Regeneration of a nickel carbonate desulfurization catalyst
by Glenn A Whan
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering
Montana State University
© Copyright by Glenn A Whan (1952)
Abstract:
The purpose of this investigation was to find the optimum conditions for regenerating, easily and
economically, a spent nickel desulfurization catalyst. Two main steps in the regeneration are the
oxidation of nickel sulfide to form nickel sulfate and wet chemical regeneration, i, e. precipitation of
nickel carbonate using sodium carbonate. The nickel carbonate is then dried and used as an active
desulfurization catalyst.
The oxidation step was investigated in a fluid oxidation unit to determine optimum conditions for
producing a soluble sulfate in the hope of eliminating the use of excessive amounts of sulfuric acid, A
sulfuric acid leach is used to sulfate all nickel not sulfated by oxidation. Optimum conditions for
oxidation were found to be a temperature of about 850°F and a contact time of one to two hours.
Aside from initial activity, the value of a nickel catalyst is determined by the extent of catalyst
utilization. Catalyst utilization, based on the percent of nickel converted to nickel sulfide, was
investigated by testing variously prepared catalysts in a comparison unit. The comparison unit was
designed so that various catalysts could be run under identical hydrofining conditions. Not only
conditions of hydrofining but also conditions of wet chemical regeneration of the catalyst affect the
extent of catalyst utilization, A study was made of catalyst utilization with respect to precipitation and
digestion conditions and the effect of entrained salt, A catalyst demonstrating maximum sulfiding was
precipitated when a slight excess of sodium carbonate was rapidly added to a solution of nickel sulfate,
with little or no time allowed for digestion. Slight traces of entrained salt appeared to be beneficial to
maximum catalyst utilization. REGENERATION OF A NICKEL' CARBONATE
' DESULFURIZATION CATALYST
by
GLENN A. WHAN
A THESIS ' ■
Subm d.ttecl t o t h e G r a d u a te F a c u l t y
in
p a r t i a l f u l f i l l m e n t o f t h e r e q u i r e m e n ts
f o r th e d e g re e o f
M a s te r o f S c ie n c e i n C h e m ic a l E n g in e e r in g
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M o n tan a S t a t e C o lle g e
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■B ozem ans M o n tan a
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TABLE OF CONTENTS
page
ABSTRACT.....................................................................................................
3
INTRODUCTION.............................................................................................................................
4
OXIDATION.................................................................................
7
A p p a r a tu s and E q u ip m e n t...................................................................................................... 8
9
P r o c e d u r e . . .................................
T herm odynam ic C a l c u l a t i o n s ...........................................
10
R e s u l t s ....................................................
13
WET CHEMICAL REGENERATION............................
15
E ffe c t o f C a ta ly s t U tiliz a tio n
......................................................................... . 1 6
A p p a r a tu s a n d E q u ip m e n t.................................
18
M a t e r i a l s and P r o c e d u r e .............................................................................
. . . .
C a l c u l a t i o n s ....................................................................................................................
R e s u l t s ......................................
20
.2 2
24
SUMMARY....................................................................................................................................... ....
ACKNOWLEDGEMENT...................................................................................................................
. 28
29
LITERATURE CITED.................................................................................................................................30
APPENDIX.................................................................................................................................................... 31
103327
ABSTRACT
The p u r p o s e o f t h i s i n v e s t i g a t i o n w as t o f i n d t h e optim um c o n d i t i o n s
f o r r e g e n e r a t i n g j , e a s i l y a n d e c o n o m i c a l ly , a s p e n t n i c k e l d e s u l f u r i z a t i o n •
c a t a l y s t . Two m a in s t e p s i n t h e r e g e n e r a t i o n a r e t h e o x i d a t i o n o f n i c k e l
s u l f i d e t o fo rm n i c k e l s u l f a t e a n d w e t c h e m ic a l r e g e n e r a t i o n , i , e . p r e ­
c i p i t a t i o n o f n i c k e l c a r b o n a te u s i n g so d iu m c a r b o n a t e . The n i c k e l c a rb o n ­
a t e i s t h e n d r i e d an d u s e d a s a n a c t i v e d e s u l f u r i z a t i o n c a t a l y s t .
The o x i d a t i o n s t e p w as i n v e s t i g a t e d i n a f l u i d o x i d a t i o n u n i t t o d e t e r ­
m in e optim um c o n d i t i o n s f o r p r o d u c in g a s o l u b l e s u l f a t e i n t h e h o p e o f
e l i m i n a t i n g t h e u s e o f e x c e s s i v e a m o u n ts o f s u l f u r i c a c i d , A s u l f u r i c a c i d
l e a c h i s u s e d t o s u l f a t e a l l n i c k e l n o t s u l f a t e d b y o x i d a t i o n . Optimum
c o n d i t i o n s f o r o x i d a t i o n w e re fo u n d t o b e a t e m p e r a t u r e o f a b o u t 850°F an d
a c o n t a c t tim e o f o n e t o tw o 1h o u rs ,,
A s id e fro m i n i t i a l a c t i v i t y , t h e v a lu e o f a n i c k e l c a t a l y s t i s d e t e r ­
m in ed b y t h e e x t e n t o f c a t a l y s t u t i l i z a t i o n .
C a ta ly s t u t i l i z a t i o n , based
o n t h e p e r c e n t o f n i c k e l c o n v e r t e d t o n i c k e l s u l f i d e , w as i n v e s t i g a t e d b y
t e s t i n g v a r i o u s l y p r e p a r e d c a t a l y s t s i n a c o m p a ris o n u n i t , "The c o m p a ris o n
u n i t w as d e s ig n e d s o t h a t v a r i o u s c a t a l y s t s c o u ld b e rub. u n d e r i d e n t i c a l
h y d r o f i n i n g c o n d i t i o n s . N ot o n l y c o n d i t i o n s o f h y d r o f i n i n g b u t a l s o con­
d i t i o n s o f w e t c h e m ic a l r e g e n e r a t i o n o f t h e c a t a l y s t a f f e c t t h e e x t e n t o f
c a t a l y s t u t i l i z a t i o n , A s t u d y w as m ade o f c a t a l y s t u t i l i z a t i o n w i t h
r e s p e c t t o p r e c i p i t a t i o n an d d i g e s t i o n c o n d i t i o n s a n d t h e e f f e c t o f en­
tra in e d s a l t ,
A c a t a l y s t d e m o n s t r a t i n g ' maximum s u l f i d i n g w as p r e c i p i t a t e d
when a s l i g h t e x c e s s o f s o d iu m c a r b o n a te w as r a p i d l y a d d e d t o a s o l u t i o n
o f n i c k e l s u l f a t e , w i t h l i t t l e o r b o t im e a llo w e d f o r d i g e s t i o n . S l i g h t
t r a c e s o f e n t r a i n e d •s a l t a p p e a r e d t o b e b e n e f i c i a l t o maximum c a t a l y s t
u tiliz a tio n .
HTRODUCTIOIT
T he e v e r - i n c r e a s i n g dem and f o r ' p e tr o l e u m p r o d u c t s a n d t h e d e p l e t i o n
o f h i g h q u a l i t y 5 lo w s u l f u r c r u d e s h a s f o r c e d r e f i n e r s t o r u n m ore and
m ore lo w q u a l i t y ? h i g h s u l f u r C r u d e s s s u c h a s t h o s e fo u n d i n t h e R ocky
M o u n ta in a r e a s W est T e x a s s a n d C a l i f o r n i a ,
R e l a t i v e v o lu m es o f h ig h
s u l f u r c r u d e o i l p ro d u c e d i n t h e U n ite d S t a t e s h a v e i n c r e a s e d c o n s i d e r ­
a b l y o v e r t h e l a s t s e v e r a l y e a r s ( 9 )»
I n c r e a s e d u s e o f h i g h s u l f u r c r u d e s h a s c r e a t e d a s e r i o u s p ro b le m o f.
d e s u lfu riz a tio n .
H ig h s u l f u r c o n t e n t i n c r u d e s t o c k s r e s u l t s i n p r o d u c t s
t h a t d e m o n s tra te ah o b je c tio n a b le o d o rs c o r r o s iv e n e s s s and p o o r c o lo r
s ta b ility ,
A ls o s d i f f i c u l t i e s h a v e a r i s e n w i t h r e s p e c t t o s lu d g e f o r m a tio n
u p o n s t o r a g e o f f u e l o i l s d e r i v e d fro m h i g h - s u l f u r c r u d e s ( l l ) ,
A c o n s i d e r a b l e num ber o f m e th o d s a r e a l r e a d y i n e x i s t e n c e f o r re m o v in g
o r c h a n g in g t h e fo rm o f s u l f u r com pounds p r e s e n t i n p e tr o l e u m d i s t i l l a t e s .
T h e s e s h o w e v e rs a r e u s e d f o r r e l a t i v e l y lo w c o n c e n t r a t i o n s o f s u l f u r com­
p o u n d s p r e s e n t i n t h e m ore r e a c t i v e f o r m .
H ig h -s u lfu r c o n te n ts i n p e tr o ­
le u m s t o c k s a r e u s u a l l y d u e t o t h e p r e s e n c e o f t h io p h e n e s a n d t h io p h a n e s
t h a t c a n b e rem o v ed o n l y b y c a t a l y t i c d e c o m p o s itio n i n t h e p r e s e n c e o f
h y d ro g e n ( 2 ) ,
N ic k e l com pounds o r f r e e n i c k e l i s a n a c t i v e c a t a l y s t f o r t h e d e s u lf u r - ?
i z a t i o n o f h y d r o c a r b o n d i s t i l l a t e s i n a h y d ro g e n a tm o s p h e re ( 6 ) ( ? ) »
The
n i c k e l o r n i c k e l com pounds' may b e c a t a l y s t s a c t i n g t o rem o v e t h e s u l f u r a s
h y d ro g e n s u l f i d e o r . may be. r e a g e n t s r e s u l t i n g i n t h e f o r m a ti o n o f n i c k e l
*
s u lfid e .
N i c k e l o x id e s u p p o r t e d o h a lu m in a o r a s i m i l a r s u p p o r t h a s b e e n
u s e d a s a c o n t a c t a g e n t f o r re m o v in g s u lf u r .c o m p o u n d s fro m l i g h t p e tr o le u m
h y d r o c a r b o n s w i t h o u t a f f e c t i n g t h e o l e f i n c o n t e n t (&)<,
F is c h b a c h ( 4 ) h a s
i n v e s t ig a t e d th e p r e p a r a tio n o f a n i c k e l o x id e d e s u l f u r i z a t i o n c a t a l y s t
t h a t c a n b e u s e d t o rem o v e e v e n t h e m o st r e f r a c t o r y s u l f u r com pounds fro m ,
f u e l o i l w ith l i t t l e
o r no h y d ro g e n c o n su m p tio n * p r o d u c in g a p r o d u c t o f
im p ro v e d a p p e a r a n c e * b e t t e r o d o r* a n d g r e a t e r s t a b i l i t y .
However* a s i d e fro m i n i t i a l a c t i v i t y * t h e v a l u e o f a n y c a t a l y s t i s
d e te r m in e d b y tw o f a c t o r s : • t h e e a s e w i t h w h ic h t h e i n i t i a l a c t i v i t y c a n
be re s to re d
a f t e r i t h a s d e c l i n e d d u r i n g u s e a n d t h e num ber o f t im e s s u c h
r e g e n e r a t i o n c a n b e a c c o m p lis h e d b e f o r e i t i s n e c e s s a r y t o d i s c a r d t h e
c a ta ly s t*
The p u r p o s e o f t h i s i n v e s t i g a t i o n w as t o d e te r m in e t h e optim um c o n ­
d i t i o n s f o r r e g e n e r a t i n g * e a s i l y a n d e c o n o m ic a lly * a s p e n t n i c k e l c a r b o n a te
d e s u lfu riz a tio n c a ta ly s t.
The g e n e r a l p r o c e d u r e o f r e g e n e r a t i o n i s t h e
o x i d a t i o n o f s p e n t n i c k e l c a t a l y s t * t h a t i s i n t h e fo rm o f n i c k e l s u l f i d e *
f o r m in g n i c k e l s u l f a t e * a n d t h e n t h e p r e c i p i t a t i o n o f n i c k e l c a r b o n a te fro m
a s o l u t i o n o f n i c k e l s u l f a t e a n d so d iu m c a r b o n a t e .
can th e n b e c a lc in e d t o n ic k e l o x id e .
T he n i c k e l c a r b o n a te ,
How ever* t h e d e s u l f u r i z a t i o n a c t i v i t y
o f n ic k e l c a rb o n a te i s r e p o r te d a s g r e a t e r th a n t h a t o f th e c a lc in e d o x id e ( 4 ) ,
The c o n d i t i o n s o f p r e c i p i t a t i o n o f n i c k e l c a r b o n a t e n o t o n l y a f f e c t i t s
a c t i v i t y b u t a l s o g r e a t l y i n f l u e n c e t h e e a s e w ith w h ic h i t c a n a g a i n b e r e ­
g e n e ra te d a f t e r u s e .
F o r t h i s r e a s o n * a s t u d y w as m ade o f t h e c o n d i t i o n s
o f r e g e n e r a t i o n t o d e te r m in e t h e optim um c o n d i t i o n s f o r . p r e p a r i n g o r r e g e n ­
e r a t i n g a n ic k e l c a rb o n a te c a t a l y s t t h a t c an a g a in be re g e n e ra te d * e a s i l y
a n d e c o n o m ic a lly * a f t e r i t s
a c t i v i t y h a s d e c l i n e d d u r in g u s e ,.
I t h a s b e e n s t a t e d t h a t n i c k e l o r n i c k e l com pounds m ay d e s u l f u r i z e a s
a t r u e c a t a l y s t i n t h e p r e s e n c e o f h y d r o g e n , o r a s a c h e m ic a l r e a g e n t w i t h
t h e f o r m a ti o n o f n i c k e l s u l f i d e .
th is
H o w ev er, t h e n i c k e l com pounds u s e d i n
i n v e s t i g a t i o n w i l l be r e f e r r e d t o a s c a t a l y s t s , w ith th e im p lic a tio n
t h a t t h e y may o r may n o t c h a n g e c h e m i c a l l y w h i l e d e s u l f u r i z i n g .
I
-7 OXIDATIOET
T he f i r s t s t e p i n t h e r e g e n e r a t i o n o f a s p e n t n i c k e l c a r b o n a t e .c a t a l y s t
i s t h e o x i d a t i o n o f n i c k e l S n i f i d e 5 fo rm in g n i c k e l s u l f a t e , w i t h a n o x y g en
c o n ta in in g g a s .
The e c o n o m ic s o f t h e r e g e n e r a t i o n i s b a s e d t o sdtiie e x t e n t
oh th e o x id a tio n s te p .
V a ria b le s in f lu e n c in g o x id a tio n a re e v a lu a te d oh th e
b a s is o f th e p e rc e n t o f t o t a l s u lf u r c o n v e rte d t o a s o lu b le s u l f a t e .
r e m a in i n g
!
The
s u l f u r w o u ld b e i n t h e fo rm o f a s u l f i d e a n d a b a s i c s u l f a t e .
'
KTickel t h a t i s n o t i n t h e fo rm o f e i t h e r a s u l f a t e o r a s u l f i d e w ould b e p r e ­
d o m in a te l y a h o x i d e .
T h is i n c l u d e s a l l n i c k e l w h ic h was n o t c o n v e r t e d t o
a s u l f i d e i n t h e h y d r o f i n i n g o p e r a t i o n a n d a l l n i c k e l o x id e o b t a i n e d fro m
t h e o x i d a t i o n o f t h e s u l f i d e o r fro m t h e d e c o m p o s itio n o f t h e s u l f a t e .
T h e se
n i c k e l o x id e s a r e n o t a c t i v e d e s u l f u r i z a t i o n a g e n ts an d a r e th e l e a s t d e­
s i r a b l e fro m a n e c o n o m ic s t a n d p o i n t b e c a u s e s u l f u r i c a c i d w i l l b e r e q u i r e d
t o c o m p le te t h e s u l f a t i o n .
The b a s i c s u l f a t e i s p r e f e r a b l e t o t h e o x i d e ,
b u t a g a in s u l f u r i c a c id w i l l b e u s e d , j u s t t o d is s o lv e t h i s
s u lfa te .
T hus,
t h e o x i d a t i o n s t e p w as i n v e s t i g a t e d -to d e te r m in e t h e optim um c o n d i t i o n s f o r
p r o d u c in g a s o l u b l e s u l f a t e .
and te m p e r a tu r e .
The v a r i a b l e s i n v e s t i g a t e d w e re c o n t a c t tim e
APPARATUS AND EQUIPMENT
A f l u i d o x i d a t i o n u n i t w as c o n s t r u c t e d t o o x i d i z e s p e n t n i c k e l c a rb o n ­
a te c a ta ly s t.
The u n i t w as c o n s t r u c t e d fro m s t a n d a r d p i p e n i p p l e s , r e d u c i n g
c o u p l i n g s , an d b u s h i n g s , a s shown i n F i g u r e 4» • The u n i t w as a b o u t 4Q i n c h e s
k
l o n g w i t h a maximum d i a m e te r o f . 3 i n c h e s a n d a minimum d i a m e te r o f I i n c h ,
A h e a t i n g c o i l w i t h r e s i s t a n c e o f H O ohms a n d a maximum o u t p u t o f 440 w a t t s
a t 220 v o l t s was u s e d on t h e u p p e r p a r t o f t h e . u n i t , an d a 22 ohm, 110 - v o l t ,
a n d 550 - w a t t c o i l w as u s e d o n t h e lo w e r p a r t o f t h e u n i t .
An a i r p r e h e a t e r , c o n s i s t i n g o f a m e t a l r e a c t o r , 24 i n c h e s lo n g and.
3 i n c h e s i n d i a m e t e r , f i l l e d w i t h s t e e l b a l l s , was u s e d .
Two 5 5 0 - w a tt
h e a t i n g c o i l s an d o n e 440 - w a t t c o i l w e re u sed , t o h e a t t h e p r e h e a t e r .
B o th t h e f l u i d u n i t and p r e h e a t e r w e re h e a v i l y i n s u l a t e d w i t h m a g n e s ia
in s u la tio n m a te ria l.
The h e a t i n g c o i l s w e re c o n t r o l l e d b y nP o w e r s ta t " a u t o -
t r a n s f o r m e r s , a n d i r o n - c o h s t a n t a n th e r m o c o u p le s w e re u s e d w i t h a p o t e n t i o ­
m e t e r t o m e a s u re t e m p e r a t u r e s .
-9 . PROCEDURE
A t t h e s t a r t o f a ru n ,, t h e r e a c t o r a n d p r e h e a t e r w e re h e a t e d t o j u s t
b e lo w t h e d e s i r e d t e m p e r a t u r e .
ju s te d to th e d e s ire d r a t e .
Then t h e a i r f lo w was t u r n e d on a n d a d - ,
When t h e r e a c t o r an d p r e h e a t e r h a d r e a c h e d
t h e o p e r a t i n g t e m p e r a t u r e , t h e a i r f lo w w as t u r n e d o f f a n d s p e n t c a t a l y s t
w as c h a rg e d i n th r o u g h t h e t o p o f t h e r e a c t o r .
T hen t h e a i r f lo w w as
t u r n e d oh a g a i n , a n d t h e t e m p e r a t u r e an d t h e a i r f lo w r a t e w e re h e ld con­
s ta n t fo r th e d u ra tio n o f th e ru n .
When t h e r u n w as c o m p le te d , t h e a i r
f lo w a n d P o w e r s t a t s Tfere s h u t o f f .
A f t e r t h e f l u i d r e a c t o r h a d c o o le d ,
t h e b o tto m c o n n e c t io n w as l o o s e n e d a n d t h e o x i d i z e d c a t a l y s t w as re m o v e d .
T h is c a t a l y s t w as t h e n a n a l y s e d f o r t o t a l s u l f u r a n d s o l u b l e s u l f a t e .
" IO "
.
THERMODBTAEIC CALCULATIONS
I n o r d e r t o h e l p e x p l a i n t h e m ech an ism o f t h e o x i d a t i o n o f n i c k e l
s u l f i d e <, a th erm o d y n am ic i n v e s t i g a t i o n o f t h e p r i n c i p a l r e a c t i o n s was
m ad e .
A ls o , tw o r e a c t i o n s i n v o l v i n g s te a m a n d s u l f u r d i o x i d e a s t h e
o x i d i z i n g a g e n t w e re s t u d i e d .
The v a l u e s f o r 'A S a n d y&H a t 2$80K w ere
u s e d , iia t h e f o l l o w i n g e q u a t i o n s :
.
A F 2^d = A H -T A S
AH
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The a c c u r a c y d e s i r e d d i d n o t r e q u i r e c a l c u l a t i o n s t o c o m p e n s a te f o r
v a r i a t i o n s i n S and A H p w ith te m p e ra tu re „
A F2 ^
s t a n d s f o r f r e e e n e rg y
a t 298 °K a n d Tgp s t a n d s f o r t h e t e m p e r a t u r e o f n e u t r a l e q u i l i b r i u m .
L
•'
' ■ •■
"
I.
2 B S f s ) + 3 0 2 ( g ) ----->. 2 N iO (s) + 2S0 2 ( g ) . '
'
A H p 2 ( -2 0 .4 )
S
2 ( 1 8 .0 )
0
3 ( 4 9 .0 3 )
2 ( - $ 8 .4 )
2 ( 9 .2 )
'
' 2 (-t0 .9 2 )
2 ( 5 9 .2 4 )
A H = - 2 1 7 .8 4 k c a l / m o l e j A S = - 4 6 .2 1 E 0U3/m o le
A F 298 - - 2 04.1 k c a l/ m o l e
N iS (B ) + 20 2 ( g ) — >
2.
A H p ' - 2 0 .4 '
S
1 8 .0 .
NiSO 4 Cs)
0
2 ( 4 9 .0 3 )
T ^ = 4 4 0 0 °C , ■
- 2 1 6 .0
'
A H = - 1 9 5 . 6 k c a l/ m o l e
2 3 .2
A S = - 9 2 . ‘8 6 -E-.U ./m o le
A ^298 “ rol 6 ? f 9 k c a l/ m o l e Tjjp = 1 8 0 0 ° C
'
I
-1 1 NiSG 4 ( S ) — >
3.
AH p. - 2 1 6 .0
,
N iO (s ) + S03 ( g )
- 5 8 .4
- 104 . 2 .
9 .2
6 3 .8
2 3 .2
S
AH=
53»4 k c a l/m tile A S = 4 9 .8 E .U './m o le
A F 2^ g = 3 8 .7 k c a l / m o l e
4.
'
= SOO0 C
2 N iS ( s ) + SSOgCg) + SO2 Cg) - — 9»
A Hf
S
2 ( -2 0 .4 )
2 (-7 0 9 2 )
-0
3 ( 1 8 .0 )
I
2 ( 5 9 .2 4 )
^"
5 ( 4 9 . 03 )
A H =
2 N iO (s) + ZtSO3 Cg)
2 ( - 5 8 .4 )
.
2 ( 9 .2 )
4 C - 1 0 4 .2 )
4 ( 63. 8)
- 3 5 1 .0 6 k c a l / m o l e A S = - 1 2 6 .0 3 E .U ./m o le
.
.
■
'
A F29^ = - 3 1 3 .5 k c a l / m o l e Th e .'== 25 O0 °C '
5.
N iS ( s ) + H20 ( g )
A F f - 2 0 .4
S
1 8 .0
■NiO'Cs) + H2S ( g )
- 5 7 .8
4 5 .1 3
- 5 8 .4
"
9 .2
■
A H = 1 4 .5 k c a l / m o l e
- 5 .3
.
49.15
■
S = - 4 . 7 8 E .U ./m o le
A f 2 98 = 1 5 .9 k c a l/m o le , T h e = -2750'°C
T h e rm o d y n a m ic a lly i t . i s - p o s s i b le t o p r o d u c e n i c k e l o x i d e fro m t h e
o x i d a t i o n o f n i c k e l s u l f i d e . . U n f o r t u n a t e l y , t h e n i c k e l o x i d e .form ed i s n o t
\ '
'. ' - - .
' " . .' ;
a n a c t i v e d e s u l f u r i z a t i o n a g e n t . A l s o , t h e c o m p e tin g r e a c t i o n w i t h t h e
f o r m a t i o n o f n i c k e l s u l f a t e , h a s - a .s tr o n g t e n d e n c y t o go u n d e r . t h e . c o n t r o l l e d
o x i d a t i o n c o n d i t i o n s t h a t m u st b e u s e d ; t o p r o t e c t t h e c a t a l y h t t h e r m a l l y .
I t i s show n ( r e a c t i o n 3 ) t h a t n i c k e l s u l f a t e w i l l d e c o m p o se , fo rm in g
s u l f u r t r i o x i d e , a t a b o u t SOO0 C.
F r i e d r i c h a n d B r i c k i e ( 5) s t a t e t h a t
n i c k e l s u l f a t e w i l l deco m p o se i n t o ■n i c k e l o x id e a t 8 4 0 ° C, t h e d e c o m p o s itio n
” 12*“
b e g in n i n g a t a b o u t 700o C.
The o x id e fo rm e d b y t h i s r e a c t i o n i s a l s o . n o t a h
a c tiv e d e s u lf u r iz a tio n c a ta ly s t*
From a th erm o d y n a m ic s t a n d p o i n t , a s show n i n r e a c t i o n 4 , t h e p r e s e n c e
o f s u lf u r d io x id e fa v o rs th e o x id a tio n o f n i c k e l s u lf id e *
H ow ever, M ilb a u e r
a n d T ucek (lO ) s t a t e t h a t n i c k e l s u l f i d e i n t h e p r e s e n c e o f . s u l f u r d i o x i d e
y i e l d s n i c k e l s u l f a t e , b u t a t t h e t e m p e r a t u r e w h e re t h e s u l f a t e t e n d s t o d e ­
co m p o se.
The r e a c t i o n i n v o l v i n g t h e o x i d a t i o n o f n i c k e l s u l f i d e w i t h s te a m i s
v e r y u n f a v o r a b l e fro m a th erm o d y n a m ic v i e w p o i n t .
I t h a s b e e n fo u n d t h a t
.t h e p e r c e n t c o n v e r s i o n i s lo w a t t e m p e r a t u r e s u p t o l$ 0 G °C o
E ven a t 1500o G,
i t d o e s n o t seem t h e r e a c t i o n c o u ld e v e r becom e e c o n o m ic a lly s o u n d b e c a u s e
o f th e c o s t o f h e a tin g w a te r to su ch a h ig h te m p e ra tu re .
-1 3 “
RESULTS
As s t a t e d b e f o r e 5 t h e v a r i a b l e s i n f l u e n c i n g t h e o x i d a t i o n o f n i c k e l
s u l f i d e a r e e v a l u a t e d o n t h e b a s i s o f t h e p e r c e n t o f t o t a l s u l f u r c o n v e r te d
to s o lu b le S u lf a te e
The r e s u l t s o f t h e o x i d a t i o n r u n s ^ a lo n g w i t h t h e c o n ­
d i t i o n s u s e d , a r e t a b u l a t e d i n T a b le I e
E f f e c t o f T e m p e ra tu re
'
■
-
F iv e r u n s w e re m ade t o d e te r m in e t h e optim um t e m p e r a t u r e f o r o x i d a t io n ,.
The r e s u l t s o f t h e s e r u n s h a v e b e e n p l o t t e d i n F i g u r e I e
e r a t u r e i s shown t o b e a b o u t 8 5 0 ° F e
T he optim um tem p­
H o w ev er, t h e p e r c e n t o f t o t a l s u l f u r
i n t h e c a t a l y s t s a m p le s t h a t h a d b e e n r u n a t 6 50°F was some t h r e e tim e s
th a t o f th e o th e r s .
T h is t e n d s t o show t h a t , w h i l e t h e h i g h e r t e m p e r a t u r e s
may f a v o r s u l f a t i o n ( r e a c t i o n 2 ) , t h e y a l s o t e n d t o b r i n g a b o u t t h e f o r ­
m a tio n o f t h e o x id e ( r e a c t i o n l )
o r t h e . d e c o m p o s itio n r e a c t i o n o r b o t h .
T h e se l a t t e r r e a c t i o n s r e s u l t i n t h e f o r m a t i o n o f t h e u n d e s i r a b l e n i c k e l
o x id e .
U n f o r t u n a t e l y , i n o r d e r t o make t h e r e a c t i o n r a t e o f s u l f a t i o n
e c o n o m ic a lly f a v o r a b l e , i t i s
n e c e s s a ry t o u s e a s h ig h a te m p e ra tu re as
p o s s i b l e w i t h o u t c a u s in g e x c e s s i v e d e c o m p o s i ti o n .
The i n d i c a t i o n s a r e t h a t
t h e optim um t e m p e r a t u r e i s a b o u t 8 5 0 ° F 6
E f f e c t o f Time
R uns 1 - 6 i l l u s t r a t e t h e e f f e c t o f r u n tim e on t h e o x i d a t i o n o f n i c k e l
s u lfid e .
The r e s u l t s o f t h e s e r u n s h a v e b e e n p l o t t e d i n F i g u r e 2 .
A g a in , '
t h e c a t a l y s t s a m p le r u n f o r o n e r- h a lf h o u r c o n t a i n e d t h r e e t i m e s a s much t o t a l
s u l f u r a s t h e o t h e r s , i n d i c a t i n g t h e te n d e n c y f o r t h e f o r m a ti o n o f t h e o x id e
to p ro ce e d a t lo n g e r c o n ta c t tim e s .
The d e c r e a s i n g p e r c e n t o f s o l u b l e s u l f a t e
i n s a m p le s r u n f o r 4 h o u r s a n d 8 h o u r s i n d i c a t e s t h e d e c o m p o s itio n o f n i c k e l
-U s u l f a t e a t s u c h lo n g c o n t a c t t i m e s .
The p e r c e n t s o l u b l e s u l f a t e fo rm e d i s
g r e a t e s t b e tw e e n I a n d 2 h o u r s , a f t e r w h ic h t h e d e c o m p o s itio n r e a c t i o n
b e g in s to p re d o m in a te .
MET CHEMICAL REGENERATION
The s e c o n d s t e p i n t h e r e g e n e r a t i o n o f a s p e n t n i c k e l c a r b o n a te d e ­
s u l f u r i z a t i o n c a t a l y s t i s t h e w e t c h e m ic a l c o n v e r s i o n o f n i c k e l s u l f a t e
t o n ic k e l c a rb o n a te .
The n i c k e l c a r b o n a te i s t h e n d r i e d a n d u s e d a s a n
a c tiv e d e s u lfu riz a tio n c a ta ly s t.
The f i r s t s t e p i n w et c h e m i c a l . r e g e n e r a t i o n i s t h e l e a c h i n g o f s p e n t
c a t a l y s t w ith s u l f u r i c a c id .
T h is s t e p i s . n e c e s s a r y t o s u l f a t e a l l n i c k e l ,
t h a t w as n o t s u l f i d e d i n t h e h y d r o f i n i n g u n i t and a l l n i c k e l . o x id e o b t a i n e d
fro m t h e o x i d a t i o n o f t h e s u l f i d e o r fro m t h e d e c o m p o s itio n o f t h e s u l f a t e .
T h e s e n i c k e l com pounds r e a c t m o le f o r m o le w i t h s u l f u r i c a c i d , a n d a s a
■c o n s e q u e n c e , l a r g e a m o u n ts o f a c i d w i l l b e n e c e s s a r y i f t h e p e r c e n ta g e o f
n i c k e l a s n i c k e l s u l f a t e i s lo w .
The s e c o n d s t e p i s t h e p r e c i p i t a t i o n o f n i c k e l c a r b o n a t e .
H e re , th e
s u l f a t e d c a t a l y s t i s p u t i n t o s o l u t i o n a n d i s m ix ed w i t h a s o l u t i o n o f
so d iu m c a r b o n a t e ( c a l c i u m c a r b o n a t e c a n a l s o b e u s e d ) fo rm in g a •p r e c i p i t a t e
o f n ic k e l c a rb o n a te .
The p r e c i p i t a t e i s t h e n f i l t e r e d a n d w ash ed w i t h w a te r
W ashing i s a s im p le t e c h n i c a l o p e r a t i o n b u t h a s b e e n fo u n d ' t o b e v e r y im­
p o rta n t .
T r a c e s o f. so d iu m s u l f a t e a r e n o t v e r y d e t r i m e n t a l t o t h e i n i t i a l
a c t i v i t y o f t h e c a t a l y s t , b u t a p p r e c i a b l e am o u n ts c a n n o t b e t o l e r a t e d
(4 ).
A f t e r t h e c a t a l y s t h a s b e e n w ash ed f r e e o f e n t r a i n e d s a l t , i t i s t h e n d r i e d
and u s e d a s a n a c t i v e c a t a l y s t .
EFFECT OF CATALYST UTILIZATION
D e s u l f u r i z a t i o n w i t h a n i c k e l c a t a l y s t i s m a in ly d e p e n d e n t on tw o
d i f f e r e n t c o m p e tin g r e a c t i o n s .
6 . NiO + RSH + H2 ----- % NiS + RH + H2O
7 . N iS + H2 -----&
N i'+ H2S
The f i r s t r e a c t i o n r e s u l t s i n t h e f o r m a t i o n o f n i c k e l s u l f i d e .
a v a ila b le n ic k e l i s
When a l l
i n t h e fo rm o f a s u l f i d e , r e a c t i o n 6 m u st end a n d
r e a c t i o n 7 w i l l p re d o m in a te .
•
H ow ever, r e a c t i o n 7 w i l l p r o c e e d a t a r a t e
o f u n e c o n o m ic o p e r a t i o n a n d t h e c a t a l y s t m u st b e r e p l a c e d .
The c o m p o s itio n o f s p e n t c a t a l y s t a t t h e b e g in n i n g o f r e g e n e r a t i o n
i s an im p o rta n t f a c t o r .
Any u n s u l f i d e d n i c k e l r e m a in in g r e p r e s e n t s an
eco n o m ic l o s s , i n t h a t t h e c a t a l y s t was n o t u s e d t o i t s f u l l e s t e x t e n t ,
a n d t h a t i t i n c r e a s e s t h e s u l f u r i c a c i d c o n s u m p tio n .
As p r e v i o u s l y s t a t e d
a l l n i c k e l t h a t i s n o t s u l f i d e d i n t h e h y d r o f i n i n g u n i t m u st b e l e a c h e d
w ith s u l f u r i c a c id .
N ot o n l y t h e c o n d i t i o n s o f h y d r o f i n i n g b u t a l s o t h e m eth o d a n d con­
d itio n s o f re g e n e ra tin g th e c a ta ly s t w ill a f f e c t th e e x te n t o f c a ta ly s t
u tiliz a tio n .
F is c h b a c h ( 4 ) h a s r e p o r t e d t h e f a c t o r s t h a t i n f l u e n c e t h e
p r e c ip ita tio n o f an a c tiv e n ic k e l d e s u lf u r iz a tio n c a t a l y s t , b u t th e s e a re
n o t n e c e s s a rily th e f a c to r s t h a t w i l l in flu e n c e th e p r e c ip ita tio n o f a
c a t a l y s t t h a t c a n b e e a s i l y a n d e c o n o m ic a lly r e g e n e r a t e d .
The a c t i v i t y o f
t h e c a t a l y s t i s d e p e n d e n t upon b o th r e a c ti o n s 6 and 7 , w h ile th e r e g e n e r­
a t i o n i s d e p e n d en t o n ly upon th e e x te n t o f r e a c ti o n 6 .
-1 7 I t w o u ld seem p r o b a b l e t h a t a n y h y d r o f i n i n g c o n d i t i o n s t h a t w o u ld t e n d
t o r e p r e s s r e a c t i o n 7 w o u ld i n c r e a s e t h e u l t i m a t e p e r c e n t o f n i c k e l 's u l f i d e d »
T he c o n d i t i o n s o f p r e c i p i t a t i o n t h a t w i l l p r o d u c e a c a t a l y s t t h a t w i l l s u l ­
f i d e t o t h e g r e a t e s t e x t e n t a r e n o t e v i d e n t fro m a th erm o d y n a m ic s t a n d p o i n t
and have been in v e s tig a te d .
C o n d itio n s , u s e d f o r p r e c i p i t a t i p n a r e shown i n
T a b le IV ; s o l u t i o n s u s e d f o r p r e c i p i t a t i o n a r e d e s c r i b e d i n T a b le I I I i
A n o th e r f a c t o r w h ic h a f f e c t s c a t a l y s t u t i l i z a t i o n i s p u r e l y p h y s i c a l .
V e ry t i g h t l y p e l l e t e d c a t a l y s t w i t h o u t a p o r o u s s u p p o r t c a n c o n t a i n a c t i v e
n i c k e l com pounds t h a t c a n n o t b e p h y s i c a l l y r e a c h e d t o b e u t i l i z e d .
T h e re ­
f o r e , c a t a l y s t d e n s i t y m u st a l s o b e c o n t r o l l e d b y t h e c o n d i t i o n s o f p r e c i p i ­
ta tio n
-1 8 APPiffiATUS AND EQUIPMENT.
A c o m p a ris o n u n i t w as c o n s t r u c t e d t o t e s t v a r i o u s ly - p r e p a r e d c a t a l y s t s 5
t o d e te r m i n e t h e c o n d i t i o n s o f h y d r o f i n i n g a n d t h e c o n d i t i o n s o f c a t a l y s t
p r e c i p i t a t i o n t h a t w i l l a f f e c t maximum c a t a l y s t s u l f i d i n g .
th is u n it i s
shown i n F i g u r e 5«
A d ia g ra m o f
The c o m p a r is o n u n i t , o r c o m p a r a to r a s i t
w i l l b e r e f e r r e d t o , w as d e s ig n e d s o t h a t v a r i o u s c a t a l y s t s c o u ld b e r u n
u n d e r t h e same h y d r o f i n i n g c o n d it io n s ,- g i v i n g a b a s i s f o r c o m p a rin g t h e
r e s u lts o f s u lfid in g .
The c o m p a r a to r was made fro m a p i e c e o f- 25 mm P y r e x g l a s s t u b i n g w i t h
a w a t e r - c o o l e d c o n d e n s e r w e ld e d on t o t h e b o tto m fo rm in g a s o l i d u n i t , a b o u t
36 in c h e s lo n g .
The t o p o f t h e t u b i n g w as f i t t e d w i t h t h e fe m a le p o r t i o n
o f a 2 9 /4 2 g ro u n d g l a s s s t a n d a r d t a p e r j o i n t .
A 3 5 /2 5 g ro u n d g l a s s b a l l
j o i n t w as s e a l e d t o t h e b o tto m o f t h e c o n d e n s e r .
H e a t was s u p p l i e d t o t h e u n i t w i t h a 5 5 0 - w a tt h e a t i n g c o i l c o n t r o l l e d
by a P o w e rs ta t.
A t h e r m o w e ll , c o n s i s t i n g o f a p i e c e o f 6 mm P y r e x g l a s s
t u b i n g s e a l e d on o n e e n d , p r o j e c t e d v e r t i c a l l y i n t o t h e c a t a l y s t b e d . • To
m e a s u re t e m p e r a t u r e s , a n i r o n - c o n s t a n t a n th e r m o c o u p le i n s e r t e d - i n t h e t h e r m o - .
w e l l was c o n n e c te d t o a p o t e n t i o m e t e r .
The e n t i r e u n i t w as wound w ith
a s b e s t o s t a p e a n d w as c o v e r e d w i t h a t h i c k l a y e r o f m a g n e s ia i n s u l a t i o n .
The c o m p a r a to r u n i t w as c o n n e c te d b y m eans o f t h e b a l l j o i n t t o a 1 0 0 0
ml s e p a ra to ry fu n n e l u sed a s an e f f lu e n t o i l r e s e r v o ir .
E x h a u s t g a s was
p a s s e d t h r o u g h a n i c e c o n d e n s e r a n d a cadmium c h l o r i d e p r e c i p i t a t o r t o r e ­
move e n t r a i n e d l i q u i d s a n d h y d ro g e n s u l f i d e .
' A c h a rg e o i l r e s e r v o i r , co n ­
s i s t i n g o f a 500 m l s e p a r a t o r y f u n n e l , w as c o n n e c te d 1 t o a b e llo w s pump.
-1 9 O i l was pumped c o n t i n u o u s l y fro m t h e r e s e r v o i r t o t h e t o p o f t h e c o m p a r a to r „
H yd ro g en was. i n t r o d u c e d i n t o t h e c o m p a r a to r a b o v e t h e o i l i n l e t .
H ydrogen
r a t e , r e g u l a t e d b y a n e e d le v a l v e , was m e a s u re d w i t h a m e r c u ry m anom eter
and o r i f i c e
"20"
MATERIALS AMD PROCEDURE
C h a rg e o i l u s e d i n t h i s
o il.
i n v e s t i g a t i o n w as a s t r a i g h t - r u n *
c le a r fu e l
I n a d d i t i o n , t h e o i l u s e d i n r u n s 7 a n d S was s a n d t r e a t e d .
The
s u l f u r c o n t e n t o f t h e s e c h a r g e o i l s v a r i e d fro m 2 .0 9 t o 2 .2 0 p e r c e n t byw e ig h t.
I n s p e c t i o n d a t a f o r t h e c h a r g e o i l s a r e p r e s e n t e d i n T a b le I I .
To p r e p a r e t h e c o m p a r a to r f o r a r u n , a b o u t 1 . 0 gram o f p y r e x g l a s s
w o o l,, s e r v i n g m e r e ly a s a c a t a l y s t s u p p o r t , was p l a c e d i n t h e c o m p a ra to r
j u s t b e lo w t h e t h e r m o w e ll .
The c a t a l y s t t o b e t e s t e d f o r maximum s u l f i d i n g
w as w e ig h e d a n d m ix e d w i t h o n e - e i g h t h i n c h p o r c e l a i n f i s h s p i n e s a n d was
th e n c h a rg e d t o th e c o m p a ra to r.
The f i s h s p i n e s p r e v e n te d t h e f i n e c a t a l y s t
fro m c a k in g a n d p lu g g in g t h e u n i t .
A la y e r o f o n e -q u a rte r in c h f i s h s p in e s ,
s e r v i n g a s a p r e h e a t s e c t i o n f o r t h e o i l , w as p l a c e d on t o p o f t h e c a t a l y s t
bed.
The c h a r g e o i l r e s e r v o i r w as f i l l e d w i t h o i l t h a t h a d b e e n p r e v i o u s l y
w e ig h e d .
A l l g ro u n d g l a s s j o i n t s w e re g r e a s e d a n d clam p ed i n p l a c e , and
t h e u n i t was t h e n r e a d y f o r o p e r a t i o n .
The P o w e r s ta t was t u r n e d o n , a n d w h i l e t h e c o m p a ra to r w as h e a t i n g , a
s m a l l am ount o f h y d ro g e n w as a llo w e d t o p a s s t h r o u g h t h e u n i t .
When t h e '
d e s i r e d t e m p e r a t u r e h a d b e e n a t t a i n e d , t h e pum p, c a l i b r a t e d t o d e l i v e r
a p p r o x i m a t e ly 420 gram s o f o i l p e r h o u r , w as t u r n e d o n , a n d t h e h y d ro g e n
f lo w w as a d j u s t e d t o t h e d e s i r e d r a t e .
O i l s a m p le s w e re p e r i o d i c a l l y w i t h ­
d raw n fro m t h e e f f l u e n t o i l r e s e r v o i r , w e ig h e d , a n d a n a ly s e d f o r s u l f u r
c o n te n t.
•
At t h e e n d o f t h e d e s i r e d r u n t i m e , t h e . pump a n d P o w e r s ta t w e re t u r n e d
o f f , b u t h y d ro g e n w as. a llo w e d t o f lo w th r o u g h t h e u n i t f o r a fe w a d d i t i o n a l
-2 1 .
m in u te s t o rem ove a l l o i l fro m t h e c a t a l y s t b e d .
som ew hat5 i t s
A f t e r t h e u n i t h a d c o o le d
e n t i r e c o n t e n t s w e re rem oved a n d w e ig h e d .
The s p e n t c a t a l y s t
was t h e n a n a ly s e d f o r t h e p e r c e n t o f t o t a l n i c k e l s u l f i d e .
O i l r e m a in in g
i n th e . e f f l u e n t r e s e r v o i r w as rem oved a n d a n a l y s e d . ■
O i l s a m p le s t h a t w e re t o b e a n a ly s e d w e re g iv e n a c a u s t i c w ash t o r e ­
move a n y h y d r o g e n s u l f i d e .
S u l f u r c o n t e n t o f t h e o i l was d e te r m in e d b y t h e
c o n v e n t i o n a l l a m p - s u l f u r m e th o d , a s d e s c r i b e d i n t h e A .S .T .M . M anual o f
S ta n d a r d s ( l ) .
I
■=22—
CALCULATIONS
A f t e r a c a t a l y s t s a m p le h a d b e e n r u n i n t h e c o m p a r a to r ^ t h e am ount o f
s u l f u r rem oved fro m t h e o i l w as c a l c u l a t e d .
The am ount o f n i c k e l i n t h e
c a t a l y s t h a d b e e n d e te r m in e d b y a n a l y s i s b e f o r e i t w as r u n .
From t h e s e
tw o f i g u r e s a v a l u e f o r t h e p e r c e n t n i c k e l a s n i c k e l s u l f i d e w as c a l c u l a t e d s
b a s e d on t h e s t o i c h i o m e t r i c r e l a t i o n s h i p b e tw e e n n i c k e l a n d s u l f u r i n a
m o n o s u l f id e .
T h is s t o i c h i o m e t r i c p e r c e n t i s , i n a l l p r o b a b i l i t y , n o t c o r r e c t
f o r t h e f o ll o w i n g tw o r e a s o n s :
some o f t h e s u l f u r w as rem oved fro m t h e o i l
a s h y d r o g e n ' s u l f i d e , a n d t h e s u l f u r t h a t d i d fo rm n i c k e l s u l f i d e c o u ld h a v e
b e e n c o n ta in e d as a p o l y s u l f i d e .
I n o r d e r t o o b t a i n a m ore a c c u r a t e f i g u r e f o r p e r c e n t n i c k e l a s n i c k e l
s u l f i d e , e a c h s p e n t c a t a l y s t w as a n a ly s e d f o r t o t a l n i c k e l a n d t o t a l s u l f u r .
H o w ev er, t h i s f i g u r e w as a g a i n b a s e d on a m o n o s u l f id e .
U s in g b o th f i g u r e s f o r p e r c e n t n i c k e l s u l f i d e d , t h e s u l f i d i n g a b i l i t i e s o f
v a r i o u s l y p r e c i p i t a t e d c a t a l y s t s w e re c o m p a re d .
Due t o s u l f u r rem oved a s
h y d ro g e n s u l f i d e t h e s t o i c h i o m e t r i c p e r c e n t s h o u ld b e g r e a t e r t h a n t h e
a n a ly tic a l p e rc e n t.
From t h i s c o r r e l a t i o n , t h e r e l a t i v e
a c t i v i t i e s o f t h e v a r i o u s c a t a l y s t s w e re o b s e r v e d .
" tru e c a ta ly tic "
A c a t a l y s t t h a t demon­
s t r a t e s a s t o i c h i o m e t r i c p e r c e n t t h a t i s much h i g h e r t h a n t h e a n a l y t i c a l
p e r c e n t w o u ld i n d i c a t e t h a t much o f t h e s u l f u r h a d b e e n rem o v ed .,.from t h e o i l
a s h y d ro g e n s u l f i d e .
• ■
C a l c u l a t i o n s f o r t h e v a r i o u s r u n s a r e i n c l u d e d i n T a b le V I , a lo n g
w ith th e h y d r o fin in g c o n d itio n s .
O i l was w ith d ra w n fro m t h e e f f l u e n t r e s e r ­
v o i r e v e r y h o u r i n t h e f i r s t 8 r u n s a n d e v e r y f o u r h o u r s i n . r e m a in in g r u n s .
"
23
“
T he w e ig h t o f o i l p a s s i n g t h r o u g h t h e . u n i t d u r i n g e a c h t im e i n t e r v a l
b e tw e e n s a m p le s w as c o r r e c t e d t o a c c o u n t f o r l o s s e s due t o c r a c k i n g w h ich
w e re d i v i d e d a s e q u a l l y a s p o s s i b l e ,among t h e t im e i n t e r v a l s .
The w e ig h t
o f o i l b e f o r e c o r r e c t i o n i s t h e t o t a l e f f l u e n t o i l , w h i l e t h e w e ig h t o f
o i l a f t e r c o r r e c tio n i s th e t o t a l o i l c h a rg e d .
Space v e lo c i ty , re p o r te d
a s g ram s o f o i l p e r gram o f c a t a l y s t p e r h o u r , w as b a s e d on t h e t o t a l
c h a rg e o i l .
The am ount o f s u l f u r rem o v ed d u r in g e a c h t im e i n t e r v a l w as d e te r m in e d
b y m u l t i p l y i n g t h e w e ig h t o f o i l a f t e r c o r r e c t i o n b y t h e d i f f e r e n c e b e tw e e n
t h e - p e r c e n t s u l f u r i n t h e c h a r g e o i l an d t h e p e r c e n t s u l f u r i n t h e e f f l u e n t
o i l f o r. t h a t tim e i n t e r v a l .
The p e r c e n t n i c k e l s u l f i d e d w as c a l c u l a t e d
fro m t h e t o t a l g ram s o f s u l f u r rem o v ed fro m t h e o i l .
.
Many c a t a l y s t s d e m o n s t r a t e a n a p p a r e n t n i c k e l s u l f i d e d g r e a t e r t h a n
100 p e rc e n t.
H ow ever, due t o s u l f u r rem o v ed a s h y d ro g e n s u l f i d e a n d t h e
m eth o d o f c a l c u l a t i o n , i t
t h a n 100 p e r c e n t .
i s p o s s ib le fo have an a p p a re n t p e rc e n t g r e a te r
-2 4 RESULTS ■
As p r e v i o u s l y s t a t e d , t h e v a r i a b l e s o f p r e c i p i t a t i n g a c a t a l y s t t h a t
c o u ld b e c o n v e r t e d a lm o s t e n t i r e l y t o n i c k e l s u l f i d e d u r i n g h y d r o f i n i n g
w e re i n v e s t i g a t e d .
A l s o , t h e c o n d i t i o n s o f h y d r o f i n i n g c o n d u c iv e t o max­
imum s u l f i d i n g w e re i n v e s t i g a t e d .
The r e s u l t s o f t h e c o m p a r a to r r u n s a r e
t a b u l a t e d i n T a b le V .
Run: Time
A s a m p le w as t a k e n e v e r y h o u r i n t h e f i r s t 8 r u n s t o . d e te r m i n e t h e
t im e r e q u i r e d t o s u l f i d e a c a t a l y s t t o i t s g r e a t e s t e x t e n t .
As t h e r u n
p r o g r e s s e d , t h e s u l f u r c o n t e n t o f t h e o i l s a m p le s g o t s t e a d i l y h i g h e r , u n ­
t i l a f t e r 4 t o 8 h o u r s , t h e s u l f u r c o n t e n t o f t h e e f f l u e n t o i l was a s h ig h
a s t h a t o f th e c h a rg e o i l .
S i n c e s u l f u r was no l o n g e r b e in g rem o v ed fro m
t h e o i l , t h e c a t a l y s t w as no l o n g e r b e in g s u l f i d e d .
I n some r u n s , t h e
s u l f u r c o n te n t o f th e e f f l u e n t o i l d id n o t g e t a s h ig h a s t h a t o f th e c h a rg e
o i l , d u e t o s u l f u r rem o v ed a s h y d r o g e n s u l f i d e .
I n F i g u r e 3 , t im e i n h o u r s
i s p l o tt e d a g a in s t s u lf u r c o n te n t o f e f f l u e n t o i l .
From t h e s e d a t a , i t was
d e c id e d t h a t a r u n tim e o f e i g h t h o u r s w as s u f f i c i e n t t o s u l f i d e a n y c a t a l y s t
t o c o m p l e ti o n .
E f f e c t o f T e m p e r a tu r e
F o u r r u n s w e re m ade v a r y i n g t h e t e m p e r a t u r e fro m 525°F t o 7 2 5 ° F .
The
l o w e s t t e m p e r a t u r e , 5 2 5 ° F , a p p e a r e d t o f a v o r f o r m a ti o n o f n i c k e l s u l f i d e .
H ig h e r t e m p e r a t u r e s a r e m ore f a v o r a b l e f o r t h e re m o v a l o f s u l f u r a s h y d ro g e n
s u lfid e .
H o w e v er, a t 7 25°F t h e r e s u l t s w e re v e r y p o o r a n d a p p r e c i a b l e c r a c k ­
i n g was n o t i c e a b l e .
*“25“
E f f e c t o f H y d ro g en R a te
The e f f e c t o f h y d r o g e n r a t e w as s t u d i e d i n r u n s 3 S 5 a n d 7»
h y d ro g e n r a t e p r o v e d t o i n d u c e maximum s u l f i d i n g .
The l o w e s t
T h is i s p r o b a b ly d u e t o
t h e f a c t t h a t a h i g h e r h y d ro g e n r a t e f a v o r s t h e re m o v a l o f s u l f u r a s h y d ro ­
gen s u l f i d e .
I n f a c t , a n y h y d r o f i n i n g c o n d i t i o n s t h a t w o u ld f a v o r rem o v al,
o f s u l f u r , a s h y d ro g e n s u l f i d e w o u ld n o t b e optim um f o r maximum c a t a l y s t
s u lfid in g .
M e th o d ' o f A dding S o l u t i o n s
R e l a t i o n s h i p b e tw e e n maximum s u l f i d i n g a n d t h e m ethod o f a d d in g s o l u t i o n s
i s d e m o n s tr a te d i n r u n s 1 0 , 1 2 , 1 3 , a n d 1 4 .
F o r tw o o f t h e r u n s , c a t a l y s t s
w e re p r e c i p i t a t e d b y a d d in g n i c k e l s u l f a t e s o l u t i o n t o a
so d iu m c a r b o n a te
s o l u t i o n , a n d f o r t h e o t h e r tw o , c a t a l y s t s w e re p r e c i p i t a t e d b y a d d in g c a r ­
b o n a te t o s u l f a t e . , R e s u l t s show t h a t maximum s u l f i d i n g i s o b t a i n e d when
t h e c a t a l y s t i s p r e c i p i t a t e d b y a d d in g c a r b o n a t e t o s u l f a t e .
C o y k e n d a ll ( 3 )
r e p o r t e d t h a t a n i c k e l c a t a l y s t o f h i g h e s t a c t i v i t y i s o b t a i n e d when so d iu m
c a rb o n a te i s added to a s u l f a t e s o l u t i o n .
F is c h b a c h ( 4 ) r e p o r t e d a d e f i n i t e r e l a t i o n s h i p b e tw e e n t h e m eth o d o f
a d d in g s o l u t i o n s and t h e p h y s i c a l c h a r a c t e r i s t i c s o f t h e r e s u l t a n t c a t a l y s t .
When t h e s u l f a t e s o l u t i o n w as a d d e d t o a c a r b o n a te s o l u t i o n , t h e c a t a l y s t
w as v e r y g r a n u l a r a n d ' c o u ld n o t b e e x t r u d e d i n t o " n o o d l e s ."
When t h e c a r b o n ­
a t e w as a d d e d t o a s u l f a t e , t h e c a t a l y s t a p p e a r e d t o b e v e r y f i n e l y d i v i d e d
a n d w as r e a d i l y e x t r u d a b l e .
T h is p h y s i c a l c h a r a c t e r i s t i c c o u ld h e l p t o
e x p l a i n why t h e l a t t e r m eth o d a l s o p r o d u c e s a c a t a l y s t t h a t w i l l e x h i b i t
maximum s u l f i d i n g .
»*
26“
E f f e c t off E x c e s s C a rb o n a te
The e f f e c t o f p r e c i p i t a t i n g b y u s i n g a n e x c e s s o f t h e s t o i c h i o m e t r i c
q u a n t i t y o f so d iu m c a r b o n a t e i s d e m o n s tr a te d i n r u n s IO 5 I l 5 a n d 1 2 ,
The
d a t a i n d i c a t e t h a t maximum s u l f i d i n g c a n b e o b t a i n e d w i t h a c a t a l y s t t h a t
h a s -b e e n p re p a re d by p r e c i p i t a t i n g w ith s to ic h io m e tr ic q u a n t i t i e s o f c a rb o n ­
a t e or. j u s t a s l i g h t e x c e s s .
Ueno ( 1 2 ) r e p o r t e d t h a t n i c k e l h y d r o g e n a tio n
c a t a l y s t s h a v e th e . g r e a t e s t a c t i v i t y when a s l i g h t e x c e s s o f so d iu m c a rb o n ­
a te is u sed .
P r e c i p i ta ti o n and D ig e s tio n
. v
S e v e r a l r u n s w e re m ade t o d e te r m in e t h e e f f e c t o f p r e c i p i t a t i o n a n d
d i g e s t i o n c o n d i t i o n s on t h e e x t e n t o f s u l f i d i n g .
S am ple P -3 1 w as p r e c i p i ­
t a t e d a t 71°F - 7 3°F a n d was d i g e s t e d a t t h e same t e m p e r a t u r e .
S am ples
P -3 0 a n d P -3 7 w e re p r e c i p i t a t e d a t 1 8 8 °F - 1 9 2 °F a n d 2 06°F - 2 0 9 ° F r e s p e c t i v e l y
a n d w e re d i g e s t e d a t t h e sam e t e m p e r a t u r e s .
R e s u l t s o f t h e c o m p a ra to r r u n s
i n d i c a t e t h a t maximum s u l f i d i n g i s o b t a i n e d when th e . c a t a l y s t i s p r e c i p i ­
t a t e d a t t h e lo w e r-te m p e ra tu re s .
S am ple P -3 7 w as p r e c i p i t a t e d o v e r a tim e
i n t e r v a l o f 72 m i n u t e s 5 w h i l e P -4 3 w as p r e c i p i t a t e d o v e r a tim e, i n t e r v a l o f
-15 -m in u te s .
S am ple P -3 7 was d i g e s t e d f o r 60 m in u te s a n d P -4 4 w as n o t d i ­
g e s te d a t a l l .
w ith v e ry l i t t l e
R e s u l t s show t h a t p r e c i p i t a t i o n o v e r a s h o r t - ti m e . i n t e r v a l 5
o r no d i g e s t i o n , r e s u l t s i n a c a t a l y s t t h a t w i l l d e m o n s tr a te
maximum s u l f i d i n g .
T h u s 5 t h e optim um c o n d i t i o n s o f p r e c i p i t a t i o n an d d i -
g e s t i o n a p p e a r t o b e r a p i d . p r e c i p i t a t i o n a t room t e m p e r a tu r e , w ith , l i t t l e
tim e a llo w e d f o r d i g e s t i o n .
F is c h b a c h ( 4 ) r e p o r t s t h a t g r e a t e r a c t i v i t y i s o b t a i n e d fro m a n i c k e l
c a t a l y s t w h en .p r e c i p i t a t i o n i s c a r r i e d o u t a t th e b o i li n g p o in t w ith
“ 2 ?”
a p p r e c i a b l e t im e a llo w e d f o r d i g e s t i o n .
u b le i n c o ld w a te r .
A l s o , n i c k e l c a r b o n a te i s i n s o l ­
I f p r e c i p i t a t i o n and d i g e s t i o n a r e c a r r i e d -o u t a t th e
, b o i l i n g p o i n t , t h e am ount o f n i c k e l l o s t i n t h e f i l t r a t e w i l l b e m in im iz e d .
E f f e c t o f E n tra in e d S a lt
R uns 1 7 , 1 8 , a n d 22 i l l u s t r a t e t h e e f f e c t o f e n t r a i n e d s a l t u p o n c a t a ­
l y s t s u lf id in g .
S am p les P -3 9 -A , P - 4 5 , a n d P -3 7 w e re w a t e r w ash ed P n ce w i t h
1 0 0 m l , ; , 't h r e e t i m e s w i t h 1 0 0 m l . , and t h r e e t i m e s w i t h 3 4 0 m l . , r e s p e c t i v e l y ,
f o llo w in g f i l t r a t i o n .
S u l f i d i n g f i g u r e s i n d i c a t e t h a t t h e m ore t h e c a t a l y s t
i s w ashed, th e l e s s i t w i l l s u l f i d e .
T h u s , i t c o u ld b e c o n c lu d e d t h a t t h e
p r e s e n c e o f t r a c e s o f so d iu m s u l f a t e , a s a n e n t r a i n e d s a l t , i s b e n e f i c i a l
t o maximum s u l f i d i n g .
H o w ev er, a n a p p r e c i a b l e am ount o f e n t r a i n e d s a l t i s
e x tr e m e l y d e t r i m e n t a l t o c a t a l y s t a c t i v i t y ( 4 ) «
■28-
SUMt-IARY
T he r e s u l t s and c o n c l u s i o n s o f t h i s i n v e s t i g a t i o n m ay b e sum m arized
as fo llo w s :
I.
Optimum c o n d i t i o n s f o r t h e o x i d a t i o n o f a s p e n t n i c k e l c a t a l y s t <,
b a s e d on t h e .p e r c e n t s o l u b l e s u l f a t e p r o d u c e d , a r e a t e m p e r a t u r e
o f a b o u t 8 5 0 °F a n d a c o n t a c t •tim e o f o n e t o tw o h o u r s ,
2«
H y d r o f in in g c o n d i t i o n s c o n d u c iv e t o maximum c a t a l y s t u t i l i z a t i o n
a r e a r e l a t i v e l y lo w t e m p e r a t u r e o f 525°F a n d a r e l a t i v e l y lo w
h y d ro g e n r a t e .
3»
Maximum s u l f i d i n g i s o b t a i n e d fro m a c a t a l y s t p r e c i p i t a t e d b y
a d d in g a s l i g h t e x c e s s o f so d iu m c a r b o n a t e s o l u t i o n t o a n i c k e l
s u lf a te s o lu tio n .
4.
R a p id p r e c i p i t a t i o n a t room t e m p e r a t u r e , w i t h l i t t l e
o r no
d i g e s t i o n , r e s u l t s i n a c a t a l y s t t h a t w i l l d e m o n s t r a t e maximum
s u lfid in g .
5.
A l a r g e am ount o f e n t r a i n e d s a l t i s e x tr e m e ly d e t r i m e n t a l t o
c a t a l y s t a c t i v i t y , b u t t r a c e s t e n d t o p ro m o te maximum c a t a l y s t
u tiliz a tio n
-
“
29-
ACKWOWLEDGEMENT
The a u t h o r w is h e s t o a c k n o w le d g e t h e c o u r t e s y o f t h e H usky O i l
■
Com pany, who f u r n i s h e d t h e f u e l o i l a n d p r e p a r e d t h e c a t a l y s t s a m p le s
used in t h i s in v e s tig a tio n .
The H usky O i l Company a l s o p e rf o r m e d much
o f t h e c h e m ic a l a n a l y s i s t h a t w as n e e d e d . .
LITERATURE CITED
(1 )
AeS 0TeM0 S t a n d a r d s o n P e tr o le u m P r o d u c ts a n d L u b r i c a n t s , 2 7 2 , D 9 0 -4 1 -T ,
(1 9 4 1 ).
(2 )
B e r g , B r a d l e y , e t a l , " C a t a l y t i c . D e s u l f u r i z a t i o n o f H igh S u l f u r S t o c k s ,
Cheme E n g r e P r o g r e s s , 4 3 , I , ( 1 9 4 7 ) .
(3 )
C o y k e n d a ll, Jo h n We , Me S e T h e s i s y .M ontana S t a t e C o l l e g e , ( 1 9 5 1 ) .
(4 )
F i s c h b a c h , R o b e r t J e , Me S e T h e s i s , M ontana S t a t e C o l l e g e , ( 1 9 5 2 ) .
(5 )
F r i e d r i c h , F . , a n d B l i c k l e A ., "T h e rm a l D a ta on R o a s t in g P r o c e s s e s , "
M e t a l l u r g i e 7 , 3 2 3 - 3 2 ; Ce Ae
1 3 8 9 , (1 9 1 1 K '
( 6 ) • Gyvmn, M a rio n He , Ue S e P a t e n t N o. 2 ,0 7 3 ,5 7 8 , M arch 9 , 1 9 3 7 .
( 7)
Gwynn/ M a r io n -He , Ue 8 . P a t e n t N o, 2 , 1 7 4 ,5 1 0 , O c to b e r 3 , 1 9 3 9 .
(8 )
H o rn e , W. Ae , a nd J u n g e , J e F 0, U 0 S e P a t e n t N o; 2 , 5 1 6 ,8 7 6 , A u g u st I ,
1950.
.
'i
■■
-
(9 )
K a lic h e v s k y , Ve Ae , " S w e e te n in g a n d D e s u l f u r i z a t i o n o f L i g h t P e tr o le u m
P r o d u c t s , " P e tr o le u m R e f i n e r . 2 9 , Noe 1 1 , 9 7 , ( 1 9 5 0 ) .
( 1 0 ) M il b a u e r , J e , a n d 'T u c e k , J e , "The E f f e c t o f SO2 on V a r io u s N a t u r a l
a n d A r t i f i c i a l S u l f i d e s , " Cheme- Z t g e , 5 0 , 3 2 3 - 5 3 Ce A . 2 0 ,
2293, (1 9 2 6 ).
( 1 1 ) Thom pson, R e B e , e t a l , " S t a b i l i t y o f F u e l O i l s i n S t o r a g e , " I n d . E n g e
Chemee £ 1 , 2 7 1 5 - 2 1 , ( 1 9 4 9 ) .
( 1 2 ) U e n o , S e , J e S o c e Gheme I n d e , J a p a n , 4 6 , 4 5 , ( 1 9 4 3 ) .
-3 1 APPENDIX
page
T a b le I
O x i d a ti o n C o n d i t io n s a n d R e s u l t s
32
T a b le I I
I n s p e c t i o n D a ta f o r C h arg e O i l .................... ' • • • • « . • .
33
T a b le I I I
S o l u t i o n s U sed i n C a t a l y s t P r e c i p i t a t i o n . . . . . . . .
34
T a b le IV
C o n d i t io n s U sed i n C a t a l y s t P r e c i p i t a t i o n s
T a b le V
C o m p a ra to r Run R e s u l t s . v . . . . . .
T a b le VI
C o m p a ra to r R un C o n d i t io n s a n d C a l c u l a t i o n s
37
F ig u re I
E f f e c t o f T e m p e ra tu re o n O x i d a ti o n . . . . . . . . . . .
44
F ig u re 2
E f f e c t o f Tim e o n O x i d a ti o n
. . . . . . . . . . . . . .
45
F ig u re 3
E f f e c t o f R u n •Time o n C o m p a ra to r Ru n s . . . . . . . . . .
46
F ig u re 4
F l u i d O x i d a ti o n U n i t
47
F ig u re 5
C o m p a ra to r U
.
.
.
n
r
-
.
.
.
.
.
e . . . . . . .
.
i
35
.
.
.
.
.
.
t
.
.
.
.
36
4^
■”
32"
'
TABLE I
OXIDATION CONDITIONS AND RESULTS
B un
N o.
T im e
H rs.
I
2
3
4
5
6
7
8 ■
9
i
I
2
3
4
8
4
4
2
T e m p e r a tu r e
dp
850
850
850
850
850
850
650
1150
644
■P e r c e n t
T o ta l
S u lfu r
1 0 .1 8
3 .7 2
3 .8 5
3 .6 7
3 .9 1
3 .8 8
1 0 .8 9
3 .9 5
9 .4 0
P e rce n t
S u lfu r as
S o l u b le S u l f a t e
.9 .1 4
7 2 .8 5
7 3 .2 5
6 5 .6 7
6 6 ,7 5
6 0 .2 6
3 6 .8 2
4 8 .8 3
3 5 .9 0
“3 3 . TABLE IT
.INSPECTION DATA FOR CHARGE OIL
S an d T r e a t e d
R e g u la r
AeP eI 0 a t 60 °FS p e G r.
A v e ra g e M oIe W te
B rom ine No.
W t1 % S u l f u r
W te % H ydrogen
AeS 0T eM0 D i s t i l l a t i o n
'
I 0B 0P 0
5$
10
20
30
40
50
x
60
70
80 •
90
95
Ee P e
R e c o v e re d
R e s id u e
L o ss
3 0 .6
3 0 .5
0 .8 7 3 5
0 .8 7 2 9
222
9 .2 4
2,20
222
7 .5 7
2 . 09 - 2 .2 0
1 0 .9
4 2 5 °F
504
536
548
558
567
575
584
594
575
584
595
613
631
625
652
651
9 9 .0 %
0.2
3 8 5 °F
499
519
536
547
555
566
611
■.
1 0 .9
"
520
0 .8
:
#
%
9 9 .0 %
0.8
0 .2
%
#
-3 4 • T A B L E 'III
SOLUTIONS USED IN CATALYST PRECIPITATION
N ic k e l S u lf a te S o lu tio n s
*
S
In g re d ie n ts
Grams
ml
C om m ercial
-HgO
NiSO 4
.
S o lu tio n
A
L e a c h e d fro m s p e n t
C a t a l y s t w i t h HgSO4
N
B
858
2994
C
843
1950
S p e c ific
. G ra v ity
, ,
-
1 .2 5 2 9
a t 2 8 .9 °C
1 .1 4 5 8
a t 2 4 .5 °C
1.2060
a t 23 . 90 C
D
E
'
.
843
1950
,8 4 3
1951
Sodium C a rb o n a te S o l u t i o n s
S o lu tio n
Grams NagCOo p e r gram
o f s o lu tio n
A
OcI 860
B
0 ,2 3 0 0
c
0.2301
D
0.2298
TABLE IV
CONDITIONS USED H CATALYST PRECIPITATIONS
C a t,
- - 'N iS O J1
S o l fIi cc
Gms
P-25
P -2 6
-P -2 7
A
A
A
P -2 8
P -2 9
A
A
- 1 2 5 .0
P -3 0
P -3 1
P -3 7
A
A
B
1 2 5 .0 2 1 .2 6
1 3 6 .3 '1 9 .5 6
P -3 9 A
P -4 2
P -4 3
B
1 3 6 .3
B
B
1 3 6 .3
1 3 6 .3
P -W
B
P -4 5
B
j
B
1 2 5 .0 2 1 .2 3
1 2 5 .0 . 21.26
1 2 5 .0 2 1 .2 6
S o lfn
NaoCOg
cc
Gms
Added
To S o l f Ii
NagiCOg
Na2 COg
Na2GOg
A
A
A
7 0 .0
8 0 .0
1 4 0 .0
1 2 5 .0
A
2 1 .2 6
2 1 .2 6 " A
7 2 .5
1 4 5 .0
1 5 .5 9
1 7 .8 2
3 1 .1 8
1 6 .1 5
3 2 .2 9
1 2 5 .0
21.26
A
-A
A
7 2 .5
7 2 .5
7 2 .5
1 6 .1 5
1 6 .1 5
1 6 .1 5
Na2 COg
Na2 COq
Na2 COg
1 9 .5 6 . A
7 2 .5
1 6 .1 5
NiSO4
■
NiSO.
NiSO,.
4
.X
1 9.56
A
A
7 2 .5
7 2 .5
1 6 .1 5
1 6 .1 5
Na2COg
Na2COg
1 3 6 .3
1 9 .5 6
A
7 2 .5
1 6 .1 5
Na2 CQg
1 3 6 .3
■T.
1 9 .5 6
A
7 2 .5
1 6 .1 5
NiSQ 4
13& .3
1 9 .5 6
A
1 3 0 .0
2 8 .9 5
NiSO4
9 8 .7
1 9 ,4 9
A
6 5 .0
1 9 .9 4
...
P -4 8
P -5 5 - C
' B
P
2 9 -3
(E
2 9 -4 (C
5
444»4 B&C 1180
2673
2223
4 4 4 .4
D 1160
1 1 9 .7 2 3 .6 4
1 4 .4 8 S I m u l - ’
ta n e o u s
Na2 COg
3 3 5 .2
3 2 9 .3
NiSO 4
P re c ip ita tio n
Temp 0F Time
M in .
B o il
B o il
(B o il
(2 0 7 -2 0 9
B o il
(B o il (2 0 3 -2 0 5
1 8 8 -1 9 2
7 1 -7 3
(B o il
'
(2 0 6 -2 0 9
(B o il
(2 0 3 -2 0 4
7 6 .5 - 7 9 .
(B o il
(2 0 4 -2 0 6
(B o il
(2 0 5 -2 0 8
(B o il
(20A -206
(B o il
(2 0 2 -2 0 7
(B o il
(2 0 0 -2 0 5
B o il
B o il
70
80
80
D ig e s tio n
Temp °F
Time
M ip ,,
B o il
60
B o il
60
B o i l 206 60
W a te r Wash
cc
N d. o f
per
W ashes
Wash
340
3
340
3
340
3
72
B o il
340
3
80
72
72
B o i l " 205
1 8 7 -1 9 3
74
60
60
340
340
340
3
3
3
340
3
60
60
72
B o i l 207
60
72
72
- B o i l 205
B o i l 205
60
100
340
I
3
15
B o i l 205
65
340
3
72
——
0
340
3
72
B o i l 206
60
100
3
'80
60
340
3
72
60
B o i l 207
" '
B o i l 206
B o il
90
60
340
1000
3
2
60
B o il
60
1000
2
60
-3 6 TABLE 7
COMPARATOR RUN RESULTS
Run N o.
xO 0 } - 3 OVTt
V) fV H
I.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
•
C a ta ly s t
NiCOn
NiCOo
NiGO3 '
NiCOn'
NiCO3
. NiGO3
2 9 -4
2 9 -5 .
2 9 -3 .
. P -2 5
.
P -2 6
P -2 7 .
P -2 8
P -2 9
P -3 0
• P -3 1
P -3 7
P -3 9 -A
P -4 2
P -4 3
P -4 4
P -4 5
P -4 8
. P -5 5 -B
S to ic h io m e tric
P e rc e n t S u lfid e d
4 6 .6
3 4 .7
4 7 .9
4 5 .2
5 5 .0
59.Q
3 5 .1
2 6 .0
A p a l y b ic a l
P e rce n t S u lfid e d
—T
■
m
mew
6 p .2
62 »8
6 7 .2
4 9 .8
4 2 .2
111
120
129
5 9 .3
5 4 .8
—
4 4 .2
4 5 .2
4 9 .8
8 2 .6
5 2 .7
6 5 .2
8 3 .7
115
8 7 .7
HO
9 7 .2
140
128
116
52.6
4 2 .8
4 4 .8
4 7 .2
4 5 .9
6 2 .4
5 2 .3
6 1 .7
4 9 .0
5 4 .5
5 7 .2
6 0 .5
O
S
I
•
II
I
NiCOo
-I
2 3 .5
O
I
t
k,
CD p
I
g H
«8 w
® e
^ -H
U. 0
<
E-i
I
. 1H
ffi O
(d CO
m' S &
n f co
62$
1 7 .5
2 .4 6
I
" •
2
NiCO3
2 3 .5
72$
1 7 .3
2*46
£
CC
IE-I
NiCOc5
2 4 .0
525
17« 0
2 .4 6
CO
CD
CO
0 0
j 6
S S -
0
I 394.3
2 4 0 5 .4
3 4 0 6 .7
4 4 02.6
5 4 1 4 .8
6 4 2 1 .7
7 4 2 4 .0
8 ,3 7 1 .7
3 2 4 1 .2
6 .7
6 .7
6 .7
6 .7
6 .7
6 .7
6 .8
6 .8
d
B B w am
I
2
3
4
5
6.
7
3
0
§
^B asm
3 7 2 .6
3 9 9 .4
4 0 3 .7
4 1 1 .1
4 1 3 .6
3 9 3 .3
4 1 2 .8
2 8 0 6 .5
5 .6
■5.6
5 .6
5 .6
5 i7
5 .7
5 .7
O
I 3 5 6 .1
2 4 1 0 .2 ':
3 '4 0 6 . 3
4 4 1 7 .8
C M B ir-l.
-
_
I
•H
*H ,-O
O 0)
^ &
• k a
^oE )
4 2 1 .5
4 2 8 .4
4 3 0 .8
3.78.5
3 2 9 5 .0
IO
&
PL,
2 .0 9 0
1 .6 8 2
1 .9 4 8 .
2 .0 2 0
2 .0 9 0
2 .0 9 0
2 .0 9 0
4 0 1 .0
412.1
■ 4 1 3 .4
409.3
9 .8 7
4 6 .6
9 .8 ?
3 4 .7
1 0 .1 0
47.9
1 .6 3 6
0 .5 8 $
0 .2 8 9
0 .0 0 0
0 .0 0 0
0 .0 0 0
0 .0 0 0
'0 .0 0 0
2 .0 9 0
2 .0 9 0
2.510
2 .0 9 0
1 .7 3 7
1 .9 9 0
2 .0 6 0
2 .0 9 0
2 .0 9 0
2 .0 9 0
2 .0 9 0
3 7 8 .2
4 0 5 .0
4 0 9 .3
4 1 6 .7
4 1 9 .3
3 9 9 .0 .
4 1 8 .5
2 8 4 6 .0
3 6 1 .8
4 1 5 .9
412.-1
4 2 3 .6
q -P
Ph 03
1 .3 3 5
0.405
0.123
0.060
.
0 .0 0 0
0 .0 0 0
0 .0 0 0
" 1.863
B a t e iM
5 .7
5 .7
5 .8
6 .8
l l
H g
&
•H -P
n ic k e l s u lfid e d
TABLE V I
COMPARATOR RUN CONDITIONS AND CALCULATIONS
•
2 .0 9 0
1 .7 0 2
1 .9 0 5 '
1.99&
2 .0 7 0
1 .4 0 4
0 i7 6 9
0 .3 7 9
0 .0 8 5
-P
iH
I
I
SNiCOc
t
i
2 4 .0
St
5 O
H
©
Ci
-£3.
4
525
Si a
1 7 .0
'
.
£-
CD O Iti
O
E-i
CO
© aSn he
O'
cM CJ
© O
m co
2 .4 6
3 ‘
E-i
5
6
7
4 1 9 .1
402.6
4 0 7 .5
I:
s
CO
CO
S
cd ♦H
MO
•H©
Cl CO
S O ho
© ,S
TJ
Cl ©
©y
Pk CO .
IS
CO Cl
O -P
-H- cti
5 .8
5 .8
5 .8
4 2 4 ,9
4 0 8 .4
4 1 3 .3
2 .0 9 0
2.090
2 .0 9 0
0 .0 0 0
0 .0 0 0
0 .0 0 0
2 .6 3 7
10.10
4 7 .9
10.10
4 5 .2
2819.6
NiCOq
2 4 .0
575
1 7 .1
2 .4 6
0
1
0
1
3 7 1 .8
2
408.6
5 .2
5 .2
5 .2
5 .2
5 .3
5 .3
5 .3
6
NiCO3
2 4 .0
525
1 7 .1
2.98
2 .0 9 0
4 .9
4 .9
4 .9
4 .9
5 .0
5 .0
2
5
2860.0
3 9 0 .3
3 0 5 .1
4 0 9 .2
4 0 3 .6
4 1 8 .4
4 1 0 .8
2 4 3 7 .4
3
4
5
3 9 5 .2
410.0
4 1 4 .1
4 0 8 .5
4 2 3 .4
4 1 5 .8
2 4 6 7 .0
1 .7 4 8
1, 9 7 0
2 010
2, 035
2( 070
2, 090
,
3 7 7 .0
4 1 3 .8
4 1 4 .4
1.668
428.2
411.2
100
120
4 0 4 .8
130
416.6
2 8 6 6 .0
1 .9 9 8
2 .050
140
•H -P
CO
1 .3 5 2
0 .4 9 2
0 .3 3 1
0 .2 2 5
0 .0 8 5
0 .0 0 0
2 .4 8 5
2.140
4 0 9 .2
4 2 3 .0
4 0 5 .9
6 3 9 9 .5
7 4 1 1 .3
2 8 2 9 .3
3
4
5
&
P erce n t
n ic k e l s p lfid e d
TABLE V I ( c o n t i n u e d )
C o m p a ra to r R un C o n d i t io n s a n d C a l c u l a t i o n s
*
10.10
1.780
0.588
0 .3 7 3
0 .1 7 1
0 .0 8 2
0.040
0 .0 0 0
3.034
55.0
to
C a ta ly s t
k
S
O
6
7
8
NiCO3
2 9 -4
2 9 -5
£
I
l>
0
cH
A
r*j
•H
0) O "cd
Si
2 4 .0
6 .5
8 .1
525
525
525
0
1 7 .1
6 4 .3 .
5 1 .9
<
(Z)
E)
■
-s I
K •H
O"0to
K CO IE-* ^ 8
Q)CT\
1 .8 9
1 .8 9
1 .8 9
CO
I
to
CO
S
0
mnww
1 Wiiin
2
3
4
5
6
7
4 1 1 .1
4 0 0 .3
4 0 7 .1
4 2 2 .7
4 0 2 .0
4 1 0 .8
4 1 6 .4
2 8 7 0 .4 .
1 .3
1 .3
1 .4
1 .4
1 .4
1 .4
1 .4
I
O
I
2
3
4
5
6
7
8
O
I
2
3
4
5
JL
<d 0
•H
•H
O
O to
e
Sg I
■■■■■■
4 1 2 .4
4 0 1 .6
4 0 8 .5
4 2 4 .1
4 0 3 .4
4 1 2 .2
4 1 7 .8
2 8 8 0 .0
__
4 0 2 .8
3 8 9 .5
4 0 7 .1
4 2 1 .0
4 1 4 .2
4 2 4 .8
4 2 3 .0
430.-2
3 3 1 2 .6
4 1 7 .1
3 9 8 .7
4 1 8 ,0
424.3
411.3
4*4
4 .4
4 .4
4 .4
4 .4
4 .4
.4 .5
4 .5
2 .4
2 .5
2 .5
2 .5
2 .5
CO.
4 0 7 .2
3 9 3 .9
4 1 1 .5
4 2 5 .4
4 1 8 .6
4 2 9 .2
4 2 7 .5
4 3 4 .7
3 3 4 8 .0
4 1 9 .5
401.2
' 4 2 0 .5
426,8
4 1 3 .8
q
•H -P
©^
gy
c4 cd
2 .1 4 0
1 .7 3 2
1 .9 7 2
2 .0 5 5
2 .0 7 0
2 .1 1 0
2 ill0
2 . I 4O
2 .2 0 0
2 .1 2 0
■2 .1 6 0
2 .1 6 5
2 .2 0 0
2 .2 0 0
2 .2 0 0
2 .2 0 0
2 .2 0 0
£0
3
I It
q -P
•H cti
S 0
1 0.10
1 .6 8 2
0 .6 7 5
0 .3 4 7
0 .2 9 7
0 .1 2 1
P e rce n t
n ic k e l s u lfid e d
TABLE V I ( c o n t i n u e d )
COMPARATOR RlM CONDITIONS AND CALCULATIONS
59 .O
•
0.124
0 .0 0 0
3 .2 4 6
—0 .3 2 6
0 .1 5 8
0 .1 4 4
0 .0 0 0
0 .0 0 0
0 .0 0 0
0 .0 0 0
0 .0 0 0
vL
?
3 .2 9
3 5 .1
4 .1 0
2 6 .0
0.628
2 .2 0 0
2 .1 4 0
2 .1 6 0
2 .1 7 0
2 .1 9 0
2 .2 0 0
0.251
0.161
0.126
0 .0 4 3
0 .0 0 0
ID
C a t a ly s t
S'
O
s
9
10
11
12
2 9 -5
2 9 -3
P -25
P -2 6
P -2 7
&
4
a .l
1 1 .7
I 6 .4
1 5 .9
1 7 .4
■
3 is
>
E-i
0)
OJ
O
O
tti- Q
s a
525
51.9
I
525
525
525
525
3 5 .9
2 4 .8
2 6 .9
2 4 .3
. CO
-P
'B
1 .8 9
6
7
8
1 .8 9
1 .8 9
1 .8 9
rQ •H
I
.rH
8
•p
O
EC CO
1 .8 9
I
■I
0) g.
O
4
8
O
4
8
O
4
8
O
4
8
W
to
(3
g
4 2 5 .1 . 2 . 5
4 2 3 .7 2 .5
4 2 9 .9 2 .5
3 3 4 8 .1
1658
1681
3339
1634
1582
3216
11
11
20
21
ICd*Hg
O
0
1649
1685
3334
1516
I s
o Sn
1
O
427.6
426.2
4 3 2 .4
.3 3 6 8 .0
1669
1692
3361
1654
16Q3.
3257
>■>— BB
1709
1687
3396
1O
-P
1724.
m
P k CO
2 .2 0 0
, 2 .2 0 0
2 i2 0 0
2 .2 0 0
2 .0 7 3
2 .1 4 0
2 .2 0 0
1 .9 7 9
2 .1 0 6
2 .2 0 0
1 .9 9 5
2 .0 8 0
3427
24
25
1673
1710
3383
2 .2 0 0
2 .1 3 0
Ii
CO J h
0 .0 0 0
0 .0 0 0
0 .0 0 0
0 .5 8 1
B-
= i
•H -P
iq f43
IO
Si O
P-,
4 .1 0
2 6 .0
5 .1 9
111
2 .1 2 0
1 .0 1 5
3 .1 3 5
f
7 .9 0
120
7 .9 3
120
3 .6 5 5
1 .5 0 7
5 .1 6 2
3 .5 3 2 2 .0 4 3
5 .5 7 5
7 .9 2
1 .1 7 2
-T - ;
n ic k e l s u lfid e d
-TABLE V I ( c o n t i n u e d )
COMPARATOR RUN CONDITIONS AND CALCULATIONS
TABLE V I ( c o n t i n u e d )
COMPARATOR RUN CONDITIONS AND CALCULATIONS
k
S
I s,
-0I
0 q
■ s,
-P
-rl W
C a ta ly st
0
13
14
15
16
P -2 8
P -2 9
P -3 0
P -3 1
lb
a,
S
I
15»6
9 .8
1 7 .4
1 4 .8
525
525
525
525
g
£
0)
0
«8
O
1
2 7 .5
4 3 .7
2 4 .8
2 9 .1
0
<•
^
ts CO
1 .8 9
1 .8 9
1 .8 9
1 .8 9
■
I
I
E-i
0
4
8
0
4
8
0
4
■8 .
O
4
8
P -3 7
1 3 .6
525
3 1 .5
1 .8 9
I
1523
im z
341 P
o r .M
_-»
1644
-
0
4
8
H 'o
•H—5
9
10
e=>ca
8
8
3392
1532
1897
3429
Cacc caa
1652
1256
3408
GCeaca
1729
1726
3455
= 3=3^
1729
im
5
6
» »
6
7
~
1669
1743
3412
'
-P & I
C=C=SCB
==•=-*•=*
3433
- -'
17
^0
6 8
<0
Sn
^ Q
CM O
1734
1Z22
3466
• -- •—
1735
1711
JhhS
BOee
3 ■ 1674
6
1749
34%
•p
S ^ •
(X, CO
2 .200
§
&
TJ
I.
tj ^
0}
S I
d I
CO &,
.3 -g
2 .0 9 3
2 .1 7 3
“““
1 ,6 3 8
0 .5 1 2
2 .1 5 0
2 .2 0 0
2 .1 0 0
2 .1 6 5
1.652
—
s t
a
Sn
y
•ti .
9? pj
S O
s
7 .9 3
4 9 .8
5 .0 3
8 2 .6
y
0 .6 1 5
2 .2 6 ?
b
s
2 .2 0 0
2 .1 2 0
2 .1 4 9
—
1 .3 8 7
0 .8 8 3
2 .2 7 0
7 .9 0
5 2 .7
2 .2 0 0
2 .1 0 5
2 .1 6 5
———
1 .6 4 8
0 .5 9 9
2 .2 4 7
6 .3 2
6 5 .2
2 .2 0 0
2 .0 7 9
2 .1 2 5
—2 .0 2 5
1 .3 1 2
3 .3 3 7
7 .3 1
8 3 .7
18 ' P -3 9 -A
M
If
I
fp
&
I
E-i
1 3 .5 525
- t o
O t
■CO
cl QQ
mh 3 1 .8
•4
i s
Ph
CNH
HTCQ
»•
*
g
-9
H
j s
13
O
<D
CO
CO
G
6
6
1 5 .0
525
2 8 .3
1664
1694
16
16
3358
P-43
14.1
525
3 0 .0
P -4 4
14.3
525
25L 7
8
P -4 5
1 3 .0
525
3 : 1.2
1662
16%
1710
14
15
1676
IZQS
. 335 S
3385
1695
1688
3382
1700
5
6
1694
3394
1 .8 9 0
4
8
1702
1729.
3431
Ig V
&t
O
P h CO
2*200
1 .9 9 4 '
13
13
1715
1742
3457
■
y 0
CO Ph
J
at
a -P
&
•H
q -P
S O
O
Ph
7.25
115
7 .4 9
8 7 .7
7 .3 0
HO
7 .3 4
9 7 .2
7 .3 4
140
3 .5 0 0
2 .1 4 0
4.543
2 .2 0 0
2 .0 5 1
2 .1 3 7
3390
1 .8 9 0
4
22
1680
1 .8 9 0
4
8
21
1698
1%28
1 .8 9 Q
4
8
20
y 0 I
Js-O
hO
Tf-
3436
3424.
P -4 2
■g
&
ra
1 .8 9 0
■4 1 6 9 2
B- 1732
19
o il a fte r
re c tio n
C a ta ly s t
b,
S
O
o i l b e fo re
r a c tio n gras.
TABLE V I ( c o n t i n u e d )
COMPARATOR RUN CONDITIONS AND CALCULATIONS
2 .2 0 0
2 .0 0 9
2 .1 3 1
2 .2 0 0
2 .0 5 5
2 .1 1 6
2 .2 0 0
1 .9 6 4
2 .1 1 1
2.503
1^28
3 .5 8 1
3 .2 0 0
1 .1 8 0
4 .3 8 0
2 .4 6 5
Lm
3 .8 8 8
4 .0 4 5
1 .5 5 0
5 .5 9 5
■
C a ta ly s t
8
23
P-48.
*
8
1 2 .0
525
tti
3 3 .3
1 .8 9
525
3 0 .9
1 .89
CO
§>
^ 0
y I
CO k
2 .2 0 0
1726
10
11
3412
>
4
1664
8
im
10.
11
8
P -5 5 -B 1 3 .9
ts
O
4
24
I
I
I
1686
1696
1737
3433
O
3417
1674
1764
3438
P ercen t
n ic k e l s u lfid e d
TABLE V I ( c o n t i n u e d )
COMPARATOR RUN CONDITIONS AND CALCULATIONS
© m
UO
*
cd JS
M
H
O
r-j -P
d ^
__ ©
O 0
0^
U) O
1d
b ©
O
n
;
t
tI i i
y
-P0 % I
^oQ )
PL, m
E-i
£ I
m cd
is o
a
7 .3 8
1 .9 9 5
3 .4 7 6
2.103
1 .6 8 5
5 .l6 l
2 .2 0 0
2 .0 0 7
3 .2 3 1
2.120
• 1 .412
123
7 .3 5
4 .6 4 3
6
IOO
UJ
H
<
U
-J
3
CO
80
Ul
_l
CD
3
-J
O
CO
60
CO
<
cr
3
U-
40
-J
3
CO
tZ
UJ
O
20
CC
UJ
Q-
0
1050
850
650
TEMP ERATURE,
F ig u re I .
0F
E f f e c t o f T e m p e ra tu re o n O x id a tio n
1250
-S T -
PERCENT SULFUR AS SOLUBLE SULFATE
TI ME, HOURS
F ig u r e 2 .
E f f e c t o f T i r e on O x id a tio n
OIL
PERCENT SULFUR IN EFFLUENT
RUN NO. 2
o RUN NO. 3
a
TIME,
F ig u r e 3
HOURS
E f f e c t o f Run T in e on C o ra p a ra to r Runs
-4 7
EXHAUST
1.
2.
3.
4.
5.
6.
7.
THERMOWELLS
NEEDLE VALVE
ORIFICE AND MANOMETER
FLUID REACTOR
PREHEATER
STEEL BALLS
INSULATION
F ig u re 4 .
F l u i d O x id a tio n U n it
—4?—
I. COMPARATOR UNIT
2 INSULATION
3. IRON PIPE
4. THERMOWELL
5. CATALYST SUPPORT
6. WATER CONDENSER
7 OIL RESERVOIRS
8. BELLOWS PUMP
9. ICE CONDENSER
10. H2 S ABSORBER
F ig u re 5 .
C o n p a r a to r U n it
103327
MONTANA STATE UNIVERSITY LIBRARIES
I!!!!!!!!!!!!!!!!
3 17 6 2
10022677 6
103327
R378
W555
cop. 2
W han, G len n ^A
R eg en era tio n o r a
n ic k e l carbonate
d e s u lfu riz a tio n c a ta ly s t
=========4
T -----
IS SU E D TO
DATE
4---------
A J508
_______W S S S
C op. A
103327