Company, In c*,
 APPENDIX

Preseure 8 pop Through Table S alt

Depth of Bed - ——— —6 Inches
XtLoneter o f V essel ~ - 1; inches
Weight of S alt Charged <* «* h pounds

B ead lT ^ -4 P L b /* *2 T in a Volume Q Sp 0
H o. I n d ie s Min* o f A ir lb /f t2 ~ h *
C arbon f t* /*
T e tr a c h lo r id e

1 0 .5 .02(166 1 .3 3 .1 3*73 .0 7 9 6
2 1 .0 .05 3 3 *66 .1 7 .5 1 .1 6 1

3 3*625 .3 3 5 5 *833 •2 1 1 .9 0 .2 5 5

t 2*375 .3 5 6 0 *2835 .1 1 7 .5 0 .3 7 5

5 3*375 .2 £0.0 *393 .2 2 5 .2 0 •52(0

6 1**125 .324(0 1 .1 9 3 1 .0 2(1 .6 .6 9 0

T U .lU o .32(50 .9 5 2 1 .0 5 2 .1 1 .3 1 5

8 .32(50 .8 1 1 .0 9 1 .2 1 .3 3 0

S a s p le C a lc u la tio n

D e n s ity o f c arb o n t e t r a c h l o r i d e 1 .5 8U x 62*U ® 98*8 l b / f t ^

D ensity of a ir ( 90 <#* 1 atmosphere) SSL x MS » .0722 Ib /ft^

359 550
Cross sectional area of vessel *0073 ft^
0 « A X *. 3*73 lb/ft^ -hr*
1*33 x *0873
Dp » *0 0 0 9 3 1 * ft* (1 0 0 0 F) « *0 U3 5 lb/hr-ft*

70
 n

P ressu re Drop Through Table S a lt

Check d oten n in atioa
06jpth o f Bed •*«*-*■*<•»«. 6 In ches

X&aaeter o f V essel «* «* •» U in ch es

h eig h t o f S a lt Charged — U pounds

H earting L b /f t2 Time Volume a Dp G

8 0. F t. ta n . o f A ir X b /ft^ h r
Water ft3 /*

1 .2125 12.35 . 86U .2 11*22 ,2k

2 .335 2 0 .9 0 3 .5 3 1 .2 16.73 .358

3 .3735 23.27 .8 9 •u 22.30 .U77

k .U750 29.62 1.0U -6 28.60 .612

5 .5250 3 2 .7 5 . 63U •fc 3 7 .7 0 .806

6 .5 3 as 3 3 .1 8 1.36 1*0 37.50 .803

7 .5U80 3U .19 1 .3 1 5 1*0 2i3*2*0 •928

8 .5525 3h.h5 .9lt3 1*0 52.60 1.128

.5570 3U.75 •® 3 1*0 58.10 1 .2 2 5

A ir Tenperature 85
A ir D e n s ity 3 2 - x &23 . .073 lb /ft3
359 5U5
 n

T able S a lt Screen A n aly sis

Weigiit o f saitiple 1005 grams ,

Mesh H a le S ie e W eight % Sisse o f W eigh ted

In c h e s R e ta in e d R e ta in e d P a r t i c l e s A v erag e

20 *0326 non© 0 **•*-■>

26 •0232 •5 . ----- —

35 .016U 30*0 3 .0 ♦0198 ,C$9h

U8 *0116 U llu 2 ia * 2 . 01U0 *5760
65 *0082 386*5 3 8 .5 .0099 ,38X 0

100 .0 0 5 8 99*1 9 .9 •0070 ,0693

o v e r 100 7U .7 7.U •OOliO *0296

T o ta l 1005*0 1*1X53

average d iam eter *0112 inches

•OOQ93U f e e t
F in e s over 100 mesh »1T% below 70 m icrons
S p e c ific G ra v ity u sin g V arsol (8Q°!F)

w eigh t o f sample 53*296 grams

in c re a s e in volume o f v a rs o l 25*00 nil
S p e c ific G ra v ity » 2*131
 73

F lo w B a te s f o r T h ree S ta g e C o u n te rc u rre n t

L a b o ra to ry F l u i d l a a tt o n U n it

(show n i n F ig u r e 2 )

A ir a n d s o l i d r a t e s a r e in d e p e n d e n t*

G as r a t e s w ere v a r ie d fro m a e ro t o tw o c u b ic f e e t p e r m inute* S o lid

r a t e s w ere v a r ie d fro m a e ro t o 280 grains p e r m inute*

Flow r a t e s f o r R e a c to r num ber 9

A ir a n d s o l i d r a t e s a r e in d e p e n d e n t*

G as r a t e s w ere v a r ie d fro m z e ro t o one c u b ic f o o t p e r m inute* S o lid

r a t e s w ere v a r ie d fro m z e ro t o 100 grams per m inute*

 7k

O p e ra tin g B a ta Bun # 1

(B e a c to r num ber l )

C harge 200 gram s t a b l e s a lt#

When t h e th e rm o c o u p le i n d ic a te d 95>OoF one q u a r te r in c h above th e

s c r e e n , s u lp h u r d io x id e w as in tro d u c e d ev en th o u g h th e p r e s s u r e d ro p w as

f l u c t u a t i n g w id e ly fro m a b o u t te n t o tw e n ty ~ fiv e in c h e s o f w ater#

A ir B a te 1*8 c u b ic f e e t p e r m in u te

T he s u lp h u r d io x id e r a t e b elo w #5 c u b ic f e e t p e r m in u te

P r e s s u r e d ro p c o n tin u e d t o f l u c t u a t e w id e ly ev en when th e a i r ro ~

t o a s t e r r e a d in g w as re d u c e d t o fiv e # A f te r a b o u t t h i r t y m in u te s th e

p r e s s u r e n a n o m e te r b lew o u t (ab o v e t h i r t y in c h e s o f w a te r)# O p e ra tio n

w as e n d ed a f t e r f o r t y m in u tes* T em p eratu re one q u a r te r in c h above th e

s c r e e n 1000QF.

S a l t Bed A n a ly s is

The b o tto m o f th e b e d h a d s e v e r a l lum ps o f c i y s t a l i n e s o l i d a d h e rin g

t o th e s c re e n w hich h a d becom e v e ry b r i t t l e an d c ra c k e d i n s e v e r a l p la c e s *

A n a ly s is o f th e b e d m a te r ia l I n d ic a te d a n e q u iv a le n t o f 10 gram s o f sodium

s u lp h a te .

The i n l e t o f th e h e a te r c o i l w as p lu g g e d w ith a ta n c o lo re d s c a le a t

a p o in t w h ere th e f i r s t ch ro m el s p r in g tu rb u le n c e p ro m o te r began# The

spring i t s e l f w as a p p a r e n tly u n a ffe c te d * A n a ly s is shew ed th e s c a le t o

b e i r o n s u lp h ite #
 7$

C hanges Made P r i o r t o Hun #2

A d o u b le pip© h e a t e x c h a n g e r w as i n s t a l l e d b etw een th e to p o f th e

h u m id ify in g to w e r an d th e ju n c tio n o f th e s u lp h u r d io x id e e n tra n c e * th e

P u rp o se o f th e e x c h a n g e r w as t o ja c k e t th e w e t a i r l i n e w ith steam t o

s u p e rh e a t t h e w a te r v a p o r a n d th u s p re v e n t c o n d e n sa tio n o f m o is tu re i n

th e l i n e w h ich o c c u rre d i n Hun # 1 .

R o ta m e te rs w ere ex ch an g ed t o p e rm it th e lo w e r c a p a c ity m e te r t o b e

u s e d cm th e s u lp h u r d io x id e f e e d lin e * '

C o n s tr u c tio n o f a d o u b le p l a t e s t a i n l e s s s t e e l d i s t r i b u t i o n p l a t e

f o r th e b o tto m o f th e r e a c t o r (R e a c to r num ber 2)* H o les w ere f i v e s i x t y

f o u r th s on t h r e e e ig h th in c h c e n te rs * s q u a re p i t c h , p l a t e s s e p a r a te d by

on e s ix te e n th in c h a s b e s to s g a s k e t, h o le s o f f s e t i n p l a t e s t o p re v e n t

dew nflow o f s o lid *

O p e ra tin g D ata Hun #2

(R e a c to r num ber 2 )

C harg es 250 grams t a b l e s a l t

A ir r a t e s .7 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e a d m itte d a t 980°F • S u lp h u r d io x id e r a t e *3 c u b ic

f e e t p e r m in u te . U n it f l u i d i z i n g s a t i s f a c t o r i l y * A f te r f i v e m in u te s r e ­

a c t o r b e d s u d d e n ly s o l i d i f i e d fo rm in g num erous sm a ll c h a n n e ls , eac h c h a n n e l

l o c a te d ab o v e a h o le i n th e s t e e l p la te * The e l s e o f c h a n n e l h o le s a b o u t

t h e pM fr a s t h e h o le s i n th e p l a t e . The o d o r o f s u lp h u r d io x id e becam e

v e ry s tr o n g an d smoke a p p e a re d com ing o u t o f th e c ra c k s a ro u n d th e d is ­

c h a rg e s i d e o f th e r e a c t o r . The u n i t was im m e d ia te ly s h u t down*

 76

C hanges P arlo r t o Run #3

A t r a p v a s I n s t a l l e d I n th e v e t a i r l i n e a t th e fu rn a c e e n tr a n c e

t o c a tc h a n y c o n d e n sa te fo rm ed i n th e u n h e a te d p o r tio n o f th e lin e *

O p e ra tin g D ata Run #3

(R e a c to r num ber 2 )

C h a rg e t 200 gram s t a b l e s a l t

A ir r a t e s 1*5 c a b le f e e t p e r m in u te

A ir flo w w as s t a r t e d th e n ste a m t o th e ja c k e t th e n h e a te r w as l i t *

T he s a l t w as a d d e d s lo w ly t o th e r e a c t o r a t a b o u t 600dS?* Bed f l u i d i a i n g

s a tis f a c to r ily * H ot w a te r a c to itte d t o h u m id ify in g tow er* S u lp h u r dl<*

o x id e s t a r t e d a t a r a t e o f *2 c u b ic f e e t p e r m in u te when r e a c to r te m p e ra tu re

re a c h e d 980c®** U n it f l u i d i s i n g s a t i s f a c t o r i l y * Smoke a p p e a re d com ing

o u t o f e x i t o f t h e s c r u b b e r to w e rj a p p e a rs t o be s u lp h u r trio a d .d e * A f te r

s i x s d n ttte e c e n te r p o r tio n u f b ed n o t f lu id ia ln g * F low o f s u lp h u r d i­

o x id e w as sto p p ed * th e r e a c t o r c o v e r w as rem oved* th e b ed was s t i r r e d

w ith a w ire * H o les i n c e n te r an d on one s id e o f p l a t e a p p e a r plugged*

* Bed t e a p e r a tu r e w as 1080°F * A ir t o b u rn e rs w as red u ced * c o v e r re p la c e d *

s u lp h u r d io x id e s t a r t e d ag ain * F lu ld iz in g a r e a o f b ed n a rro w ed t o a

e r e s e n t s e c tio n on one edge* c o n tin u e d t o d e c re a s e in s iz e u n t i l o n ly a

fe w h o le s w ere f l u l d i z i n g . The s c ra p in g was re p e a te d b u t a h eav y cak e

a p p e a rs t o b e fo rm ed on t h e p l a t e a n d c a n n o t b e s c ra p e d o ff* Hun te r-*

E dna t e d a f t e r tw o m ore m in u tes*

 11

O p e ra tin g U rta Run #3 (C o n tin u e d )

A p p earan ce o f Bed A f te r C o o lin g

B ottom p o r tio n c o n s i s t s o f a lo o s e cake c o n ta in in g w h ite c o re s s i m il a r

t o th o s e o f Run #2# T he o u te r p e r ip h e r y w as n o t cak ed a n d c o n s is te d o f

d a rk e r c o lo r e d s a l t c r y s t a l s h a v in g a s p h e r ic a l a p p ea ra n c e# The c e n te r

p o r tio n o f th e u p p e r p l a t e w as p lu g g ed # R ad i h o le c o n ta in e d some r u s t y

lo o k in g c r y s t a l i n e d e p o s it i n d ic a t i n g c o rr o s io n o f th e p l a t e a t th e h o le #

T he b o tto m p l a t e m s c le a r #

C hanges P r i o r t o Run #1*

A eorrundum p l a t e w as made t o f i t on tc p o f th e u p p e r s t a i n l e s s s t e e l

p l a t e a n d h o le s w ere d r i l l e d i n i t t o c o rre sp o n d w ith th e h o le s i n th e

p la te # G la s s w o ol w as p la c e d betw een t h e tw o s t e e l p la te s * (R e a c to r

number 3 )
O p e ra tin g D ata Run #2*

(R e a c to r num ber 3 )

R e s u lts w ere th e sam e a s Run #3 w ith th e e x c e p tio n t h a t h o le s d id

n o t p lu g up# The b e d s o l i d i f i e d a f t e r t e n m in u te s o p e ra tio n a t h ig h

te H p e ra tu re #

C hanges P r i o r t o Run #5

A ta p e r e d g la s s r e a c to r h a v in g a tw o an d one h a lf in c h d ia m e te r an d

o v e r a l l h e ig h t o f e ig h te e n in c h e s w ith a ta p e r e d s e c tio n o f tw e lv e in c h e s

a t th e b o tto m a n d a b o tto m o p en in g o f th r e e e ig h th s in c h w as made# A

h a l f in c h p e r f o r a te d ceram ic d is k was p la c e d i n th e lo w e r p o r tio n t o su p ­

p o r t th e s a l t bed# (R e a c to r num ber U)

 ?8

O p e ra tin g D ata Bun #5

(R e a c to r num ber U)

A ir r a t e s *5 c u b ic f e e t p e r m in u te

S u lp h u r Dioxide r a t e s #1 c u b ic f e e t p e r m in u te
T e ^ e r a tu r e * 1*2Q°C a v e ra g e

Bed fluidised s a t i s f a c t o r i l y ; p r e s s u r e d ro p s i x in c h e s o f w a te r ;

bed depth four in c h e s* When th e te m p e ra tu re re a c h e d i*QO®C th e s a l t b e­

came s t i c k y ; p a r t i c l e s stuck t o th e w a lls o f th e r e a c to r * A t U2G&C th e

bed w o u ld s o l i d i f y u n t i l th e r e a c t o r w as ta p p e d an d th e n i t f l u i d i c ed
a g a in * The s o l i d i f i c a t i o n a n d n e c e s s a ry ta p p in g began t o in c r e a s e i n
frequency ( th e a i r w as c u t o f f fro m th e f u e l g a s t o th e fu rn a c e b u t th e
temperature remained a t U20°C ) u n t i l i t w as n e c e s s a r y one© a second*
A t t h i s p o in t th e ru n w as d is c o n tin u e d * A bout te n t o tw e n ty p e rc e n t o f

the s a l t w as a d h e rin g t o t h e w a lls * T o ta l tim e a t i*00°C a b o u t tw e n ty

m in u te s , t o l d tim e ab o v e UOO°C a b o u t t h i r t y m in u tes*

T he r e a c t o r when c o o le d c o n ta in e d loos© p ro d u c t a s w e ll a s c ak e on

the ceramic d is k w h ich c o n ta in e d th e f a m i li a r c h a n n e ls* I t a p p e a re d t o

be f u s e d cak e r a t h e r th a n s in te r e d * A n a ly s is o f lo o s e m a te r ia l, 60$ so**

dlwm s u lp h a te b a s e d on s u lp h a te a n a l y s i s , th e c a k e w as 98*5# sodium s u lp h a te .

O p e ra tin g D ata Bun #6

T he u n i t w as o p e ra te d a t a lo w e r te m p e ra tu re th a n Run #5 b u t a t th e

sam e g a s r a te s *
 19

$3jne T en p er& tu re P re s s u re P rop Kem arks

1&eu °C In c h e s o f w a te r

0 315 6

5 31*3 ?

11 371 7

18 377 7

20 377 7 ® a lt i s s t i c k y

23 388 7 re d u c e d f u e l t o f u rn a c e

25 371 7

28 371 7 cak e fo rm in g
v e ry s t i c k y

33 366 7 le s s s tic k y

36 3b3 7 s tic k y -m o re cake

p r e s e n t (m o lte n )

39 338 7 m ore cak e p r e s e n t

bo 3b9 7 s u lp h u r dload.de c u t
o f f a i r r a t e in c r e a s e d

k2 35U 7 re d u c e d f u e l t o fu rn a c e

2i3 3b 9 7 f lu id iz ir * g w e ll a g a in

Jig 332 7 f l u i d i z i n g w e ll a g a in

b6 315 7 f l u i d i z i n g w e ll a g a in

ii9 te r m in a te d th e ru n

A n a ly s is o f t h e b ed 60$ sodium S u lp h a te
 80

Screen. A n a ly s is o f P ro d u c t a n d P e e d Hun # 6

W eight P e r c e n t P ro d u c t P eed

C aught on 20 Mesh 0 0

C au g ht on 28 Mesh 3*0 tr a c e

C au gh t on 35 Mesh 10*5 3 .0

C au gh t on 1*8 Mesh 3 7 .7 ia .2

C au g h t on 65 Mash 3 7 .1 38*5

C aught on 100 Mesh 9*6 9*9

P a s s e d 100 Mesh 2*1 7*h

100*0 100*0
 ax

C hanges P r i o r t o Run #7

The ceramic disk w as rem oved an d a n in e ty d e g re e b en d w as made i n

the tube a t th e b o tto m o f th e r e a c to r *

O p e ra tin g B a ta Bun #7

C harg e m esh ro c k s a l t a b o u t 20 gram s

A Lr r a t e s #18 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s #1 c u b ic f e e t p e r m in u te

Tim e T em p era tu re Rem arks

Min. °C

0 260
9 326 s a l t i s s tic k y

Us 3U3 s tic k y m c u t f u e l o u t e n tir e ly

15 3h3 bed s o lid if ie d

P ro d u c t a n a l y s i s 39$ sodium s u lp h a te

C hanges P r i o r t o Bun # 8

A tu r b u le n c e p ro m o te r w as made o f g la s s r o d I n th e fo rm o f a s p i r a l

t o f i t i n to t h e b o tto m o f t h e r e a c t o r . T h is w as u s e d t o p re v e n t c a r r y ­

o v e r a t h ig h g a s r a te s *

O p e ra tin g B a ta Bun # 8

C harge same a s Run # 7

A ir r a t e 1 .2 1 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s .0 9 c u b ic f e e t p e r m in u te

A f te r s i x m in u te s th e te m p e ra tu re re a c h e d 2820C, th e s a l t w as s t i c k y ,
 82

a n d l i q u i d h a d fo rm ed a ro u n u th e tu r b u le n c e p ro m o te r -which h a d beccrne

s tu c k i n t h e r e a c to r *

P ro d u c t a n a l y s i s l£ $ sodium su lp h a te *

O p e ra tin g R a ta Hun #9

C harge same a s Run # 7

A ir r a t e I *16 c u b ic f e e t, p e r m in u te

Sulp h u r d io x id e r a t e s *06 c u b ic f e e t p e r m in u te

A f te r f o u r m in u te s th e te m p e ra tu re r e a d ie d 27?°C and t h e b ed h ad

fo rm ed c a k e i n th e bottom * The f lu x d i z a t i on p ro m o te r became s tu c k i n

l i q u i d a t t h e bottom * A h a llo w c o re o f cak e fo rm ed upw ard in to th e

lo o s e s a l t*

P ro d u c t a n a ly s is 12# sodium s u lp h a te .

O p e ra tin g R a ta Run #1 0

Chare® a s Run # 7 a b o u t 20 gram s

A ir r a te * *29 c u b ic f e e t p e r m in u te

S u lp h u r diood.de r a te * *09 c u b ic f e e t p e r m in u te

The s u lp h u r d io x id e w as s t a r t e d when th e te m p e ra tu re re a c h e d 170°C .

A f te r 18 m in u te s th e te m p e ra tu re w as ZZCPC a n d a f t e r 66 m in u te s 2U0°C,

S a t i s f a c t o r y f l u i d i z a t i o n w as o b ta in e d , how ever a s l i g h t am ount o f cak e

fo rm ed (*23U gram s) a ro u n d th e f l u i d i z a t i on p ro m o ter* The cak e c o n ta in e d

8C# sodium s u lp h a te *

P ro d u c t a n a ly s is U9# sodium su lp h a te *
 m

O p e ra tin g B a ta Run # 1 1

C harge sam e a s Run #7 a b o u t 20 gram s

A ir r a t e : .2 7 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e : *09 c u b ic f e e t p e r m in u te
Tim e T em p era tu re Rem arks
Min* or*

0 190 ^ lu i d i a i n g

3 200 F lu id is in g

10 230 F lu id ia in g

15 22*0 F lu id iz in g

18 250 F lu id iz in g

19 260 F lu id ia in g

22 26 0 S tic k in g t o w a lls o f

2h 21*0 C ut s u lp h u r d io x id e

27 230 Bed s tu c k c o u p le t e ly

P ro d u c t a n a ly s is $1$ sodium s u lp h a te

O p e ra tin g B a ta Rim #12

C harge sam e a s Run #7

A ir r a t e s *6 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e unknown due t o w ide o s c i l l a t i o n o f th e ro ta m e te r

f l o a t ( a s m a lle r ro ta m e te r w as i n s t a l l e d on th e s u lp h u r ic d io x id e } #

T he u n i t w as o p e ra te d f o r h7 m in u te s w ith o u t a n y 'v is ib le s ig n s o f re *

a c t io n , th e o d o r o f s u lp h u r d io x id e was a b s e n t a n d th e a s s u n p tio n w as made

t h a t s u lp h u r d io x id e w as n o t flo w in g in to th e system *

P ro d u c t a n a l y s i s — no s u lp h a te
 at

O p e ra tin g D ata Run #13

P r e s s u r e f l u c t u a t i o n s a t th e new ro ta m e te r w ere re d u c e d b y in**

s e r t i o n o f a p lu g o f g la s s w ool i n th e lin e *

C h arg e sam e a s Run # 7 20 gram s

tim e fex a p ev a tu re A ir R a te S u lp h u r R ioxid© Rem arks

°C Gfm* R a te Cfm.

0 280 •6 •05 F lu id ia in g

2 290 •6 •05

5 300 •6 •05 some s a l t c a rry o v e r

6 30 0 •h i •05

7 3 00 *h i •05 s a l t i s g e ttin g
s tic k y

8 305 •h i •05 P lu id iZ in g a g a in

9 305 •h i •05 s t i c k y a g a in

10 R educed s u lp h u r d io x id e r a t e b e c a u se s a l t i s s tic k in g
t o g e th e r an d t o th e r e a c t o r w all* S u lp h u r t r i o x i d e
sm oke com ing o u t o f sc ru b b er*

IX 306 •hi •02

12 R a is e d a i r r a t e t o *6

18 3U0 •6 , •02 f lu id ! s in g b u t
s t i c k y ©moke coming
o u t o f s c ru b b e r

21 3U0 •6 •02

29 350 •6 •02

hi 360 •6 •02

te r m in a te d th e ru n

P ro d u c t a n a ly z e d 8#£ sodium s u lp h a te
 O p e ra tin g D ata Han # lb

T u rb u le n c e p ro m o te r o m itte d

C harge sam e a e Hun # 7 2 0 gram s

Time Temperature A ir H ate Sulphur Id oxide Remark®
%2U °C Cfm* H ate Cfm*
0 230 •6 *023
2 220 .6 *023 g e ttin g s a l t c a rry ­
over c u t r a te s

k 220 *5 *020
8 230 ♦5 •020

11 235 *5 •020 to o k sam ple 1 fro m b e d

23 21*0 .5 *020 b ed d e p le te d b y c a rry *

over*
T e rm in a te d th e ru n

O p e ra tin g D ata Hun #35

The h u m id ify in g to w e r w h ich w as o p e ra te d a t an i n l e t w a te r tern-*

p e r a tu r e o f 6?*8°C i n a l l p re v io u s ru n s w i l l how be o p e ra te d a t a n i n l e t

w a te r t e s p e r a tu r e o f 3 2 . 2°C# A tu r b u le n c e p ro m o te r w i l l b e used*

C harge aamft a s Bun #7 2 0 grams*

 86

O p e ra tin g D ata Hun #35 (C o n tin u e d )

Tim e A ir R a te S u lp h u r DicodLde
l& n . Cfm* R a te Cfm*
0 280 •6 .035 f lu id iz in g
2 300 ♦6 .0 3 5
h 320 ♦6 .015
8 3kO .6 .035 smoke com ing o u t o f
sc ru b b e r
12 s a s p le 1
Hi 350 .6 ,013 f lu id iz in g
35 shew ing s ig n s o f s t i c k i n e s s - h a n g in g on w a lls n o t s tic k in g
36 360 .6 .0 3 3
18 s& sp le 2
20 360 .6 .013 p e r i o d i c a l ly h an g in g
on w a lls
23 rem oved e l e c t r i c h e a t fro m r e a c t o r
25 3
27 380 .6 .0 3 3
30 375 .6 .0 3 3
32 370 sample U
33 365 ►013
3k r e p la c e d e l e c t r i c h e a t t o r e a c t o r
36 360 .6 ,013
39 aanple 5
1*1 360 .6 .0 1 3
hZ 365 rem oved e l e c t r i c h e a t fro m r e a c to r
I n l e t w a te r te m p e ra tu re t o h u m id if ie r 33*9OG
U3 370 .6 .0 1 3 s tic k y - h an g in g on w a lls
U5 370 .6 .0 1 3
k9 375 *6 #033 sam ple 6
51 375 *6 *033 smoke s t i l l coining o u t
o f s c ru b b e r
sa m p lin g tu b e sm okes when w ithd raw n fro m r e a c to r
*56 365 .6 .0 1 2
60 3 U0 .6 .012 sample 7
61 335 .6 #012 ta p p in g r e a c t o r t o g e t
good f l u i d i z a t i o n .
A few se co n d s a f t e r ta p p in g smoke conies o u t o f sc ru b b er*
69 325 *6 .0 1 2 a a n p le 8
b e d i s em pty o r n e t f l u id ! z in g
70 re d u c e d s u lp h u r d i 02d.de r a t e t o a e ro
71 smoke s t i l l com ing o u t o f s c ru b b e r
77 smoke s t i l l com ing o u t o f s c ru b b e r
81 smoke s t i l l com ing o u t o f s c ru b b e r
BU smoke s t i l l com ing o u t o f s c ru b b e r
te r m in a te d th e ru n - a v e ra g e w e ig h t o f sam ple .3 gram s
 87

Appearance of Reactor and Product from Run #35

S & cro sco p ic e x a m in a tio n o f sam ple 1 in d ic a te s r e a c tio n h a s progre®-*

e a d f a r enough on t h e s u r f a c e t o make th e c r y s t a l s c o m p le te ly o p aq u e,

t e f a c e c r y s t a l s o f sam ple 8 a r c v e ry l a r g e a n d w e ll d e fin e d in d ic a tin g

n e a r ly c o m p le te r e a c t i o n , She i n s i d e o f th e r e a c to r w as c o a te d w ith

s t i c k y p a r t i c l e s t h r t a p p e a re d t o h av e b e e n w e t o r m elted* The b o tto m

c o n ta in e d a l a r g e lum p o f p a r t i c l e s v e ry e a s i l y b ro k e n up b y p ic k in g i t

u p w ith thum b a n d f o r e f in g e r * T h is lump h a d th e a p p e a ra n c e o f v e ry n e a r ly

c o m p lete c o n v e rs io n t o sodium s u lp h a te ( l a t e r a n a ly s e d a s 99 / % b a se d

on s u l p h a te s ) . I t i s b e lie v e d t h a t th e e l e c t r i c h e a t may h av e c a u se d th e

r e a e t o r w a lls to g e t h o t enough t o fo rm th e m e lte d cake w hich w as fo u n d

on th em .

C o n v e rsio n C a lc u la tio n s B ased on S u lp h a te A n a ly s is

X m p ounds o f r e a c tio n m ix tu re p e r pound o f f e e d

X m w e ig h t f r a c t i o n o f sodium s u lp h a te i n th e r e a c tio n m ix tu re

F m f r a c t i o n o f so d iu m c h lo r id e r e a c te d

"X* i s o b ta in e d f o r e ac h s a irp le b y c h e m ic a l a n a ly s is th e m x «* F » x ( l -* y )
C o n v e rsio n B ata f o r Run #1$

\ ULn, X 3 - F F
H

Sam ple H o, T: X
I

1 12 •16 .8 b 3 .0 3 0 .86 5 .3 3 5
2 18 ,2 8 .7 2 3.05U .7 5 9 .21*3
3 25 .3 8 .6 2 3 .0 7 3 .6 6 6 .331*
h 32 *51 .1*9 3 .3 0 0 .5 3 9
5 39 ,6 0 .1*0 3 .3 2 0 .10*8 .5 5 2
6 U9 .7 9 .2 3 3 .3 6 2 .210* .7 5 6
7 60 .9 2 5 .3 7 5 3 .6 9 6 .2 0 9 .7 9 3
8 69 •95 .0 5 3 .2 0 2 .0 6 0 3 .91*
p ro d u c t 80 .9 9 5 0 3 .2 3 5 0 3 .0 0
 sa

O p e ra tin g D ata Run. #16

C h arg e sam e a s Rim # ? I4O gram s

A ir r a t e 1 *6 c u b ic f e e t p e r m in u te

S u lp h u r d i oxid e r a t e ! *025 c u b ic f e e t p e r m in u te

T e s p e ra b u re m a in ta in e d th ro u g h o u t th e r u n t 2U0®C

ftn o o th f l u i d i a a t l o n w as o b ta in e d th ro u g h o u t th e ru n w ith o u t s t i c k i n e s s

o r c a k e fo rm a tio n * No sm oke w as s e e n com ing fro m th e s c ru b b e r o u t l e t a t

a n y tim e d u r in g th e run* Sam ples w ere ta k e n a n d a n a ly s e d f o r sodium s u lp h a te

b a s e d on a s u lp h a te a n a ly s is * th e r e s u l t s w ere c o n v e rte d t o f r a c t i o n re a c te d *

A v erag e sa m p le w e ig h t #6 gram s*

C o n v e rsio n R a ta Run #16

Sam ple No* Tim e Min* X F

1 10 *010 *008
2 19 *019 *035
3 30 ♦030 .02k
1* hi *0lt5 *036
5 55 *051 •0 H
6 70 *069 .0 5 6
7 S3 *078 *063
8 97 *091 .0 7 3
9 110 *110 *090
10 323 *125 *103
11 3 i2 *161 *138
12 356 *175 •1U6
33 171 *205 *17U
1k 1© •2h0 .205
15 200 *270 *232
16 235 .3 0 0 *261
17 230 *380 *33h
18 2b0 •1*10 .361*
P ro d u c t 250 *500 •H I
 89

O p e ra tin g I& ta Run #17

C harg e sam e a s Run # 7 UO gxems

A ir r a t e s «6 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s *015 c u b ic f e e t p e r ir&imte

T u rb u le n c e p ro m o te r s t i l l i n u se* H u m id ifie r 31*1°C

The te n p e n a tu r e a v e ra g e d a b o u t 290OC f o r a 116 m in u te ru n f sam p les

m ere ta k e n a t i n te r v a l s * T he o n ly n o te w o rth y o b s e rv a tio n was a one h a l f

in c h v a r i a t i o n i n p r e s s u r e d ro p th ro u g h th e e n t i r e a p p a ra tu s a s th e b ed

fo rm ed h o llo w c o n es o f s a l t w h ich g r a d u a lly f e l l a p a r t from th e b o tto m t o

resum e f l u id ! s a t io n * One gram sam p les w ere tak en #

C o n v e rsio n D ata Run #17

SangO* Tim e Kin* Y F

1 IS .031* .0 2 7

2 30 .07 5 .0 6 2

3 iS .1 2 7 .3 05

It $8 .19U .1 ®

5 72 .2 6 0 .2 2 3

6 83 .3 0 5 .2 ®

7 92 .3 9 0 .3l*U

8 102 .1 5 7 .U l l

9 H I •1*9 .1*1*2

10 116 .5 3 .1*61*

P ro d u c t .5 5 .1*69
 90

O p e ra tin g B ata Rom # 18

Charge sam e a s Run #7 30 gram s

A ir r a te * *6 c u b ic f e e t p e r m in u te

S u lp h u r D io x id e s a te * #015 c u b ic f e e t p e r .m inute

T u rb u le n c e p ro m o te r u s e d b u t b ro k e n , H u m id ifie r 30*6°C

An a v e ra g e te m p e ra tu re o f 310®C m s m a in ta in e d a f t e r in tr o d u c tio n o f

s u lp h u r d io x id e , th e te m p e ra tu re b e fo r e i t s in tr o d u c tio n 290°C* S tic k in e s s

b eg an t o b e n o tic e a b le a f t e r t h i r t y f i v e m in u te s when th e b ed fo rm ed i n t o

a cone an d then f e l l a p a r t a g ain * A t a b o u t f o r t y m in u te s th e s u lp h u r d i~

o x id e r o ta m e te r w e n t o f f s c a le due t o a f a u l t y v a lv e a n d th e te m p e ra tu re

r o s e r a p i d l y t o 355°C . The ru n w as en ded a f t e r f i f t y s i x m in u tes* Average

w e ig h t o f sa m p le s one gram*

C o n v e rsio n D ata Hun # 1 8

Sam ple Ho* Tim e Min* 1 F

1 15*5 .0 6 #050

2 28 ♦15 *126

3 36 *20 *170

h U7 *29 #252

5 56 *36 #316

P ro d u c t •U6 •1|X2
 n

O p e ra tin g D ata Bun #19

C h arg e t a b l e s a l t &0 gram s

A ir r a te * *6 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s *015 c u b ic f e e t p e r m in u te

F l u i d i z a t i a n p ro m o te r e lim in a te d b y e x te n d in g th e r e a c t o r h e ig h t one

fo o t* H u m id ifie r 32*£°C»

An a v e ra g e te m p e ra tu re 31D°C m e u s e d a n d s t i c k i n e s s becam e n o tic e ­

a b le a f t e r s ix ty - tw o m in u tes* H ollow co n es fo rm ed o c c a s io n a lly fro m

e ig h t y - f iv e m in u te s u n t i l one h u n d r e d - f o r ty m in u te s when th e ru n was

te rm in a te d *

C o n v ersio n D ata Hun #19

S u q p le No* Tim e ttLn# X F

1 12 *Q9U .0 7 9

2 26 *177 .1U8

3 Ii3 *268 *231

h 53 *300 *261

5 71 •1*53 *1*05
6 92 *520 *1*70

7 108 •610 .563

8 120 *670 *626

9 136 *770 *73li

p ro d u c t *800 *767

D u st c a rry o v e r .8 6 0
 92

O p e ra tin g B a ta Hun #2 0

R e a c to r numbe r 8 w as i n s u l a t e d a n d p ro v id e d w ith a h e a te d f e e d con­

t a i n e r w hich w as f i l l e d w ith one pound o f t a b l e s a l t .

F e e d te m p e ra tu re # 316°C

A ir r a te s *25 c u b ic f e e t p e r m in u te

S u lp h u r di ox i d e r a t e s *015 c u b ic f e e t p e r m in u te

The s u lp h u r dioari.de a s s t a r t e d b e fo r e th e s a l t * The s a l t f e e d

v e s s e l w as p lu g g e d a t th e b o tto m , b u t flo w w as s t a r t e d b y c le a r in g th e

f e e d p o r t w ith a w ir e , how ever s e v e r a l lum ps o f s a l t e n te r e d a t th e be­

g in n in g * T h is s a l t w h ich w as a t th e b o tto m o f th e f e e d v e s s e l was n o t

c lo s e enoujdi t o th e h e a t e r w ire t o h av e re a c h e d th e r e a c to r te m p e ra tu re *

The f i r s t s a l t t o f lo w im m e d ia te ly s tu c k t o th e g la s s v e s s e l a t w id e ly

s c a t t e r e d p o i n t s , m a in ly a t th e c o n s tr ic tio n s re d u c in g t h e i r d ia m e te r an d

pr e v e n tin g downward flo w * The ru n w as te r m in a te d due t o th e p o o r flo w

c o n d itio n s *

O p e ra tin g B ata Hun # 2 1

B e a c to r num ber 8* A v erag e i n l e t gas te m p e ra tu re i 260°C

A ir r a t e s *22 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e ) *00? c u b ic f e e t p e r m in u te

T o ta l p r e s s u r e d ro p th ro u g h e n t i r e a p p a ra tu s b e fo re in tr o d u c tio n

o f s a l t one a n d one h a l f in c h e s o f w a te r j a f t e r in tr o d u c tio n o f s a l t

f i v e a n d o n e h a l f in c h e s o f w a te r*

F iv e m in u te s o f s a t i s f a c t o r y o p e ra tio n was o b ta in e d by s t a r t i n g th e
flo w o f s u lp h u r d io x id e g a s a f t e r s t a r t i n g th e flo w o f s a l t* b iq u id was

n o tic e d co n d en sed to fo rm a s in g le d ro p a t th e b o tto m o f th e r e a c to r *

 n

l i q u i d c o n d e n s a tio n was assu m ed t o b e th e c a u se o f th e s a l t s tic k in g t o

t h e g l a s s a t th e lo w e r c o n s tr ic tio n #

C hanges P r io r t o Hun #22

T he s u lp h u r d io x id e e n tr a n c e was changed fro m th e fu rn a c e i n l e t t o

th e o u tle t#

O p e ra tin g l a t a Bun #22

B e a e to r num ber 6* A v erag e i n l e t g as te m p e ra tu re 38£°C .

A ir r a t e s #2U c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s #006 c u b ic f e e t p e r m in u te

T he a i r r a t e w as g r a d u a lly d e c re a s e d o v e r a p e r io d o f f o r ty - n in e

m in u te s fro m th e i n i t i a l r a t e o f #21* cfra* t o #19 efm* The s u lp h u r di*»

o x id e r a t e w as h e ld c o n s ta n t# The p ro d u c t c o n ta in e d no s u lp h a te s #

O p e ra tin g B a ta Bun #23

B e a e to r num ber 8* A v erag e i n l e t g as te m p e ra tu re l*2U°C#

A ir r a t e s #29 c u b ic f e e t p e r m in u te

The r e a c t o r w as o p e ra te d f o r f o u r te e n m in u te s a n d g av e a p ro d u c t

sh o v in g a t r a c e o f s u lp h a te s e s tim a te d t o b e a b o u t one o r tw o p e r c e n t.

O p e ra tin g D ata Bun #21*.

B e a e to r num ber 8# A v erag e I n l e t g a s te m p e ra tu re U02°C#

A ir r a t e s #3 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s #003 c u b ic f e e t p e r m in u te

A s o l u t io n o f f e r r o u s c h lo r id e was s p ra y e d on th e f e e d w hich was th e n

d rie d * The am ount o f i r o n on th e s a l t w as e s tim a te d t o b e a b o u t *2$*

T w elve m in u te s o p e r a tio n r e s u l te d i n a p ro d u c t show ing a t r a c e o f s u lp h a te s #

 O p e ra tin g D ata Bun #35

B e a e to r num ber 8* A v erag e i n l e t g a s te m p e ra tu re UOO°C*

A ir r a t e i *26 c u b ic f e e t p e r m in u te

^ u lp h u r d io x id e r a te * *0)45 c u b ic f e e t p e r m in u te

T he sam e f e e d w as u s e d a s i n Run #2U* A f te r tw e lv e m in u te s opera***

t i a n th e p ro d u c t show ed a t r a c e o f s u lp h a te s * The c o n v e rsio n h ad ta k e n

p la c e o n ly on th e l a r g e s t s a l t p a r t i c l e s w h ich w ere th o u g h t t o have

b een lo c a te d a t t h e lo w e r p o r tio n o f th e r e a c t o r w here th e te m p e ra tu re

w as t h e h i p e s t *

C hanges P r i o r To Run # 2 6

T he r e a c t o r w as r e i n s n la te d a n d w rapp ed w ith h e a te r w ire t o p ro d u ce

m ore ev en h e a tin g a n d h ig h e r te m p e ra tu re s •

O p e ra tin g D ata Run #26

R e a c to r num ber 8* A v erag e i n l e t g a s te m p e ra tu re k77°0

A ir r a te * *2 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a te * *026 c u b ic f e e t p e r m in u te

The sam e f e e d w as u s e d a s i n Run #2ii

A f t e r e ig h t y - s i x m in u te s o p e ra tio n th e p ro d u c t show ed a t r a c e o f

s u lp h a te s *

O p e ra tin g D ata Run #27

R e a c to r num ber 2* A v erag e r e a c t o r te m p e ra tu re 390°C

A ir r a te * 1*5 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a te * #Qli5 c u b ic f e e t p e r m in u te

A h a l f in c h b ed o f t a b l e s a l t w as p la c e d in th e re a c to r*
 95

A f t e r tw e n ty m in u te s smoke w as n o te d a t th e s c ru b b e r e x it* The ru n

w as te r m in a te d a f t e r t h i r t y - e i g h t m in u tes* T he p ro d u c t c o n ta in e d a t r a c e
o f s u lp h a te *

O p e ra tin g D ata Bun # 2 8

B e a e to r num ber 9* ( e l e c t r i c a l l y h e a te d a n d in s u la te d )

A v erag e te s p e r a tu r e o f i n l e t g a s 5U60C

A ir r a t e I ,U l c u b ic f e e t p e r m in u te

Su lp h u r d io x id e r a te * ,0 b c u b ic f e e t p e r m in u te

T he u n i t w as o p e ra te d f o r t e n m in u te s . T he p ro d u c t c o n ta in e d a

t r a c e o f s u lp h a te . The te a p e r a tu r e o f th e s a l t was assum ed t o b e much

lo w e r th a n t h e i n l e t g a s te m p e ra tu re b e c a u se o f u n in s u la te d dovmcomer

ta b e s *

O p e ra tin g B a ta Bun # 2 ?

B e a e to r num ber 7 u n in s u la te d

C harge 100 gram s t a b l e s a l t p lu s 5 gram s ir o n o x id e . The h ig h e s t

te m p e ra tu re o b ta in a b le w as 2b0°C a t an a i r r a t e o f *b c u b ic f e e t p e r

m in u te . B ecau se o f th e lo w tem perature s u lp h u r d io x id e was n o t s t a r t e d

a n d t h e r u n w as d is c o n tin u e d *

O p e ra tin g B a ta Bun # 3 0

R e a c to r num ber 7 wound w ith h e a te r w ire a n d i n s u la te d

C h arg e sam e a s Bun # 2 9

The te m p e ra tu re i n th e r e a c t o r re a c h e d hO O O C w ith o u t s a l t p r e s e n t

and n o g a s flo w in g . A f te r th e flo w o f r e a c tio n g as w as s t a r t e d an d th e

s a l t w as p la c e d i n th e r e a c t o r t h e te m p e ra tu re re a c h e d 3 8 0 ° C f The lo w e r
 96

s e c tio n , o f t h e r e a c t o r b e n t da© t o it® om -w eight a f t e r a b o u t tw e n ty

m im te s * The p ro d u c t c o n ta in e d & t r a c e o f su lp h a te # M ic ro sc o p ic ex ­

a m in a tio n show ed a p i t t e d s u r f a c e on th e s a l t b u t n o t s u f f i c i e n t r e a c tio n

t o r e n d e r th e c r y s t a l opaque#

C hanges P r io r t o ftim #31

S e v e r a l ch an g es i n t h e d e s ig n o f th e f u r n a c e w ere made i n an a tte m p t

t o o b ta in h ig h e r g a s te n ^ e r a tu r e s a t lo w e r r a te s # S a t is f a c to r y r e s u l t s

w ere o b ta in e d w ith tw e n ty - f iv e f e e t o f one e ig h th in c h p ip e* R e a c to r

num ber 7 u s e d i n th e fo llo w in g ru n s*

O p e ra tin g D ata Hun #31

C h arg e 30 grains t a b l e s a l t p lu s 5 gram s o f i r o n o x id e re d u c e d fro m

i r o n s u lp h a te *

A ir r a t e f *b c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e 1 a b o u t *05 c u b ic f e e t p e r m in u te

Tim e T e m p e ra tu re Rem arks

Ifin* OC s u lp h u r d io x id e ro ta m e te r f l u c t u a t i n g o v e r
e n t i r e s c a le
0 5 20

u 5U0 smoke fo rm s i n u p p e r p a r t o f r e a c to r an d
e s c a p e s fro m le a k s a t r e a c t o r c o v e r

7 600 rem oved a i r fro m f u e l m ix tu re

13 560 no s ig n s o f f l u i d i z a t i o n s u lp h u r d io x id e
ro ta m e te r s to p p e r f lu c tu a tin g # Run te rm in a te d #

T he b e d w as s o l i d w ith a h o le on one aid e* A la r g e cak e h a d fo rm ed

w h ich c o n ta in e d a p p r e c ia b le su lp h a te # Iro n c a t a l y s t on t h e s u r f a c e h a s

p a r t i a l l y tu r n e d b lack *
 9?

Operating Seta Hun #32

Charge 1)0 graas ta b le s a lt , no c a ta ly st
T ine T esperature A ir Hate Sulphur d io x id e Remarks
M in. °C Cjtau B ate Cfm,

0 500 .35 .01

1 510
3 500
5 U95
10 1)80
15 U80 sam ple 1 s lig h t tr a c e o f su lp h ate
In creased sulphur d io x id e r a te «0 li5
22 1)85 .35 .01*5
2U to o .3 5 .01)5
27 b95 .35 .0lj5
33 U95 sam ple 2 heavy tr a c e o f su lp h ate
In creased fu e l ra te to th e fu rn ace reduced a ir ra te
38 500 .3 0 ,0U5
ID 520 .3 0 «0i)5
1(2 580 .3 0 .01)5 stopped fluidH ning
Cut sulphur dload.de ra te to sere
li5 tapped rea cto r — flu id ls in g in cen ter - cake on r a ils
1)7 1»60
b8 m»np\e 3 sane tra ce o f su lp h ate as sam ple 2
55 added 1 0 grams o f s a lt containing c a ta ly s t, sta r te d gas
61 15 0 .3 0 .0 2 6
62 1)60 .3 0 .0 2 6
63 1)70 .3 0 .026
61) U80 .3 0 .0 2 6 changed gas ra tes
68 U90 .3 2 .021)
72 500 .3 2 .021)
80 510 .3 2 . 021) sam pleU heavy tra ce
sn ilp h a te
95 510 *32 «02li sample 5heavy trace
s u lp h a te
T e rm in a te d th e ru n
 O p e ra tin g D ata &u» #33

Ch& rge i|.0 grains t a b l e s a l t p lu s 5 gram s a c t iv a t e d ir o n o x id e

A ir r a t e s *35 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s *012 c u b ic f e e t p e r m in u te

T im e T e m p e ra tu re Rem arks
j£ n * «C

0 350 H e a t w as in c r e a s e d a f t e r e a c h sanpl©

10 3 80 w as ta k e n * H a ss le 1 no s u lp h a te s *

36 1*30 sam ple 2 n o s u lp h a te s

69 1*95 sam ple 3 t r a c e o f s u lp h a te

95 5h0 sam ple 1* h eav y t r a c e o f s u lp h a te

117 590 sam ple 5 h eav y t r a c e o f s u lp h a te

121* 580 s u lp h u r d io x id e r a t e r a i s e d t o *01*5 cfm*

lh2 5 90 sam ple 6> r e a c t o r s t i l l fX u id ia in g *

T e rm in a te d th e ran *

Sam ple 6 c o n ta in e d 5^ so d iu m su lp h a te *
 99

O p e ra tin g Itetta. Run #3U

Q ia ig e 1*0 gram s t a b l e s a l t

A ir r a te s *liU c u b ic f e e t p o r m in u te

S u lp h u r t r l 02d.de r a t e s *006 c u b ic f e e t p e r m inute# S u lp h u r trdL*»

aati.de w as g e n e ra te d by h e a tin g 3G$ oleum *

Tim e T em p era tu re Rem arks

Min* OG

0 310 f lu id ls s in g m i l

7 300

11 sam ple 1 t r a c e o f s u lp h a te

13 2 ?0 no smoke • v is ib le a t a n y p o in t

S u lp h u r t r i o x i d e f l o a t s ti c k i n g w ith l i q u i d a n d tu rn in g
b la c k * l i q u i d s a y b e s u lp h u r ic a d d

18 295

21 sam p le 2 t r a c e o f s u lp h a te

2 li S u lp h u r t r i o x i d e ro ta m e te r f u l l o f l i q u i d . Run sto p p ed *

C hanges P x io r t o Run #35

A new r o ta m e te r f l o a t w as made o f p o ly e th y le n e f o r m easu rin g s u lp h u r

dioad.de flo w * A c a t a l y s t cham ber w as p la c e d i n th e fu rn a c e * I t c o n s is te d

o f a f orfcy in c h s e c tio n o f h a lf in c h p ip e c o n ta in in g a c t iv a t e d ir o n o x id e

s u p p o rte d on a s b e s to s f ib r e *

O p e ra tin g D ata Run #35

The u n i t w as o p e ra te d w ith o u t h e a t o r s a l t t o d e te rm in e i n i t i a l s u l­

p h u r d io x id e c o n c e n tra tio n * S u lp h u r d io x id e was d e te rm in e d by a b s o r p tio n

o f t h e g a s i n a volum e o f I o d in e s o lu tio n o f known s tr e n g th , a n d a ls o by

a b s o r p tio n i n a c a u s tic s o lu tio n o f known s tre n g th *

 100

T he I n i t i a l c o n c e n tr a tio n d e te rm in e d m s U*55% by* volum e* W ith th e

u n i t h e a te d t o g iv e a g a s t© i^ > era tu re o f 310°C th e s u lp h u r d io x id e concen­

t r a t i o n d ro p p ed t o 1*Q£ b a se d on a b s o rp tio n i n Io d in e s o lu tio n * A b s o rp tio n

i n c a u s t i c in d ic a te d a t o t a l o f 2*7$ o f b o th s u lp h u r d io x id e a n d trio x L d e *

The g a s sa m p lin g tu b e when, w ith d raw n fro m th e r e a c t o r T utted s tr o n g ly in d i­

c a tin g th e p re s e n c e o f l i q u i d oleum * The c o n d e n sa tio n i s th o u g h t t o a c c o u n t

f o r th e le e r c o n c e n tr a tio n o f g as o b ta in e d b y a b s o r p tio n i n c a u s tic s o lu tio n *

A f te r in tr o d u c tio n o f s a l t i n th e r e a c t o r th e e v o lu tio n o f e aoke s to p p e d

completely a n d a n a ly s e s show ed o n ly #59$ s u lp h u r d io x id e a n d *53$ o f b o th

g a se s* T he d if f e r e n c e o f th e l a s t tw o f i g u r e s i s assum ed t o r e s u l t fro m

e x p e rim e n ta l e r r o r * T he u n i t w as o p e ra te d f o r an h o u r a n d gave a p ro d u c t

w h ich c o n ta in e d 37% so d iu m c h lo r id e b a se d on c h lo r id e a n a ly s is * A sm a ll

am ount o f c a k e h a d fo rm ed i n th e b o tto m o f th e r e a c to r *

O p e ra tin g D ata &un # 3 6

C harge 1*0 gram s t a b l e s a l t

A ir r a t e s *51* c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a te * *02 c u b ic f e e t p e r m in u te

T e m p era tu re * 230°C
A f t e r se v e n m in u te s th e s a l t beg an t o s t i c k to g e th e r a n d t o th e r e a c to r

fo rm in g a f u n n e l sh a p e d s e c tio n i n th e c e n te r o f th e b e d from w hich s a l t

w as blow n a s h ig h a s th e to p c o v e r o f th e r e a c to r* The ru n w as sto p p e d

a f t e r t e n m in u te s due t o s t i c k i n e s s a n d l i q u i d c o n d e n sa tio n on th e r e a c ­

t o r w a lls * T he p ro d u c t c o n ta in e d sodium c h lo r id e b a se d on a c h lo r id e

a n a ly s is *
 io i

C hanges P r i o r t o Run #37

An e x te r n a l j a c k e t h e a te r w as p la c e d a ro u n d th e tip p e r s e c tio n o f th e

r e a c to r * The te m p e ra tu re o f th e i n t e r n a l h e a t e r w a s re d u c e d t o e lim in a te

th< e x is te n c e o f a l o c a l h o t s p o t fo u n d a t th e r e a c t o r i n l e t * The h u ia id i-

f i e r w as p a r t i a l l y d r ie d o u t t o p e rm it th e u s e o f a i r o f a lo w e r h u m id ity *

O p e ra tin g D ata Run #37

Ch&zge UO gram s t a b l e s a l t

A ir r a t e i *U c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s *02 c u b ic f e e t p e r m in u te

Denr p o in t o f a i r a t s t a r t o f ru n * 2!*1°C $ a t en ds 30*0°C

T e m p e ra tu re a t b o tto m o f r e a c t o r s 3U0OC a n d 300OC a t b e d l e v e l

u s in g e x te r n a l h e a te r s o nly*

Tim e T e m p e ra tu re Rem arks

l& n . °C

0 300
17 330 No smoke v i s i b l e
23 3U0 s a u p le 1
35 3U5 No c o n d e n sa tio n e v id e n t
37 3U5 sam p le 2
50 31(5 s a n p le 3
63 3U0 sam p le U w h ite f i n e s in d is c h a rg e
75 3l*0 sanqple 5
90 3U0 sam ple 6
10U 3U0 sam p le 7
121 3U0 sam ple 8
122 335 sm oke b e g in n in g t o a p p e a r fro m le a k s i n sc ru b *
b e r a n d fro m r e a c t o r when c o v e r i s r a is e d *
130 325 s a n p le 9
iTt2 325 sam p le 10 sm oke v i s i b l e i n u p p e r r e a c t o r , f i n e s
h a v e d isa p p e a re d *
1U5 320
320 sam p le 11
15*7 320 oacg>le 12
180 3 20 sam ple 13
187 320 n o te d c o n d e n sa te d rip p in g i n to b ed fro m e x i t tu b e*
S to p p ed th e run*

A v erag e w e ig h t o f sam p les — one gram

 2M

A p p earan ce o f B e a e to r F o llo w in g Bun #37

A f te r t h e r e a c t o r h a d c o o le d p a r t i a l l y i t w as r©moved a n d th e p ro d u c t

w as p o u re d fro m th e b o tto m g a s i n l e t - no e v id e n c e o f cak e fo rm a tio n , how ever

t h e r e w e re s m a ll h a rd b a l l s o f p ro d u c t due t o t h e a c i d w hich h a d co n d en sed

o n t h e e x i t tu b e a n d d ro p p ed i n to t h e re a c to r # E v id e n tly h ig h te m p e ra tu re

in t h e i n l e t elb o w h a d c a u se d p y ro s u lp h a te t o m e lt i n e a r l i e r ru n s c a u s in g

cake# Low te m p e ra tu re i n s u l a t i o n on th e u p p e r p a r t h a d p ro b a b ly a llo w e d

a c i d c o n d e n s a tio n c a u s in g s a l t t o s t i c k t o th e w a lls #

Sam ple A n a ly s is Run #37 B ased on C h lo rid e

i e H o. Tim e HLn. %H ad P

1 23 95 .0 5 0

2 37 9 1 .8 .0 8 2

3 50 6b .1 6 0

b 63 7 7 .2 .2 2 8

5 75 6b .3 6 0

6 90 5 5 .5 «bb5

7 lo t; b5 .5 5

8 121 1 9 .2 .8 0 8

9 130 1 1 .5 .8 ®

10 lb 2 10*3 .8 9 7

11 35b 7 .9 .9 2 1

12 167 6 .7 .9 3 3

33 180 3 .3 .9 6 7
 O p e ra tin g D ata Hun #3 8

C h arg e ho grains ro c k s a l t p a s s e d ££> mesh

Dew p o in t o f a i r s 3 2 *2 °C

A ir r a t e t *16 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e I *0l£ c u b ic f e e t p e r adarrat©

T e m p e ra tu re in c r e a s e d fro m 280°C t o 310®C o v e r a t h i r t y - f o u r m in u te

ru n * T he s a l t b egan t o a p p e a r s ti c l q r a n d fo rm ed 1 ub$>s * T he run. w as die-*

c o n tin u e d . T he p ro d u c t c o n ta in e d ?3$ sodium c h lo rid e * T he r e a c tio n r a t e

i s CGB^ar&hle t o Run #36 b u t g a s r a t e s a r e to o low f o r s a l t o f t h i s p a r t i c l e

s iz e * H ig h e r g a s r a t e s c a u s e e x c e s s iv e c a rry o v e r* H igh a i r dew p o in t a n d

lo w te s p e n a tn r e may h a v e c a u se d th e fo rm a tio n o f lum ps#

O p e ra tin g D ata Run # 3 9

C h arg e UO gram s t a b l e s a l t

A ir r a t e s *35 c u b ic f e e t p e r m in u te

Sulphur d io x id e r a t e s *02 c u b ic f e e t p e r m in u te
Dew p a i n t o f a i r 32*2°C

Some s t i c k i n e s s w a s n o tic e d a f t e r a n h o u r o f o p e ra tio n * The p r e s s u r e

b u i l t up d u rin g th e ru n u n t i l th e m erc u ry m anom eter blew o u t a t a p r e s s u r e

o f f i f t e e n in c h e s* The f u rn a c e w as fo u n d t o be plu gg ed *

O p e ra tin g D ata Run #U0

R e a c to r num ber 8 i n s u l a t e d a n d wound w ith h e a te r w ire re a c h e d a tem ­

p e r a tu r e o f 260°C w ith o u t s o l i d o r g as flo w in g * The a v e ra g e i n l e t te m p e ra tu re

o f th e g a s w as 2£5°C* The a i r dew p o in t w as a b o u t 25 °C

C harge 60 gram s o f t a b l e s a lt*

 1 th

i n i t i a l a i r ra te s *22 c u b ic f e e t p e r m in u te

F in a l a i r r a te s #10 c u b ic f e e t p e r m in u te

S u lp h u r d io x id e r a t e s a v e ra g e #015 c u b ic f e e t p e r m in u te

A f te r s e v e r a l m in u te s th e s o l i d r a t e d e c re a s e d t o a e ro due t o condense**

l i o n o f l i q u i d a t th e b o tto m o u t l e t o f th e r e a c to r # The u n i t m s o p e ra te d

b a tc b w is e f o r two h o u rs when th e e v o lu tio n o f smoke i n d ic a te d n e a r ly cqkm

p l e t e r e a c tio n * T he p ro d u c t c o n ta in e d iU .5 $ sodium c h lo r id e b a se d on a

c h lo r id e a n a ly s is * a n d s i x t y —f i v e p e r c e n t sodium b is u lp h a te b a se d on ti**
t

t r a t i c n . o f t h e a c id ity #

A c id ity D e te rm in a tio n s

C a lc u la tio n o f th e w e ig h t p e r c e n t o f sodium b is u lp h a te in s e v e r a l

sa m p le s w as made b a s e d on t i t r a t i o n w ith so dium h y d ro x id e u s in g m eth y l

o ra n g e f o r a n in d ic a to r * T he r e s u l t s a r e shown below *
% C o n v e rsio n % Sodium b is u lp h a te
P ro d u c t Bun #1/6 50«0 8*0
P ro d u c t Bun #15 99 f 2U#Q
Sam ple 7> Bun #15 P2#5 0
 ID?

C hea& cal A a a ly s is

S u lp h a te s w ere d e te rm in e d u s in g a c a l i b r a t e d P& rr tu rb id im e te r* A

s a u p le o f m a te r ia l wbls w eig h ed a n d d is s o lv e d i n 200 m l o f s o lu tio n con-*

t a i n i n g I;* 8 grants o f sodium c h lo r id e a n d *i; ml o f h y d r o c h lo r ic a c id * One

grsuB o f b a riu m c h lo r id e w as th e n added; th e s o lu tio n sh ak en f o r one m in u te

a n d th e tu zb i& L m eter re a d in g ta k e n * The c a l i b r a t i o n w as made u s in g e a u p le s

o f pare sodium s u lp h a te a c c o rd in g t o th e sam e p ro c e d u re *

C h lo rid e s w ere d e te rm in e d b y t i t r a t i o n u s in g a s ta n d a r d is e d s i l v e r

n i t r a t e s o lu tio n an d p o ta s s iu m ch ro m ate a s a n in d ic a to r * A c id ity w as

n e u t r a l i z e d b y t i t r a t i o n w ith sodium h y d ro x id e b e fo r e t h e c h lo r id e d e te r ­

m in a tio n w as made*
 BICGBiPHY

B o g er F o s t e r B e tm n w as b o m i n Long Is la n d * New Y ork i n X91?*

He a tte n d e d e le m e n ta ry a n d gram m ar s c h o o ls i n New York* F lo r id a a n d

P e n n sy lv a n ia * He a tte n d e d h ig h s c h o o ls i n P e n n sy lv a n ia an d M is s is s ip p i*

g r a d u a tin g fro m h ig h s c h o o l a t C olum bia, M is s is s ip p i* H is u nd e-n g rad u ate

w ork le a d in g t o th e b a c h e lo rs d e g re e i n c h e m ic a l e n g in e e rin g wlb done a t

L o u is ia n a S t a te U n iv e r s ity fro m 193U t o 1939* He w as em ployed by th e

Humble O il an d D e fin in g Company a l t e r g r a d u a tio n u n t i l c a l le d t o a c tiv e

d u ty i n th e Anzgr i n 19ii2* w here h e s e rv e d a s a r a d a r o f f ic e r * He w as

r e le a s e d fro m th e arm ed s e r v ic e i n th e g ra d e o f c a p ta in a n d r e - e n te r e d

L o u is ia n a S t a te U n iv e r s ity i n 19ii6 t o p u rs u e g ra d u a te s tu d ie s i n c h e m ic a l

e n g in e e rin g * He o b ta in e d th e M a ste r o f S c ie n c e d e g re e in 19it8* a n d i©

a t p r e s e n t a c a n d id a te f o r th e d e g re e o f D o c to r o f P h ilo so p h y *

106
 EX A M IN A TIO N AN D TH ESIS R E PO R T

Candidate: R o g e r F . Detm an

Major Field: C h e m ic a l E n g in e e r in g

Title of Thesis: a F l u i d i s a t i o n P r o c e s s f o r P r o d u c ti o n of Sodium S u lp h a te fro m

Sodium C h lo r id e

Approved:

ajor Professor and Chairman

D eal the Graduate School

EXAM INING COMMITTEE:

Date of Exam ination:

A u o u st 3 i 191-9