The catalytic desulfurization of Wyoming fuel oil
by Bradley L Munro
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 Bradley L Munro (1952)
Abstract:
The primary purpose of this investigation was to compare various destructive hydrogenation catalysts
at various operating conditions to determine the most effective catalyst and operating conditions with
which to reduce the sulfur content of a petroleum distillate from 2.1 to less than 0.5 percent without
carbon-to-carbon fissure.
The various destructive hydrogenation catalysts which were investigated were molybdena alumina,
cobalt molybdate, molybdenum sulfide and tungstic oxide, A nickel oxide catalyst was briefly
investigated at destructive hydrogenation operating conditions* The three to six hour tests were
performed with 850 to 1000 grams of catalyst in a fixed bed reactor at reactor pressures of 300 and 500
psig, temperatures between 375 and 430°C, space velocities between 0.75 and 1.3 grams oil per gram
catalyst per hour and hydrogen-to-oil ratios between 0.2 and 1.2 liters exit gas per gram of oil. Cobalt
molybdate, molybdenum sulfide, and molybdena alumina catalysts produced effluent oil containing
less than 0.5 percent sulfur. Cobalt molybdate and molybdenum sulfide displayed nearly similar
catalyst activity which was greater than the activity of molybdena alumina.
The secondary purpose of this investigation was to determine the duration of effective catalyst activity
of molybdenum sulfide at operating conditions of 500 psig and 410°C* Molybdenum sulfide was
capable of reducing the effluent oil sulfur content to less than 0*5 percent for an operating period in
excess of 2000 hours with only a 35 percent decline in catalyst activity. THE CATALYTIC DESULFURIZATION
OF WYOMING FUEL OIL
by
BRADLEY L . MUNRO
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 th e re q u ire 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 i n e e r in g
at
M o n tan a S t a t e C o lle g e
A p p ro v e d :
Bozem an 5 M ontana
A u g u s t 5 1952
H d W
AA S
(/ c.
-2-
TABLE OF CONTENTS
page
A b s t r a c t ..................................................................................................................................
3
I n t r o d u c t i o n .............................
k
E q u ip m e n t, M a t e r i a l s a n d M e th o d s . ..................................................................................
8
E q u ip m e n t ..................................................................................................................................
^
M a t e r i a l s .................................. .... ...........................................................................................
M e t h o d s .......................................................................................................................................
S am ple C a l c u l a t i o n s ..................................................... ..............................................................
T herm odynam ic C a l c u l a t i o n s . .............................................................................
D is c u s s io n o f R e s u lts
. . . . 16
..........................................................................................................
The e f f e c t o f o p e r a t i n g c o n d i t i o n s u p o n d e s u l f u r i z a t i o n w i t h
v a r i o u s d e s t r u c t i v e h y d r o g e n a t io n c a t a l y s t s a t s u p e r a tm o s p h e r ic
p r e s s u r e . ...................................................................................................................
20
The e f f e c t o f o p e r a t i n g c o n d i t i o n s u p o n t h e L i f e S tu d y Run o f
m olybdenum s u l f i d e c a t a l y s t . . . . .
........................ . . . . . . . .
23
C o n c lu s io n
............................................
. . . . . . . . . .
......................... . . . 2 8
L i t e r a t u r e C i t e d . .............................
A ck n o w led g m en t.........................................................
. . . 3 0
. . . . . . . . . . 3 1
A p p e n d ix .................................................................................................................................................
103333
ABSTRACT
The p r im a r y 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 was t o com pare v a r i o u s
d e s t r u c t i v e h y d r o g e n a t io n c a t a l y s t s a t v a r i o u s o p e r a t i n g c o n d i t i o n s t o
d e te r m i n e t h e m o st e f f e c t i v e c a t a l y s t a n d o p e r a t i n g c o n d i t i o n s w i t h w h ic h
t o r e d u c e t h e s u l f u r c o n t e n t o f a p e tr o l e u m d i s t i l l a t e fro m 2 ,1 t o l e s s
t h a n O05 p e r c e n t w i t h o u t c a r b o n - t o - c a r b o n f i s s u r e , .
The v a r i o u s d e s t r u c t i v e h y d r o g e n a t io n c a t a l y s t s w h ic h w e re i n v e s t i ­
g a t e d w e re m o ly b d e n a a lu m in a ,, c o b a l t m o ly b d a te 9 m olybdenum s u l f i d e an d
t u n g s t i c o x i d e , A n i c k e l o x id e c a t a l y s t w as b r i e f l y i n v e s t i g a t e d a t d e ­
s t r u c t i v e h y d r o g e n a t io n o p e r a t i n g c o n d i t i o n s * The t h r e e t o s i x h o u r t e s t s
w e re p e rf o r m e d w i t h 850 t o 1000 g ram s o f c a t a l y s t i n a f i x e d b e d r e a c t o r
a t r e a c t o r p r e s s u r e s o f 300 a n d 500 p s i g , t e m p e r a t u r e s b e tw e e n 375 a n d
430 °C 5 s p a c e v e l o c i t i e s b e tw e e n 0,7 5 a n d 1*3 gram s o i l p e r gram c a t a l y s t
p e r h o u r a n d h y d r o g e n - t o - o i l r a t i o s b e tw e e n 0*2 a n d 1*2 l i t e r s e x i t g a s
p e r g ram o f o i l *
O o b a lt m o ly b d a te 9 m olybdenum s u l f i d e , a n d m o ly b d e n a
a lu m in a c a t a l y s t s p ro d u c e d e f f l u e n t o i l c o n t a i n i n g l e s s t h a n 0*5 p e r c e n t
s u l f u r . C o b a lt m o ly b d a te a n d m olybdenum s u l f i d e d i s p l a y e d n e a r l y s i m i l a r
c a t a l y s t a c t i v i t y w h ic h w as g r e a t e r t h a n t h e a c t i v i t y o f m o ly b d e n a a lu m in a *
The s e c o n d a r y 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 d u r ­
a t i o n o f e f f e c t i v e c a t a l y s t a c t i v i t y o f m olybdenum s u l f i d e a t o p e r a t i n g
c o n d i t i o n s o f 500 p s i g a n d AlO 0 C, M olybdenum s u l f i d e w as c a p a b l e o f r e d u c ­
i n g t h e e f f l u e n t o i l s u l f u r c o n t e n t t o l e s s t h a n 0*5 p e r c e n t fo r a n o p e r a t ­
i n g p e r i o d i n e x c e s s o f 2000 h o u r s w i t h o n l y a 35 p e r c e n t d e c l i n e i n c a t a l y s t
a c tiv ity .
INTRODUCTION
The i n c r e a s e d u t i l i z a t i o n o f h i g h s u l f u r c o n t e n t c r u d e p e tr o le u m fo u n d
i n W est T e x a s 5 W yoming 5 M o n ta n h 5 a n d C a l i f o r n i a h a s c a u s e d a n e v e r i n c r e a s ­
i n g p e tr o l e u m r e f i n i n g p r o b le m »
Some c r u d e p e tr o le u m s t o c k s c o n t a i n a s
m uch a s 4 t o 5 p e r c e n t s u l f u r a n d t h e r e d u c t i o n o r e l i m i n a t i o n o f t h i s ob­
j e c t i o n a b l e c o n s t i t u e n t fro m r e f i n e d p e tr o l e u m p r o d u c t s i s n e c e s s a r y »
S u l f u r may o c c u r i n c r u d e p e tr o l e u m and v a r i o u s r e f i n e d f r a c t i o n s a s o n e o r
m ore o f t h e f o l l o w i n g f o rm s ;
.e le m e n t a l s u l f u r , m e r c a p t a n s , h y d r o g e n s u l f i d e
I
c a rb o n d i s u l f i d e , th io p h e n e s , th io p h a n e s , t h i o a l c o h o l s , o rg a n ic s u l f i d e s ,
d i s u l f i d e s , p o l y s u l f i d e s , an d s u l f a t e s ( 6 ) e
The p r i n c i p a l o b j e c t i o n s t o
s u l f u r com pounds i n r e f i n e d p r o d u c t s a r e t h e i r a c t u a l o r p o t e n t i a l c o r r o s ­
iv e n e s s , d is a g r e e a b le o d o r, d e le te r io u s e f f e c t on c o lo r s t a b i l i t y , u n fa v o r­
a b le in f lu e n c e on t e t r a - e t h y l le a d s u s c e p t i b i l i t y and o x id a tio n c h a r a c te r ­
is tic s
( 6) .
A l i t e r a t u r e s u r v e y o f t h e v a r i o u s p e tr o l e u m t r e a t i n g m eth o d s d i s c l o s e d
t h a t a num ber o f schem es a r e a v a i l a b l e t o ' c o n v e r t im m e d ia te ly c o r r o s i v e
s u l f u r com pounds s u c h a s m e r c a p ta n s i n t o l e s s o b j e c t i o n a b l e s u l f u r com pounds
T h e s e m eth o d s f o r t r e a t i n g a m o to r f u e l w o u ld n o t a c c o m p lis h a r e d u c t i o n i n
s u l f u r c o n t e n t a n d t h e p o t e n t i a l c o r r o s i v e n e s s o f t h e f u e l w o u ld s t i l l b e
p re s e n t♦
O th e r t r e a t i n g m e th o d s f o r r e m o v a l o f s u l f u r . f r o m g a s o l i n e and
n a p h th a , d i s t i l l a t e s t a k e a d v a n ta g e o f t h e r e l a t i v e l y a c i d i c t y p e s u l f u r
co m pounds,
A l k a l i n e s o l u t i o n s w i l l rem ove some s u l f u r com pounds a c i d i c i n
n a t u r e w h i l e a c t i v a t e d b a u x i t e s w i l l c a u s e t h e d e c o m p o s itio n o f c e r t a i n
s u l f u r com pounds ( 8 ) e
The a b o v e m e th o d s o f d e s u l f u r i z a t i o n a r e e f f e c t i v e f o r d i s t i l l a t e s
=»5”
b o i l i n g b e lo w 4Q0°F a n d o n l y s l i g h t l y e f f e c t i v e f o r h e a v i e r d i s t i l l a t e s o f
t h e 400 t o 7 0 0 °F b o i l i n g r a n g e .
The u s e o f a s o l v e n t e x t r a c t i o n m eth o d t o
rem o v e s u l f u r c o n t a i n i n g m o le c u le s i n a h i g h s u l f u r c o n t e n t «, h i g h b o i l i n g
d i s t i l l a t e w o u ld n o t b e p r a c t i c a l b e c a u s e a h ig h p r o p o r t i o n o f t h e o i l
m o le c u le s c o n t a i n s s u l f u r and a h i g h l o s s o f p r o d u c t w o u ld r e s u l t .
The u s e
o f a n a c t i v a t e d b a u x i t e o r ■F u l l e r s e a r t h t y p e c a t a l y s t w ould b e e f f e c t i v e
i n d e c o m p o sin g o n l y t h e l e s s s t a b l e s u l f u r com pounds w h i l e i t w o u ld h a v e
little
e f f e c t u p o n t h e c y c l i c —t y p e s u l f u r com pounds,
K o sk i ( ? ) r e p o r t e d a
50 p e r c e n t d e c r e a s e i n s u l f u r c o n t e n t o f a f u e l o i l i n t h e b o i l i n g r a n g e o f
z
4 4 0 t o 6 50°F w i t h t h e u s e o f b a u x i t e a n d a c i d - a c t i v a t e d b a u x i t e c a t a l y s t s .
T he r e c e n t i n t e r e s t i n t h e u t i l i z a t i o n o f d i s t i l l a t e s h e a v i e r t h a n
g a s o l i n e f o r D i e s e l e n g i n e s 9 g a s t u r b i n e s 3 and J e t a i r c r a f t m o to r s h a s i n ­
c r e a s e d t h e n e e d f o r e f f e c t i v e r e f i n i n g m e th o d s o f h ig h s u l f u r c o n t e n t f u e l
o ii d is tilla te s ,
A f u e l o f h ig h s u l f u r c o n te n t u se d i n h ig h -s p e e d D ie s e l
e n g in e s c a u s e s f o r m a ti o n o f d e p o s i t s o n t h e c y l i n d e r s a n d w e a r o f v a r i o u s
p a r t s o f t h e e n g in e ( 8 ) ,
The c o m b u s tio n p r o d u c t s o f s u l f u r a l s o . c a u s e
w e a k e n in g a n d c o r r o s i o n o f t h e v i t a l p a r t s o f g a s t u r b i n e s a n d j e t e n g i n e s .
The b o n d e n e r g y . f o r a c a r b o n - t q c a r b o n bond ( $ 8 ,6 K e a l / m o l ) i s o n ly
s l i g h t l y h i g h e r t h a n a c a r b o n - t o - s u l f u r b o n d (54» 5 K c a l / m o l ) ,,
T h erefo re9
a c o n ta c t a g e n t u se d f o r d e s u l f u r i z a t i o n o f h eav y d i s t i l l a t e s 5 w ith o u t
c a r b o n - t o - e a r b o n f i s s i o n , m u st b e v e r y s e l e c t i v e t o t a k e a d v a n ta g e o f t h e
s l i g h t d i f f e r e n c e i n bond e n e rg y .
C e r t a i n c o n t a c t a g e n t s s u c h a s NiO w h ic h
fo rm s t a b l e s u l f i d e s o n c o n t a c t w ith s u l f u r - b e a r i n g h y d r o c a r b o n s a r e v e r y
e f f e c t i v e u n t i l t h e c o n t a c t a g e n t s a r e c o n v e r t e d t o t h e s u l f i d e fo rm w h ic h
d is p la y s l i t t l e
C a ta ly s tic d e s u lf u r iz a tio n a c t i v i t y ,
T h e refo re 9 fre q u e n t
a n d c o s t l y r e g e n e r a t i o n m e th o d s a r e a s e r i o u s d i s a d v a n t a g e i n r e c l a i m i n g
t h e e x p e n s iv e c h e m ic a l r e a g e n t t y p e c o n t a c t a g e n t e
D e s u l f u r i z a t i o n h a s b e e n a c c o m p lis h e d b y t h e u s e o f d e s t r u c t i v e h y d r o ­
g e n a t i o n c o n t a c t a g e n t s w h ic h do d>r do n o t fo rm m e t a l s u l f i d e s »
E xam ples
f o u n d i n t h e l i t e r a t u r e p o i n t to w a rd t h o s e m e t a l s i n G ro u p s V I a n d V I I I
o f t h e P e r i o d i c t a b l e w i t h p a r t i c u l a r e m p h a s is u p o n c h r o m i u m C o b a l t s I r o n 9
m olybdenum ,, n i c k e l a n d t u n g s t e n a s b e i n g t h e m o st e f f e c t i v e a g e n t s f o r d e ­
s t r u c t i v e h y d r o g e n a t io n a n d d e s u l f u r i z a t i o n *
D e s t r u c t i v e h y d r o g e n a t io n r e a c t i o n s a r e c a r r i e d o u t a t t e m p e r a t u r e s
a t .which, i n c i p i e n t c a r b o n - t o - c a r b o n c r a c k i n g o c c u r s a t m o d e r a te t o h i g h
h y d ro g e n p r e s s u r e s a n d w i t h a c a t a l y s t c o n t a i n i n g a n o x id e o r s u l f i d e o f
a n e le m e n t i n G ro u p s V l a n d V I I I o f t h e P e r i o d i c t a b l e *
P r e v io u s w ork, h a q b e e n d o n e i n t h e i n v e s t i g a t i o n o f d e s u l f u r i z a t i o n
a g e n t s t o r e d u c e t h e s u l f u r c o n t e n t b y m o re t h a n 75 p e r c e n t i n a f u e l o i l
w i t h a b o i l i n g r a n g e o f 4 4 0 t o 6 5O0F*
H aas ( 5 ) a n d F is c h b a c h ( 3 ) p e rfo rm e d
t e s t s o n v a r i o u s n i c k e l o x id e c o n t a c t ■a g e n t s a n d d i s c o v e r e d t h a t t h e a c t i v e
■d e s u l f u r i z a t i o n l i f e
c u lt*
o f t h e c a t a l y s t w as s h o r t a n d r e g e n e r a t i o n w as d i f f i ­
K o s k i ( 7 ) i n v e s t i g a t e d t h e u s e o f l e s s e x p e n s iv e c o n t a c t a g e n ts
s u c h a s b a u x i t e and a lu m in a a t l e s s d r a s t i c o p e r a t i n g c o n d i t i o n s , b u t r e ­
s u l t s d i s c l o s e d t h a t a maximum o f o n l y $0 p e r c e n t s u l f u r r e m o v a l c o u ld b e
a c c o m p lis h e d *
The i n v e s t i g a t i o n o f d e s t r u c t i v e h y d r o g e n a t io n c a t a l y s t s a t s u p e r a tm o s p h e r i c p r e s s u r e s w i t h a v a r i e t y o f c a t a l y s t s t o i n d i c a t e a p o s s i b l e
.
a p p r o a c h to w a r d m ore c o m p le te d e s u l f u r i z a t i o n w as r e p o r t e d b y K o sk i ( ? )
a s w e l l a s i n t h i s w ork*
The c a t a l y s t s i n v e s t i g a t e d w e re m o ly b d e n a a lu m in a
c o b a l t m o ly b d a te ^ t u n g s t i c o x i d e s n i c k e l o x i d e s a n d m olybdenum s u l f i d e *
O f t h i s g r o u p o f c a t a l y s t s t h e m o st p r o m is in g w as MoSg o n t h e b a s i s o f
a c t i v i t y and p a te n ta b ility *
The v a r i a b l e s o f h y d r o g e n - t o - o i l r a t i o s
p r e s s u r e s s p a c e V e l o e i t y s a n d t e m p e r a t u r e w h ic h . e f f e c t t h e p e rf o r m a n c e o f
t h e v a r i o u s c a t a l y s t s w e re b r i e f l y s t u d i e d *
An e x t e n s i v e c a t a l y s t l i f e
s t u d y w as p e rf o r m e d o n t h e m olybdenum s u l f i d e c a t a l y s t t o g i v e a d d i t i o n a l
d a ta on th e v a r ia b le s o f h y d r o g e n - to - o il r a t i o s and sp a ce v e lo c ity *
G reen
( 4 ) r e p o r t e d o n a d d i t i o n a l i n v e s t i g a t i o n s o f MoS2 c a t a l y s t a n d t h e e f f e c t s
o f p r e s s u r e s a i r o x id a tio n r e g e n e r a t io n s and d i l u t i o n o f h y d ro g en w ith
h y d ro ca rb o n g ases*
EQUIPMENT? MATERIALS AND METHODS
EQUIPMENT
The tw o r e a c t o r s t h a t w e re u s e d f o r t h e i n v e s t i g a t i o n w e re d e s ig n e d
f o r u s e a t p r e s s u r e s u p t o 900 p s i g ,
The e s s e n t i a l d i f f e r e n c e o f t h e
r e a c t o r s was t h e volum e o f t h e c a t a l y s t bed„
The l a r g e v o lu m e p r e s s u r e r e a c t o r w h ic h w as u s e d f o r s h o r t o p e r a t i n g
p e r i o d s w i t h c a t a l y s t c h a r g e s o f n e a r l y 1 0 0 0 gram s i s i l l u s t r a t e d i n F ig ­
u re I ,
An e x c e l l e n t d e t a i l e d d e s c r i p t i o n o f t h e c o n s t r u c t i o n o f t h i s r e -
a c t o r w as g i v e n b y C r e c e l i u s ( 2 ) „
The r e a c t o r w as u s e d w i t h a h y d ro g e n
g a s .s u p p ly t a n k f i t t e d w i t h a h i g h - p r e s s u r e r e g u l a t o r 9 a n
p i s t o n pum p, a n
o i l c h a rg e
e f f l u e n t o i l r e c e i v e r , a n d a n e x h a u s t g a s blow-down s y s te m
w h ic h c o n ta i n e d a c a u s t i c w ash a n d . a w e t t e s t m e t e r „
The s m a l l vo lu m e p r e s s u r e r e a c t o r w h ic h w as u s e d f o r t h e c a t a l y s t l i f e
s t u d y w i t h a c a t a l y s t c h a r g e o f 100 g ram s i s i l l u s t r a t e d i n F i g u r e " 2 . "■ The
r e a c t o r c o n s i s t e d o f a 16 i n c h l e n g t h o f lg . in c h e x t r a - s t r o n g b l a c k p ip e
f i t t e d w i t h a I g t o 3 /4 i n c h r e d u c e r a t t h e t o p a n d - a I g t o |
a t t h e b o tto m .
in c h re d u c e r
E x t r a - s t r o n g p i p e a n d f i t t i n g s w e re u s e d th r o u g h o u t t h e
r e a c t o r s y s te m w h ic h was u n d e r p r e s s u r e .
The t o p o f t h e r e a c t o r w§.s f i t t e d
w i t h a u n i o n , tw o c r o s s e s , a n d a n a s s e m b ly o f v a l v e s f o r h y d ro g e n i n l e t , o i l
i n l e t , o i l f e e d - l i n e b l e e d , a i r i n l e t f o r r e g e n e r a t i o n , b lo w o u t- d ig k e x h a u s t
s y s te m , a n d th e r m o w e ll t u b e .
The t h e r m o w e ll t u b e was a 1 / 4 i n c h b l a c k p i p e
w h ic h e x te n d e d fro m t h e c r o s s a t t h e t o p o f t h e r e a c t o r a lo n g t h e v e r t i c a l
a x i s o f t h e r e a c t o r t o w i t h i n one i n c h o f t h e b o tto m .
The th e r m o w e ll w as
c a p p e d a t t h e b o tto m en d and p r o v id e d room f o r i n s e r t i o n o f t h r e e tn er'm o c o u p le s ,
The h o t j u n c t i o n s o f t h e th e r m o c o u p le s w e re p l a c e d a t an y d e s i r e d
courts
p o s i t i o n i n t h e th e rm o w e ll*
, A t t h e b o tto m o r d i s c h a r g e e n d o f t h e r e a c t o r w e re f i t t e d a § i n c h
p i p e u n i o n , a t e e , p r e s s u r e g a g e , a n d a s m a ll- v o lu m e G rove s p r i n g - l o a d e d •
b a c k - p r e s s u r e v a l v e w h ic h w as c a p a b l e o f c o n t r o l l i n g b a c k p r e s s u r e s b e tw e e n
0 and IGOO p s ig „
A M a s o n -N e ila n s m a ll- v o lu m e a i r - t o - c l o s e r e g u l a t o r v a l v e
w as s u b s t i t u t e d f o r t h e G ro v e v a l v e d u r i n g t h e l a t t e r h a l f o f t h e c a t a l y s t
life
s t u d y ru n *
A F i s h e r W iz a rd p r o p o r t i o n a l c o n t r o l l e r w as u s e d t o s u p p ly
t h e c o r r e c t c o n t r o l p r e s s u r e t o t h e M a s o n -N e ila n v a l v e d ia p h ra g m *
The F i s h e r
W iz a rd w as s u p p l i e d w i t h c o m p re s se d a i r a t 20 p s i g fro m t h e l a b o r a t o r y
c o m p re s s e d a i r sy ste m *
The p r e s s u r e g a g e w as c o n n e c te d t h r o u g h a n o i l - s e a l e d p i g t a i l t o t h e
te e f ittin g
a b o v e t h e b a c k p r e s s u r e v a lv e *
The v a p o r s p a s s i n g t h r o u g h t h e
b a c k p r e s s u r e v a l v e w e re c o n d e n s e d i n a w a t e r - c o o l e d c o p p e r t u b e c o n d e n s e r
a n d w e re c o l l e c t e d i n a o n e - l i t e r E r le n m e y e r f l a s k *
The n o n - c o n d e n s a b le
e x h a u s t g a s e s w e re p a s s e d i n s e r i e s ' t h r o u g h tw o g a s s c r u b b i n g f l a s k s co n ­
t a i n i n g so d iu m h y d r o x id e s o l u t i o n t o rem o v e t h e h y d r o g e n . s u l f i d e p r e s e n t i n .
th e e x h au st gases*
The s w e e te n e d g a s w as m e te r e d t h r o u g h a w e t t e s t m e te r
m a n u f a c tu r e d b y t h e P r e c i s i o n S c i e n t i f i c Company.
The h e a t i n g e le m e n ts f o r t h e r e a c t o r c o n s i s t e d o f t h r e e 3 3 - f o o t l e n g t h s
o f b e a d e d N ichrom e c o i l s s u p p l i e d w i t h c u r r e n t fro m t h r e e 1 1 0 - v o l t P o w e r s ta t
a u to tra n s fo rm e rs *
The c o i l s w e re wound u p o n t h e r e a c t o r o v e r a l a y e r o f
a s b e s t o s t a p e a n d i n s u l a t e d w ith a n a d d i t i o n a l c o v e r i n g o f a s b e s t o s t a p e
a n d a o n e - i n c h l a y e r o f m a g n e s ia mud*
The o i l f e e d s y s te m c o n s i s t e d o f a tw o c y l i n d e r a d j u s t a b l e s t r o k e
p i s t o n pump a n d a n o i l r e s e r v o i r *
The d e s i g n o f t h e r e a c t o r m ade i t n e c e s s a r y t h a t c a t a l y s t a n d p r e h e a t
m e d ia b e c h a r g e d t o t h e r e a c t o r t h r o u g h t h e b o tto m w h i l e t h e r e a c t o r was
i n an in v e r te d p o s itio n *
P r e h e a t m e d ia c o n s i s t e d o f e i t h e r 1 / 4 i n c h d i a ­
m e te r s t e e l o r Alundum (alu m in u m o x i d e ) b a l l s .
The i r o n - c e n s t a n t a n th e r m o c o u p le s f o r t e m p e r a t u r e m e a su re m e n ts, w e re
u s e d i n c o n j u n c t i o n w i t h a L e e d s a n d N o r th r u p i n d i c a t i n g p o t e n t i o m e t e r ,
MATERIALS
The p r i n c i p a l m a t e r i a l s u s e d f o r t h e d e s u l f u r i z a t i o n s t u d i e s w e re a
# 3 ' f u e l o i l , c o m p re s se d h y d r o g e n , a n d v a r i o u s c a t a l y s t s .
The #3 g r a d e f u e l o i l s p ro d u c e d b y t h e H usky O i l Com pary .from O regon
B a s i n , Wyoming c r u d e o i l c o n t a i n e d 2 ,0 9 t o 2,3.9 p e r c e n t s u l f u r .
A d d itio n a l
i n s p e c t i o n d a t a o f t h e o i l s a r e l i s t e d i n T a b le I ,
The c a t a l y s t s i n v e s t i g a t e d w e re c o b a l t m o ly b d a te , m o ly b d e n a -a lu m in a ,
t u n g s t i c o x i d e , n i c k e l o x i d e a n d m olybdenum d i s u l f i d e .
The c o d e l e t t e r s
a n d c o m p o s itio n o f t h e v a r i o u s c a t a l y s t s may b e fo u n d i n T a b le I I ,
The h y d r d g e n u s e d i n t h i s r e s e a r c h w as o b t a i n e d fro m t h e W hitm ore
O xygen Company o f S a l t L ak e C i t y , U ta h ,
METHODS
The o i l c h a r g e pump w as d e s ig n e d w i t h a n a d j u s t a b l e p i s t o n s t r o k e
l e n g t h t o g i v e a n y d e s i r e d o i l pum ping r a t e a s a m eans o f c o n t r o l l i n g t h e
space v e lo c ity .
The p r e s s u r e o f t h e r e a c t o r w as m a i n t a i n e d a t t h e d e s i r e d v a l u e b y
a d ju s t m e n t o f t h e b a c k p r e s s u r e v a l v e a n d s u p p ly p r e s s u r e fro m t h e h y d r o g e n
ta n k r e g u la to r .
W ith t h e h y d ro g e n s u p p l i e d a t a s l i g h t l y h i g h e r p r e s s u r e
=11=
t h a n t h e c o n t r o l s e t t i n g o f t h e b a c k p r e s s u r e v a lv e , g a s f lo w w as m ain­
t a i n e d t h r o u g h t h e r e a c t o r an d t h e e x i t g a s m e t e r i n g s y ste m *
life
D u rin g t h e
s t u d y r u n t h e w e t t e s t m e t e r w h ich m e a s u re d t h e am ount o f e x i t g a s w as
r e a d e v e r y 15 m in u te s a n d t h e v a l u e w as r e c o r d e d *
C lo s e c o n t r o l o f t h e g a s
r a t e w as m a i n ta i n e d d u r i n g t h e o p e r a t i o n b y t h i s m eans*
The t e m p e r a t u r e o f t h e r e a c t o r w as m a i n ta i n e d b y b e a d e d N ichrom e r e ­
s i s t a n c e e le m e n ts s u p p l i e d w i t h t h e p r o p e r q u a n t i t y o f c u r r e n t fro m a u to ­
tra n s fo rm e rs *
An a v e r a g e t e m p e r a t u r e w as d e te r m in e d b y means, o f tw o th e rm o ­
c o u p le s p l a c e d i n t h e th e r m o w e ll a t t h e c a t a l y s t s e c t i o n *
T h e se a v e r a g e
t e m p e r a t u r e s d e te r m in e d a t 15 m i n u t e ■i n t e r v a l s w e re in . t u r n a v e r a g e d f o r
e a c h e i g h t h o u r s a m p le p e r i o d .
The p r e s s u r e r e a c t o r w as p l a c e d i n o p e r a t i o n by a p p ly i n g c u r r e n t t o
t h e r e s i s t a n c e c o i l s w h i l e h y d r o g e n g a s w as a llo w e d t o f lo w t h r o u g h t h e
re a c to r.
Nhen t h e t e m p e r a t u r e o f t h e c a t a l y s t cham ber r e a c h e d 3 OO0 C t h e
r e a c t o r w as p r e s s u r i z e d t o t h e d e s i r e d o p e r a t i n g p r e s s u r e - a n d t h e g a s
t h r o u g h p u t w as a d j u s t e d a n d m a in ta in e d *
Nheh t h e c a t a l y s t t e m p e r a t u r e
r e a c h e d 3 SO0 C t h e o i l pump w as t u r n e d on t o c h a r g e o i l t o th e . r e a c t o r a n d
t h e h e a t i n g e le m e n t c u r r e n t w as a d j u s t e d t o m a i n t a i n t h e p r o p e r r e a c t o r
te m p e ra tu re .
A l l r e c o r d e d r e a d i n g s w e re b e g u n a t t h e tim e t h e r e a c t o r
c o n d i t i o n s becam e c o n s t a n t »
The o p e r a t i o n o f t h e l a r g e volum e r e a c t o r w as e s s e n t i a l l y t h e same a s
th e c a ta ly s t l i f e
s tu d y r e a c to r *
The t o t a l o p e r a t i n g p e r i o d s f o r t h e l a r g e
vo lu m e r e a c t o r se ld o m e x c e e d e d a t o t a l o f s i x h o u r s w i t h e f f l u e n t o i l s a m p le
p e r i o d s a t e i t h e r 1 5 , 3 0 , o r 60 m in u te i n t e r v a l s *
J fe p ip e ra tu re m e a s u re m e n ts
w e re t a k e n a t 5- m i n u te i n t e r v a l s w i t h t h e a r i t h m e t i c a v e r a g e com puted f o r
t h e r e c o r d e d s a m p le p e r io d s .
The e x i t g a s m e t e r i n g s y s te m f o r t h e l a r g e
volum e r e a c t o r c o n s i s t e d o f tw o w e t t e s t m e t e r s a r r a n g e d i n p a r a l l e l t o
m e te r a c c u r a t e l y l a r g e v o lu m e s o f e x i t g a s .
The c o l l e c t e d e f f l u e n t o i l s a m p le s w ere, w e ig h e d a n d 1 0 t o 15 gram
p o r t i o n s o f o i l w e re rem o v ed fro m ' e a c h s a m p le f o r s u l f u r c o n t e n t d e te r m in a ­
tio n ,
D is s o lv e d H2S g a s w as rem o v ed fro m t h e 1 0 -1 5 gram p o r t i o n s o f o i l b y
w a s h in g w i t h a 10 p e r c e n t so d iu m h y d r o x id e s o l u t i o n f o llo w e d b y a w a t e r
w ash.
The s u l f u r c o n t e n t w as d e te r m in e d b y a m o d if ie d lam p s u l f u r m ethod
( l ) u s i n g a p p r o x i m a t e ly 2 , 0 ' e q u i v a l e n t s o f so d iu m c a r b o n a te t o a b s o rb t h e
s u l f u r d i o x i d e fro m t h e lam p c o m b u s tio n g a s e s .
One t e n t h n o rm a l HCl w as
u s e d t o n e u t r a l i z e t h e r e m a in in g so d iu m c a r b o n a te s o l u t i o n b y t i t r a t i o n w i t h
a b ro m -p h en o l i n d i c a t o r .
I
-13-
SAMPLE CALCULATIONS
I e
A t y p i c a l S h o r t D u r a ti o n Run
Run 95
V -2 KGBM
O c to b e r 6 , 1951
O i l = #3 F u e l O i l ( 2 .0 9 $ S )
B a ro m e te r 6 4 0 .1 mm Hg
R e a c to r P r e s s u r e , 300 p s i g .
C a t a l y s t = 8 8 9 .5 Gm. H arshaw M0 S 2 K0 -X -L 3 2 1 -4 2 T - l / 8 "
Time
M in u te s
0-60
60-120
S am ple
N o.
S am ple
W eig h t
(g ra m s )
I
6 2 1 .5
2
761.0
P ercen t
s u lfu r
in
E fflu e n t
o il
.4 4 2
1 2 0 -1 8 0
3
7 4 2 .5
.360
.386
180-240
4
827.0
.4 9 3
A v e ra g e
T e m p e ra tu re
°C
L ite r s E x it
G as a t 2 2 ° C
408
406
410
404
721
1390
2135
2780
2 9 5 2 .0
O i l c h a r g e d 3 2 6 1 .0 gram s
C a lc u la tio n o f Space V e lo c ity
“ 0 ”917 Gram 011 Z0ram C a t a l y s t / H o u r
C a l c u l a t i o n o f E x i t G as L i t e r s STP p e r M in u te
Gas m e te r e d i n Wet T e s t M e te r 5 t h e r e f o r e , a ssu m e g a s s a t u r a t e d w ith
w a te r v a p o r.
V apor p r e s s u r e H^O a t 2 2 ° C = 1 9 .8 mm Hg
6 4 0 .1 - 1 9 .8 = 6 2 0 .3 mm Hg d r y g a s
C o r r e c t e d t o STP o f 760 mm Hg an d O0 C
6 2 0 .3
273
760.0 x (273 + 2 2 ) x
721 l i t e r s / h r
60 m i n u t e / h r
9 .0 7 l i t e r s S T P /m in u te
C a l c u l a t i o n o f L i t e r s E x i t Gas STP p e r Gram o f C harge O i l
T o t a l e x i t g a s f lo w 2780 l i t e r s
T o t a l e x i t g a s f lo w STP 2085 l i t e r s
C h a rg e o i l w e ig h t 3 2 6 1 gram s
| Q j5, l i t e r s JjffT B 0 .6 4 0 L i t e r s E x i t G as STP/G ram O i l
3261 g ram s o i l
—14—
C a l c u l a t i on o f C o m p o site S u l f u r C o n te n t
S am ple
W eig h t
P e rce n t
S u lfu r
Grams
S u lfu r
6 2 1 .5
0 .4 4 2
7 6 1 .0
7 4 2 .5
0 .360
0.386
8 2 7 .0
0 .4 9 3
2 .7 5
2 .7 4
2 .8 7
4 .0 8
1 2 .4 4
2 9 5 2 .0
1 2 ,4 4 x 100
2952
T o ta l
0 ,4 2 2 P e r c e n t S u l f u r
C a l c u l a t i o n o f O i l C h arg e W e ig h t L o s s e s
3 2 6 1 .0 W e ig h t C h a rg e o i l
2 9 5 2 .0 W e ig h t e f f l u e n t o i l
3 0 9 ,0 Gram C h arg e l o s s
3
2,
2
6
= 9 ,4 7 P e r c e n t L o s s
1
We i g h t B a s i s
A T y p i c a l Two Day E n t r y D u rin g MoS2 C a t a l y s t L i f e S tu d y Run
V -2
KGBM
LSR
O i l = #3 F u e l O i l (2.14% S )
C a t a l y s t = 100 gm, H arsh aw MoS^
R e a c to r P r e s s u r e , $00 p s i g ,
Hour
232
240
248
256
264
272
S am ple
No.
29
30
31
32
33
34
S am ple
W e ig h t
Grams
5 4 9 .5
5 5 5 .5
5 5 1 .0
5 4 9 .5
5 5 7 .5
5 4 5 .5
3 3 0 8 .5
Novem ber 2 6 , 2 7 , 1951
M0 -X -L 3 2 1 -4 2
P e rce n t
S u lfu r
in
E fflu e n t
O il
.420
.3 9 8
.4 6 7
.4 5 3
.4 3 5
.426
A v erag e
T e m p e ra tu re
OC
411
410
411
412
411
411
L ite rs
E x i t Gas
1012
1040
860
929
869
952
“15“
' C a l c u l a t i o n o f C h arg e W e ig h t P e r c e n t L o ss
C h a rg e o i l w e ig h t
E f f l u e n t o i l w e ig h t
2606 x 100
37397
= 6 .9 7
■ 3 7 3 9 7 gram s
3 4 7 9 0 g ram s
2606 g ram s l o s s
P e r c e n t .W e i g h t L o s s e s b e tw e e n Novem ber 1 6 a n d
D ecem ber 8 S 1951
C a lc u la tio n o f Space V e lo c ity
S am ple w e ig h t i n c l u d e s a p p r o x i m a t e ly 93 p e r c e n t o f t h e c h a r g e o i l w e ig h t
d u e t o 6 .9 7 p e r c e n t l o s s e s .
.
E= 591 Grams C h a rg e W eig h t
- °* 739 Gram 0 3 i/a r8 ffi
C a l c u l a t i o n o f L i t e r s E x i t Gas STP p e r Gram o f C harge O i l
The f a c t o r t o c o r r e c t t h e o b s e r v e d w e t t e s t m e te r r e a d i n g t o STP o f
760 mm Hg a n d 0 °C ,a v e r a g e s 0 .7 5 a t t h e a v e r a g e b a r o m e t r i c p r e s s u r e
and m e te rin g te m p e ra tu re .
(1 0 1 2 l i t e r s g a s ) ( j,7 5 l
59I gram c h a r g e o i l
= • 1 .2 8 L i t e r s Gas STP/Gram O i l
C a l c u l a t i o n o f Grams o f S u l f u r Removed fro m O i l p e r gram o f C a t a l y s t p e r
E i g h t H our S am ple
C h a rg e o i l w e ig h t = 591 gram s a t 2.14% .S u l f u r
E fflu e n t o i l
- 549»5 g ram s a t 0.42% S u l f u r
$ 9 1 .0 x 0 .0 2 1 4 = 1 2 .6
5 4 9 .5 x 0.0042 = _ 2 .3
1 0 .3 g ram s s u l f u r rem oved
1 0 .3 g ram s s u l f u r rem o v ed • _
1 0 0 g ram s c a t a l y s t
q .103
Grams S u l f u r Rem oved/G ram .
C a t a ly s t/ S a m p le
-16-
THERMODYNAMIC CALCULATIONS
I n p o s t u l a t e d d e s u l f u r i z a t i o n r e a c t i o n s t h e s u l f u r com pounds r e l e a s e
t h e s u l f u r a to m s fro m t h e o i l b y c a r b o n - t o - s u l f u r bond f r a c t u r e a t t h e
p ro p e r te m p e ra tu re i n th e p re s e n c e o f th e c a t a l y t i c a g e n t.
The r e s u l t a n t
f r e e s u l f u r ato m s a r e rem o v ed fro m t h e d i s t i l l a t e by c o m b in in g w i t h t h e
m u l t i - v a l e n t c a t a l y t i c a g e n t t o fo rm a h i g h e r m e t a l s u l f i d e .
Upon t h e c o n ­
v e r s io n o f th e c a t a l y t i c a g e n t t o a h ig h e r m e ta l s u l f i d e f u r t h e r d e s u l f u r i ­
z a t i o n w o u ld c e a s e a n d r e g e n e r a t i o n w o u ld b e n e c e s s a r y .
T h e re fo re , d e s u l­
f u r i z a t i o n r e a c t i o n s w e re c a r r i e d o u t i n t h e p r e s e n c e o f a n e x c e s s o f h y d ro ­
g e n t o h y d r o g e n a te t h e u n s a t u r a t e d s u l f u r f r e e h y d r o c a r b o n m o le c u le s a n d t o
r e a c t w ith t h e r e l a t i v e l y u n s t a b l e h i g h m e t a l s u l f i d e c o n t a c t a g e n t t o r e ­
fo rm t h e lo w s u l f i d e a n d h y d ro g e n s u l f i d e .
The s u l f u r t h u s rem oved fro m t h e
p e tr o le u m a p p e a r s a s h y d ro g e n s u l f i d e a n d c a n b e e a s i l y rem o v ed fro m t h e
e f f l u e n t g a se s and o i l .
The th e rm o d y n a m ic s o f t h e r e a c t i o n s o f d e s u l f u r i z a t i o n , h y d r o g e n a tio n
a n d d e c o m p o s itio n o f m e t a l s u l f i d e c a t a l y s t w e re s t u d i e d t o s u p p o r t t h e
p o s t u l a t e d m ech an ism in v o lv e d i n t h e r e a c t i o n o f s u l f u r co m p o u n d s, h y d r o g e n ,
a n d m olybdenum s u l f i d e c a t a l y s t .
T herm odynam ic c a l c u l a t i o n s w e re p e rfo rm e d
on f o u r s p e c i f i c r e a c t i o n s w h ic h a r e a s f o l l o w s :
1.
+ 4 H g (g )
C4Hi o ( g ) +
2.
2M0 S3
2MoS 2 + S 2 ( g )
3.
MoS2 + G^H^S( g) + 3 %
4.
MoS^ + H2 ( g ) - ^ - M o S 2 + H2S ( g )
—
M0 S 3 +
g)
The f i r s t r e a c t i o n i s c o n c e r n e d w i t h t h e o v e r a l l c o n v e r s i o n o f t h i o ­
p h e n e a n d h y d ro g e n t o a s a t u r a t e d h y d r o c a r b o n a n d h y d ro g e n s u l f i d e .
The
-17-
d e c o m p o s itio n o f m olybdenum t r i s u l f i d e i n t h e s e c o n d r e a c t i o n i s o f i n t e r e s t
b e c a u s e a g r e a t d e a l o f e l e m e n t a l s u l f u r w as e v o lv e d u p o n h e a t i n g 96 p e r c e n t
m olybdenum t r i s u l f i d e .
A p o s t u l a t e d d e c o m p o s itio n m echanism w as s t u d i e d t o d e te r m in e t h e e f f e c t
o f p r e s s u r e a n d t e m p e r a t u r e i n c u r b i n g t h e u n d e s i r a b l e e v o l u t i o n o f e le m e n t a l
s u l f u r fro m a f r e s h c a t a l y s t .
The t h i r d a n d f o u r t h r e a c t i o n s d e a l d i r e c t l y
w i t h t h e p o s t u l a t e d r o l e w h ic h m olybdenum s u l f i d e c a t a l y s t p l a y s i n t r a n s ­
f e r r i n g t h e s u l f u r fro m t h e o i l t o h y d ro g e n s u l f i d e .
T h io p h e n e was u s e d a s t h e s u l f u r b e a r i n g compound i n t h e s e r e a c t i o n s
b e c a u s e a l a r g e p a r t o f t h e s u l f u r c o n ta i n e d i n t h e #3 f u e l o i l w as p r o b a b ly
i n t h e fo rm o f t h i o p h e n i c ty p e s u l f u r com pounds.
The b o i l i n g p o i n t o f p u r e
t h i o p h e n e (8 4 °C ) i s f a r lo w e r t h a n t h e b o i l i n g r a n g e o f f u e l o i l .
Thermo­
d y n am ic d a t a w as n o t a v a i l a b l e f o r h i g h m o le c u la r t h i o p h e n i c com pounds t h e r e ­
f o r e t h io p h e n e w as u s e d t o o b t a i n some d a t a t o i n d i c a t e t h e e a s e o f e f f e c t ­
i n g s i m i l a r r e a c t i o n s w i t h t h e h i g h e r b o i l i n g com pounds.
D a ta a n d E q u a tio n s f o r T herm odynam ic C a l c u l a t i o n s
I.
C^H^S(g) + AHgig)
+
AH a t 29 SOK = - 6 2 ,4 0 0 c a l / m o l
A F a t 298 °K = - 4 1 ,3 0 0 c a l / m o l
TNeEe = 8 8 2 ° K = 609*0
A Frp = -5 8 9 1 4 - 9 . 2 T I n T + 1 2 .3 x l O ^ T ^
AF
K
ea =
V
ln
1-
_
y=
~ BT
9FT°
1 2 8 Pc T
if C4 H1 0
I f c 4H4 S ^
y
(1 6
2
1I s
U
T2
h2 s
4 H2
)
- 6 .5 x 10” 6t 3 + 3 .5 7
-18-
X2 (5 - 3X)3
eq
K P AN
2.
2Mo8^
2 M0
S2
(I -X )(4-AX)4
SgXg)
^ H a t 298°K = 4 1 ,4 4 0 c a l / m o l
A F a t 298°K = 2 5 ,6 9 0 c a l / m o l
Tn e = 7 S4°K = 5 1 1 ° C
A F m = 45580 + 1 3 .2 4 T I n T + 2 .1 3 x 10“ 3 t 2 - 143T
Keq
_ Keq
% =
K pON
Ky p
AF
K
=
eq
K
3.
2
0 MoS2
S2
IC m0S3
“
=
MoS2 + C4 H4 SCg) + 3H2 ( g )
(2 * X )(2 -2 X )2
MoS3 + C4 H1 0 Cg)
A H a t 298 °K = - 2 1 ,3 3 0 c a l / m o l
A F a t 298°K = - 3 6 ,6 4 0 c a l / m o l
Tn e = 715°K = 442 ° C
A F
t
^
= 2 .4 3 T I o g 10 T + -0125T 2 - 0 .6 6 1 x 10 “ 5t3 _ 6 1 ,7 3 0 + 75T
^ X 2 (5 _ 3 X )5
Keq P3
( l - x ) 2 (3 -3 X )3
^
4.
^
MoS^ + Hg ( g )
M0 S 2 + H gStg )
H a t 298°K = 440 c a l / m o l
A F a t 2980K = -4,660 c a l / m o l
Tne = 25.6°K = -247.4°C
A
A
ft
= 2800 + 18.75 T I o g 10 T - O.OOO76T2 - 0*801 x 10”7t3 _ TlT
X2
y
_
kn
' Ti^xT2 =
Keq
Ky
= 19“
The c a l c u l a t e d , r e s u l t s o f t h e a b o v e e q u a t i o n s a r e l i s t e d i n T a b le I I I 0
The e f f e c t o f i n c r e a s i n g t h e r e a c t i o n t e m p e r a t u r e fro m 250 t o IOOO0 C c a u s e s
a
r a p i d r e d u c t i o n i n p e r c e n t c o n v e r s i o n a t a l l p r e s s u r e s b e tw e e n o n e an d
100 a tm o s p h e r e s f o r t h e r e a c t i o n w h ic h y i e l d s b u t a n e and h y d r o g e n s u l f i d e
fro m t h io p h e n e a n d h y d r o g e n .
The i n c r e a s e o f p r e s s u r e , fro m o n e t o 100
a tm o s p h e re s w o u ld c a u s e a n i n c r e a s e i n p e r c e n t c o n v e r s i o n fro m 94=7 t o 99
p e r c e n t a t 375°Co
T h e r e f o r e , h ig h e r v a lu e s o f p e r c e n t c o n v e rs io n w ith h ig h
r e a c t i o n r a t e s w o u ld b e a c h i e v e d a t 10 t o 50 a tm o s p h e re s o f p r e s s u r e an d
t e m p e r a t u r e s o f 375 t o 500° C0
The d e c o m p o s itio n o f MoS^ t o MoS2 w as n e a r l y c o m p le te i t IOOO0 C a n d o n e
a tm o s p h e re p r e s s u r e ,
A t p r e s s u r e s a b o v e 50 a tm o s p h e re s a n d t e m p e r a t u r e s b e ­
lo w 375°C l e s s t h a n 5 p e r c e n t c o n v e r s i o n w as p o s s i b l e .
I n t h e r e a c t i o n o f MoS^5 t h io p h e n e a n d h y d ro g e n t o y i e l d MoS^ an d
b u t a n e , t h e p e r c e n t c o n v e r s i o n w as s l i g h t l y i n c r e a s e d b y a n i n c r e a s e o f
p r e s s u r e w h i l e a r a p i d d e c l i n e i n p e r c e n t c o n v e r s i o n was c a l c u l a t e d a t i n ­
c r e a s i n g t e m p e r a t u r e s b e tw e e n 3 7 5 ° an d 5 0 0 °C ,
T e m p e ra tu re s b e lo w t h e n e u t r a l
e q u i l i b r i u m t e m p e r a t u r e o f 442°G w o u ld g i v e i n c r e a s i n g p e r c e n t c o n v e r s i o n .
The e f f e c t o f p r e s s u r e u p o n t h e c o n v e r s i o n o f MoS^ a n d h y d ro g e n t o MoS2
a n d HgS w o u ld b e v e r y s l i g h t w h i l e i n c r e a s e o f t e m p e r a t u r e s b e tw e e n 25 a n d
IOOO0 C. w o u ld c a u s e o n l y a d e c r e a s e o f 9 8 ,1 t o 9 4 ,4 p e r c e n t c o n v e r s i o n a t o n e
a tm o s p h e re t o i n d i c a t e t h a t t h e r e a c t i o n w o u ld b e h i g h l y f a v o r a b l e a t a n y
chosen o p e ra tin g c o n d itio n .
DISGUSSIOU OF RESULTS
The E f f e c t o f O p e r a ti n g C o n d i t io n s Upon D e s u l f a r i z a t i Q n w i t h V a r io u s D e s t r u c t ­
i v e H y d r o g e n a tio n C a t a l y s t s a t S u p e r-A tm o s p h e r i c P r e s s u r e s <>
The c a t a l y s t s em p lo y ed i n t h e i n v e s t i g a t i o n w e re c o b a l t m o ly b d a te , m o ly b d e h a a lu m in a , t u n g s t i c o x i d e , n i c k e l o x id e a n d m olybdenum s u l f i d e »
The o p e r ­
a t i n g c o n d i t i o n s o f t h e v a r i o u s t h r e e - t o - s i x - h o u r t e s t s w e re r e a c t o r p r e s s u r e s
o f 300 an d 500 p s i g , t e m p e r a t u r e s o f 3 7 5 t o 430 ° C , s p a c e v e l o c i t i e s o f 0*75
t o 1*3 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 and h y d r o g e n r a t e s o f 2 t o
12 s ta n d a rd l i t e r s
p e r m in u te *
A #3 g r a d e f u e l o i l c o n t a i n i n g 2*10 p e r c e n t
s u l f u r c o n s t i t u t e d t h e c h a r g e o i l t o t h e r e a c t o r s y s te m i l l u s t r a t e d i n t h e
s c h e m a tic d ia g r a m i n F i g u r e 1«
F i g u r e 3 show s t h e e f f e c t o f s p a c e v e l o c i t y u p o n d e s u l f u r i z a t i o n *
D a ta
f o r t h e s e c u r v e s a r e fo u n d i n T a b le I ? fro m a num ber o f r u n s m ade w i t h tw o
t y p e s o f m o ly b d e n a a lu m in a a n d m olybdenum s u l f i d e c a t a l y s t s „
The g e n e r a l •
e f f e c t o f i n c r e a s i n g t h e s p a c e v e l o c i t y o r r e d u c i n g t h e c o n t a c t tim e w as t o
re d u c e th e d e s u lf u riz a tio n *
The d a t a fro m t e s t i n g t h e m olybdenum s u l f i d e
c a t a l y s t ( T a b le IV ) w e re o b t a i n e d w i t h t h e s m a l l volum e r e a c t o r s y s te m a s
i l l u s t r a t e d i n F ig u re 2 .
One g e n e r a l i z a t i o n t h a t c a n b e d raw n fro m t h e p l o t
o f d e s u lf u r iz a tio n v e rs u s sp a ce v e lo c i ty i s th e s i m i l a r i t y o f r a t e o f change
o f d e s u l f u r i z a t i o n w i t h s p a c e v e l o c i t y f o r m o ly b d e n u m -c o n ta in in g c a t a l y s t s .
The r e l a t i o n s h i p o f t e m p e r a t u r e t o d e s u l f u r i z a t i o n i s i n d i c a t e d i n F i g ­
u r e .4 fro m d a t a t a b u l a t e d i n T a b le V c o n c e r n in g t e s t s m ade a t r e a c t o r p r e s ­
s u r e s o f 3 0 0 a n d 500 p s i g ,
5 ,6 p e r c e n t SiO g
The m o ly b d e n a a lu m in a c a t a l y s t M o-0201 c o n ta i n e d
w h i l e t h e m o ly b d e n a a lu m in a M o-0602 c o n t a i n e d no s i l i c a .
N e a r ly l i n e a r r e l a t i o n s h i p s o f d e s u l f u r i z a t i o n a n d t e m p e r a t u r e w e re d i s p l a y e d
=Sli=
b y e a c h o f t h e m o ly b d e n a a lu m in a c a t a l y s t s a t a n o p e r a t i n g p r e s s u r e o f 300
p s ig „
The s p a c e v e l o c i t y o f t h e s e l e c t e d d a t a o f T a b le V v a r i e s b e tw e e n
0 . 8$0 a n d 0.943 g ram s o i l p e r gram c a t a l y s t p e r h o u r w i t h t h e e x c e p t i o n o f ,
t h e v a l u e o f I „26 g ram s o i l p e r gram c a t a l y s t p e r h o u r f o r t h e m o ly b d en a
a lu m in a Mo~0201 c a t a l y s t .
T h u s , t h e r e l a t i v e l y h ig h s p a c e v e l o c i t y o f t h e
m o ly b d e n a -a lu m in a M o-0201 c a t a l y s t g a v e t h e f a l s e im p r e s s i o n o f a lo w e r c a t ­
a l y s t a c t i v i t y t h a n t h e m o ly b d e n a a lu m in a Mo~0602 c a t a l y s t s .
M olybdenum
s u l f i d e a t o p e r a t i n g p r e s s u r e s o f 300 a n d 500 p s i g d i s p l a y e d n e a r l y s i m i l a r
r e l a t i o n s h i p s b e tw e e n d e s u l f u r i z a t i o n c a p a c i t y a n d t e m p e r a t u r e w i t h a s l i g h t l y
h ig h e r a c t i v i t y a t th e h ig h e r o p e ra tin g p r e s s u r e .
C o b a lt m o ly b d a te c a t a l y s t
a t 500 p s i g w o u ld g i v e s l i g h t l y h i g h e r a c t i v i t y t h a n m olybdenum s u l f i d e a t
500 p s i g y e t t h e r e w as n o t s u f f i c i e n t o p e r a t i n g d a t a on c o b a l t m o ly b d a te a t
v a r i o u s t e m p e r a t u r e s t o m ake a n y b r o a d s t a t e m e n t s .
F ig u re 4 a ls o in d ic a te s
t h a t t h e m olybdenum s u l f i d e w as m ore a c t i v e t h a n t h e m o ly b d e n a a lu m in a M o-0201
M o-0602, a n d t u n g s t i c o x i d e c a t a l y s t s .
TJae c u rv e o f d e s u l f u r i z a t i o n v e r s u s
t e m p e r a t u r e f o r m olybdenum s u l f i d e a t 500 p s i g g a v e a d d i t i o n a l i n f o r m a t i o n
t h a t t h e r e l a t i o n o f d e s u l f u r i z a t i o n v e r s u s t e m p e r a t u r e was n o t l i n e a r a n d
t h a t i n c r e a s i n g t e m p e r a t u r e a b o v e 410 ° C h a s l i t t l e
e f f e c t .on d e s u l f u r i z a t i o n ®
.K o s k i ( 7 ) fo u n d t h e sam e r e l a t i o n s h i p f o r m o ly b d e n a a lu m in a c a t a l y s t a t 3 GO
p s ig .
T h u s , t h e s e d a t a p o i n t t o a b o u t 400 t o 41G°C a s t h e optim um te m p e ra ­
t u r e t o i n v e s t i g a t e t h a t c a t a l y s t t o o b t a i n maximum d e s u l f u r i z a t i o n w i t h o u t
t h e d a n g e r o f e x c e s s i v e c r a c k i n g a n d c o k e f o r m a ti o n t o c a u s e t h e d e c r e a s e o f
th e c a ta ly s t a c ti v it y .
The e f f e c t o f r e a c t o r p r e s s u r e u p o n d e s u l f u r i z a t i o n i s p r e s e n t e d i n
F i g u r e 5 a n d T a b le V I .
H ig h e r p r e s s u r e s i n c r e a s e d d e s u l f u r i z a t i o n w h ic h
-
22-
w as s u b s t a n t i a t e d b y t h e th e rm o d y n a m ic c a l c u l a t i o n s on t h e p o s t u l a t e d d e ­
s u l f u r i z a t i o n m e c h a n is m s »
The g r e a t e s t e f f e c t o f .p r e s s u r e c h a n g e on d e ­
s u l f u r i z a t i o n was d i s p l a y e d b y t h e m o ly b d e n a a lu m in a Mo-0602, c a t a l y s t and.
t h e l e a s t e f f e c t b y m o ly b d e n a a lu m in a M o-0201 w h ic h c o n t a i n s $«6 p e r c e n t
s ilic a .
T h re e s h o r t d u r a t i o n r u n s d i d n o t f u r n i s h s u f f i c i e n t d a t a t o s u b ­
s t a n t i a t e th e s l i g h t l y n e g a tiv e e f f e c t o f p re s s u re upon d e s u lf u r iz a tio n
w i t h m o ly b d e n a -a lu m in a M o-0201 c a t a l y s t .
The e f f e c t o f a p r e s s u r e i n c r e a s e
u p o n d e s u l f u r i z a t i o n was s i m i l a r w i t h m olybdenum s u l f i d e a n d t u n g s t i c o x id e
c a ta ly s ts .
G re e n ( 4 ) r e p o r t e d m ore d e t a i l e d s t u d y o f t h e e f f e c t o f p r e s ­
s u r e s fro m a tm o s p h e r ic t o 500 p s i g w i t h m olybdenum s u l f i d e c a t a l y s t t o f u r ­
n i s h m ore c o n c l u s i v e d a t a ' fro m c o n tin u o u s r e a c t o r o p e r a t i o n .
F i g u r e 6 show s t h e e f f e c t o f o n - s t r e a m tim e and d e s u l f u r i z a t i o n .
D a ta f o r t h e s e c u r v e s a r e f o u n d i n T a b le V I I f o r t h e tw o t y p e s o f m o ly b d e n a
a lu m in a , n i c k e l o x i d e , a n d m olybdenum s u l f i d e .
N ic k e l, o x i d e d i s p l a y e d a v e r y
r a p i d p a t t e r n o f d e a c t i v a t i o n d u r in g t w o - f i v e h o u r r u n s .
The f i r s t r u n
in v o lv e d o p e r a t i o n w i t h a f r e s h c a t a l y s t c h a r g e o f 10 p e r c e n t n i c k e l , o x id e
o n a lu m in a f o r f i v e h o u r s f o ll o w e d b y an, a i r o x i d a t i o n r e g e n e r a t i o n o f t h e
c a ta ly s t„
The s e c o n d r u n w as p e rf o r m e d a t n e a r l y t h e sam e c o n d i t i o n s t o
y i e l d n e a r ly i d e n t i c a l c u rv e s f o r b o th r u n s .
The d a t a i n d i c a t e d t h a t
n i c k e l i n t h e p r e s e n c e o f s u l f u r b e a r i n g o i l fo rm s a s t a b l e s u l f i d e w h ic h i s
r e l a t i v e l y i n a c t i v e i n re m o v in g f u r t h e r s u l f u r fro m t h e o i l .
Upon a i r r e g e n ­
e r a t i o n a n a c t i v e n i c k e l o x id e o r s u l f a t e w as fo rm e d w h ic h w as c a p a b le o f
a c c o m p lis h in g n e a r l y t h e same d e g r e e o f d e s u l f u r i z a t i o n o v e r a f i v e h o u r
p e r i o d a s a' f r e s h n i c k e l o x i d e c a t a l y s t .
The e x h a u s t a i r r e g e n e r a t i o n g a s
c o n t a i n e d s u l f u r d i o x i d e t o g i v e f u r t h e r i n d i c a t i o n t h a t a n i c k e l o x id e
=23™
w as fo rm ed ' u p o n r e g e n e r a t i o n e
The a d d i t i o n a l c u r v e s o f d e s u l f u r i z a t i o n v e r s u s o n - s t r e a m tim e f o r
m olybdenum s u l f i d e a n d m o ly b d e n a a lu m in a fo u n d i n F i g u r e 6 w e re draw n t o
l e n d some s u p p o r t t o t h e h y p o th esis t h a t a m olybdenum s u l f i d e w as t h e
a c tiv e d e s u lf u riz in g a g e n t»
The c u r v e s o f t h e tw o t y p e s o f f r e s h m oly­
b d e n a a lu m in a c a t a l y s t i n d i c a t e i n c r e a s e d a c t i v i t y d u r i n g t h e r e s p e c t i v e
f i r s t ru n s o f th e c a ta ly s t s „
A d d i t i o n a l u s e o f t h e m e t a l o x id e c a t a l y s t
c a u s e d t h e im p ro v e m e n t o f t h e c a t a l y s t a c t i v i t y w h e re a s t h e a c t i v i t y o f
m olybdenum s u l f i d e w as i n i t i a l l y h i g h .
I n t h e a i r r e g e n e r a t i o n o f m o ly b d e n a
a lu m in a c a t a l y s t s t h e b u r n o f f g a s e s c o n t a i n e d s u l f u r d i o x i d e t h u s i n d i c a t ­
i n g t h e o c c u r r e n c e o f a n a c t i v e s u l f i d e c a t a l y s t fo rm e d fro m a n o x id e c a t ­
a l y s t o f s l i g h t l y lo w e r a c t i v i t y .
The d a t a o b t a i n e d fro m t h e s h o r t f o u r t o f i v e h o u r r u n s i n d i c a t e d t h a t
d e s u l f u r i z a t i o n t o a p r o d u c t c o n t a i n i n g l e s s t h a n 0 ,5 p e r c e n t s u l f u r w as
p o s s i b l e b y d e s t r u c t i v e h y d r o g e n a t io n a t p r e s s u r e s o f 300 a n d a b o v e 9 tem p ­
e r a t u r e s a b o v e 390 °C S s p a c e v e l o c i t i e s l e s s t h a n o n e gram o i l p e r gram
c a t a l y s t p e r h o u r a n d h y d ro g e n t o o i l r a t i o s o f a b o u t o n e l i t e r h y d ro g e n
p e r gram c h a r g e o i l .
The m o st p r o m is in g c a t a l y s t s w e re c o b a l t m o ly b d a te 5
m o ly b d e n a a lu m in a an d m olybdenum s u l f i d e w h i l e t u n g s t i c o x i d e a n d n i c k e l
o x i d e w e r e som ew hat i n f e r i o r .
The E f f e c t o f O p e r a ti n g C o n d itio n s Upon t h e L i f e o f M olybdenum S u l f i d e
C a ta ly s t,
From t h e r e s u l t s o f t h e s h o r t r u n c a t a l y s t t e s t s a d d i t i o n a l d a t a w e re
d e s i r e d c o n c e r n in g t h e c a t a l y s t a c t i v i t y o v e r e x te n d e d o p e r a t i n g p e r i o d s ,
A s c h e m a tic d ia g r a m o f t h e a p p a r a t u s f o r t h e c a t a l y s t l i f e
s tu d y i s i l l —
u s t r a t e d i n F ig u re 2 ,
The c a t a l y s t c o n t a i n i n g a p p r o x i m a t e ly 15 p e r c e n t
m olybdenum d i s u l f i d e im p r e g n a te d o n a lu m in a w as c h o s e n f o r t h e l i f e
s tu d y
b e c a u s e t h a t c a t a l y s t a p p e a r e d t o h a v e a c t i v i t y c o m p a ra b le t o a n y o t h e r
m olybdenum o r c o b a l t m o ly b d a te c a t a l y s t s p r e v i o u s l y t e s t e d «
The m olyb­
denum s u l f i d e c a t a l y s t h a d a n a d d i t i o n a l f e a t u r e i n t h a t i t w as n o t ex­
te n s iv e ly p a te n te d o
The c a t a l y s t l i f e
s t u d y r u n e x te n d e d f o r a t o t a l o f 2010 o p e r a t i n g
h o u r s t o p r o d u c e a p p r o x i m a t e ly 37 g a l l o n s o f t r e a t e d f u e l o i l w ith a s u l f u r
c o n t e n t l e s s t h a n 0 ,5 p e r c e n t .
D u rin g t h e r u n t h e c a t a l y s t t r e a t e d 1233
g ram s o f o i l p e r gram o f c a t a l y s t , a t a n a v e r a g e s p a c e v e l o c i t y o f Oe 6l 3
>•
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 . The o v e r a l l o i l c h a r g e l o s s e s
w e re 6 ,2 6 p e r c e n t o n w e i g h t b a s i s o r 4 ,3 6 p e r c e n t on volum e b a s i s a t an
a v e r a g e h y d r o g g n - t o - o i l r a t i o o f 1 ,6 0 l i t e r s o f e x i t g a s p e r gram o f o i l , '
The r e a c t o r p r e s s u r e w as m a i n ta i n e d a t 500 p s ig ,. w ith h y d ro g e n g a s and t h e
o p e r a t i n g t e m p e r a t u r e w as c o n t r o l l e d a t a n a v e r a g e o f 4 1 0 ° G t h r o u g h o u t t h e
ru n .
The l i f e s t u d y r u n was d i v i d e d i n t o f i v e o p e r a t i n g p e r i o d s c a u s e d b y
f o u r s h u t- d o w n s ,
A t i n t e r v a l s a s f r e q u e n t a s 200 a n d a s l o n g a s 500 o p e r ­
a t i n g h o u r s c a r b o n a n d c o k e d e p o s i t s w e re fo rm 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 r e a c t o r c a u s i n g e x c e s s i v e f lo w r e s i s t a n c e a n d p r e s s u r e d i f f e r e n t i a l
th ro u g h th e r e a c t o r .
The f o u r s h u t-d o w n s n e c e s s i t a t e d t h e re m o v a l o f t h e
c a t a l y s t a n d c a r b o n c o v e r e d p r e h e a t m a t e r i a l f o llo w e d b y r e c h a r g i n g t h e
r e a c t o r u n i t w ith c le a n p r e h e a t m a te r ia l and r e p la c in g th e o r i g i n a l c a t­
a ly s t,
E x p e r ie n c e p r o v e d t h a t f o l l o w i n g e a c h s h u t-d o w n t h e c a t a l y s t r e ­
sp o n d e d som ew hat d i f f e r e n t l y fro m t h e p r e v i o u s p e r i o d a n d r e a c t o r o p e r a t i n g
-
25-
cohditions such as space velocity and hydrogen throughput had to be changed
to maintain an effluent oil containing less than 0,5 percent sulfur.
The d a t a o f T a b le V I I I a r e p l o t t e d i n F i g u r e 7 t o g i v e a g r a p h i c
p i c t u r e o f t h e a v e r a g e r e s u l t s o b t a i n e d a n d t h e c o n d i t i o n s u s e d d u r in g t h e
life
s tu d y .
T a b le V I I I c o n t a i n s t h e a r i t h m e t i c a v e r a g e s f o r a p p r o x im a te ly
o n e h u n d r e d h o u r p e r i o d s o f g ram s o f s u l f u r rem oved fro m t h e o i l p e r gram
o f c a t a l y s t p e r e i g h t h o u r s 5 t h e e x i t g a s —t o —o i l r a t i o s s p a c e v e l o c i t y <, a n d
p e rc e n t s u lfu r in th e .e f f lu e n t o i l .
The c a l c u l a t e d a v e r a g e v a l u e s o f gram s
o f s u l f u r rem o v ed fro m t h e o i l p e r gram o f c a t a l y s t p e r e i g h t h o u r s , t h e
e x i t g a s - t o - o i l r a t i o , a n d s p a c e v e l o c i t y w e re p l o t t e d v e r s u s o n - s tr e a m
t im e i n F i g u r e 7 w i t h t h e o c c u r r e n c e o f t h e v a r i o u s s h u t-d o w n s i n d i c a t e d i n
c o n j u n c t i o n w i t h t h e 1n u m b ered o p e r a t i n g p e r i o d s ,
The o v e r a l l t r e n d o f t h e
s u l f u r re m o v a l i n d i c a t e d t h a t t h e c a t a l y s t l o s t a p p r o x i m a t e ly 35 p e r c e n t
a c t i v i t y b y c o m p a rin g t h e i n i t i a l 4.00 h o u r s w i t h t h e f i n a l 400 h o u r s o f t h e
ru n .
The p l o t o f s p a c e v e l o c i t y i n d i c a t e d t h e sam e p a t t e r n a s d o e s t h e
s u l f u r re m o v a l p l o t ,
I t w i l l b e n o t e d t h a t f o l l o w i n g t h e f i r s t s h u t —dow n,
p e r i o d #2 d i s p l a y e d a s h a r p d e c r e a s e i n c a t a l y s t a c t i v i t y y e t t h e a c t i v i t y
i n p e r i o d s #3 an d #4 re s u m e d n e a r l y t h e same l e v e l o f a c t i v i t y a s p e r i o d
#1,
D u rin g p e r i o d #1 t h e r e a c t o r p r e h e a t m a t e r i a l c o n s i s t e d o f l / 4 i n c h
s t e e l b a l l s a n d f o l l o w i n g t h e f i r s t s h u t-d o w n 1 / 4 i n c h a lu n d u m c e ra m ic
b a l l s w e re s u b s t i t u t e d f o r t h e s t e e l b a l l s w h ic h w e re th o u g h t t o h a v e
c a t a l y z e d c r a c k i n g a n d c o k e f o r m a ti o n i n t h e p r e h e a t s e c t i o n .
The re su m e d
l e v e l o f a c t i v i t y i n p e r i o d s #3 a n d #4 w i t h a lu n d u m p r e h e a t b a l l s d i s c o u n t s
t h e f a c t t h a t lo w c a t a l y s t a c t i v i t y fo u n d i n p e r i o d #2 w as c a u s e d p r i m a r i l y
by a change in th e p re h e a t m a te r ia l.
The c h a r g e o i l u s e d f o r t h e f i r s t 87
h o u r s o f p e r i o d #5 w as t r e a t e d a t t h e H usky O i l Company r e f i n e r y b y p a s s i n g
#3 f u e l o i l t h r o u g h a b e d o f s a n d a t
c o k e fo rm in g , com pounds„
fo u n d i n T a b le I e
0 C t o rem o v e t h e u n s t a b l e gum a n d
I n s p e c tio n d a ta f o r th e sand t r e a t e d o i l a re
The c a t a l y s t w as u n a b le t o r e d u c e t h e s u l f u r c o n te n t
o f t h e s a n d t r e a t e d o i l b e lo w 0 ,$ p e r c e n t d e s p i t e a 15 p e r c e n t r e d u c t i o n
o f t h e s p a c e v e l o c i t y a n d a 19 p e r c e n t i n c r e a s e o f t h e h y d r o g e n - t o - o i l
ra tio o
The v i r g i n #3' f u e l o i l w as u s e d a g a i n a f t e r 8 ? h o u r s o f u n s u c c e s s ­
f u l u s e o f sand t r e a t e d o i l .
The c a t a l y s t a c t i v i t y d i d n o t im p ro v e w i t h
t h e u s e o f #3 f u e l o i l i n d i c a t i n g a lo w l e v e l o f c a t a l y s t a c t i v i t y .
G re e n
( 4 ) r e p o r t e d t h a t t h e u s e o f a i r r e g e n e r a t i o n u p o n m olybdenum s u l f i d e c a t ­
a l y s t r e s t o r e d th e a c t i v i t y to a l e v e l h ig h e r th a n f r e s h c a t a l y s t .
The p l o t o f t h e g a s - r t o - o i l r a t i o v e r s u s o n - s t r e a m tim e i s p r e s e n t e d
i n F ig u re 7 ,
T h is p l o t i n d i c a t e d t h e n e e d o f a h i g h e r h y d r o g e n g a s th r o u g h ­
p u t n e c e s s a r y , t o d e s u l f u r i z e t h e sam e q u a n t i t y o f o i l when t h e c a t a l y s t b e ­
com es d e a c t i v a t e d .
The d a t a l i s t e d oh T a b le IX a n d p l o t t e d i n F i g u r e B show t h 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 a n d 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 .
The
t e r m s p a c e v e l o c i t y i s i n v e r s e l y p r o p o r t i o n a l t o t h e c o n t a c t tim e o f o i l on
t h e c a t a l y s t g t h e r e f o r e w i t h l o n g e r c o n t a c t tim e s o r lo w e r s p a c e v e l o c i t i e s
th e s u lf u r c o n te n t o f th e e f f l u e n t o i l i s lo w e r.
The c u r v e s o f F ig u r e 8
w e re o b t a i n e d 'fro m t h e c u r v e s w h ic h m o st n e a r l y c h a r a c t e r i z e d , t h e p l o t s o f
a l l t h e s a m p le s f o r d e s u l f u r i z a t i o n v e r s u s s p a c e v e l o c i t y i n t h e i n d i v i d u a l
o p e ra tin g p e r io d s .
I n s p e c t i o n o f F i g u r e 8 w o u ld r e v e a l t h a t t h e c u r v e s f o r
th e f i r s t th r e e p e rio d s in d ic a te d s im ila r s lo p e s ex c ep t t h a t a d i f f e r e n t
r a n g e o f a c t i v i t y w as d i s p l a y e d b y t h e t h r e e p e r i o d s ,
P e r i o d s #1 and #3
=27«=*
h a d n e a r l y i d e n t i c a l a c t i v i t i e s w h i l e t h e p e r i o d ^2 c u r v e w as s h i f t e d t o
th e l e f t t o i n d ic a te re d u c e d a c t i v i t y .
The c u r v e s o f p e r i o d #4 a n d #5
d i s p l a y g r e a t e r s l o p e s w h ic h i n d i c a t e t h e i n c r e a s e d e f f e c t i v e n e s s o f s p a c e
v e lo c i ty upon th 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 il*
The c u r v e o f p e r i o d
#5 c o r r e s p o n d s o n l y t o t h e d a t a o b t a i n e d d u r i n g t h e u s e o f ? a n d t r e a t e d
c h a rg e o i l .
#4 a n d # 5 »
F i g u r e 8 i n d i c a t e s t h e g r e a t l y r e d u c e d a c t i v i t y b e tw e e n p e rio d 's
In. g e n e r a l d u r in g t h e l i f e
s tu d y r u n a r e d u c tio n o f sp a ce v e l­
o c i t y b y 0 .1 gram o i l p e r gram c a t a l y s t p e r h o u r w o u ld e f f e c t t h e r e d u c t i o n
o f a b o u t 0 .0 5 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 .
The r e l a t i o n s h i p o f l i t e r s
e x i t g a s - t o - o i l r a t i o a n d .d e s u l f u r i z a t i o n
f o r th e v a rio u s p e rio d s o f th e l i f e
F i g u r e 9»
s t u d y r u n i s p r e s e n t e d i n T a b le X and
The c u r v e s o f F i g u r e 9 w e re o b t a i n e d fro m t h e c u r v e s w h ic h m o st
n e a r ly c h a r a c te r iz e d th e p l o ts o f a l l th e v a lu e s o f d e s u lf u r iz a tio n v e rs u s g a s - t o - o i l r a t i o s f o r each o p e ra tin g p e r io d .
The p l o t s c h a r a c t e r i z i n g t h e
v a rio u s o p e r a tin g p e rio d s i n F ig u re 9 r e v e a l t h a t a d e f i n i t e r e l a ti o n s h ip
o f i n c r e a s e d g a s - t o - o i l r a t i o s w o u ld y i e l d a r e d u c e d s u l f u r c o n t e n t i n t h e
e f f l u e n t o i l . ' The s l o p e s o f p e r i o d s #1 a n d #3 w e re n e a r l y a l i k e w i t h a r e ­
d u c e d s l o p e o n t h e c u rv e o f p e r i o d .#2 w h ic h c h a r a c t e r i z e d a p e r i o d o f lo w
a c t i v i t y when a l a r g e c h a n g e ini g a s - t o - o i l r a t i o h a d l i t t l e
d e s u lfu riz a tio n .
e f f e c t on t h e
O p e r a tin g p e r i o d #5 w as d i v i d e d i n t o tw o c u r v e s , one
r e p r e s e n tin g th e u s e o f san d t r e a t e d o i l and th e o th e r r e p r e s e n tin g th e u s e
o f #3 f u e l o i l .
I t w as n o t e d t h a t t h e #3 f u e l o i l r e q u i r e d a lo w e r g a s -
t o - o i l r a t i o t o e f f e c t t h e s ame r e d u c t i o n i n s u l f u r c o n t e n t t h a n d i d t h e
sand t r e a t e d o i l .
P e r i o d #4 r e q u i r e d f a r l e s s g a s t h a n p e r i o d #5 f o r t h e
sam e s u l f u r r e d u c t i o n b u t m ore t h a n p e r i o d s #1 an d # 3 .
/
I
°»26«=» ■
COMLUSIOM
A l l t h e m olybdenum c o n t a i n i n g c a t a l y s t s s t u d i e d d i s p l a y e d n e a r l y t h e
sam e r e l a t i o n s h i p o f d e s u l f u r i z a t i o n a n d s p a c e v e lo c ity ®
An a v e r a g e i n ­
c r e a s e i n s p a c e v e l o c i t y o f O0I gram o i l p e r gram c a t a l y s t p e r h o u r w ould
c a u s e a d e c r e a s e o f n e a r l y 0 ol 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 il®
e f f e c t o f t e m p e r a t u r e i n c r e a s e a b o v e 4 1 0 t o 420°C c a u s e d l i t t l e
o f d e s u l f u r i z a t i o n f o r m o ly b d e n u m -c o n ta in in g c a t a l y s t s ®
The
in c re a s e
T e m p e ra tu re c h a n g e s
b e lo w 400°C e f f e c t a much, g r e a t e r c h a n g e i n d e s u l f u r i z a t i o n p e r d e g r e e
te m p e ra tu re v a r i a t i o n .
The a c t i v i t y o f m olybdenum s u l f i d e , a n d c o b a l t m oly­
b d a t e c a t a l y s t s w e re n e a r l y i d e n t i c a l w h i l e t h e m o ly b d e n a a lu m in a c a t a l y s t s
w e re som ew hat l e s s a c t i v e *
T u n g s t ic o x i d e c a t a l y s t d i s p l a y e d t h e l e a s t
a c t i v i t y u n d e r o p e r a t i n g c o n d i t i o n s c o m p a ra b le t o t h o s e u s e d f o r m olybdenum
s u l f i d e a n d c o b a l t m o ly b d a te .
The i n c r e a s e o f r e a c t o r p r e s s u r e fro m 3 0 0 t o
500 p s i g g a v e a p p r o x i m a t e ly OcI p e r c e n t r e d u c t i o n i n s u l f u r c o n t e n t when
u s i n g m olybdenum and t u n g s t e n c a t a l y s t s ® .
The c a t a l y s t o f n i c k e l o x id e im p re g n a te d , o n a lu m in a g a v e t h e h i g h e s t
i n i t i a l a c t i v i t y b u t d e c re a s e d r a p i d l y and fo llo w in g th e tr e a tm e n t o f f o u r
g ram s o i l p e r gram c a t a l y s t t h e e f f l u e n t o i l h a d a s u l f u r c o n t e n t o f
a p p r o x i m a t e ly I 0O p e r c e n t 0
One a i r r e g e n e r a t i o n t r e a t m e n t r e s t o r e d t h e
c a t a l y s t t o n e a r l y t h e same i n i t i a l a c t i v i t y w i t h a s i m i l a r r a t e o f d e c r e a s e
d u r i n g a s e c o n d - f i v e h o u r run®
The o x i d e t y p e m olybdenum c a t a l y s t d i s p l a y e d a n i n c r e a s e i n a c t i v i t y
f o l l o w i n g t h e f i r s t t h r e e t o f i v e h o u r s o f d e s u l f u r i z a t i o n s e r v i c e w h ile
t h e m olybdenum s u l f i d e c a t a l y s t d i s p l a y e d h i g h u n if o r m a c t i v i t y th r o u g h o u t
t h e sam e i n i t i a l p e r i o d i n d i c a t i n g t h a t t h e s u l f i d e t y p e m olybdenum c a t a l y s t
■”29*°*
w as t h e m ore 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 n d t h a t t h e o x id e ty p e c a t a l y s t
e x p e r i e n c e d some fo rm o f s u l f i d i n g w h ic h y i e l d e d a m ore a c t i v e c a t a l y s t *
The d a t a o b t a i n e d fro m t h e m olybdenum s u l f i d e c a t a l y s t l i f e
s tu d y
r u n i n d i c a t e d t h a t t h e c a t a l y s t e x p e r i e n c e d a 35 p e r c e n t l o s s o f a c t i v i t y
f o l l o w i n g a n o p e r a t i n g p e r i o d i n e x c e s s o f 2 6 0 0 h o u r s t o t r e a t 1200 gram s
o f o i l p e r gram c a t a l y s t „
D u rin g t h e l i f e s t u d y .r u n a n a p p r o x im a te i n c r e a s e
i n s p a c e v e l o c i t y o f 0 ol g ram s o i l p e r gram c a t a l y s t p e r h o u r r e d u c e d t h e
a f f l u e n t o i l s u l f u r c o n t e n t b y Oe05 p e r c e n t w h i l e a n i n c r e a s e o f t h e e x i t
g a s - t o - o i l r a t i o o f a p p r o x i m a t e ly O02 l i t e r s
p e r .gram- o f o i l r e d u c e d t h e
s u l f u r c o n t e n t b y O0I p e r c e n t «,
I n c o n c l u s i o n , i t was p o s s i b l e t o o b t a i n a n e f f l u e n t o i l c o n t a i n i n g
l e s s t h a n 0*5 p e r c e n t s u l f u r t h r o u g h o u t a n
o p e ra tin g p e rio d i n e x c ess o f
2000 h o u r s w h i l e u s i n g a m olybdenum s u l f i d e c a t a l y s t u n d e r d e s t r u c t i v e
h y d r o g e n a t io n c o n d i t i o n s o f 500 p s i g a n d 41 O0 Go
(
re^Qca
LITERATURE CITED
(1 )
A „S eTeMe S t a n d a r d s on 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 5 A m erican
S o c i e t y f o r T e s t i n g M a t e r i a l s 9 .- P h ila d e lp h ia 3 p» 2 ? 2 (1 9 4 1 )»
(2 )
G r e c e l i u s 9 He L 65 MeS e T h e s i s 9 M ontana S t a t e C o l l e g e , (1 9 4 9 )*
(3 )
F i s c h b a c h 9 E c J 09 M» S e T h e s i s 9 M ontana S t a t e C o l l e g e , (1 9 5 2 )»
(4 )
G r e e n 9 K0 J 09 M0 S 0 T h e s i s , M ontana S t a t e C o l l e g e , ( 1 9 5 2 ) e
(5 )
H a a s ,-P » :Ae , M0 S e - T h e s is , M o n tan a S t a t e C o l l e g e , ( l 9 5 l )
(6 )
K a lic h e v s k y , Ve Ae a n d S t a g n e r , B 0 A0, " C h e m ic a l R e f in i n g o f P e t r o ­
leu m "
( T e x t) R e in h o ld P u b l i s h i n g C o r p o r a t i o n 9 Nevr Y o rk 9 (1 9 4 2 )„
(7 )
K o s k i9- Oe H 09 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 1 )»
.(8 )
S a c h a n e n 9 A0 N 09 " C o n v e rs io n o f P e tr o le u m "
C o r p o r a t i o n 9 Nevr Y o rk 9- (1 9 4 8 )»
( T e x t) R e in h o ld P u b l i s h i n g
ACKNOWLEDGEMENT
The a u t h o r w is h e s t o t h a n k t h e H usky O i l Company o f C ody 5 Wyoming
f o r t h e i r c o u r t e s y i n s p o n s o r i n g t h e w o rk on t h i s p ro b le m a n d f o r s u p p ly ­
in g th e f u e l o i l and m a te r ia ls u se d th ro u g h o u t th e p r o j e c t «
”32'="
APPENDIX
Pag'®'
T a b le I
F u e l O i l I n s p e c t i o n D a ta . . . . o . , , . . . , , * , *
34
T a b le I I
C a t a l y s t s e » ® e e » e o e e o e e o » » » o ® o e o e »
35
T a b le I I I
T h e rm o d y n a m c s ® ® ® ® o ® ® ® ® ® ® ® ® ® * ® ® ® ® * *
3^
T a b le H
D e s u l f u r iz a ti o n v e r s u s Space V e lo c ity w ith
M olybdenum C a t a l y s t s ® ® ® . ® . ® ® . ® . . ® . ® , ® «
38
T a b le V
T a b l e 'Y I
T a b le V H
T a b le V I I I
D e s u l f u r i z a t i o n v e r s u s T e m p e ra tu re w i t h V a r io u s
C a ta ly s ts » ® ® ® ® ® o ® ® * ® ® ® ® ® ® ® ® ® ® ® ® * *
. .
39
1
D e s u l f u r i z a t i o n v e r s u s P r e s s u r e w i t h V a r io u s
Ca t a l ys t s ®®®®*®®®®**®*®o®»®®®*»®®®
40
D e s u l f u r i z a t i o n v e r s u s O n -S tre a m Time w i t h V a r io u s
C a ta ly s ts ® ® ® ® ® ® ® ® ® ® a ® ® ® ® e ® ® ® ® ® ® * ®
41
D e s u l f u r i z a t i o n C h a r a c t e r i s t i c s o f M olybdenum S u l f i d e
C a t a l y s t D u rin g L i f e S tu d y Run- ® ® o . ® . ® . ® ® ® ® .
42
T a b le TI
D e s u l f u r i z a t i o n v e r s u s S p a c e V e l o c i t y D u rin g V a r io u s
O p e r a tin g P e r i o d s o f t h e MoS2 C a t a l y s t L i f e S tu d y Run® ® 43
T a b le X
D e s u l f u r i z a t i o n v e r s u s L i t e r s E x i t Gas P e r Gram O i l
D u rin g V a r io u s O p e r a ti n g P e r i o d s o f t h e MoSg C a t a l y s t
L i f e S tu d y Run ® ® ® ® o ® ® * ® ® ® ® ® ® ® ® ® ® ® ® ®
45
D ia g ra m o f H y d r o g e n a tio n E q u ip m e n t f o r L a r g e Volume
S u p e r - a tm o s p h e r ic Work ® ® . , ® ® , . » ® ® » ® . * ® .
47
D ia g ra m o f H y d r o g e n a tio n E a u ip m e n t f o r S m a ll Volume
S u p e r - a t m o s p h e r i c Work f o r L i f e S tu d y R u n . ® . . ® ® . «
48
The E f f e c t o f S p a c e V e l o c i t y Upon D e s u l f u r i z a t i o n w ith
M olybdenum C a t a l y s t s . . . i . . .
49
■Figure I
F ig u re 2
F ig u re 3
■•
F ig u re 4
The E f f e c t o f T e m p e ra tu re Upon D e s u l f u r i z a t i o n w i t h
V a r io u s C a t a l y s t s . . . . o . . . . . . . . . . . * . . .
'
-■58
F ig u re 5
T he E f f e c t o f R e a c to r P r e s s u r e Upon D e s u l f u r iz a ti o n ®
$1
F ig u re 6'
The E f f e c t o f O p e r a tin g Time Upon D e s u l f u r i z a t i o n
, .
. , ® $2
52
”33"
APPENDIX ( c o n t i n u e d )
page
F ig u re 7
F ig u re 8
F ig u re 9
P l o t o f Grams S u l f u r R em oval,, L i t e r s E x i t Gas p e r
Gram Q i l 5 a n d S p a c e V e l o c i t y v e r s u s O n -s tre a m
Tim e f o r L i f e S tu d y o f MdSg C a t a l y s t . . . . . . . . . . .
53
The E f f e c t o f S p a c e V e l o c i t y Upon D e s u l f u r i z a t i o n f o r
t h e O p e r a ti n g P e r i o d s o f MoSg C a t a l y s t L i f e S tu d y . . . .
54.
The E f f e c t . o f E x i t G as t o O i l R a t i o Upon D e s u l f u r i z a t i o n
f o r t h e O p e r a ti n g P e r i o d s o f MoSg C a t a l y s t L i f e S tu d y
55
TABLE I
FUEL OIL INSPECTION DATA
C h arg e S to c k
N o. 3 O i l
A4P 0I , a t 6 0 °F
3 0 .6
S p 0 GE. a t 6O0 F
0 ,8 7 2 9
d 6 0°F ( C a l c . )
0 .8 7 0 9
222
A v e ra g e M o l, W t0
U 0O0P 0 K F a c t o r
1 1 .5
B ro m in e N o,
7 .5 7
% O le fin
1 0 .5
W t. % S u l f u r
2 .2 2 3
W t0 % H2 i n O i l
1 0 .9
A0S 0T 0M0 D i s t i l l a t i o n
0F
I 0B0P
425
504
5%
520
10%
20%
536
548
30%
40%
558
$0% '
567
60%
575
584
70%
80%
594
611
90%
625
95%
652
E. P.
R e c o v e re d
R e s id u e
C h a rg e S to c k
S an d T r e a t e d
N o. 3 O i l
L i f e S tu d y Run
E f f l u e n t O i l U sin g
N o. 3 O i l c h a rg e S to c k
3 4 .0
0 .8 5 5 0
0 .8 5 3 0
208
1 1 .6
4*44
5 .7
0 .4 6 0
1 1 .2
3 0 .5
0 .8 7 3 5
0 .8 7 1 5
222
1 1 .5
9 .2 4
1 2 .8
2 .1 8 1
1 0 .9
op
Op
385"
499
519
536
547
555
197™
443
478
506
520
532
543
566
575
584
595
613
631
651
.
566
582
601
624
65 O
9 9 .0 %
9 9 .0 %
9 9 .0 %
0 .8 %
0 .8 %
0 .8 %
=35-
TABLE I I
CATALYSTS
P ro d u c e r:-
H arsh aw C h e m ic a l Co0
C a t a l y s t a n d C o m p o s itio n
C o b a lt M o ly b d a te
MoOg
CoO
I d e n t i f i c a t i o n Code
CoMo-0201 T - l / 8 "
9»5%
3»0^
SiOg 5.0%
G ra p h ite
AlgO^
2 o0#
B a la n c e
M olybdena A lum ina
MoOo 1 0 .4 - 1 1 .0 #
S iO ^
5 .6 #
AlgO^ B a la n c e
M o-0201 T - l / 8 "
M o ly b d en a A lum ina
MoOg A p p ro x . 1 0 .0 #
AlgOq B a la n c e
M o-0602 T - l / 8 "
N i c k e l O x id e
NiO
A p p ro x , 10#
AlgOq B a la n c e
N i-0 3 0 1 T - l / 8 "
T u n g s t ic O x id e
WoOg
A p p ro x 10#
AlgOq B a la n c e
W o-OlOl T - l / 8 "
M olybdenum S u l f i d e
MoSg
15#
A l 2 Oq
B a la n c e
M o-X -L 321-42 T - l / 8 "
-36ta b le I I I
THERMODYNAMICS
C4 H4 SCg) + 4H2 ( g )
Temp. °C
25
100
C4 H10 Cg) + H2 S ( g )
% C o n v e r s io n
% C o n v e rs io n
% C o n v e rs io n
% C o n v e rs io n
a t I ATM P r e s s
a t 10 ATM P r e s s
a t 50 ATM P r e s s
a t 100 ATM
P re ss
100
100
100
100
250
375
9 9 .6
9 4 .7
500
1000
7 0 .0
9 9 .9
9 8 .5
9 2 .7
0 .5
2 .0
25
100
250
% C o n v e rs io n
a t 1 . 0 ATM P r e s s
a t 50 ATM P r e s s
0 .7
5 .0
30.
75.
0 .9 5
500
1000
3 5 .0
9 5 .5
MoSg + C4 H4 SCg) + 3Hg
25
375
500
1000
100
.100
9 9 .6
9 7 .5
2 7 .0
0
0
0
0
1 2 .0
100
250
1 9 .0
% C o n v e r s io n
375
Temp. 0 C
9 9 .5
9 7 .2
100
ZMoS2 + 8 2 ( g )
2M0 S3
Temp. 0 C
100
100
100
MoS^ + C4 H^QCg)
% C o n v e rs io n
% C o n v e rs io n
% C o n v e rs io n
% C o n v e rs io n
a t I ATM P r e s s
At 10 ATM P r e s s
a t 50 ATM P r e s s
a t 100 ATM P r e s s
100
100
100
100
9 9 .6
9 7 .2
0 .7
0
9 9 .9
9 9 .3
1 8 .0
0 .9
100
100
100
9 9 .9
7 2 .0
2 .6
100
100
100
9 9 .7
7 1 .0
2.6
-37-
TABLE I I I ( c o n t i n u e d )
THERMODYNAMICS
M0 S3 + H z (g )
% C o n v e rs io n
a t 10 ATM P r e s s
% C o n v e rs io n
% C o n v e rs io n
a t I ATM P r e s s
a t 50 ATM P r e s s
a t 100 ATM
P re ss
25
9 8 .1
9 8 .2
9 8 .3
100
250
9 8 .0
9 8 .1
9 7 .9
9 7 .0
9 6 .7
9 4 .4
98 .2
9 8 .0
Temp. 0 C
375
500
1000
% C o n v e r s io n
M0 S 2 + H2 S ( g )
9 7 .8
9 6 .9
9 6 .7
9 4 .4
9 7 .2
9 6 .7
9 4 .5
9 8 .5
9 8 .3
9 8 .1
9 7 .5
9 6 .7
9 4 .6
-3 8™
TABLE IV
DESULFURIZATION VS. SPACE VELOCITY
WITH MOLYBDENUM CATALYSTS
R a t io
L ite rs
E x i t Gas
p e r gram
O il
O n -S tre a m
Tim e i n H ours
C a t a l y s t and
R e a c to r P r e s s u r e
PSIG
P e rce n t
S u lfu r in
E fflu e n t
O il
A v erag e
Space
V e l o c i t y Temp.
gram s O i l °C
p e r gram
c a ta ly s t
p e r hour
M olybdena
A lum ina
M o-0201
.9 2 5
1 .2 6
398
.4 9 0
6
.4 8 4
0 .8 4 1
412
.6 3 0
12
.4 7 3
.7 6 4
402
.4 3 5
6
.5 7 8
1 .0 1 1
399
.2 4 4
8
.7 3 8
1 .2 4
410
0 .5 5
31
.6 7 1
1 .2 8
408
0 .8 7
34
.4 9 3
0 .9 8
413
1 .1 6
40
.4 9 3
0 .8 3 5
410
1 .1 9
44
300
M olybdena
A lum ina
M o-0602
500
M olybdenum
S u lfid e
M o-X -L 321-42
500
-39table V
DESULFURIZATION VS. TEMPERATURE
WITH VARIOUS CATALYSTS
1 .0 5 4
0 .9 4 0
0 .8 5 5
0 .7 1 0
379
392
400
428
7 .8 5
1 1 .9 0
9 .6 7
7 .2 0
1 . ; 26
M olybdena
A lum ina
M o-0602
0 .7 0 9
O.656
0 .5 7 3
O.665
393
404
427
397
4 .3 4
4 .1 7
3 .1 9
4 .3 2
0 .9 2 6
0 .3 1 5
0 .3 8 3
0 .4 5 4
410
405
401
9 .6 7
8 .9 5
7 .8 5
0 .9 4 3
0 .9 4 3
0 .9 4 3
406
398
403
8 .9 5
0 .8 6 2
8 .5 8
500
0 .7 6 1
0 .8 1 6
0 .8 1 1
M olybdenum
S u lfid e
300
0 .4 1 2
0 .4 2 9
0 .5 4 7
409
405
395
9 .5 0
M olybdenum
S u lfid e
0 .3 5 5
0 .3 6 5
0 .3 3 2
0 .4 6 3
0 .6 5 5
412
410
421
398
390
1 0 .8 7
1 1 .4 7
9 .9 1
1 0 .8 0
9 .5 3
300
C o b a lt
M o ly b d a te
300
T u n g s te n
W o-OlOl
500
V/
0 .9 2 6
0 .9 2 7
0 .9 2 6
8 .0 8
I'
9 .2 7
.9 1 7
8 .3 2
4
Y
tv o vn H
M olybdena
A lum ina
Mo-0201
300
O n -S tre a m
Time
N> O N> H
S p ace
V e lo c ity
Grams O i l
p e r gram
c a t. per hr
vn -P-
L ite rs
E x i t Gas
p e r m in .
ro H
A v erag e
Temp 0 C
O -P- ro
C a ta ly s t and
% S u lfu r in
R e a c to r P r e s s . E f f l u e n t O i l
PSIC
11
.9 1 7
.8 5 0
.8 5 5
.8 5 5
13
15
.1355
18
16
-40“
TABLE VI
DESULFURIZATION VS. PRESSURE
WITH VARIOUS CATALYSTS
% S u lfu r
in
E fflu e n t
O il
.4 8 4
300
A v erag e
Temp °C
R a t io
L ite rs
E x i t Gas
P e r Gram
O il
O n -S tream
Space
V e lo c ity
Time i n
g ram s o i l H ours
p e r gram
c a ta ly s t
412
0 .6 3 0
0 .8 4 1
12
0 .6 0 3
0 .8 8 8
16
8
M olybdena
A lum ina
M o-0201
R e a c to r
P re ssu re
PSIG
V l
C a ta ly s t
414
M olybdena
A lum ina
M o-0602
.7 3 4
300
399
0 .2 7 8
0 .9 2 4
3
.5 9 3
500
399
0 .2 4 4
1 .0 1 1
8
T u n g s te n
W o-OlOl
.7 9 7
500
402
0 .6 4 3
0 .8 6 2
3
.8 5 2
300
406
0 .7 5 7
0 .8 2 1
9
.4 4 2
300
414
0 .8 3 9
0 .9 1 7
9
.3 7 8
500
415
0 .7 0 5
0 .8 5 0
15
M olybdenum
S u lfid e
.4 9 3
TABLE VII
DESULFURIZATION VS. ON-STREAM TIME
WITH VARIOUS CATALYSTS
C a ta ly s t and
Space V e lo c ity
Grams O i l p e r
g ram s C a t a l y s t
p e r H o u r.
M olybdenum
S u lfid e
Mo-X -L 321“ 42
O n -S tre a m
Time
( M in u te s )
P e rce n t
S u lfu r
in
A fflu e n t
O il
0 -6 0
6 0 -1 2 0
1 2 0 -1 8 0
1 8 0 -2 4 0
.4 4 2
.3 6 0
.3 8 6
.4 9 3
408
406
410
404
.2 8 2
.4 7 8
.7 5 3
.864
395
402
399
398
.9 5 7
397
8 .9 7
4 .4 7
7 .5 3
.2 9 8
.6 2 4
.7 6 1
412
407
404
402
398
6 .1 1
1 0 .4 3
6 .0 5
1 1 .6 1
1 1 .6 0
A v erag e
Temn.
°C
E x i t Gas
L ite rs per
M in u te
O n -S tre a m
Time i n
H ours
9 .0 7
8 .4 1
9 .3 9
8 .2 4
I
2
3
4
8 .2 2
I
2
3
4
0 .9 1 7
N ic k e l
O x id e
N i-0 3 0 1
0 .8 1 7
N ic k e l
O x id e
R e g e n e r a te d
0 .8 6 3
M o ly b d en a
A lum ina
M o-0602
0 .9 2 4
M olybdena
A lum ina
M o-0201
1 .2 6
0—60
6 0 -1 2 0
1 2 0 -1 8 0
1 8 0 -2 4 0
2 4 0 -3 0 0
0 -6 0
6 0 -1 2 0
1 2 0 -1 8 0
1 8 0 -2 4 0
2 4 0 -3 0 0
0-30
.865
.8 9 5
6.83
3 0 -6 0
6 0 -9 0
9 0 -1 2 0
1 2 0 -1 5 0
I 5 0 -1 8 0
.7 6 5
.6 5 3
.7 7 2
.7 2 4
.7 3 0
.7 6 8
400
398
392
401
400
4 .5 0
4 .5 0
4 .8 0
4 .4 3
4 .8 0
2 .6 3
0 -6 0
6 0 -1 2 0
1 2 0 -1 8 0
1 8 0 -2 4 0
2 4 0 -3 0 0
3 0 0 -3 6 0
1 .0 5 4
0 .7 1 0
1 .0 3 9
0 .9 9 5
0 .9 4 0
0 .8 5 5
379
428
398
393
392
400
7 .8 5
7 .2 0
7 .3 4
9 .6 5
1 1 .9 0
9 .6 7
402
5
I
2
3
4
5
0 .5
1 .0
1 .5
2 .0
2 .5
3 .0
I
2
3
4
5
6
-42-
TABLE V I I I
DESULFURIZATION CHARACTERISTICS OF
MOLYBDENUM SULFIDE CATALYST DURING LIFE STUDY RUN
H o u rs
O p e r a ti n g
Time
0 -9 1
9 1 -2 0 0
2 0 0 -3 1 2
3 1 2 -4 0 2
4 0 2 -4 9 8
4 9 8 -6 0 2
6 0 2 -6 9 9
6 9 9 -7 9 5
7 9 5 -8 9 9
8 9 9 -9 9 6
9 9 6 -1 0 9 2
1 0 9 2 -1 1 9 6
1 1 9 6 -1 2 9 2
1 2 9 2 -1 3 9 6
1 3 9 6 -1 4 9 2
1 4 9 2 -1 5 8 4
1 5 8 4 -1 6 9 6
1 6 9 6 -1 7 9 2
1 7 9 2 -1 8 9 6
1 8 9 6 -2 0 1 0
A v e ra g e
Grams S u l f u r
Removed p e r
Gram C a t a l y s t
p er 8 h o u rs.
.0 9 8 5
.1 2 0 0
.1 0 3 7
.1 0 2 2
.0 8 5 1
.0 7 2 4
.0 6 7 7
.0 8 7 0
.1 0 7 1
.0 9 6 8
.0 9 0 6
.0 9 2 0
.0 9 3 0
.0 8 8 8
.0 8 9 0
.0 7 0 8
.0 6 7 4
.0 5 7 0
.0 6 1 6
.0664
A v e ra g e
Space V e lo c ity
Grams O i l p e r
Gram C a t a l y s t
p e r H o u r.
.7 0 1
.8 8 ?
.7 4 6
.7 3 6
.646
.5 3 1
.4 8 6
.6 1 3
.7 8 8
.6 8 7
.6 8 3
.6 7 1
.6 8 0
.6 5 9
.6 5 0
.5 5 3
.4 8 5
.4 2 8
.4 4 9
.4 7 5
A v erag e
R a tio L i t e r s
E x i t Gas ( S . T . P . )
P e r Gram O i l
1 .2 1 3
1 .0 1 7
1 .1 6 0
1.226
1 .5 0 0
1 .6 4 5
1 .8 9 0
1 .5 0 5
1 .2 6 0
1 .4 6 0
1 .3 6 4
1 .4 5 5
1 .4 6 0
1 .5 4 0
1 .5 5 5
1 .8 5 3
2 .1 0 0
2.230
2 .2 0 0
2 .2 4 0
A v erag e %
S u lfu r c o n te n t
o f E fflu e n t o i l
0 .4 1 2
0 .4 5 3
0 .4 3 0
0 .4 4 0
0 .5 0 9
0 .4 6 4
0 .4 0 5
0 .3 8 0
O.466
0 .5 0 5
0 .5 1 5
0 .4 5 0
0 .4 6 1
0 .4 7 3
0 .4 5 6
0 .6 4 8
0 .5 8 0
0 .4 9 5
0 ,4 4 4
0 .4 1 6
-43
TABLE EC
DESULFURIZATION VS SPACE VELOCITY DURING
VARIOUS OPERATING PERIODS OF THE MoS2 CATALYST LIFE STUDY RUN
O n -S tre a m
Time i n
H ours
%S
Space
V e lo c ity
Grams O i l
p e r gram
C a ta ly s t
p e r Hour
L ite rs
E x i t Gas
L i te r s E x it
G as P e r
Gram O i l
Grams S
Removed p e r
gram C a t a l y s t
p e r 8 H ours
P e r io d No. I
24
56
112
184
232
320
378
.4 0 7
.3 9 8
.4 7 5
.5 2 5
.4 2 0
.4 5 2
.3 2 6
.7 0 9
.6 7 9
.8 5 7
.8 8 ?
.7 3 9
.8 0 4
.568
988
955
888
909
1012
865
877
1 .3 0 5
1 .3 2
0 .9 7 1
0 .9 6 2
1 .2 8
1 .0 1
1 .4 4 5
.0 9 9 9
.0 9 5 9
.1 1 6 5
.1 1 6 9
.1 0 3 1
.1 1 0 5
.0 8 3 4
1 .2 6 3
2 .5 6
1 . 518
1 .5 3 3
1 .5 0
1 .7 8
2 .9 8 5
.0 9 5 2
.0 5 2 5
.0 7 6 7
.0 7 3 5
.0 7 2 3
.0 6 8 0
.0 4 6 9
2 .0 5
1 .6 2 5
1 .5 2 3
1 .5 4 7
1 .3 5 0
1 .1 5 1
1 .2 0 2
1 .3 6 1
*0681
.0 7 4 8
.0 7 9 4
.0 8 6 1
.0 9 5 8
.1 0 8 9
.1 1 2 0
.1 0 4 2
1 .5 3 8
1 .4 0
1 .3 6 3
1 .5 9 0
1 .5 5 6
.0 9 3 7
.0 9 3 1
.0 9 0 9
.0 8 9 0
.0 8 2 2
P e r i o d No; 2
410
466
506
554
562
602
618
.6 4 1
.3 4 6
.4 7 8
.4 4 2
.4 9 0
.4 7 4
.2 9 8
.7 9 6
.3 6 1
.5 6 7
.5 3 2
.5 3 6
.5 0 1
.3 1 5
1008
956
891
843
832
923
971
P e r i o d N o. 3
683
715
739
755
787
843
867
915
.2 8 2
.3 3 6
.3 5 4
.3 8 9
.4 1 8
.4 7 6
.4 9 6
.4 4 4
.4 7 4
.5 1 8
.5 4 8
.6 0 8
.6 8 3
.8 0 3
.8 3 6
.7 5 5
1004
870
863
973
954
958
1041
1065
P e r i o d No. 4
956
972
1020
1180
1196
.5 8 0
.4 8 9
.5 1 6
.4 2 4
.3 9 4
.7 3 4
.6 9 0
.6 9 1
.6 3 9
.5 7 9
1020
999
972
1048
934
-44t a b l e IX (continued)
DESULFURIZATION VS SPACE VELOCITY DURIlNG
VARIOUS OPERATING PERIODS OF THE MoS2 CATALYST LIFE STUDY RUN
O n -S tre a m
Tim e i n
H ours
%S
1204
1420
1476
.3 5 1
.4 5 1
.3 9 8
Space
V e lo c ity
Grams O i l
p e r gram
C a ta ly s t
p e r Hour
L ite rs
E x i t Gas
.5 8 9
.6 1 9
.6 1 0
977
944
857
P e r io d 5
1500
1508
1512
1520
1528
1536
1544
1552
1560
1568
1576
.7 0 6
.7 2 6
.6 7 0
.7 5 4
.7 4 6
.6 7 0
.6 2 5
.5 8 4
.5 9 9
.5 7 5
.6 1 5
.6 5 1
.6 3 2
.6 3 2
.6 6 0
.6 3 3
.5 5 0
.5 0 3
.4 8 5
.464
.4 4 5
.4 5 7
L i te r s E x it
Gas P e r
Gram O i l
1 .6 0 4
1 .4 7 5
1 .5 4 3
Grams S
Removed p e r
gram C a t a l y s t
p e r 8 H ours
.0 8 5 2
.0 9 4 4
.0 9 7 1
Sand T r e a t e d #3 F u e l O il
1287
1092
513
998
975
1114
1049
1100
911
958
981
1 .9 1 0
1 .6 7 0
1 .5 7 0
1 .4 6
1 .4 9
1 .9 7
2 .0 2
2 .1 9
1 .8 6
2 .0 8
2 .0 8
.0 8 0 7
.0 7 7 5
.0 8 0 0
.0 7 9 2
.0 7 6 7
.0700
.0 6 5 5
.0 6 4 8
.0 6 2 7
.0 6 0 0
.0 6 0 0
-45'
TABLE X
DESULFURIZATION VS LITERS EXIT GAS PER GRAM OIL DURING
VARIOUS OPERATING PERIODS OF THE MoS2 CATALYST LIFE STUDY RUN
O n -S tre a m
Time i n
H o u rs
% 8
L ite rs
E x i t Gas
P e r gram
O il
L ite rs
E x i t Gas
Space
V e lo c ity
Grams O il
p e r gram
C a ta ly s t
p e r Hour
957
.7 3 5
.8 5 7
P e r io d No . I
.400
1 .2 2
112
120
.4 7 5
.4 3 5
0 .9 7 1
128
.360
192
.5 5 1
288
.426
320
.4 5 2
.3 9 0
64
.352
378
.326
Grams S u l f u r
Removed p e r
gram C a t a l y s t
p e r 8 h o u r.
.1040
1 .1 0
888
1130
1 .3 6
0 .7 7 4
1 .1 7 8
1165
767
913
.8 0 5
1 .0 1
865
.1 1 0 5
1 .1 9
1 .4 4 5
931
877
.8 0 4
.7 3 4
.568
.0 8 3 4
.8 2 9
.6 5 4
.6 1 3
.5 3 3
.5 1 4
.5 4 8
.5 3 6
.5 2 7
.5 0 8
.1070
.960
.928
.726
.1 1 6 5
.1 3 3 1
.1 1 6 3
.1 2 0 7
.1012
.1040
P e r io d No . 2
418
442
498
514
538
546
$62
570
578
.5 6 4
.5 2 1
.480
.428
.4 7 7
.5 1 7
.4 9 0
.4 7 1
.4 4 7
1 .0 7 3
1 .4 6
1 .4 6 5
1 .9 0 4
1 .7 8 5
1 .3 4
1 .5 0
1 .8 2
1 .9 7 5
920
986
928
1048
946
760
832
993
1004
.0 8 6 3
.0 8 2 8
.0 7 4 3
.0 6 9 7
.0724
.0 7 2 3
.0 7 1 8
.0 6 9 0
P e r io d No . 3
715
723
739
763
795
811
915
931
.3 3 6
.3 6 9
.3 5 4
.4 5 4
.4 2 4
.465
•4 4 4
.4 9 8
1 .6 2 5
1 .6 3
1 .5 2 3
1 .2 4
1 .3 8 3
1 .2 0
1 .3 6 1
1 .1 1 5
870
927
863
871
961
948
1065
865
.5 1 8
.5 5 0
.5 4 8
.6 8 0
.6 7 0
.7 6 1
.7 5 5
.7 5 0
.0 7 4 8
.0 7 8 4
.0 7 9 4
.0 9 3 2
.0 9 3 5
.1 0 3 9
.1 0 4 2
.1 0 0 0
-46TABLE X (continued)
DESULFURIZATION VS LITERS EXIT GAS PER GRAM OIL DURING
VARIOUS OPERATING PERIODS OF THE MoS2 CATALYST LIFE STUDY RUN
O n -S tre a m
Time i n
H ours
%S
L ite rs
E x i t G as
p e r gram
O il
L ite rs
E x i t G as
S p ace
V e lo c ity
Grams O i l
p e r gram
C a ta ly s t
p er hour
Grams S u l f u r
Removed p e r
gram C a t a l y s t
p e r 8 hour
P e r io d N o. 4
964
1052
1156
1300
1380
1396
1412
1420
1452
1492
.6 0 6
.5 2 0
.5 6 6
.4 6 4
.4 7 6
.4 3 6
.4 4 6
.4 5 1
.4 2 9
.4 4 1
1 .2 0
1 .3 5
1 .2 5 5
1 .4 8 6
1 .4 1 8
1 .5 5 6
1 .5 5
1 .4 7 5
1 .7 5 5
1 .7 2 8
948
958
915
1043
982
1034
1027
944
1163
1.200
.7 6 4
1 .5 2 8
1 .9 2
2 .0 4
2 .5 2
2 .3 1
913
971
897
1138
979
1022
1107
1052
1037
1108
.5 7 7
.4 8 4
.4 2 4
.4 3 5
.4 1 0
.4 5 6
.687
.7 0 5
.6 7 9
.669
.6 4 4
.6 4 2
.6 1 9
.6 4 2
.6 7 3
.0 9 6 0
.0 8 9 8
.0 9 0 8
.0 9 3 0
.0 9 0 4
.0 8 0 8
.0 9 8 3
.0 8 4 2
.0 8 8 3
.0920
P e r io d N o. 5
1632
1656
1752
1776
1800
1832
1840
1872
1944
1952
.6 6 3
.6 0 7
.5 5 8
.3 6 3
.4 3 9
.5 2 5
.3 1 5
.4 8 0
.4 6 1
.3 8 4
2 .1 7
2 .5 3
2 .0 9 5
2 .1 8
2 .3 4
.422
.4 8 6
.4 6 1
.4 5 6
.0 7 1 7
.0 6 1 4
.0 5 4 3
.0 6 2 2
.0 5 6 1
.0 5 9 6
.0 6 1 8
.0 6 5 5
.0 6 2 6
.0 6 4 5
3.
n
F ig u re I .
D ia g ra m o f H y d r o g e n a tio n E q u ip m en t f o r L a rg e
VolutrLe S u p e r - a tm o s p h e r ic Vfork
/*
/3
EXHAUST
1. H2 TANK
2. REGENERT I ON AIR
3. BLOWOUT DISK $
EXHAUST
4. UNION
5. HEAT EXCHANGE
PACKING
GCATA L Y S T
7. HEATING COILS
8. P R E S S U R E G A G E
9. C O N D E N S E R (WATER)
10. T H E R M O W E L L S
//. W f T T E S T M E T E R
12. HIGH P R E S S U R E
PUMP
13.
J ER GUSO N GAGE
14. OIL R E S E R V O I R
15. I N S U L A T I O N
-48-
THERMOWELL
3 THERMOCOUPLE/,
A
BLOW-OUT
LINE
AIR FOR
REGENERATION
CERAMIC
BALL S "
3 - I I O VOL T
RESISTANCE,
COILS
HIGH PRESSURE
PUMP
CATALYST
BACK PRESSURE
VALVE
HYDROXIDE
PRESSURE
c-GAUGE
WASH
CONDENSER
EXHAUST-*
WET TEST
METER
RECEIVING
- FLASK
HIGH PRESSURE CONTINUOUS R E AC T OR
F ig u re 2 .
D iag ram o f H y d r o g e n a tio n E q u ip m en t f o r S m a ll Volume
S u p e r - a tm o s p h e r ic Work f o r L i f e S tu d y Run
O MOLYBDENA-ALUMINA
-I
1.2
W
1 .0
D
MO- 0201
3 0 0 RS.I.G.
MO- 0 6 0 2
500
405°C
MOLYBDENUM DISULFIDE
GRAMS
CHARGE OIL PER
Figure 3«
GRAM CATALYST PER
The Effect of Space Velocity Upon Desulfurization
with Molybdenum Catalysts
HOUR
OI L
IN E F F L U E N T
SULFUR
OMOLYBDENA-ALUMlMA M 0 - 0 2 0 I
.26 S V.
•
3 0 0 PSJ.6.
MOLYBDENA-ALUMINA
HR- l O 926 S.V.
A MOLYBDENUM
DISULFIDE
HR-1 0.SI7 S.V.
3 0 0 P.S I Q.
A MOLYBDENUM
D IS U L F ID E
HR- I 0 .8 9 3 S.V.
O COBALT
9 0 0 RS.I.G.
MOLYBDATE
HR-1 0 .94 3 S.V.
T U N G S T IC
H R -I
MO- 0 6 0 2
3 0 0 RS.I.G.
3 0 0 RS.I.G
OXIDE
0 . 8 6 2 S.V.
9 0 0 RS.I.G.
380
T EMPERATURE
Pigur
4.
The Effect of Temperature Upon Desulfurization with Various Catalysts
O MOLY BDENA-ALUMINA M0-0201
MO 0 6 0 2
A TUNGSTIC
OXIDE
• MOLYBDENUM
NUMBERS
INDIC
4 0 4 eC
DlSML FIDE
SPACE
VE LO CI TY
0.821
0.862
=> 0.8
0 .9 2 4
0.841
■O*—
0.868
3 0.4
0.917
0.850
300
500
REACTOR P R E S S U R E
Figure 5 .
IN
LBS. PER SQ. INCH
GAGE
The E ffe c t o f Reactor Pressure Upon D e su lfu r iz a tio n
MOLYBDENUM
DISULFIDE
H R '*0.917 S.V.
407°C
A NICKEL OXIDE
HR_ , 0 .8 I 7 S.V.
S B r4 C
▲ NICKEL OXIDE REGENERATED
HR** 0 . 9 6 3 S.V.
4 0 4 #C
MO LYBDENA-ALUMINA M 0 - 0 6 0 2
HR-1 0 . 9 C 4 S.V.
SBB0C
M O L Y B DE N A- ALUMI NA
1.26 S.V.
ON- STREAM
Figure 6 .
TIME
M 0-020I
SBB0C
IN MI NUTES
The E ffe c t o f Operating Tic® Upon D e su lfu r iz a tio n
S A MP L E
GRAM OF CATALYST
PER EI GHT HOUR
PER
REMOVED
_o
"O
O
O
t
I.
O
O 2
.08
O
O
3
°
O
4 --
O
O
O
O
O
°
O
O
O
BARS INDICATE REACTOR S H U T - DOWNS
NUMBERS INDICATE OPERATI NG PERIO DS
O
O L
O
1.8
OI L
PER GRAM
OF CHARGE
5.
O
“
. 06
2.2
1.4
I
O
o
1.0
°
O
O ■
O
-
O
°
I O
O
3 Ji l o j
O
I
°
(I
O
O
4.
°
°
4.
O
5.
i
O
VJ
I
O
0 8
IN HR"1
SPACE
VELOCITY
GAS ( S T P )
GRAMS OF SULFUR
EXI T
LITERS
O
.12
O
0.6
o
2.
3.
O
°
04
O
F ig u re 7
O
200
400
600
800
1000
ON-STREAM
T I ME
o
O
O
0
1200
1400
1600
IN
HOURS
5.
O
O
1800
0
2000
P l o t o f Grams S u l f u r R e m o v a l, L i t e r s E x i t G as p e r Gram O i l , a n d S p a c e
V e l o c i t y v e r s u s O n -s tre a m Time f o r L i f e S tu d y o f KoGp C a t a l y s t
IN E F F L U E N T
OIL
0.7
I
LFUR
f
5?
NUMBERS
INDICATE
OPERATING
PERIODS
0.21---------------------------------------------0.3
0.4
GRAMS
Figure 8.
0.5
CHARGE
0.6
0.7
0.8
0.9
OIL PER GRAM CATALYST PER
HOUR
The Effect of Space Velocity Upon Desulfurization for the Operating
Periods of MoSp Catalyst Life Study
1.0
0.8
o
CO
CO
CO
CO "
0.31--------------- -----0.9
1.1
RATIO
Figure 9.
OF
1.3
LITERS
1.5
1.7
EXIT GAS(STP)
1.9
PER GRAM
2.1
OIL
The Effect of Exit Gas to Oil Ratio Upon Desulfurization for
the Operating Periods of HoS2 Catalyst Life Study
2.3
MONTANA STATE UNIVERSITY LIBRARIES
3 1762 1001 504
NS 78
__ M92fin
c o p . ^ T " 103355
f
author
J t o r o . B radley J r
T«T«The c a ta ly tic desulfurizationT
-^f -WynimInc fr'^l n i l ,
date d u e
BORROW ER'S NAME
T
31 O'SR
...'
^ 7-7 7
m z r 5*
C op. Z-
103333