The preparation of a nickel oxide desulfurization catalyst
by Robert J Fischbach
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 Robert J Fischbach (1952)
Abstract:
The purpose of this investigation was to find the optimum conditions for the preparation of an active
nickel oxide desulfurization catalyst.
The various catalyst samples were prepared by precipitating nickel carbonate from solutions of nickel
sulfate and sodium carbonate* A few samples were prepared from nickel sulfate and calcium
hydroxide* The various catalyst samples were tested in a comparison unit under the same conditions of
temperature, hydrogen rate, and oil rate. The activity of the catalysts was based on the grams of sulfur
removed per gram of nickel, A study was made of catalyst activity with respect to precipitation and
digestion conditions, entrained salt, time and temperature of calcining, and the effect of oven drying.
The most active catalyst was obtained when the precipitation and digestion were carried out at the
boiling point, and the precipitate was washed free of entrained salt. Oven-dried catalysts showed more
activity than those which were calcined. • THE PREPARATION OF.A NICKEL OXIOB
DESULFURIZATION CATALYST'.
by
>
■ ROBERT J . FISCHBACH
A THESIS
S u b m itte d 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
fo 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
a t'
M ontana S t a t e C o lle g e
A p p ro v e d :
H e a d , M a jo r D epartm ^ifb
C h a irm a n , E x a m in i
m m itte e .
Dda'n, G r a d u a te D i v i s i o n
B ozem an, M o n tan a
■ .J u n e 1, 1 9 5 2
.2TABLE OF CONTENTS
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R e s u l t s ...........................................................................................................................................
Summary ........................................................... . . . . . . .
A cknow ledgem ent . . . . . . . .
L ite r a tu r e C ite d . . . . .
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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 t h e p r e p a r a t i o n o f - a n a c t i v e 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 o
The v a r i o u s c a t a l y s t s a m p le s w ere p r e p a r e d b y p r e c i p i t a t i n g n i c k e l
c a r b o n a te fro m s o l u t i o n s 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 te *
A few
s a m p le s w e re p r e p a r e d fro m n i c k e l s u l f a t e a n d c a lc iu m h y d ro x id e *
The v a r i o u s c a t a l y s t , s a m p le s w e re t e s t e d i n a c o m p a r is o n " u n it u n d e r
t h e same c o n d i t i o n s o f t e m p e r a t u r e , h y d ro g e n r a t e , a n d o i l f a t e . The
a c t i v i t y o f t h e c a t a l y s t s w as b a s e d on t h e g ram s o f s u l f u r reimqved p e r
gram o f n i c k e l ,
A s t u d y w as made o f c a t a l y s t a c t i v i t y 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
a n d d i g e s t i o n c o n d i t i o n s , e n t r a i n e d s a l t , tim e a n d t e m p e r a t u r e o f c a l c i n ­
i n g , a n d t h e e f f e c t o f o v e n d r y i n g . The m o st a c t i v e c a t a l y s t w as o b t a i n e d
w hen t h e 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 w e re c a r r i e d o u t a t t h e b o i l i n g p o i n t ,
a n d t h e p r e c i p i t a t e w as w a sh e d f r e e o f e n t r a i n e d s a l t .
O v e n - d rie d c a t a l y s t s
show ed m ore a c t i v i t y t h a n t h o s e w h ic h w e re c a l c i n e d .
HTRODUOTIOH
The 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 h a s c a u s e d a
s e r i o u s d e p l e t i o n o f t h e h i g h g r a d e c ru d e s t o c k s .
T h i s h a s f o r c e d th e o i l
r e f i n e r i e s t o u t i l i z e t h e lo w e r g r a d e , h i g h - s u l f u r c r u d e s , s u c h a s th o s e
fo u n d i n .th e . R o cky M o u n ta in - a r e a ,. W est T e x a s , and C a l i f o r n i a *
R ecent s u r­
v e y s show ed t h a t b o t h t h e a b s o l u t e a n d r e l a t i v e v o lu m e s o f h i g h s u l f u r
c ru d e o i l s . p ro d u c e d i n t h e U n ite d S t a t e s , h a s 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 (7 )«
The u t i l i z a t i o n o f t h e s e h i g h e r s u l f u r . c r u d e s h a s p r e s e n t e d th e p r o b ­
le m o f d e s u l f u r i z a t i o n *
The s u l f u r may be p r e s e n t - a s , e l e m e n t a l s u l f u r ,
h y d r o g e n s u l f i d e , m e r c a p t a h s , s u l f i d e s a n d p o l y s u l f id e e ,,, t h i o p h e n e s , and
th io p h a n e s *
V a r io u s m e th o d s s u c h a s t h e U n i s o l p r o c e s s , a n d t h e S o l u t i z e r
p ro c e s s , a re q u ite e f f e c tiv e
i n - e l i m i n a t i n g m e r c a p ta n s u l f u r frq m g a s o l i n e s ,
b u t t h e h i g h e r b o i l i n g t h i o p h e n i c s u l f u r , m ore com m only..found i n th e f u e l
o i l f r a c ti o n s , i s h o t a p p re c ia b ly a f f e c te d by th e s e . tre a tm e n ts .
T h io p h e n e s
a n d t h io p h a n e s c a n b e rem oved o n l y be 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 ) ,
S u lf u r in k e ro s e n e s and g a s o i l s to c k s g iv e s , r i s e , to o b je c tio n a b le
o d o r , c o r r o s i o n , p o o r c o l o r s t a b i l i t y , an d i s r e s p o n s i b l e f o r " a c r i d fum es
on b u r n i n g .
. S t o c k s o f h i g h s u l f u r c o n t e n t a r e ! d i f f i c u l t , t o c r a c k ca ta ly ™
t i e a l l y , b e c a u s e a l l o r m o s t ‘o f t h e c r a c k i n g c a t a l y s t s now i n c o m m e rc ia l
u s e a r e p o is o n e d b y s u l f u r ( 2 ) .
Compounds o f m e t a l s s u c h a s c o b a l t , m olybdenum , a n d n i c k e l h av e l o n g
b e e n r e c o g n i z e d a s e f f e c i e n t . h y d r o g e n a t io n c a t a l y s t s , a n d v a r i o u s p a t e n t s
Have b e e n p r o c u r e d f o r t h e u s e o f t h e s e c a t a l y s t s i n d e s u l f u r i z i n g c e r t a i n
p e tr o l e u m f r a c t i o n s , .
P a t e n t s p e r t a i n i n g t o t h e u s e o f n i c k e l o x id e a s a
d e s u l f u r i z i n g c a t a l y s t i n th e . r e f i n i n g o f h y d r o c a r b o n d i s t i l l a t e s , have .
b e e n d e s c r i b e d . b y . Me .Ho Gwynn (4 )
(5 )e
The p u rp 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 a m eth o d f o r t h e p r e p ­
a r a t i o 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 , .
The p r e p a r a t i o n o f
s u c h a c a t a l y s t i s a co m p lex p ro b le m b e c a u s e o f th e many v a r i a b l e s t h a t
a p p e a r to a f f e c t th e c a t a l y s t a c t i v i t y ,
The w ord " c a t a l y s t ” a s u s e d i n t h i s
in v e s tig a tio n i s a l i t t l e
e rro n ­
e o u s b e c a u s e i t h a s b e e n f o u n d t h a t n i c k e l o x i d e , when u s e d a s a d e s u l f u r ­
i z a t i o n a g e n t, b e h a v es b o th a s a t r u e c a t a l y s t , c o n v e rtin g th e s u lf u r i n
t h e o i l t o h y d ro g e n s u l f i d e , a n d a s a r e a g e n t , b y .c o m b in in g w i t h t h e s u l f u r
t o fo rm n i c k e l s u l f i d e .
The n i c k e l o x id e u s e d i n t h i s i n v e s t i g a t i o n h a s
b e e n r e f e r r e d t o a s a c a t a l y s t , b u t i t s h o u d be u n d e r s t o o d t h a t i t b e h a v e s
b o th a s a c a t a l y s t and r e a g e n t.
The g e n e r a l p r o c e d u r e f o r m ak in g t h e v a r i o u s s a m p le s w as t o p r e c i p i ­
t a t e n i c k e l c a r b o n a te fro m a m ix tu r e o f n i c k e l s u l f a t e a n d so d iu m c a rb o n ­
a t e , a c c o rd in g t o th e f o llo w in g r e a c t i o n :
N iS 04 4 - NagCOg
■
NiCOg
NagSO^
A s t u d y w as made o f c a t a l y s t a c t i v i t y w i t h r e s p e c t t o tim e an d t e m p e r a t u r e
o f p r e c i p i t a t i o n , tim e a n d t e m p e r a t u r e o f d i g e s t i o n , e f f e c t o f e n t r a i n e d
s a l t , a n d tim e a n d t e m p e r a t u r e . o f c a l c i n i n g .
When t h e n i c k e l c a r b o n a te
w as c a l c i n e d , i t w as p r o b a b l y c o n v e r t e d t o n i c k e l o x id e w i t h a s u b s e q u e n t
l o s s o f c a rb o n d io x id e .
APPARATUS AM) EQUIPMENT
The v a r i o u s c a t a l y s t s w e re t e s t e d f o r a c t i v i t y i n t h e c o m p a ris o n
u n it®
A d ia g r a m o f t h i s , u n i t m ay be ,s e e n i n F ig u r e I *
The c o m p a ris o n
U n i t 9 o r c o m p a r a to r , a s i t w i l l h e n c e f o r t h be 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 d i f f e r e n t c a t a l y s t s c o u ld be t e s t e d . a t t h e s a m e ■o p e r a t i n g c o n d i­
t i o n s , a n d t h e i r r e l a t i v e a c t i v i t y d e te r m i n e d .
The m a in b o d y o f t h e c o m p a r a to r w as
g l a s s t u b i n g , a b o u t 15 i n c h e s l o n g .
made fro m a p i e c e o f 25 mm p y re x -
The t o p o f t 6 e t u b i n g w as f i t t e d w i t h
t h e f e 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 t a p e r j o i n t .
C o n n e c te d t o t h e
b o tto m o f t h e u n i t w as a w a t e r - c o o l e d c o n d e n s e r on t o w h ic h w qs s e a l e d t h e
m a le p o r t i o n o f a 3 5 /2 5 g ro u n d g l a s s b a l l j o i n t .
The c o n d e n s e r , f i t t i n g s ,
a n d g l a s s t u b i n g , w e re w e ld e d , a s shown i n F ig u r e I , t o fo rm a s o l i d u n i t
a b o u t 36 i n c h e s l o n g .
H e a t w as s u p p l i e d t o t h e u n i t b y a n i chrom e w ir e h e a t i n g c o i l w h ic h
w as c o v e r e d w i t h . 1 / 8 i n c h p o r c e l a i n f i s h s p i n e s ,.
The. h e a t i n p u t t o t h e
u n i t w as c o n t r o l l e d , b y a 1 1 0 - v o l t v a r i a c , w h ic h c o u ld be m a n u a lly a d j u s t e d
t o a t t a i n t h e d e s i r e d t e m p e r a t u r e . The h e a t i n g c o i l
e n t i r e l e n g t h o f a ijg i n c h s t a n d a r d
w as p l a c e d a ro u n d t h e u n i t .
w as wound a ro u n d th e
i r o n p i p e , a b o u t 12 i n c h e s l o n g , w h ic h
T h is a rr a n g e m e n t e n a b le d th e u n i t t o be d i s ­
a s s e m b le d f o r r e p a i r s w i t h o u t d i s r u p t i n g th e. h e a t i n g c o i l ,
A th e r m o w e ll w as i n s e r t e d i n t o t h e g l a s s u n i t j u s t b e lo w th e i r o n
p ip e .
The th e r m o w e ll c o n s i s t e d 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 one e n d , a n d p r o j e c t i n g 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 f o r a
d i s t a n c e o f a p p r o x i m a t e ly 4 i n c h e s .
-7 =
I n s e r t e d i n t o t h e th e r m o w e ll wgs a n i r o n - o o n a t a n t a n th e rm o c o u p le *
The l e a d w i r e s w ere a l s o o f i r o n an d e o n s t a n t a n , a n d w ere c o n n e c te d t o a
L e e d s a n d K o r th r u p p o t e n t i o m e t e r , w h ic h w as c a l i b r a t e d d i r e c t l y i n d e g r e e s
C e n tig ra d e 0
The i r o n p ip e w as wound w i t h a s b e s t o s t a p e , and t h e e n t i r e u n i t 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 n
o i l r e s e r v o i r an d e x h a u s t s y s te m .
The e x h a u s t o u t l e t w as p l a c e d im m edi-
a t e I y b e lo w t h e f e m a le p o r t i o n o f t h e b a l l j o i n t .
i,
The e x h a u s t g a s 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 fro m t h e r e t o a cadmium c h l o r i d e b u b b l e r ,
w h ic h 're m o v e d t h e h y d ro g e n s u l f i d e fro m t h e w a s te g a s , .
The o i l r e s e r v o i r c o n s i s t e d o f a 500 m l c a l i b r a t e d s e p a r a t o r y f u n n e l .
The o u t l e t o f t h e r e s e r v o i r w as c o n n e c te d t o a M erkle= -K orff t y p e b e llo w s
pump, w h ic h pumped t h e o i l 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
th e u n i t ,
A t h r e e - w a y s to p c o c k w as l o c a t e d b e tw e e n t h e pump a n d t h e r e ­
s e r v o i r , a n d s e r v e d a s a m eans t o w ith d ra w a n o i l sam ple f o r a n a l y s i s .
H y d ro g e n w as i n t r o d u c e d ab o v e t h e o i l i n l e t , a n d w as r e g u l a t e d - by a
n e e d le v a lv e .
The q u a n t i t y o f h y d ro g e n w h ic h p a s s e d t h r o u g h t h e u n i t w as
d e te r m in e d b y a m e r c u ry m an o m eter a n d o r i f i c e , p r e v i o u s l y c a l i b r a t e d b y a
w e t - t e s t g as m e te r.
The h y d ro g e n an d o i l i n l e t s w e re c o n n e c te d t o th e m ale p o r t i o n o f t h e
g ro u n d g l a s s . t a p e r j o i n t .
s t e e l tu b in g ,
'
The o i l l i n e w as made fro m l / 8
in c h s t a i n l e s s
.
ea0<=>
...
.
MATERIALS AM) PROCEDURE
The o i l u s e d i n t h i s 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 , l i g h t c o lo r e d
f u e l o i l j, r e f i n e d a t t h e H u sk y ..O il Coulpany i n C ody9 Wyoming*
The a v e ra g e
m o le c u la r w e ig h t w as a b o u t 2 2 2 , an d t h e s u l f u r c o n te n t v a r i e d frp m 2*09 t o
2*20 p e r c e n t -by w e ig h t* . . The A* S* T* M0 d i s t i l l a t i o n d a t a f o r t h i s o i l i s
p r e s e n t e d i n T a b le I*
The c a t a l y s t s a m p le s t h a t w ere u s e d i n t h i s i n v e s t i g a t i o n w ere p r e ­
p a r e d a t t h e H usky R e f i n e r y i n C ody, Wyoming*
The same p r o c e d u r e w as u s e d f o r t e s t i n g a l l c a t a l y s t sam p les*
A bout
0*8 gram o f :p y r e x g l a s s w o o l w as p l a c e d i n t h e c o m p a r a to r j u s t b e lo w t h e
th e rm o w e ll*
T h is s e r v e d m e r e ly a s a c a t a l y s t s u p p o r t , a n d p r e v e n t e d t h e
f i n e l y g ro u n d c a t a l y s t fro m w a s h i n g .th r o u g h w i t h . t h e o i l v a p o r*
■
The c a t a ­
l y s t t o be t e s t e d w as t h e n w e ig h e d , a n d m ix ed w i t h 40 g ram s o f 1 /8 in c h
p o r c e l a i n f i s h s p in e s *
The f i s h s p i n e s p r e v e n t e d th e f i n e p a r t i c l e s o f
c a t a l y s t fro m c a k in g , a n d p l u g g i n g ,t h e u n i t *
The c a t a l y s t a n d f i s h - s p i n e s
w ere i n t i m a t e l y m ix ed w i t h a s m a ll p o r t i o n o f o i l (p r e v i o u s l y w e ig h e d ) a n d
■ then c h a rg e d t o t h e c o m p a r a to r .
On t o p o f t h e c a t a l y s t b e d w as p la c e d a
l a y e r o f 1 / 4 i n c h f i s h s p i n e s w h ic h s e r v e d a s a p r e h e a t s e c t i o n f o r th e o i l .
An o i l c h a r g e o f 420 g ram s w as w e ig h e d an d p l a c e d i n t h e r e s e r v o i r *
The
pump w as p r e v i o u s l y c a l i b r a t e d t o d e l i v e r 420 gram s o f o i l p e r h o u r ,
■ C a l i b r a t i o n w as a c c o m p lis h e d b y a t r i a l an d e r r o r p r o c e d u r e *
The
pump w as aillo w ed t o o p e r a t e f o r a d e f i n i t e tim e i n t e r v a l , a n d t h e o i l w as
d e l i v e r e d t o a w e ig h e d b e a k e r *
A f t e r w e ig h in g th e o i l , t h e pump was a d ­
j u s t e d a n d a g a i n a llo w e d t o o p e r a t e f o r a g i v e n tim e i n t e r v a l . ' A f t e r a
t
-
\
s e r i e s o f s u c h a d j u s t m e n t s , t h e d e s i r e d pump r a t e was o b ta in e d *
When t h e c o m p a r a to r h a d b e e n c h a rg e d i t w as p l a c e d i n t h e p r o p e r
p o s itio n *
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 c la m p ed i n p la c e * The
. u n i t w as t h e n r e a d y f o r o p e r a t io n *
The v a r i a c w as t u r n e d o n , and w h ile t h e c o m p a r a to r w as h e a t i n g a
s m a ll am ount o f h y d rp 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 pump w as t u r n e d on a n d th e
h y d ro g e n r a t e w as i n c r e a s e d t o a p p r o x i m a t e ly 2*5 s t a n d a r d c u b ic f e e t p e r
h o u r.
The o i l w as v a p o r i z e d i n t h e p r e h e a t s e c t i o n o f t h e c o m p a r a to r and
p a s s e d t h r o u g h t h e c a t a l y s t b e d i n t o t h e w a t e r c o n d e n s e r , w here i t was r e '
- •.
tu rn e d a s a l iq u i d to th e r e s e r v o i r .
A s m a ll s e p a r a to r y f u n n e l,, n o t p i c t u r ­
e d i n F ig u r e I , w as i n s e r t e d i n t o t h e e x h a u s t l i n e t o t r a p e n t r a i n e d l i q u i d s
n o t rem oved b y t h e i c e c o n d e n s e r*
The e x c e s s ,w a te r i n t h e i c e c o n d e n s e r
w as rem o v ed b y a s ip h o n * ■
The u n i t w as a llo w e d t o o p e r a t e f o r s i x h o u r s .
O il s a m p le s w ere p e r i ­
o d i c a l l y w ith d r a w n , w e ig h e d , a n d a n a ly z e d f o r s u l f u r c o n t e n t .
A t t h e en d
o f s i x h o u r s , t h e pump a n d h e a t w ere 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 p a s s t h r o u g h t h e u n i t f o r a few a d d i t i o n a l m in u te s t o rem ove a n y o i l
h o ld u p i n t h e c a t a l y s t b e d .
t h e n dum ped an d w e ig h ed *
The e n t i r e
c o n t e n t s o f th e c o m p a r a to r w ere
The o i l w as l i k e w i s e w ith d ra w n fro m t h e r e s e r v o i r
a n d i t s w e ig h t r e c o r d e d *
The o i l s a m p le s t h a t , w e re t o be a n a ly z e d w ere g i v e n a c a u s t i c w ash t o
rem ove a n y h y d ro g e n s u l f i d e , an d t h e n w ash ed t h r e e t im e s w i t h w a t e r .
The
s u l f u r c o n t e n t o f t h e o i l w as 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
=IO=
m eth o d ,- .a s d e s c r i b e d , in. t h e -A6 S e- T» M0 M anual o f S t a n d a r d s ( I ) e
I n o r d e r t o s t a n d a r d i z e t h e c o n d i t i o n s u n d e r w h ic h t h e v a r i o u s e a ta =
l y s t s w ere t e s t e d , a t e m p e r a t u r e o f 625 d e g r e e s F a h r e n h e i t a n d a h y d ro =
g e n r a t e o f a b o u t 2«5 s t a n d a r d c u b ic f e e t p e r h o u r w ere u s e d f o r t e s t i n g
e a c h sam p le *. H a a s (6 ) r e p o r t e d t h a t t h e r e i s a c o n s i d e r a b l e r a n g e o f tem p ­
e r a t u r e . , 600=675 d e g r e e s F a h r e n h e i t , w h ere t h e am ount o f d e s u l f u r i z a t i o n
i s in d e p e n d e n t o f t h e t e m p e r a t u r e , a n d a l s o t h a t t h e h y d ro g e n r a t e d i d n o t
seem t o be a c r i t i c a l f a c t o r e x c e p t t h a t h i g h h y d ro g e n r a t e s c a r r i e d th e
o i l th r o u g h f a s t e r , and t h u s r e d u c e d t h e c o n t a c t tim e *
”11"*
CALCULATIONS
The s u l f u r b a l a n c e s f o r t h e v a r i o u s r u n s .a re in c l u d e d i n T a b le Ve
The w e ig h t o f t h e o i l i n i t i a l l y c h a rg e d t o t h e u n i t w as 420 g ra m s , b u t t h e
v a lu e w as a l t e r e d e a c h tim e a sam p le was w ith d ra w n .
T h e r e f o r e , t h e w e ig h t
o f t h e o i l p a s s i n g t h r o u g h t h e u n i t f o r e a c h tim 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 t h e sam ple t h a t w as w ith d ra w n , a n d a l s o f o r
t h e o i l l o s s , w h ic h w as 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 tim e i n t e r ­
v a ls .
The w e ig h t o f t h e o i l a f t e r c o r r e c t i o n w as o b t a i n e d b y s u b t r a c t i n g
t h e sum o f t h e d i s t i l l a t i o n l o s s an d sam p le w e ig h t fro m t h e w e ig h t o f t h e
o i l b e fo re c o rr e c tio n .
The w e ig h t o f t h e s u l f u r a f t e r c o r r e c t i o n w as c a l c u l a t e d b y - m u l t i ­
p l y i n g t h e p e r c e n t s u l f u r i n t h e sam p le b y 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 .
The f i g u r e s o o b t a i n e d i s t h e a c t u a l w e ig h t o f t h e s u l f u r i n th e
g i v e n am ount o f o i l .
The am ount o f s u l f u r rem o v ed d u r i n g e a c h tim 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 b e f o r e 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 i n i t i a l ,and f i n a l p e r c e n t s u l f u r f o r t h a t p a r t i c u l a r tim e i n t e r ­
v a l.
The sum o f t h e s e v a l u e s f o r e a c h tim e i n t e r v a l , d i v i d e d b y t h e w e ig h t
o f c a t a l y s t u s e d , w as t h e g ram s o f s u l f u r rem oved p e r gram o f c a t a l y s t .
K now ing t h e am ount o f n i c k e l i n t h e s a m p le , t h e gram s o f s u l f u r rem oved p e r
g ram o f n i c k e l c o u ld r e a d i l y be c a l c u l a t e d .
The s p a c e v e l o c i t y w as r e p o r t e d i n T a b le V on a w e ig h t b a s i s r a t h e r
t h a n a volum e b a s i s i . e « , gram 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 .
•=12=»
RESULTS
As p r e v i o u s l y s t a t e d , t h e 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 a s t o f i n d
a m eth o d f o r p r e p a r i n g 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 ere
w e re a num ber o f v a r i a b l e s i n v o lv e d a n d e a c h w i l l be c o n s id e r e d s e p a r a t e l y .
The ;c a t a l y s t s a m p le s 'u s e d i n t h i s i n v e s t i g a t i o n v a r i e d i n w e ig h t fro m
I 09 gram s t o 3 0 .5 g ra m s .
The o i l r a t e w as h e l d c o n s t a n t a t 420 gram s p e r
h o u r f o r e a c h r u n ; c o n s e q u e n t l y , t h e s p a c e v e l o c i t y v a r i e d a c c o r d in g ly *
I n o r d e r t h a t a s e r i e s o f. r u n s . c o u l d be co m p ared w i t h r e s p e c t t o c a t a l y s t
a c tiv ity
(g ra m s o f s u l f u r rem o v ed p e r gram o f n i c k e l ) , a common s p a c e v e l ­
o c i t y h a d t o be a r b i t r a r i l y c h o s e n a n d some m eth o d d e v is e d t o com pare a l l
t h e r u n s on t h e b a s i s o f t h e same s p a c e v e l o c i t y .
N i c k e l c a r b o n a te i s a v e r y h y g r o s c o p ic m a t e r i a l a n d w i l l a b s o r b v a ry =
i n g a m o u n ts o f w a t e r w hen e x p o s e d t o a i r .
F o r t h i s r e a s o n , a sp ace v e lo c i ty
b a s e d on t h e w e ig h t o f c a t a l y s t w o u ld t e n d t o be m is l e a d i n g b e c a u s e w h ile
one sam p le may h av e c o n t a i n e d a n e g l i g i b l e am ount o f w a t e r , a n o t h e r one
w o u ld h av e c o n s i d e r a b l e w a t e r c o n t e n t .
F o r p u r p o s e s o f c o m p a r is o n , th e
s p a c e v e l o c i t y w as e x p r e s s e d a s gram s o f o i l p e r gram o f n i c k e l p e r h o u r ,
r a t h e r t h a n t h e 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 h ic h w as r e ­
p o r t e d i n t h e s u l f u r b a l a n c e s (T a b le V )„
A ny f o r e g o i n g r e f e r e n c e t o s p a c e
v e l o c i t y w i l l be u n d e r s to o d t o m ean gram s q f o i l p e r gram o f n i c k e l p e r
h o u r.
T h i s q u a n t i t y w as d e te r m in e ,! f o r e a c h r u n , m e r e ly b y d i v i d i n g 420
g ram s o f o i l p e r h o u r b y t h e g ram s o f n i c k e l i n a n y p a r t i c u l a r s a m p le .
I t i s w e l l t o n o t e t h a t t h e w e ig h t o f n i c k e l i n th e s a m p le s may be
{
=■13=
i n s l i g h t e r r o r b e c a u s e o f t h e c o m p l e x it y a n d i n a c c u r a c y o f t h e n i c k e l
a n a ly s is ®
H o w ev er, a n y f u t u r e c o r r e c t i o n o f t h e n i c k e l c o n t e n t , r e s u l t i n g
fro m a n im p ro v e d a n a l y t i c a l p r o c e d u r e , w o u ld c a u s e t h e v a l u e s t o be c h a n g e d
e i t h e r a l l h i g h e r o r a l l lower®
S uch a c o r r e c t i o n w o u ld h a v e l i t t l e
o r no
e f f e c t on t h e d e t e r m i n a t i o n o f optim um c o n d i t i o n s w i t h r e s p e c t t o c a t a l y s t
a c tiv ity ®
F iv e s e r i e s o f r u n s w e re made (R uns 1 = 2 3 ), w h ic h show th e r e l a t i o n s h i p
b e tw e e n s p a c e v e l o c i t y an d c a t a l y s t a c t i v i t y ®
w e re d i v i d e d i n t o s a m p le s o f d i f f e r e n t siz e ®
.h a v e ' b e e n . g y a p h e d i n . F i g u r e 2®
The f i v e d i f f e r e n t c a t a l y s t s
The r e s u l t s o f t h e s e r u n s
I t a p p e a rs t h a t a fa m ily o f c u rv e s i s re =
p r e s e n t e d , e m a n a tin g fro m t h e o rig in ®
V a r io u s o p e r a t i o n a l d i f f i c u l t i e s
h a v e c a u s e d a fe w o f th e p o i n t s t o d e v i a t e c o n s i d e r a b l y fro m t h e i r r e s p e c t =
i v e curves®
' A s p a c e v e l o c i t y o f 60 w as c h o s e n a s a s t a n d a r d b y w h ic h t o com pare
t h e v a r i o u s ...c a t a l y s t s a m p le s .
The p r o c e d u r e f o r d e te r m i n in g t h e a c t i v i t y
on t h i s b a s i s w a s .a s f o l l o w s .
The p a r t i c u l a r sam p le u n d e r q u e s t i o n wa$
l o c a t e d on F ig u r e 2 , k n o w in g t h e s p a c e v e l o c i t y a n d t h e g ram s o f s u l f u r r e =
moved p e r gram q f n ic k e l®
By f o l l o w i n g t h e g e n e r a l t r e n d . o f t h e f a m i l y o f
c u r v e s , t h i s p o i n t w as t h e n t r a n s p o s e d t o a v a lu e o f 60 g ram s o f o i l p e r
gram o f n i c k e l p e r h o u r , a n d t h e c o r r e s p o n d in g a c t i v i t y w as r e a d on th e
o r d in a te ®
I t w as assu m ed t h a t a n y p a r t i c u l a r c a t a l y s t s a m p le , w hen l o c a t e d
o n F ig u r e 2 , f e l l on a c u r v e w h ic h f i t
r e p r e s e n te d ®
i n t o t h e f a m i ly o f c u r v e s a l r e a d y
The a c t i v i t i e s o f a l l t h e s a m p le s h av e b e e n d e te r m in e d on
t h i s b a s i s a n d a r e . p r e s e n t e d i n T a b le I I I , a lo n g w i t h t h e v a r i o u s s p a c e
“
14
=
v e l o c i t i e s a n d m akeup o f th e c a t a l y s t s a m p le S0
M ethod o f A d d in g S o l u t i o n s
The r e l a t i o n s h i p b e tw e e n a c t i v i t y a n d th e m eth o d f o r a d d i n g t h e
s o l u t i o n s j , ioOoj, w h e th e r t h e n i c k e l s u l f a t e
s h o u ld be a d d e d t o t h e c a r b o n ­
a t e s o l u t i o n , o r w h e th e r t h e so d iu m c a r b o n a te s h o u ld be a d d e d t o th e s u l f ­
a te s o lu t i o n , i s n o t c l e a r l y u n d e rs to o d a s y e t ,
C o y k e n d a ll (3 ) r e p o r t e d
t h a t t h e h i g h e s t a c t i v i t y w as o b t a i n e d w hen t h e c a r b o n a te w as a d d e d t o th e
n ic k e l s o lu tio n ,
A d e f i n i t e r e l a t i o n s h i p h a s b een n o te d in th e p h y s ic a l C h a r a e te ris t=
i c s o f th e c a t a l y s t .
When t h e n i c k e l s u l f a t e
s o l u t i o n w as a d d e d t o t h e
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 , and c o u ld n o t be ex=
.
tru d e d i n to " n o o d le s " .
When t h e c a r b o n a te s o l u t i o n was a d d e d t o t h e
n i c k e l s o l u t i o n , t h e c a t a l y s t a p p e a r e d t o be 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 ily e x tru d a b le .
E f f e c t o f E x c e s s C a rb o n a te
A g r o u p ;o f c a t a l y s t s have b e e n p r e p a r e d t o s tu d y t h e e f f e c t o f a d d in g
t h e c a r b o n a te i 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 , .
A t t h e tim e o f
t h i s w r i t i n g , t h e s e sa m p le s, h a d n o t y e t b e e n t e s t e d i n t h e c o m p a ris o n u n i t ,
TJeno (8 ) 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 t io n c a t a l y s t s , p r e p a r e d b y p r e c i p ­
i t a t i n g n i c k e l c a r b o n a te fro m 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 te s o l u t i o n s ,
h a v e t h e g r e a t e s t , a c t i v i t y w hen 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 te i s u s e d .
E f f e c t o f C a lc iu m H y d ro x id e
The p u r p o s e o f R uns 8 4 -2 8 w as t o t e s t c a t a l y s t s a m p le s p r e c i p i t a t e d
fro m n i c k e l s u l f a t e
and c a lc iu m h y d r o x id e .
T h i s ty p e o f c a t a l y s t a p p e a r e d
t o show a c t i v i t y c o m p a ra b le t o t h e n i c k e l c a r b o n a t e , a s s e e n b y t h e d a t a
--15~
o f T a b le I I I 0
S a m p le s P -4 6 a n d P -4 7 w e re p r e c i p i t a t e d a n d d i g e s t e d a t
room t e m p e r a t u r e , w h i l e s a m p le s 'P -5 0 -B a n d P -5 1 -B w e re p r e c i p i t a t e d a n d
d ig e s te d a t a b o i l .
tio n ,
I n a l l c a s e s t h e lim e was a d d e d t o t h e n i c k e l s o lu ­
The a c t i v i t i e s o f t h e s e f o u r s a m p le s w e re v e r y s i m i l a r , w h ic h i n d i ­
c a t e d t h a t t h e p r e c i p i t a t i o n c o n d i t i o n s , when u s i n g c a lc iu m h y d r o x id e , w e re
not a c r itic a l fa c to r.
S am ple P -3 6 - A was p r e c i p i t a t e d a t room t e m p e r a t u r e ,
a n d d i g e s t e d a t a b o i l , b u t f o r t h i s s a m p le t h e n i c k e l s o l u t i o n was a d d e d
to t h e lim e .
The a c t i v i t y o f P - 3 6 - A a p p e a r e d t o b e s l i g h t l y g r e a t e r t h a n
t h a t o f t h e o t h e r s a m p le s p r e p a r e d fro m l i m e .
One m ig h t c o n c lu d e t h a t a
m ore a c t i v e c a t a l y s t i s o b t a i n e d when t h e n i c k e l s o l u t i o n i s a d d e d t o t h e
c a lc iu m h y d r o x i d e ,
A m ore th o r o u g h i n v e s t i g a t i o n w ould b e r e q u i r e d , h o w ever
to d e f in ite ly e s ta b lis h th is f a c t.
A l l f i v e s a m p le s w e re d r i e d i n a n o v e n f o r IB h o u r s a t a b o u t 2 2 5 ° F ,
a f te r p re c ip ita tio n .
P r e c i p i t a t i o n and D ig e s tio n
T h re e r u n s w e re m ade (R uns 2 9 - 3 1 ) 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 an d d i g e s t i o n c o n d i t i o n s on t h e a c t i v i t y o f a n i c k e l c a r b o n a te c a t a —■
Iy s t,
S am ple P -3 2 w a s ' p r e c i p i t a t e d a t 7 6 °F o v e r a tim e i n t e r v a l o f 72 m in -
.
u t e s , a n d d i g e s t e d a t t h e b o i l i n g p o i n t f o r 60 m i n u t e s ,
S am ple P -3 3 was
p r e c i p i t a t e d a t t h e b o i l i n g p o i n t f o r 16 m in u te s an d d i g e s t e d a t t h e b o i l i n g
p o i n t f o r 60 m i n u t e s .
Sam ple P -3 4 was p r e c i p i t a t e d a t t h e b o i l i n g p o i n t f o r
72 m i n u t e s , b u t w i t h no tim e a llo w e d f o r d i g e s t i o n .
O n .th e b a s i s o f gram s
s u l f u r rem o v ed p e r gram n i c k e l ( b a s e d on a s p a c e v e l o c i t y o f 6 0 ) , P -33 show­
ed th e g r e a t e s t a c t i v i t y w ith a v a lu e o f 0 ,3 4 0 ,
P -3 4 w e re 0 ,2 5 0 a n d 0 ,2 8 0 , r e s p e c t i v e l y .
The a c t i v i t i e s o f P -3 2 a n d
T h e se r e s u l t s i n d i c a t e d t h a t a
- 16 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 w hen t h e p r e c i p i t a t i o n i s c a r r i e d o iit a t t h e
b o i l i n g p o i n t w i t h a p p r e c i a b l e tim e a llo w e d f o r d ig e s tio n ®
The 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 a t t h e b o i l i n g p o lr ii i s d e s i r ­
a b l e fro m a n o t h e r s t a n d p o i n t , a lso ®
N i c k e l c a r b o n a te i s i n s o l u b l e i n h o t
w a t e r , b u t i s s l i g h t l y s o l u b l e i n c o l d w ater®
I f t h e 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 t h e b o i l i n g p o i n t , . t k $ am o u n t 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 inim ized®
E f fe c t o f E n tra in e d S a lt
R uns 3 2 , 3 3 , a n d 3 4 , i l l u s t r a t e t h e d e t r i m e n t a l e f f e c t t h a t e n t r a i n e d
s a l t h a s upon th e a c t i v i t y o f th e c a ta ly s t®
S am ples P -3 S , P - 3 9 -B , a n d P - 4 0 ,
w e re w a sh e d w i t h 3 4 0 , 1 0 0 , a n d 0 m i l l i l i t e r s o f w a t e r , r e s p e c t i v e l y , f o ll o w ­
in g th e p re c ip ita tio n ®
T h e i r r e s p e c t i v e a c t i v i t i e s w e re 0® 400, 0 .3 0 0 , a n d .
•
,
OeOSO g ram s o f s u l f u r rem o v ed p e r gram o f n i c k e l .
On t h e b a s i s o f t h e s e ■
r e s u l t s , i t w as 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 so d iu m s u l f a t e , a s a n en ­
tr a in e d s a l t , i s v e ry d e trim e n ta l to th e c a ta ly s t a c t i v i t y .
Time a n d T e m p e r a tu r e o f C a l c in i n g
The e f f e c t o f t h e c a l c i n i n g t e m p e r a t u r e o n t h e a c t i v i t y o f t h e c a t ­
a l y s t was s t u d i e d i n R uns 3 5 -4 5 o
A l a r g e b a t c h o f c a t a l y s t w as p r e p a r e d
a n d d i v i d e d i n t o p o r t i o n s c o n t a i n i n g n e a r l y e q u a l a m o u n ts o f n i c k e l .
The
v a r i o u s s a m p le s w e re t h e n c a l c i n e d i n a m u f f l e f u r n a c e f o r 16 h o u r s a t
t e m p e r a t u r e s r a n g i n g fro m 2 5 0 °F t o 1070°F®
s t u d y h a s b e e n p r e s e n t e d i n T a b le IV®
The d a t a o b t a i n e d fro m t h i s
The r e s u l t s w e re v e r y in c o n c lu s iv e ®
The a c t i v i t y o f t h e v a r i o u s s a m p le s v a r i e d fro m 0 .0 4 2 t o 0 .2 7 8 , b u t no
. d e f i n i t e r e l a t i o n s h i p a p p e a r e d t o e x i s t b e tw e e n t h e a c t i v i t y a n d t h e c a l ­
c in in g te m p e ra tu re .
I n m any c a s e s , tw o s a m p le s c a l c i n e d a t t h e s a m e , o r
"17"
1
n e a r l y t h e sam e t e m p e r a t u r e 5 show ed v e r y i n c o n s i s t e n t a c t i v i t i e s .
Sam ple
C=44» c a l c i n e d a t 1066oF , h a d t h e l o w e s t a c t i v i t y w i t h 0 ,0 4 2 gram s s u l f u r
rem o v e d p e r gram o f n i c k e l .
T h is seem ed t o s u b s t a n t i a t e t h e f i n d i n g s o f
O o y k e n d a ll ( 3 ) » who r e p o r t e d a d e c r e a s e i n a c t i v i t y u p o n c a l c i n i n g a t tem p­
e r a t u r e s i n e x c e s s o f IOOO0F e
I t i s p o s s i b l e t h a t a t t h e h i g h e r te m p e ra ­
t u r e s , t h e n i c k e l c a t a l y s t i s s i n t e r e d , a n d u n d e rg o e s s t r u c t u r a l c h a n g e s
w h ic h d e a c t i v a t e i t a s a d e s u l f u r i z a t i o n a g e n t , ' F u r t h e r s t u d y w o u ld b e r e ­
q u ir e d t o d e f i n i t e l y a s c e r t a i n th e e f f e c t o f c a lc in in g te m p e ra tu re i n th e
r e g i o n b e lo w IOOO0F ,
The e f f e c t o f c a l c i n i n g tim e was s t u d i e d i n Runs 4 6 -4 8 «
Cook 2 7 -1
a n d Cook 3 1 " 2 w e re c a l c i n e d f o r I g a n d 7 h o u r s , r e s p e c t i v e l y , a t t e m p e r a - .
t u r e s o f 8 3 0 °F a n d 790°F<,
The s m a l l d i f f e r e n c e i n t e m p e r a t u r e w as n e g l e c t ­
e d b ecau se th e c a lc in in g te m p e ra tu re does n o t a p p e ar to be to o c r i t i c a l .
Cook 2 9 s 3 0 - 2 was c a l c i n e d f o r 5 h o u r s a t 8 3 0GF ,
Cook 2 7 - 1 a n d Cook 2 9 9
3 0 - 2 show ed s i m i l a r a c t i v i t i e s o f 0 ,2 8 5 a n d 0 ,2 8 0 , r e s p e c t i v e l y .
Cook 31=2
h a d t h e l e a s t a c t i v i t y w i t h 0 ,2 3 5 g ram s s u l f u r rem oved p e r g ram o f n i c k e l .
I t a p p e a r s t h a t c a l c i n i n g f o r l o n g e r t h a n 5 h o u r s t e n d s t o lo w e r t h e a c t i v ­
ity ,
A lth o u g h t h i s ' a p p e a r s t o b e t r u e f o r c a l c i n i n g t e m p e r a t u r e s o f a b o u t
SOO0F , i t may n o t n e c e s s a r i l y h o l d t r u e f o r lo w e r c a l c i n i n g t e m p e r a t u r e s .
Oven D ry in g v s C a l c in i n g
A num ber o f r u n s w e re m ade t o s t u d y t h e e f f e c t o f o v e n d r y i n g , a t
t e m p e r a t u r e s v a r y i n g fro m 2 3 O0F down t o room t e m p e r a t u r e .
The e f f e c t o f
o v e n d r y i n g f o llo w e d b y c a l c i n a t i o n a t 8 5 0 °F was a l s o s t u d i e d .
Runs 4 9 -5 1 show ed t h e e f f e c t o f o v e n t e m p e r a t u r e on t h e c a t a l y s t
a c tiv ity .
S am ple P -6 4 -X ^ w as d r i e d f o r 18 h o u r s a t 230 ° F , a n d show ed a h
=18"
a c t i v i t y o f 0 ,1 9 0 g ram s o f s u l f u r rem o v ed p e r gram o f. n i c k e l , •S am ples
P " 64 “X j_2 a n d P-»64-Xp; w e re b o t h d r i e d a t room t e m p e r a t u r e f o r 1 4 0 h o u r s 9 '
b u t P - 6 4 - Xp;. was a f t e r w a r d s d r i e d f o r 16 h o u r s a t 225°F e
t h e l a t t e r tw o s a m p le s w as 0 ,3 0 0 ,
The. a c t i v i t y o f
T h is i n d i c a t e d t h a t a c a t a l y s t d r i e d a t
room t e m p e r a t u r e t e n d s t o h a v e a n e v e n g r e a t e r a c t i v i t y t h a n o n e w h ic h i s
■
oven d r ie d a t 2 2 5 °F ,
•
.
■
H ow ever 9 t h e a c t i v i t y o f P -6 4 -X p^ i n d i c a t e d t h a t o v e n
d r y in g i s e v i d e n t l y n o t d e t r i m e n t a l t o t h e a c t i v i t y i f t h e p r e c i p i t a t e i s
d r i e d a t room t e m p e r a t u r e p r e v i o u s t o t h e o v e n d r y i n g .
The s a m p le s u s e d i n R uns 5 2 -5 4 w e re o v e n d r i e d i n e x a c t l y t h e same
m an n er a s t h e s a m p le s f o r Runs '4 9 -5 1 ■> r e s p e c t i v e l y s b u t a f t e r t h e oven,
d r y i n g t h e s e s a m p le s w e re c a l c i n e d f o r 8 h o u r s a t 850 ° F ,
P " 64 -X ^ 2_As P“ 64 “X - ^ j and
The a c t i v i t i e s o f
s w e re 0 . 2 2 0 , 0 . 2 1 0 , a n d 0 . 2 1 0 , r e s p e c t ­
i v e l y , i n d ic a ti n g a d e f i n i t e d e c re a s e i n a c t i v i t y upon c a lc in in g i n th e
h ig h e r te m p e ra tu re r a n g e .
I t a p p e a r e d t h a t t h e m o st a c t i v e c a t a l y s t w as
p r e p a r e d b y d r y i n g t h e p r e c i p i t a t e a t room t e m p e r a t u r e .
H ow ever^ t h e c a l ­
c i n e d s a m p le s show a n a c t i v i t y c o m p a ra b le t o t h e s a m p le s t h a t w ere oven .
d r i e d a t 225 ° F ,
~19~
SUMMARY
I 0
The 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 a c a t a l y s t depend., i n p a r t a t l e a s t ,
/
u p o n t h e m ethod o f a d d in g t h e p r e c i p i t a t i n g s o l u t i o n s . When t h e n i c k e l
s o lu tio n i s added t o th e c a r b o n a te . s o l u t i o n , th e c a t a l y s t i s v e ry g ran ­
u l a r ; w hen t h e a d d i t i o n i s c a r b o n a t e t o n i c k e l , t h e c a t a l y s t i s v e r y
f in e l y d iv id e d ,
2,
N i c k e l h y d r o x i d e , p r e p a r e d b y r e a c t i n g c a lc iu m h y d r o x id e a n d n i c k e l
s u l f a t e s o l u t i o n s , s h o w e d ■a c t i v i t y a s a d e s u l f u r i z a t i o n c a t a l y s t com par­
a b l e t o n i c k e l c a r b o n a te
3o
A m ore a c t i v e c a t a l y s t i s o b t a i n e d w hen t h e 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 t h e b o i l i n g p o i n t w i t h c o n s i d e r a b l e t im e a llo w e d f o r d i g e s t i o n ,
4,
Sodium s u l f a t e , a s a n e n t r a i n e d s a l t o n t h e c a t a l y s t , g r e a t l y r e d u c e s
th e c a ta ly s t a c t i v i t y ,
5,
The e f f e c t o f c a l c i n i n g t e m p e r a t u r e o n c a t a l y s t a c t i v i t y c a n n o t b e
d e f i n i t e l y e s t a b l i s h e d fro m t h e r e s u l t s o f t h i s i n v e s t i g a t i o n .
The
optim um t im e f o r c a l c i n i n g i s q u e s t i o n a b l e , b u t a p e r i o d o f f i v e h o u r s
o r l e s s seem s t o b e i n d i c a t e d ,
6,
'
A c a t a l y s t d r i e d a t room t e m p e r a t u r e show s more, a c t i v i t y t h a n one w h ic h
i s d r i e d a t 2 25°F o r c a l c i n e d a t 8 5 0 ° F ,
«=20®=»
ACKNOWLEDGMENT
The a u t h o r w is h e s t o a c k n o w le d g e w i t h t h a n k s $ t h e c o u r t e s y o f t h e
H usky O i l Company, who s p o n s o r e d t h e f e l l o w s h i p u n d e r w h ic h t h i s w ork
w as c a r r i e d o u t*
The H usky O i l Company a l s o f u r n i s h e d t h e f u e l o i l an 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 u s e d i n t h i s i n v e s t i g a t i o n .
LITERATURE CITED
(1 )
A. S e Te Me S t a n d a r d s on P e tr o le u m P r o d u c ts an d L u b e s 3 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 ig h S u l f u r S to 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 ¥ . , M. S , T h e s i s , M o n tan a S t a t e C o l l e g e , (1 9 5 1 )
(4 )
Gwynn, M a rio n He., Ue S e P a t e n t N o, 2 ,0 7 3 ,5 7 $ , M arch 9 , 1 9 3 7 .
(5 )
Gwynn, M a rio n H , , 'B e S e 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 .
(6 )
H a a s , P a u l , M. 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 1 )«
(7 )
K a l ic h e v s k y , V; 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 tro 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 , N o, 1 1 , 9 7 , ( 1 9 5 0 ) ,
(8 )
U eno, S e ,
S o c e Chem, I n d e , J a p a n , 4 6 , 4 5 , ( 1 9 4 3 ) .
«*22'
.. APPENDIX
page
T a b le I
I n s p e c t i o n D a ta f o r C h a rg e O il*
T a b le 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 s * * * * .
I
T a b le I I I I n g r e d i e n t s a n d A c t i v i t y o f C a t a l y s t S a m p le s . * * *
T a b le IV
C a l c in i n g D a ta * * * * * * * * * * * * * * * * * * *
T a b le V
S u l f u r B a la n c e s * * * * * * * * * * * * * * *
F ig u re I
C o m p a riso n U n i t * * * * * * * * * * * * * * * * * *
F ig u re 2
E f f e c t o f S p a c e V e l o c i t y o n S u l f u r Rem oval* . * . *
***
24-
•
—23=
TABLE I
INSPECTION DATA FOR CHARGE OIL
A .S .T .M . DISTILLATION
T e m p e ra tu re
op
P ercen t
D is tille d
F i r s t D rop
.
460
$00
#
w .
■
.2 0 ^
518
534
546
4Q^
356
.5 #
566
6#
576
70#
586
80#
600
9#
620
660
End P o i n t
f P e rce n t rec o v e ry ;
98#
B a r o m e tr ic p r e s s u r e s
S p e c ific g r a v ity :
638 mm Hg
0 o877 a t 6O0F
. TABLE I I
SOLUTIONS USED IN CATALYST PRECIPITATIONS
N ic k e l S o lu tio n s
S o lu tio n
No o
In g re d ie n ts
Grams Comme
ml
NiSO 4
K2O
S p e c ific
G ra v ity
A
L e e c h e d fro m s p e n t
c a t a l y s t w i t h HgSO4
1.2529 a t
28.9°C
B
858 ■
2994
1.1458 a t
. 2 4 .5 ° C
C
843
1951
1 .2 0 6 0 a t
23»9°C
F
1301
4000
unknown
Y
A n hydrous NiSO,
c r u s h e d t o 1 4 m esh
Z
Same a s Y 9 c r u s h e d
t o 4 8 m esh
C a rb o n a te S o l u t i o n s
S o lu tio n
. N o.
Grams NagCO^ p e r
gram o f s o l u t i o n
A
0 .1 8 6 0
E
0 .2 0 1 8
L
0.2631
“25"
TABLE I I I
INGREDIENTS AND ACTIVITY O F•CATALYST SAMPLES
Run
No.
. I
2
3
4
5
6
C a ta ly s t
S am ples
W“ 1
WamS
W“ 3
W==Zlr
W"5
W“ 6
7
¥=7
8
W-8
9
W-9
IO
11
12
13
14
15
16
17
18
19
20
21
W=IO
w -n
W“ 12
. P-53-1
P -53-2
P-53-3
P -56-1
P « 5 6 -2
P-56-3
P“ 56“4
P-56-5
p= 56"6
22
23.
P-56-7
P-56-8
24
25
P -3 6 -A '
26
2?
28
29
P-46
P-47
P-5G«B
P“ 51“ B
■. P-32
30
P-33
P-34
31 '
32
P-38
P-39-B
33
34
P -4 0
35
0-35
0-36
36
37
38
0 -3 7
C-38
N ic k e l
S o lu tio n s
C a rb o n a te
S o lu tio n s
- A ■
A
A
A
'A
A
A
A
A
A
A
A
A
A
'
•
A
Z
Z
Z
Z
Z
■ Z
Z
Z
A
A
A
A
A
B
B
B
B
B
■ B
A
A
A
A
m ilk
m ilk
m ilk
m il k
m ilk
.
A
A
A
A■
A
A
A
A
A
A
A
A
E
E
E
E
E
E
E
E
E
E
E
o f lim e
o f lim e
o f lim e
o f lim e
o f lim e
A
A
A
A
A
A
A
A
A
A
Gram s o f O il
Gram N i c k e l / h r
Grams o f S u l f u r
Removed p e r Gram
o f N ic k e l
(B a s e d on 60 gms o i l )
Gm N i / h r
)
76.5
58.1
1 1 6 .9
4 6 .4
6 9 .8
1 2 5 .0
5 6 .7
90:8
1 6 0 .2
3 i;o
9 8 .2
5 0 .8
4 H .5
*—
="=
—
1 9 0 .0
9448
4 0 0 .0
203:0
8 8 .9
6 6 .4
5 7 .1
4 9 .9
3 9 .4
3 1 .5
1 0 0 .6
.
89:6
9 1 .6
5 9 .4
9 1 .3
6 3 .0
62:9
63:0
1 0 1 .7
7 2 .5
8 4 .6
60:9
60:8
6 0 .7
6 0 .3
—
0.390
0.300
0.310
0.280
0,300
0.250
0:340
0:280
0:400
0:300
0:080
0.270
0.233
0.266
0.233
—26==
TABLE III (continued)
Run C a t a l y s t
N o , ' S am p les
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
C-39
q-40
N ic k e l
S o lu tio n s
A
A
A
A
A
A
A
Y
Y
0 -4 1
C -42
C-43
0=44
C-45.
Cook 2 7 -1
Cook 3 1 - 2
Cook 2 9 ,3 0 - 2
P—64"X t
F
F
P-64-%1 O
F
P=64-X2^
F
P=64“ X^2.4
F
p „ 6 4 “ Xn 1
P-64-&27
-F
C a rb o n a te
S o lu tio n s
A
A
A
A
A
A
A
L
L
H arshaw N o.3
L
L
L
L
L
L
Grams o f O i l
Gram N i c k e l / h r
6 0 ,6
6 1 .0
6 0 .9
60:9
6 0 .8
6 0 .9
.6 1 .0
5 2 .6
55 .5
7 0 .4
5 2 .1
59:5
64:9
3 9 .0
4 9 .0
1 0 4 .5
. Grams o f S u l f u r
Removed p e r Gram
o f N ic k e l
(B a s e d on 60 gms o i l )
gm Ni / h r
)
•
0 .1 3 9
0 ,1 4 7
0 .1 5 9
0 .1 7 9
0 .2 1 5
0 .0 4 2
0 .2 7 8
0 .2 8 5
0.235
0 .2 8 0
0 .1 9 0
0 .3 0 0
0 .3 0 0
6 .220
0 .2 1 0
0 .2 1 0
■-27TABLE IV
CALCINING- DATA
C a ta ly s t
Sam ple
' .
'
C a lc in e T e m p e r a tu r e
op
Grams o f S u l f u r
Removed p e r G rai
o f N ic k e l
G-35
362
0 .2 7 0
C-36 ■
661
0 .2 1 3
0-37
850
0 .2 6 6
0-38
250
0.233
0-39
478
0-40 '
-
0.139
'0 .1 4 7
C -41
758
0 .1 5 9
0-42
947
0 .1 7 9
0-43
550
0 .2 1 5
C—44
. 1066
0 .0 4 2
0-45
955
0
. 4%)
•
TABLE V
SULFUR BALANCES
5
rS
o) m
S-'S
C a ta ly s t
O
I
2
3
w -l
W-2
W-3
% ti
■ °5
H -P
•H O
S
-P
« o cd
o
O
cd to
1 5 .7
2 0 .5
1 0 .4
2 6 .8
2 0 .5
4 0 .4
ii
-P CO
CO CO
4|
g
Js CO
0
I
2
3
4
5
6
2 .0 9 0
1 .9 7 2
1 .9 3 2
1 .8 9 8
1 .8 5 1
1 .8 1 7
1.785
0
1
2.09Q
2 .0 8 2
.6
1 .9 8 2
-p
3
4 2 0 .0
2 .090
2.025 . 4 2 0 .0
4 0 5 .7
1 .9 7 3
1 .9 2 0
3 9 0 .4
1 .8 7 8
375.3.
1 .8 5 1
3 6 0 .5 .
1 .8 3 2
345.3
3 2 .0 3 5
4 . 2 .0 2 3
• 5 1 .9 9 8
I & ^I
tp e
O <D
0
I
2
3
4
5
6
2 ■2.048
. ' u
CO
0)
O
s
2 .0
1 2 .3
1 3 .3
1 3 .1
,,1 2 .8
1 3 .2
2 .0
% 3.3
-
2 .0
2 .0
^2.0
2 .0
4 2 0 .0
4 2 0 .0
4 0 0 .8
382.0
3 6 3 .8
344.3
3 2 6 .6
4 2 0 .0
4 2 0 .0
4 0 6 .9
392.7
380.3
.3 6 5 .3
3 5 0 .4
5 .7
5 .8
5 .7
5 .7
5 .8
5 .8
3 2 0 .8
Q.9
1 .0
0 .9
0 .9
1 .0
0 .9
1 2 .2
1 3 .2
1 1 .5
1 4 .1
1 3 .9
349.5
1 3 .5
1 3 .0
1 2 .5
1 3 .8
1 1 .9
I
I
'CD § )
-S
J j "0
tH
«h
a
til
Jl
0)
d t
■ CO 0
O
Xi U
hO 0) •
•H - P M
i2 O
4 2 0 .0
405.7
390*4 .
375.3
3 6 0 .5
3 4 5 .3
0 0 .0
rCJ
'
>
eg
Il 9- I Rl
'
in - P H
y ^ A
CO rCd -H
8 .7 8
8 .2 2
7 .7 1
7 .2 0
6 .7 6
6 .3 8
6 .2 9
-
8 .7 8
-
7 .9 0
0 .4 9 5
0 .1 6 0
0 .1 3 0
0 .1 7 1
0 .1 1 7
0 ,1 0 5
4 2 0 .0
8 .7 8
-
406.9
392.7
8 .4 8
8.05
7 .7 4
0 .0 3 4
0 .1 3 8
0 .0 5 1
365.3
350.4
7 .4 0
0 .0 4 6
7.06
0 .0 9 1
0 0 .0
7 ,0 2
0 .0 5 6
3 8 0 .3
6 .3 7
5 .9 4
5 .8 4
0 .1 6 1
0 .2 7 3
0 .1 7 1
0 .2 0 7
0 .1 5 8
0 .0 9 7
0 .0 6 6
4 2 0 .0
4 0 0 .8
382.0
363.8
3 4 4 .3
326.6
0 0 .0 ;
7.3 9
6 .8 9
III
L
ft
0.1 4 9 '
0 .1 0 8
TABLE V (Continued)
SULFUR BALANCES
i
B OI
Fd
«
4
5
6
W-4
W-5
W"6
I
O
y
i
8)
9
!s
2 5 .6
Jb
>
©q g
cd w
p. a a
to
Sq Sb
16.4
17.6- 2 4 .7
9 .6
43.7
03
■0 O
I
E
•ti
©^
■-H O
O©
h
PIhs
|2 O
O
i
2
3
4
5
6
2.090
1.985
1 .9 0 4
1 .8 7 2
1.843
1.818
1.802
420.0
420.0
-406.3
391.8
377.4
3 6 3 .2
345.7
G
I
2
3
4
5
6
2 .0 9 0
1 .9 9 8
1 .9 1 2
1.885
1 .8 6 9
1.842
1.820
420.0
420.0
4 0 1 .0
380.9
363.6
3 4 6 .2
328.4
0
I
2
3
4
5
6
2.090
2 .0 4 0
1 .9 8 8
1 .9 7 5
1 .9 6 0
1 .9 4 8
1 .9 2 0
4 2 0 .0
420.0
4 0 6 .0
389.9
374.5
359.6
3 4 6 .1
•H
i?
hp O
CO
II
Id E
jzj
•H ©
ra ra
•H O
Q^
"fab1Q1
©I
^ CO
'
0 .6
0 .6
0 .7
0 .6
6.6
0 .6
-
1 3 .1
13.9
13.7
13.6
1 6 .9
345.1
■
1 5.0
1 6 .2
13.3
1 3 .4
1 3 .9
324.4
—
4 .0
3 .9
4 .0
4 .0
3 .9
4 .0
—
™
0 .8
0 .7
0.8
0 .8
0.7
0.8
.
■
1 3.2
15.4
14.6
14.1
12.8
345.3
I
0
-ViS
■jg tj
$8♦H
■C
gO0g
d |
°. §
si
420.0
406.3
391.8
377.4
363.2
345.7
00.0
4 2 0 .0
401.0
380.9
363.6
346.2
328.4
0 0 .0
420.0
406.0
389.9
374.5
359.6
346.1
0 0 .0
%).© c
© ctdi S
lb
Si
^ ■ Q
I l d1 IlS
0 0
IJfI ""Sg
SIS
^
6 .2 2
—
0.441
0.329
0.125
0.109
0.091
0,055
8.78
8.00
7.29
6.85
6.47
6.05
5.98
0.386
0,345.
0.103
0.058
0.094
0.072
8.78
8.29
7.75
7.40
7.05
6.75
6.65
0.210
0.212
0.050
0.056
0.043
0.097
8.78
8.06
7.46
7.06
6 .6 9
6.27
0,117
B
T
• 0.161
0.181
TABLE V . ( C o n tin u e d )
SULFUR BALANCES
0
o '- r a
i>a
o .- i)
03
O
S3
.g
s
&
O
W-7
O
-P
^
19.8
I l
e
c o bq 60
21.2
Eh
0
I
2
3
4
5
6
8
W-8 12.6
3 3 .3
0
I
2
3
4
5
6
9
n
sc.
O
40
S
©
d
©
O
CO 03
6H O
Q
H
-P
°o
O
•P
cti
O
7
■
W -9
7 .4
56.8
tp
•0
"© si
O
O
2
1 9
a . co
:
Zs
2 .0 9 0
I o 945
1 .8 7 2
1.828
1.791
1.762
1.740
420.0
420.0
4 0 3 .3
385.2
367.3
352.7
337.0
2 .0 9 0
1.988
1 .9 2 0
1.885
1.855
1 .8 3 5
1.805
420.0
420.0
4 02.9
388.8
373.1
358*6
342.6
420.0
0 2.090
420.0I 1.990
4 0 3 .8
2 1 .9 4 8
3 1.915 ' 3 8 9 .5
3 7 4 .4
4 1=898
3 59.6,
5 1 .8 8 2
3 4 2 .8
6 1.870
°*
1 .8
1 .7
1 .8
1 .8
1 .7
1 .8
-
5
O
I
I l S CO
-
14.9
1 6 .4
16.1
1 2 .8
1 4 .0
335.2
«*
1 .0
0 .9
1 .0
1 .0
0 .9
1 .0
1 6 .1
1 3 .2
14.7
13.5
. 15.1
341.6
1.5
1 .4
1 .4
1=5
1.5
1=4
14=7
12.9
13.7
1 3 .3
.1 5 =3
341=4
„3 •
■ Ss
<. B "0
• "Sn ©
• -P
Sn a ■
‘
<d O
O
H +3
O ©
bo© «
. h
S 8
^ <d bo
I
t0
4 2 0 .0
4 03.3
3 8 5 .2
367.3
352.7
337.0
0 0 .0
. 5 .9 4
5 .8 6
4 2 0 .0
.8=78
402.9
8 .0 0
3 8 8 .8
3 7 3 .1
7 .4 6
-7.03
358.6
6=65
6 .2 9
6.1 9
3 4 2 .6
OOcO
4 2 0 .0
4 0 3 .8
389.5
8 .7 8
7 .8 4
7 .2 1
6 .7 1
6=32
8 .7 8
8 .0 3
7 .5 8
374=4
7 .1 8
359.6
342.8
6=82
0 0 .0
6.4 5
6 .4 2
Q)'
!>
e
ra
I I s '
Fh -P H
cd
ais
Fh
■H
03
CS b GO
-
.
0.183
0 .6 0 9
0 .2 9 4
0 .169.
0 .1 3 6
0 .1 0 2 :
0 .074
0 .4 2 8
0 .2 7 4
8
?
0 .2 3 1
0.136
0 .1 1 2
0=072
0 .103
0 ,4 2 0
0 .1 6 9
0 .1 2 8
0 .0 6 4
0 .0 5 8
0 .0 4 1
0 .3 1 1
TABLE V (Continued)
SULFUR BALANCES
b
«
I
O
-O
S
S
PS
10
11
12
I
^
-P
Cd
O
i
g>
«
rP
^
W-IO 20.1
1 -1 1
1 -1 2
6 .5
12=3
CO
£
<
Q) O I
-H
CO bq 6b
I
EH
2 0 .9
6 4 .6
34=2
I i
15
o ^
1
9
Pu, CO
-s I
H -P
O CD '
o P,
-P O
is O
-O ,n«
Io &
d to
d CD
to w
. -H O
Q Pl
0
I
2
■3
4
5
6
2=090
1 =792
1=690
1 ,6 2 2
1=590
1=545
1 .5 3 2
4 2 0 =0 ' ’
4 2 0 .0
■ 7 .4
3 9 8 .2
7=4
376=1
7=3
3 5 4 .0
7=4
3 3 0 .8
7 .3
3 0 8 .2
7 .4
0
2 .090
I
1=946
420=0
420=0
2
3
4
1 .8 3 0
1 =782
1=748
4 0 3 .9
390.0
3 7 5 .6
5
1 .7 2 5
361.3
6
1 .6 9 8
346=6
0
2 .090
420=0
4 2 0 ,0
I
1 .8 3 2
2
3
4
5
6
1.755
1 =722
1=690
1= 664
1=640
4 0 3 .2
387.1
3 7 1 .0
3 5 4 .7
337=0
£
P
O !
Ji I
1S jrCL
3 i
Is CO
-
1 4 .4
1 4 .7
1 4 .8
15=8
15=3
300=8
™
2=3
1 3 .8
2 .3
2 .3
2 .3
2 .3
2 .3
1 1 .6
12=1
1 2 =0
12 = 4
3 4 4 .3
r*
3 .3
3=3
3 .4
3 .4
3=3
1 3 .5
1 2 .8
12=7
3 .4
336,6
1 2 .9
14=4
-p
f. I r*t
^ S
.H P
O 0)
e
P O
Is O
4 2 0 .0
398.2
376=1
3 54.0
330.8
308=2
00=0
420=0
4 0 3 .9 390=0
-
I
b -g '
CD
Is
O
Sb h '(p
Sn 0
-H P CQ
to Sn g
IS Cd 6 0
8 .7 8
7=14
6 .3 6
5 .7 5
0
I I I
cd
I I I
y
& -g
CO Sd -H
«=»
4 .7 6
4 .7 2
1=250
0,4 0 6
0=256
0=113
0=149
0.040
8 .7 8
-
7 .8 5
7=14
0=605
0 .4 6 8
0=187
0=128
0=083
0=094
5=26
6 .6 9
3 6 1 .3
346=6
6=31
00=0
5=88
420=0
4Q3.2
8=78
7 .3 8
387=1
6 .7 9
6 .39
5 .9 9
3 5 4 .7
337=0
0 0 .0
■
to
i
375.6
3 71.0
<D
I
5 .9 8
5=61
5=52
-
. 1=082
0 .3 1 0
0=128
0.119
0.092
0 .0 8 1
ai H S
1 > ®
i n
Cd b
GO
0 .1 5 5
.a
VO
■t*
8
0=341
0 .2 0 8
'
TABLE V (Continued)
sulfur Balances
k
SO
q
S
O
h
H
I
wp
O
^
g
13
14
a
to
P-53-1 1.9
P-53-2 4.1
C
O
h
X!
© O- p 8 ra O
M
g, E-i
221. 0
102.5
50.6
210
Ii
S i
td 4
d ©
53 g
2 .0 1 5
366.7
0
2 .1 4 0
2 .0 0 0
4 2 0 ,0
eU
1.918
420:0
404.9
391:8
373.3
3.3
3 .4
3 .4
3.3
2 .1 4 0
2 ; 010
4 2 0 .0
4 2 0 .0
"»
1 .9 0 5
1 ,7 8 2
403:7
386:8
369.3
0
0
I
2
4
6
1.970
1 .9 3 6
1.764
2.200
2:083
2.075
2:060
2.050
420:0
420:0
Sp
•
13.5
12:6
12:9
361.9
■
1 1 .8
9.7
1 5 :i
370.0
ea
4 .7
4:8
4:7
4 .8
12:1
12.8
364^5
6 :0
1 6 ,2
1 1 .6
4 2 0 .0
4 2 0 :0
397:8
375.6
351.7
C
ra m
H 8)
-P ©
33 II
6
2
4
6
P-56-1 2.0
' -Tj-g
O©
•O't‘0
CO
oH
4 0 1 :8
3 8 4 .4
I
16 ■
"©
la 3
-
x
4:7
4:8
4:8
4 .8
2
4
6
P-53-3 &.3
P'to
o-'4
%H
0 2.140
I 2.060
2 2; 050
4 2:020
I
15
■
6:1 . 1 6 :1
17.8
. 6 ,1
345.6
6 .1
I
rU
Ol • 0
4' .. r3o
!>
C
O
cp <D - 44 ti " ’H
Jh
I
i
a
tti eHq
©
jL,-H
+3 H
g O
g
d-g
-P
O©
ii) ^ e <§ S ^
si
I,
420:0
401:8
384:4
366:7
00.0
8:98
8:27
7:90
4 2 0 :0
8.98
8:10
7:71
7.23
7.15
7 :4 0
7.38
404:9
391.8
373:3
0 0 .0
4 2 0 ,0
4 0 3 .7
386:8
369.3
0 0 .0
420:0
397:8
375:6
351.7
0 0 .0
•
8:98
8:10
7.36
6:58
6.51
9:24
8:30
7:78
7:24
7.20
l! & ©
H
5 -ti -H
WI ^
1 ill
0:336
0,514
0 :0 4 0
0:115
0.018
0:588
0:121
" 0 ,4 2 4
0 .1 3 4
0 ,0 6 7
0.350
0 :5 4 6
0:423
0:475
0.067
0:491
6 ,0 3 2
0:056
0.035
0L573
TABLE V (Continued)
SULFUR BALANCES
e
S
8
(§
17
18
"E ' Eia
■H
43
O
P ^ 56^2
•
P -56-3
6
S
A ol
8 .8
>
O
I
>
©O
O
„8
I aE Ei EIH
Ph
CO
102
- 4 r\ 7
4
6
1 .8 9 0
1 .8 5 2
0
2 .2 0 0
1 .8 8 3
1 .7 8 8
4 2 0 .0
4 2 0 .0
4 0 2 .6
1.765
385.0
369.5
3i) .9
3 0 .2
1 .7 5 4
2
4
6
2 .1 4 0
1 ,8 7 0
1 .7 8 0
1 .7 1 3
1 .6 8 2
0
2 .2 0 0
0
■l
&
4
6
1 .9 3 1
1 .7 9 5
1 .6 7 8
1 .6 2 4
rj
■0
E
d ©
5 i
Q °
.id
©
4 2 0 .0
4 2 0 .0
4 0 1 .3
3 8 4 .8 .
3 6 8 .4
-O 2 .2 0 0
I: 1 .9 7 8
2 1.935
I
P - 5 6 - 5 1 3 .9
Z
M
2
4
6
P - 5 6 - 4 1 1 .7
Ph M
-P O
S 8
CO
I
19
"ti £. ■
© fJ
'SI
© CS ■
O
dO "S
2 .0
1 .9
2 .0
2 .0 ;
1 .4
1 .4
1 .4
1 .4
Lp O
H bO
-P ©
nd ■
bo &
g E
^ CO
-
1 6 .0
1 6 .2
1 4 .1
368 a
3 8 5 .0
4 .0
365.5
4 .0
359.5
-"=■
420#
4 0 2 . 0"
383.5
365.5
3 .9
3 .8
. 3 ,9
3 .9
1 4 .1
1 4 .7
1 4 .1
3 6 1 .6
y &
H S
•H O
O ©
Fh
O
g S E
9 .2 4
7 .9 4
7.45
6 .9 6
6 .8 4
0
4H -H ©
1 §
CO 1CJ -H
CiS Fh to
0 .6 5 5
0,932
0 ,1 7 3
0 .1 7 3
0 .1 4 0
06382
'0 .0 8 8
6 .5 1
6 . 4 8 . ; 0 .0 4 1
0 .3 9 1
1 .3 3 0
-
365.5
3 .9 8
7 .5 2
6.85
. 6 .2 3
■ 0 0 .0
6 ,1 1
4 2 0 .0 '
4 0 2 .0
383.5
365.5
0 0 .0
9 .'2 4
7 .7 7
6 .8 9
6 .1 2
■1 .1 3 0
0 ,5 4 7
5.9 4
0 ,1 9 7 .
3 8 5 .0
P
O
CO-P-H
©S
eg i>
3 9 3
385.0
369.5
7 .5 8
6 .8 8
3 § 5
hj i ai A
9 .2 4
4 2 0 .0
4 0 2 .0
'
M O
O
-P
Fh
60©
Q © S
E -E ®
4 2 0 .0
4 0 2 .6
0 0 .0
™
-
% S
3 6 8 .4
0 0 .0
-
4 2 0 .0
4 0 2 .0
-H
., PO
cH ©
4 2 0 .0
4 0 1 .3
384.8
3 6 6 .4
1 4 .0
1 3 .O
1 7 .5
2
& a
iP _
^
1 6 .7
1 4 .6
1 4 .4
4 .0
"4 .0 -
4 2 0 .0
-
S g
.
0 .2 9 4
1 .1 3 3
0.3620.258
0 .1 1 3
0 ,4 4 9 .
•
0 .3 1 6
TABLE V (Continued)
SULFUR BALANCES
• to
9
o
to
t<DH f*
O
E
I h(8 bb
M
C a ta ly s t
o
21
P-$6-6 15=9
O
.5
Cd
IO
&
CO
2 6 .4
1 1
••'
G> F'ti
P
h
O 2 .2 0 0
1 .7 6 8
2 1 .5 9 4
4 1 .5 5 5
1
6
-0 S
d -s
O
.
0)
U
4) 0
4 2 0 .0
420=0
4 0 2 .0
3 8 3 .0
S
»
-
-P
»
=CO CO
•H
■s
d
-P
to
•1:!
I
3
CO
<D
CO
CO
O
rd
■to f t
n t-q
a
-P 0
3 -1
CO
Ca
3 .5
3=5
3 =5
• 1 4 .5
1 5 .5
1 5 .5
|: a
I
I? 0
, =H 0)
cd o
“
CD
6
0o
I
rrrS
0U
>
■ *'
O
to
?H-P
H
fn
txO0 0
•6H -P CO cp.H m
g, co nd -H .
420=0
402=0
3 8 3 .0
9 .2 4
7 ,1 1
6 .1 0
364= 0
5=66
03
fH O fn
.
0 .3 1 2 •
1 .8 1 5
0 .700
0.149
—
'8
£
22
P-56-7 19=9 2 1 .1
O 2 .2 0 0
4 2 0 .0
1
1=712
2
1 .6 1 6
1 .5 0 9
9 .2
3 9 6 .2 . 9 .3
9 .2
3 6 7 .2
9=2
336.9
■ J 1= 448
23
P -56-8 24=8 1 6 ,9
0 , 2= 200
420=0
Ca
1
1=752
2
1 .5 8 8
1 .4 7 4
1=410
4 2 0 .0
3 9 4 .5
3 6 8 .6
343.3
' 1 0 .5
1 0 .6
1 0 .5
1 0 .5
2 .2 0 0
1 .9 3 9
2 1 .8 7 8
4 1 .7 6 0
6 1 .7 0 0
4 2 0 .0
4 2 0 .0
3 9 7 .7
3 7 4 .5
3 5 2 .7
4
6
24
P-36=A 2 2 .1
17= 8
4 2 0 .0 .
O
1
3 2 7 .7
420=0
3 9 6 .2
3 6 7 .2
3 3 6 .9
00.0
9 .2 4
6 .7 8
5.93
5 .0 7
4 .8 7
15=0
4 2 0 .0
3 9 4 .5
9 .2 4
6 .9 1
5 .8 5 '
5»06
1 .8 8 0
0 .6 4 7
0.420
4=84
0 ,2 2 0
9.2^
7=70
7=04
1 .0 9 7
0=242
1 4 .6
1 9 .7
21=1
1 5 .3
368.6
14= 8
343.3
00.0
3 3 2 .8
CS
5=6
5.6;
5 .7
5=7.
1 6 .7
17=6
16=1
3 4 7 .0
420=0
3 9 7 .7
3 7 4 .5
3 5 2 .7
00.0
6=21
6 ,0 0
0=284
2=045
0.380
0.392
0.206
=»
0 .2 3 8
0=477
. 0.441
0=212
TABLE V ( C o n tin u e d )
' S u l f u r B a la n c e s
© ra
&&
% g.
4
O
W
-0.9
h
I
I)
S
I
E
O
«
P "46
25
P -4 7
26
rfl
■ Es
2 0 .0
O
CO
O
<
I
Si Sb
21=0
20.& 21=0
27
CD
I
EH
0
P -5 0 -B 30=5
13=8
2=200
6
1=900
1=832
1=790
0
2.200
I
1 .9 1 0
1=875
0
6
O
21=0
Ui
2
4
2
4
P =51aB
h
1.969
I
28
P
p
•I
2
4
6
-
H
.g
0
I
1.826
1 =782
2=200
1=898
1=820
1 .7 4 7
1 .7 0 8
O
-P
©
0 E
HO O
&
O
4 2 0 .0
4 2 0 .0 "
403= 0
3 8 5 .0
363.9
4 2 0 .0
420=0
402=5
384=0
364=5.
O
®
I,
'
I-I
oH
ra
CO
Q)
cq
0H O
Q ^
-
3.6
3.6
3=7
3 =7
- —
2 .8
2=8
2=9
383.1
360.1
3 .0
3 .0
401=4
382=4
361=2
• +5
=
S i
rS ir^,
g I
! s co
-
13.4
14= 4
17=4
360.2
-
1 4 =7
2 .8
15 =7
2 .8 . 16=7
420= 0
4 2 0 .0
4 0 1 .8
2.200 4 2 0 .0
1.969 420= 0
2 "1=892
4 1 .8 3 2
6 1=785
k
ti
™
2.9
361=7
<=
15=3
15=8
20.0
357=1
”
3=4
15=2
3=3
3 .4
15=7
1 7 .8
3=4
357.8
■
J
sl
%
§
0H
H -P
•H O
O CU
M U
■ hO (D
'H-P
"9.24
4 2 0 .0
402.5
384.0
364.5
00=0
9 .2 4
7.6 9
420=0
4 0 1 .8 '
383=1
360.1
0 0 .0
420=0
401=4
382.4
3 6 1 .2
0 0 .0
e
CO
7=93
7 .3 2
6=66
6 .5 1
7 .2 0
6 =6 5 .
6 .5 0
g l
I S 60
fn - P H
..
420=0
4 0 3 .0
385.0
363.9
0 0 .0
•.
Q
1E E
CQ O
O
•p
.= E
i # 8
■I
; . s i
E g ' E
m
-
6=96
6=28
6 .1 5
" I S !
Ui >
I
l
a
*
l
&
0 .3 5 3
D
Vj O
' •«*
0=372
1=219
0=141
-0.188
0 .1 6 1
.
0 ,2 8 0
1=270
0=314
0 .2 8 0
0=140
9=24
-
7 .9 0
0=970
0=309
7=24
6=6l
6=45
Sn H
0 .9 7 0
- 0 .2 7 8
0=262
0 .1 5 3
9 .2 4
7 .6 2
E
- H Q 1S
pi
O
0 .2 3 0
0=170
0.365
Y1
TABLE V (Continued)
Space v e lo c i ty
gras o i l
SULFUR BALANCES
O
29
P -3 2
1 2 .9
3 2 .6
Z
5
1 2 .7
3 3 .0
CO
3 2 .8
5 3 .1
CO
•8 ra
o
Q
O ..
2 .2 0 0
1 .8 9 2
1 .7 7 0
1 .6 7 4
1 .6 2 8
4 2 0 .0
4 2 0 .0
4 0 1 ,1
3 82.6
3 6 5 .4
1 .6
1 .6
1 ,7
1 .7
2 .2 0 0
1 .9 6 0
1 .8 6 6
1 .7 8 2
1 .7 3 4
4 2 0 .0
4 2 0 .0
4 0 2 .8
3 8 7 .9
3 7 1 .7
0 .9
.1 .0
1 .0
1 .0
2 .2 0 0
1 .9 4 7
1 .8 3 2
1 .7 2 8
1.663
4 2 0 .0
4 2 0 .0
4 0 2 .5
3 8 5 .0
3 6 5 .0
O
I
2
7 .4
-•g
Js O
3 8-
1 .7 7 3
6
P -3 8
d 'S
O <D
6
4
32
1d %
4
' 6
1 2 .8
eH
4 2 0 .0
4 2 0 .0
4 0 1 .9
384.3
3 6 5 .7
4
P-34
-H - CQ
2 .2 0 0
1 .9 8 6
1 .8 8 2
1 .8 0 8
O
I
2
31
I0
19
O «
<D "S3
/3 O
I
. ■2
3 0 ■ P -33
‘i
O
I
2
4
6
e*
'2.3
2 .3
2 .3
2 .3
I
-P
bO
Q)
,"Sd,
Il
**
1 5 .8
1 5 .3
.1 6 .3
3 6 3 .4
SB
C=
—
—
1 7 .3
1 6 .9
1 5 .5
3 6 3 .7
C=
1 6 .3
1 3 .9
-1 5 .2
3 7 0 .7
=
2 .4
2 .4
1 5 .1
1 5 .1
2 .4
1 7 .6
3 6 2 .6
2 .4
# W
^ ti
lti O
•H
H -P
eH O
O <D
S 8
4 2 0 .0
I
0
I
I O1 © p d
g
SI
w) as
©
ISS
Is Cd
-P
U
384.3
3 6 5 .7
0 0 .0
9 .2 4
7 .9 8
7 .2 4
6 ,6 0
6 .4 8
4 2 0 .0
4 0 1 .1
3 8 2 .6
3 6 5 .4
0 0 .0
9 .2 4
7 .6 0
6 .7 7
6 .1 1
5 .9 4
4 2 0 ,0
4 0 2 .8
3 8 7 .9
3 7 1 .7
0 0 .0
9 .2 4
7.8 9
4 0 1 ,9
4 2 0 .0
4 0 2 .5
385»0
3 6 5 .0
0 0 .0
CO rU -H
Ii
S
0 .2 6 0
0.899
0 .4 1 8
0 .2 8 4
0 .1 2 8
&
0 .347
1 .2 9 2
.
0 ,4 9 0
0.368
0 .1 6 8
<a»
0 .284
1 .0 0 9
0 .3 7 8
7 ,2 4
6 .6 3
6 .4 4
9 .2 4
7.83
7.05
6 .3 0
6 .0 6
G -W ■
0.326
0 .1 7 8
.
=
1 .0 6 2
0.463
0 .4 0 0
0 .237
0.522
~
T
TABLE V (Continued)
SULFUR BALANCES
O
S
O
5
I
I ■I '
33
P-39-B 10.4 37.8
34 ^ P-40
35
9
<
I§D . <D OI
•9 Cd CO
6
S I I
C -35
1 4 .0 28.1
1 3 .7 3 0 .6
C
O
S
•H ^ k
to ^
8
CMM
®§
rj ip
O to
I
4 1
Is O
E -I
13
P
h
to
k
0
2.200
I
1 .9 5 2
2
1.864
4 0 1 .9
4
6
1 .7 8 0
1.728
384.1
366.5.
0
2.200
I
2 .1 0 5
2
4
6
2,100
2.100
2.095
0
2.090
1.845
I
2
3
4
1 .7 3 1
1 .6 5 3
1.641
5 1.608
6 1.570
420.0
420.0
420,0
420.0
398.1
377.4
3 5 5 .1
420.0
420.0
405.0
389.5
3 7 5 .0
3 6 1 .6
344.8
k,
•0 »
ip I
d to
re
•H
to to
S3
e.
2 .2
2 .2
2.3
2.3
,0
Lp *
Br
1 .7
1 .7
1 .7
1.6
1 .7
1 .7
«
&8
O
•H
I I
do
-P O
rC! rH
O to
. £
S I
i W
£ 8
h -g
=H to
O
O
I
CD-
0
' Il
& Ii &rM
H-PH
W-Ci-H
ail
S n ItsIii
H-hO
9.24
1.040
7.85.
7.16 . 0.354
6.50
0.322 ■
6 .3 1 1 0.191
0.328
15.9
15.6
15.3
364.2
420.0
401.9
384.1
366.5
00.0 .
15.8
14.6
16.1
348.9
420,0398.1
377.4
355.1
oq.o
9 .2 4 8.38
7.92
7.45
7.43
0.088
CW
»
6,1
6 .1
6,2
6 .2
•
W eighi
a fte r.
gm s.
9
<D ro
420.0
405.0
13.3
13.8
389.5
12.8
375.0
11,8 ■ 361.6
344.8
15.1
00.0
343.1
—
8.78
7.46
6.75
6.20
5.94
5.54
5.41
0.399
0.020
0,000
0.018
Ca
1.029
0.461
0.304 •
0.045
0,012
0.013
0.270
TABLE V (Continued)
SULFUR BALANCES
Si>5
-p
6
S ■ t
O
Pti
I
36
£-36
•
O
La
I§) I0)nO
Jp
is
10.9
38
0-37
0 -3 8
10.5
14.6
•3
40.0
28.8
"g
!« §
Pn C
O
U O
OO
« In
H
is 00
O 2.090
I 1.938
2 1.876
3 1.800
4 1.768
5 1.748
6 1.720
420.0
420.0
404.5
389.0
374.9
358.2
343,4
2.090
4 2 0 .0
4 2 0 .0
I I
\
37
I
I a ab
CO Mj E
En
38.6
0) to ■
S-;§)
to a
O
I
2
3
4
5
6
0
I
2
3
.4
5
6
e ,
1 .8 7 5
1.800
1 .7 4 4
1,690
1 .6 6 5
1.632
2.090
1.942
1.855.
1 . 805
1.751
1.718
1.685
ee»
I“
B9<
' 1 .4
12.9
1.3
1.3
1 2 .9
1 2 .9
1 3 .1
•
&O
-S C
-H P
O
0) Sn s
is Cd hO OD eH
S g-HO CD
4 2 0 .0
H
HI
0.639
0.251
0.296
6 .3 4
0 .1 2 0
6.00
5.90
0.072
0.096
8.78
7.61
7.05
6.59
-5.80
5.69
1 1 .9
1 1 .6
1 2 .2
420.0
407.6
395.5
382.7
8.78
7.92
7.34
6.92
13.6
3 6 8 .6
6 .4 6
1 2 .9
355.2
354.7
0 0 ,0
6.10
5.98
ca
APH
8,78
7.84
7.30
6.75
405.7
391.5
377.3
362.8
348.0
00.0
13.4
346.7
0)
0
'n m S
H -P
0 0 .0
15.0
-g
-S I
p
fi
COO
O
341.7
1 2 .5
0.5
0.5
0 .6
0.5
0.5
0.5
CD
1 3 .1
1 .6
1 .7
1 .7
1 .7
Ca
■
420.0
404.5
389.0
374.9
358.2
343.4
Oe
1 .7
1 .7
1 .4
1 .4
1 .3
-
is C
O
13.8 '
- 13.8
oca
405.7
391.5
377.3
362,8
348.0
420.0
420.0
407.6
395.5
382.7
368.6
355.2
O-0
6H C
Q
"g
8,
H ^
•H <D
tQ CQ
»H O
OH
l>s
,Q
1TOm
H B
6 .1 4
am
-
Sm
^ H
1 1®
- 111
S a 8)
0.213
f
0 .2 6 6
0.904
0.304
0.220
0.204
0.091
0 . 115 .
0.622
0.354
0.198
0.206
0.122
0.117
-
'
0.233
■
TABLE V ( C o n tin u e d )
SULFUR BALMCES
»
C a ta ly s t
39
ril
13
0-39
1 1 .7
40
41
O
I
1 2 .4
C=iZjl
10.8
£ •
0
1
I n is •H
Q) OI
tC ro
Aa a S
CO U fao H
Ia
So-.§)
n
eq
H
H -P
O 0)
P-,
-p 0
^ 8
I
35.9
33.8
38.9
CO
. O 2.090
I 1.962
2 1.925
3 1.895
4 1.888
5 1.872
6 1.861
O 2.090
I 2 .0 1 0
2 1.920
3 1.871
4 1.850
5 1.835
6 1.812
O 2.090
I 2.020
2 1.975
3 1.928
4 1.895
5 1.852
6 1.815
4 2 0 .0
4 2 0 .0
4 0 4 .2
388.3
372.7
356.4
339.6
ti
Q
ip e
'Cd CtO
S#,
•0
!p a
H om
d
ra S
Q.S
2 .6
2.5
4 2 0 .0
CO
3 .0
3 .0 .
2.9
3 .0
3 .0
3 .0
398.4
377.7
356.5
333.2
309.1
13.3
13.4
13.0
13.8
14.2
337.1
12.8
1 3 .9
1 2 .4
13.0
13.4
336.6
=,
420.0
4 2 0 .0
%
Is CO
a
2.5
2.5
2.6
2.5
4 2 0 .0
4 0 4 .2
387.3
372.0
356.0
339.6
•g
9.2
9.1
9.2
9.2
9.1
9.1
12.4
1 1 .6
12.0
1 4 .1
15.0
300.0
a
* i .
I
I
IlO
.. . I j
rO
(J) • O
> ■2
m iO -H
Sfsrt ./1\
k A
t«tUviz w
Ifn *Pl rH5
<d
an
^ Cd QO
" 5 "d
CO Td -H
S
420.0
404.2
388.3
372.7
356.4
339.6
00.0
8.78
7.94
7.48
7.06
6.73
0.537
0.149
6.32
0.026
0.057
O.037
4 2 0 .0
8.78
8.12
7.43
6.96
6.59
6.22
6.15
0.336
0.274
0.190
0.078
0.053
0.078
§ g
H Ip .
O O
» Fh
O
^ O
404.2
387.3
372.0.
356.0
339.6
OOoO
420.0
398.4
377.7
356.5
333.2
3 0 9 .1
00.0
6 .3 6
8.78
8.05
7.45
6 .8 6
6.31
5.72
5.61
H P .^J
i
0.139
0 .1 1 6
■vi>
vO
6
0 . 14 ?
0.159
0.294
0.179
0.177
0 .1 1 8
0.143
0 .1 1 4
TABLE
Y
(Continued)
SULFUR BALANCES
O.
S
■&
nl
I
I 'I
42
43
44
C-42 10.7
C-43
11.2
C-44 10.4
CQ
S
5
I I is
Il I E-i CU «
0) O
39.3
37.5
40.4
O
O (!)
■
- ®b
S p
0 2.090
1 1.950
2 1.272
3 1.848
4 1.828
5 1.795
6 1.781
420.0
420.0
403*5
387.2
370*1
353.8
336.1
O 2.090
1 1.922
2 1.838
3 1.785
4 1.725
5 1.693
6 1.670
420.0
420.0
400.9
385.7
370.1
355.3
340.5
2.090
1 2.080
2 2.060
3 2.045
4 2.030
5 2.020
6 2.015
420.0
420.0
405.9
389.3
372.8
355.2
339.2
0
-O'''*
>
4S
Ie
rl E
-P <D
I
to to
•rl O
Q
1»
3 .7
3 .8
3 .7
3 .7
3 .8
3.8
e=»
2 .8
2.8
2.7
2.8
2.8
2 »8
Ca
2.9
2.9
2.9
2.9
2.9
2,9
-O
|3 CO
_
12.8
12.5
13.4
12.6
13.9
332.3
CL*
16.3
12.4
12.9
12.0
12.0
337.7
Ca
11.2
13.7.
13.6
14.7
13.1
336.3
XS
S I
+5
cH P
tti O
-H
H -P
-H O .
O ©
U
« P
;P O
g O
-420.0
403.5
387.2
370.1
353.8
336.1
00.0
£ ©
CH .©
I—I P
0 U
Oi O
O
-P
-C
PD o
bfl-C
-H -P ra
© tH e
. Cd 60
■
4 2 0 .0
400.9
385.7
370.1
355.3
340.5
00.0
420.0
405.9
389.3
372.8
355.2
339.2
0 0 .0
'
O■ 0
C
Q
I-# B
>
Jh -P H
cd
Sn
3 U H
ch
©©
S S 1S
y ^
tn -ti *h
© Eg
■ro t>
H ll
3
SH -H ©
8.78
7.86
7.25
6.84
6.46 ~
6.04
5.99
0.588
0.314
0.093
0.074
0.117
0.047
8.78
7.70
7.08
6.61
6.13
5.76
5.69
0.705
0.336
0.204
0.222
0.114
0.078
8.78 .
8.44
8.01
7.64
7.20
6.85
6.82
0.042
0.081
0.058
0.056
0.036
0.017
CB
2
&
0.179
=Otf"
O
2 8
«8-M .
O
53
0,.215
CM
0.042
TABLE
V
(Continued)
SULFUR BALANCES
-P
O
S
g
(§
45
46
47
‘
S '
" i
e
r
C
1«'
O
$
C-45
Cook
2 7 -1
Cook
3 1 -2
1 0 ,5
£
I
<D
2#
<S 610
O ti
*
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O
Il
I
i
4 0 .0
I
•H
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<D d
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I
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^
f t
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0
m
2.090
1.848
2 1.775
3 1.728
0
I
10.8
1 0 .5
38.9
4 0 ,0
El -g
0 m
4
5
1 .6 4 8
6
1.615
1 .6 7 4
*
P-I
S S
4 2 0 .0
4 2 0 .0
4 0 6 .1
4 2 0 .0
4 2 0 ,0
2
4
6
404.0
387.8
370.5
1 .6 1 8
1 .6 0 0
0
2 .1 4 0
I
1.928
1.807
1.745
1.718
2
4
6
•H
CO
td §j
4 2 0 .0
4 2 0 ,0
4 0 1 .5
383.4
363.9
.
1o
M
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I
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CO
f t
ene
©
Bi
ft n
cd 0
r-l
1.8
1.9
392.5 . 1 .8
378.7. 1 .8
363.7
1.9
1.8
347.5
G 2 .1 4 0
I 1 .8 2 4
1 .7 3 5
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-
*
• CO
in I si
k -p f t
d
§ - ti
CO T i f t
8 .7 8
7 .5 0
1 .0 1 6
1 1 .7
3 9 2 .5
6 .9 7
0 .2 9 6
1 2 .0
3 7 8 .7
6 .5 4
0 .1 8 5
3 6 3 .7
•6 ,0 9
0 .2 0 4
1 3 .2
,
»
1 4 .3
3 4 7 .5
5 .7 2
0 .0 9 5
3 4 5 .7
0 0 .0
5 .6 1
0 .1 1 5
8 * 9 8
C
2.4
2 .4
1 4 .2
2.5
2.5
1 4 .8
3 6 8 .0
es
C
O
7 .3 6
1 . 3 2 9
3 8 7 .8
6 .7 1
0 .3 5 9
3 7 0 .5
6 .0 0
0 .4 5 3
0 0 .0
5 .8 3
0 ,0 6 7
4 2 0 . 0
8 .9 8
W Ti f t
•H y
^
Cb
H
bo
0 .2 7 8
T
6
• 0 .2 7 6
-
i:
0 .2 2 8
4 .1
4 .1
4 .2
1 4 .4
1 4 .0
4 0 1 .5
7 .7 5
0 .8 9 0
3 8 3 .4
6 .8 2
0 .5 1 0
1 5 . 3
3 6 3 .9
6 .3 5
0 .2 3 8
4 .1
3 5 9 .8
6 . 2 5
0 .0 9 8
0 0 .0
U
<§ ^
4 2 0 ,0
4 0 6 .1
B
S
4 2 0 .0
4 0 4 ,4
'BS
£
ft
H
1 2 ,1 .
1 3 .2
Ca
*>
§
e
O
W eighi
a fte r
g m s.
•
TABLE V ( C o n tin u e d )
SULFUR BALANCES
.<0 m
0 &
Ch
rO O
'
.1
O
H
CQ
M
c
ES
+D • e
R
I
H
Eo
<D M
•H
"
d
(DO I
•£ .
Cd
U
O
^
g.
CO SI Si
p1-i 302
48
Cooks
1 2 .1
34
29,30- .
2
49
P“64_
1 8 .1
2 3 .2
xI
50
P -6 4 -
1 8 .1
2 3 .2
X1 2
I
E-i
P -6 4 “
X0 ,
24.
1 4 .5
2 9 .0
S r3
'
Jg ^ O
0
1
2
4
>
2 .1 4 0
1 .9 5 1
1 .8 6 0
1 .7 5 3
1 .7 0 3
4 2 0 .0
4 2 0 .0
4 0 2 .7
3 8 5 .1
3 6 7 .4
0
I
2
4
6
2 .1 4 0
1 .9 8 5
1 . 918
4 2 0 .0
4 2 0 .O
4 0 4 .0 .
3 8 6 .6
0
•I
2
4
6
51
H «P
a I
0
I
2
4
6
1.853
1.782
369.3
g
r*j
•O '*0
3I
H
•h
02
•H
O
m
m
m
O
3 .7
£
- JU
*p 0
3
1
Il
Is CO
3.6
3.7
1 3 .6
1 4 .0
1 4 .0
3 .7
363.7
3 .1
1 2 .9
3 .2
3.2
3.2
1 4 .2
1 4 .1
3 6 6 .1
-
1 1 .4
1 5 .1
2 .1 4 0
1 .8 8 5
1 .7 5 6
1 .6 6 8
1 .6 2 8
4 2 0 .0 .
4 2 0 .0
4 0 4 .4
2 .1 4 0
1 .8 5 0
1 .7 7 2
1 .6 9 7
4 2 0 .0
4 2 0 .0
4 0 4 .0
3 .1
3.2
1 2 .9
1 4 .3
386.5
366.7_
3 .1
3 .1
13.6
363.6
1.636
385.0
365.0
4 .2
4 .3
4 .2
4=3
1 5 .8
3 6 0 ,7
I
to
-C^h 0(U
S
'
cd 0
In
O 0)
si
420.0
402.7
385.1
367.4
00.0
°
^ 0
•H -P M
g,
8.98
7.85
7.16
6.44
6.24
>
m
Ik -PI Hft Jjd o>m
III Hs
III I eI
0.294
-
0.794 .
0.366
0.411
0.184
420.0
8.98
8.00
404.0
386.6
7.41
6.84
369.3
00.0 a .6.58
0.651
0.270
0.252
0.262
420.0
404.4
385.0
365.0
00.0
8.98
7.60
6.75
6.09
5.94
1.070
0.520
0.338
0.175
420,0
404:0
386.5
369.8
00.0
*■
8.98
7.46
1,219
0.314
6.85
6.27 - 0.290
6.00
0.224
™-
.
0.178
-
0.298
0.316
I
8
5
TABLE V
Gontinned)
(
SULFDE BALANCES
0
CO
O
§
5
52
P -64-
IGb
0
P -64-
"a) d0
cd w
>
■
x IU
54
P-6427
-S
4)
^
TO I 1,
2
15.6
26,9
0
1
2
4
6
1 2 .0
35. 0
77. 8
iOscH
SI
d -8
0 ®
6&
S O
2.200 420.0
1.966 420.0
1.854 403.6
1.7&5 384.9
1.700 367.3
Q 2.200 420.0
I 1.978 420.0
2
4
6
5 .4
% ti
IS
V
53
<D CO
0 §>
1.900
1.818
1.795
403.6
387.3
369.0
O 2.200 420.0
I 2.045 420.0
2
4
6
2.010
1.960
1.985
4 0 4 .6 '
387.7
371.1
•0 .
■ -H eg
-A
S
cd bo
pH
H m
•H ®
-P
l
CO K
CO
•H O
Q Pl
-
3 .4
3.4
3 .4
3 .4
-
2.4
2.3
2 .4
2.4
™■
2 .4
2 .4
2 .4
2.4
O
g
§3 s>
I s•H
-P CD
®I
S TO
-
13.0
15.3
14.2
363.9
-
14.0
14.0
J-5.9
366.6
-
13.0
14.5
14.2.
368.7
i—I-P •
. ^
jp
|3 0O
I
.rC
Qi) • «
i> w
Ph-P H
Sm
III
: i » rf
Cd GO TOTj.Ti
S£S,
0
43
SD
n e
60-C
9.24T.92
7.15
6.48
6.'24
—
•
0^98>
0.451
0,342
0.-238
■ '9.24
7.97
7.35
6.71
OSfeO
6.62
0.932
0.314
0.317
' 0.085
420.0
403.6
384.9
-367.3
O o.o
420.0
403.6
387.3
: 369.0
420.0
404.6
387.7
371.1
00.0
9.24
8.28
7.79
7.26
7.04
-
0.651
0.142
0.193
0.204
-
.
0.187
?
G
8.
'
0.192
0.296
&
W
«<■
A
W
CO
I
1 PREHEAT SECTION
2 CATALYST BED
3 INSULATION
4 IRON PIPE
5 THERMOWELL
6 CATALYST
SUPPORT
7 H2O CONDENSER
8 OIL RESERVOIR
9 ICE CONDENSER
IO
ABSORBER
F ig u re I .
C o m p a riso n U n it
(V
r—
GRAMS SULFUR REMOVED PER GRAM NICKEL
0.7
h
0.6
0.5
0.4
0.3
A
Y
0.2
0. I
0 0 Ou
30
IOO
ISO
200
230
GRAMS OIL PER GRAM NICKEL
Figure 2.
300
330
PER HOUR
Effect of Space Velocity on Sulfur Removal
400
MONTANA STATE UNIVERSITY LIBRARIES
762 1001 3705 6
^
7 8
rbXlp
1 0 5 0 1 1
c o p T r^
AUTHOR
i 'l s c h b a c h , R o b e r t J
P r e p a r a t i o n o f a" n i c k e l ----------o x id e desulfurization cetalYst.
T iT U E l l h e
DATE DUE
S O R R O W E R 'S N A M E
'
M A R
1 2
M n ftg
PW D w
uLt*l'-- ■• E
,
/ 4 3 }
'^QUaJ
t
c
I
2)1?
L £ y U £ / * £ 4 L
t j
-y ~ b
f
O
>~s * * - * / p
o
p
.
LdM
z
.
X
A T