The catalytic hydrodesulfurization of fuel oils
by Howard C Hooper
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 Howard C Hooper (1954)
Abstract:
Desulfurization studies utilizing a No. 3 fuel oil and a vacuum heavy gas oil (from Husky Oil
Company, Cody, -Wyoming) containing 2.176 percent sulfur and 3.18 percent sulfur respectively were
carried out on Harshaw's (Harshaw Chemical Company) molybdenum oxide and cobalt molybdate
catalysts, -A critical hydrogen content (minimum amount of hydrogen present in a recycle gas
necessary to produce an oil containing less than 0.5 percent sulfur) for cobalt molybdate after 1568
hours of operation on No, 3 fuel oil was less than 40 volume percent hydrogen.
Cobalt molybdate and molybdenum oxide catalysts were compared as to activity and life, In every case
the cobalt molybdate catalyst proved superior to the molybdenum oxide catalyst, -Preliminary
desulfurization studies were made on a crude tower overhead containing 0,874 percent sulfur from
Continental Oil Company at Billings, Montana, The oil was desulfurized to less than 0,163 percent
sulfur during 128 hours of operations, The catalyst used was Harshaw’s Cobalt molybdate. The recycle
gas for desulfurization contained less than 35 volume percent hydrogen.
Two oils containing 0.600 percent sulfur and 1,28 percent sulfur from Farmers Union Central
Exchange at Laurel, Montana, were desulfurized with Union Oil Company’s cobalt molybdate 3/l6"
catalyst to less than 0,109 and 0.534 percent sulfur respectively. The recycle gas contained less than 18
volume percent hydrogen, -Data was collected on the effect of regeneration of an activated bauxite
(Cyclocel) catalyst after desulfurizing an oil blend containing' approximately 0,8 percent sulfur.
Regeneration decreased catalyst life, but seemed to increase the initial catalyst activity.
All research was carried out in bench scale equipment. THE CATALYTIC HYDRODESULFURIZATION
OF FUEL OILS
by
HOWARD C. HOOPER
A THESIS
Subm itted to th e G rad u ate F a c u lty
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 aster o f S c ie n ce i n Chemical E n g in ee rin g
at
Montana S ta te C o lleg e
Bozeman, Montana
J u n e , 1954
—2—
14
C x f i 7-
TABLE OF CONTENTS
page
A b s tr a c t....................................................................................................................................
3
I n tr o d u c tio n ...........................................
4
Equipment ................................................................................................................................
n
M a t e r i a l s ..............................................................................
12
Methods .................................................................................... . . . . . . . . . . .
13
Sample C a l c u l a t i o n s ........................................................
15
D isc u ssio n o f R e s u l t s ....................................................................................................
17
Sum m ary...............................................................................
26
L i t e r a t u r e C ite d ...................................................................................
27
Acknowledgment............................................................................................................................27
A ppendix..............................
28
120375
ABSTRACT
D e s u lf u r iz a tio n s tu d ie s u t i l i z i n g a Ho. 3 f u e l o i l and a vacuum heavy
gas o i l (from Husky O il Company, Cody, -Wyoming) c o n ta in in g 2.176 p e rc e n t
s u l f u r and 3*18 p e rc e n t s u l f u r r e s p e c t i v e l y were c a r r ie d o u t on Harshaw1s
( Harshaw Chemical Company) molybdenum o x id e and c o b a lt m olybdate c a t a l y s t s .
-A c r i t i c a l hydrogen c o n te n t (minimum amount o f hydrogen p re s e n t i n a
r e c y c le gas n e c e s s a ry t o produce an o i l c o n ta in in g l e s s th a n 0 .5 p e rc e n t
s u l f u r ) f o r c o b a lt m olybdate a f t e r 1568 h o u rs o f o p e ra tio n on No. 3 f u e l
o i l was l e s s th a n 40 volume p e rc e n t hydrogen.
■Cobalt m olybdate and molybdenum o x id e c a t a l y s t s were compared a s to
a c t i v i t y and l i f e . In e v e ry c ase th e c o b a lt m olybdate c a t a l y s t proved
s u p e r io r t o th e molybdenum o x id e c a t a l y s t .
-P re lim in a ry d e s u l f u r i z a t i o n s tu d ie s w ere made on a cru d e tow er o v e r­
head c o n ta in in g 0 .874 p e rc e n t s u lf u r from C o n tin e n ta l O il Company a t
B i l l i n g s , M ontana. The o i l was d e s u lf u r iz e d t o l e s s th a n 0.163 p e rc e n t
s u l f u r d u rin g 128 h o u rs o f o p e r a tio n s . The c a t a l y s t u sed was Harshaw?s
Cqbalh m o ly b d a te . The re c y c le gas f o r d e s u lf u r iz a ti o n c o n ta in e d l e s s th a n
35 volume p e rc e n t hydrogen.
Two o i l s c o n ta in in g 0 .6 0 0 p e rc e n t s u l f u r and 1 .2 8 p e rc e n t s u l f u r from
Farm ers Union C e n tra l Exchange a t L a u re l, M ontana, were d e s u lf u r iz e d w ith
Union O il Company’s c o b a lt m olybdate 3 /1 6 " c a t a l y s t to l e s s th a n 0.109 and
0 .5 3 4 p e rc e n t s u lf u r r e s p e c t i v e l y . The r e c y c le gas c o n ta in e d l e s s th a n 18
volume p e rc e n t h y drogen.
-Data was c o lle c te d on th e e f f e c t o f re g e n e r a tio n o f an a c ti v a te d
b a u x ite ( C y c lo c e l) c a t a l y s t a f t e r d e s u lf u r iz in g an o i l b le n d c o n ta in in g '
a p p ro x im a te ly 0 .8 p e rc e n t s u l f u r . R e g e n e ra tio n d e c re a se d c a t a l y s t l i f e ,
b u t seemed t o in c r e a s e th e i n i t i a l c a t a l y s t a c t i v i t y .
A ll r e s e a r c h was c a r r i e d o u t i n bench s c a le equipment®
•INTRODUCTION
About 35 p e rc e n t o f a l l cru d e i n th e U n ited S ta te s may be c o n sid e re d
h ig h i n s u l f u r (above 0„5 p e rc e n t) w ith n e a r ly a l l o f th e h ig h s u lf u r cru d e
coming from C a lif o r n ia and West T exas,
G u lf c o a s t c ru d es a r e u su a lly 'lo w -
i n s u l f u r , w h ile th e Mid C o n tin e n t a re a h a s ab o u t 25 p e rc e n t o f i t s p ro ­
d u c tio n c l a s s i f i e d as h ig h s u l f u r cru d e ( l ) ,
S u lf u r may o c cu r i n p e tro le u m as f r e e s u lf u r * hydrogen s u lf id e * m erc a p ta n s , s u lf id e s * d is u lf id e s * c y c lic s u lf id e s * and th io p h e n e s ( 2 ) ,
E lem en tal s u l f u r and i t s compounds i n p e tro le u m p ro d u c ts a re u n d e s ir­
a b le i n th e fo llo w in g re s p e c ts ?
1,
Have u n d e s ir a b le odor
2,
Are c o r r o s iv e o r a re p o t e n t i a l l y c o rro s iv e
3»
Have poor c o lo r s t a b i l i t y
4»
G ive o f f a c r i d fumes when burn ed
Many s u c c e s s f u l and economic p ro c e ss e s have been dev elo p ed t o e i t h e r
remove o r c o n v e rt s u l f u r compounds found i n l i g h t d i s t i l l a t e s to l e s s
o b je c tio n a b le fo rm s.
G e n e ra lly th e s e p ro c e s s e s a re e i t h e r e x tr a c ti v e o r
a b s o r p tiv e and do n o t remove th e more complex r e f r a c t o r y compounds found i n
.h e a v ie r d i s t i l l a t e s .
Husky O il Company a t Cody* Wyoming* i s m a n u fa ctu rin g p e tro le u m p ro d u c ts
from a h igh s u l f u r Wyoming (Mid C o n tin e n t) cru d e o il*
H usky’s No* 3 . f u e l
o i l c o n ta in s betw een 2 .0 and 2 .2 w eig h t p e rc e n t s u l f u r .
For th e p a s t fo u r y e a r s Husky O il Company has sp o n so red r e s e a r c h
p r o j e c t s concerned w ith re d u c in g th e s u l f u r c o n te n t o f t h e i r No'. 3 f u e l o i l
t o O05 w e ig h t p e rc e n t o r l e s s .
The f i r s t work was done by P . A, Haas i n 1950-1951 ( 3 ) ,
He i n v e s t i ­
g a te d th e u se o f n ic k e l o x id e a s a c a t a l y s t f o r d e s u lf u r iz a ti o n o f f u e l o i l .
V ario u s n ic k e l o x id e c a t a l y s t s were t e s t e d u n d er s p e c if ie d c o n d itio n s o f
te m p e ra tu re , space v e l o c i t y j hydrogen r a t e , and o i l r e c y c lin g i n a g la s s
re a c to r.
The r e s u l t s o f th e s tu d y w ere summarized a s fo llo w s t
I,
D e s u lf u r iz a tio n was in d e p en d e n t o f te m p e ra tu re
betw een 600-675°?«
I
2 o The n ic k e l o x id e c a t a l y s t d e s u lf u r iz e s a s a
ch em ical r e a g e n t,
3,
I n a c tiv e form s o f n ic k e l o x id e e x is t e d ,
4»
D e s u lf u r iz a tio n depends d i r e c t l y on t o t a l c o n ta c t
tim e , seem in g ly in d ep en d en t o f w hether th e tim e was
from one o r more p a s s e s ,
5«
Hydrogen r a t e d id n o t seem to 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 ig h r a t e s re d u c ed th e c o n ta c t tim e ,
6,
O x id a tio n o f n ic k e l s u l f i d e w ith a i r produced n ic k e l
s u l f a t e , which had no a c t i v i t y a s a d e s u lf u r iz a ti o n
a g e n t,
7»
N ic k e l o x id e p re p a re d by d e co m p o sitio n o f n ic k e l
h y d ro x id e and n ic k e l c a rb o n a te p r e c i p i t a t e d from
s o lu tio n s c o u ld n o t be a c t i v a t e d w ith a i r o r hydrogen
to produce a c ti v e d e s u l f u r i z a t i o n c a t a l y s t s .
Working c o n c u r re n tly w ith Haas w ere J , W0 C oykendall (4 ) and 0 , J .
Koski ( 5 ) .
The in v e s t i g a t i o n by C oykendall was Concerned w ith th e d e s u lf u r iz a ti o n
a c t i v i t y o f a re g e n e ra te d n ic k e l o x id e c a t a l y s t .
H is r e s u l t s were th e
fo llo w in g ;
I,
A c tiv e n ic k e l o x id e c a t a l y s t s may be. p re p a re d b y d is s o lv in g ■
s p e n t c a t a l y s t i n s u l f u r i c a c i d , p r e c i p i t a t i n g th e c a rb o n a te .
and c a lc in in g th e p r e c i p i t a t e i n an a i r stre am i n th e
neighborhood o f 8G0°Fe
2.
F resh Harshaw (Harshaw Chem ical Company) c a t a l y s t c o n ta in in g
53*24 p e rc e n t n i c k e l , 4*47 p e rc e n t c arb o n , 17=34 p e rc e n t
s i l i c a , and 24=95 p e rc e n t oxygen and Gwynn c a t a l y s t c o n ta in in g
3 8 ,4 4 p e rc e n t n i c k e l , 2*22 p e rc e n t carbon a s g r a p h ite , 0*15
p e rc e n t carbon a s c a rb o n a te , 37 p e rc e n t s i l i c a and 22,19
p e rc e n t oxygen show a d e c re a se i n a c t i v i t y upon c a lc in in g a t
te m p e ra tu re s i n ex cess o f IOOO0F 6
3«
M c k e l o x id e a c ts b o th a s a c a t a l y s t and a ch em ical re a g e n t i n
d e s u lf u r iz in g f u e l o i l ,
v
Koski (5 ) made d e s u l f u r i z a t i o n s tu d ie s a t atm o sp h eric p r e s s u r e w ith
th e fo llo w in g c a t a l y s t i n 500 gram sam p les:
I*
Chrome alum ina
2»
Molybdena alum ina
3»
C obalt m olybdate
4*
Acid a c t i v a t e d alum ina
5*
Acid a c t i v a t e d b a u x ite s
The c o n d itio n s w ere 418-422°C,, sp ace v e l o c i t y o f o n e , and hydrogen
r a t e o f 482 SC F/bbl o f o i l .
Of th e s e c a t a l y s t s th e a c id a c t i v a t e d baux­
i t e s gave th e maximum d e s u l f u r i z a t i o n o f 1 ,0 1 p e rc e n t s u lfu r*
In a p re s s u re r e a c t o r u s in g 1000 grams o f c a t a l y s t , b o th molybdena
alu m in a and c o b a lt m olybdate gave a p ro d u c t o i l c o n ta in in g l e s s th a n 0 ,5
p e rc e n t s u lfu r*
Koski s t a t e d t h a t w ith molybdena alu m in a th e fo llo w in g f a c t o r s a l l
d e c re a s e d 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*
P re s s u re up t o 500 p s ig
2*
T em perature up to 430°G
3«
Hydrogen t o o i l r a t i o up to 750 SC F/bbl
o il
•The fo llo w in g y ear* 1951-1952, R. J » ' F isch b ach ( 6 ) , Be L e -Mxanro ( ? ) ,
and Ke J e G reen (B) c o n tin u e d th e work upon d e sx ilfx a riz a tio n „
Re J e F isch b ach ( 6 ) c a r r ie d on th e d e s u lf u r iz a ti o n s tu d ie s concerned
w ith n ic k e l o x id e e
The s tu d y was made o f c a t a l y s t a c t i v i t y w ith r e s p e c t
t o v a rio u s p ro c e d u res o f s y n th e s e s o f n ic k e l o x id e C a ta L y ste
A c a ta ly s t
d r ie d a t room te m p e ra tu re showed more a c t i v i t y th a n one w hich i s d r ie d a t
225°F o r c a lc in e d a t 850°Fe
A ll n ic k e l o x id e c a t a l y s t s tu d ie d r e q u ir e d chem ical m ethods o f r e ­
g e n e r a tio n and d is p o s a l o f th e b y -p ro d u c t sodium s u l f a t e „
T h e .re g e n e ra tio n
o f such a c a t a l y s t i s i n h e r e n tly uneconom ical and im p ra c tic a l*
The work by K oski was c o n tin u e d b y Munro ( ? ) and G reen (B )e
They
in v e s tig a te d th e fo llo w in g h y d r o d e s u lf u r iz a tio n c a t a l y s t s s
Ie
A c tiv a te d b a u x ite (e y e lo c e l)
2«
Molybdena alum ina
3e
C obalt m olybdate
4«.
Molybdenum s u l f i d e
5o
T u n g stic s u l f i d e
A n ic k e l o x id e c a t a l y s t was b r i e f l y s tu d ie d a t h y d ro d e s u lfu riz a tio n
c o n d itio n s (300-500 p s ig hydrogen p r e s s u r e , 375- 43O0G5 and sp ace
v e l o c i t i e s o f Oe75 t o 1*3 gram o i l p e r gram c a t a l y s t p e r h o ur)*
C obalt m o ly b d a te , molybdenum s u l f i d e , and molybdena alu m in a c a t a l y s t s
produced o i l c o n ta in in g l e s s th a n 0*5 p e rc e n t s u lfu r*
At c o n d itio n s o f 500 p s ig and AlO0C molybdenum s u l f i d e c a t a l y s t p ro ­
duced o i l c o n ta in in g l e s s th a n 0*5 p e rc e n t s u l f u r i n e x ce ss o f 2000 hoxirs
w ith sp ace v e l o c i t i e s i n th e neighborhood o f 0 *6 *
U sing a gas m ix tu re o f hydrogen and m ethane th e y found t h a t o i l con­
ta in in g l e s s th a n 0 o5 p e rc e n t s u l f u r c o u ld b e produced from, a gas c o n ta in ­
in g 45 p e rc e n t m ethane and 55 p e rc e n t h y d ro g en , w ith sp ace v e l o c i t i e s l e s s
th a n 0 .4 5 w h ile u s in g th e molybdenum s u l f i d e c a t a l y s t .
T his c a t a l y s t was
•
.
n o t a d v e r s e ly a f f e c t e d by r e g e n e r a tio n w ith a i r , i n f a c t , th e a c t i v i t y
a f t e r r e g e n e r a tio n was tw ic e th e o r i g i n a l a c t i v i t y .
The a c ti v a te d b a u x ite
c a t a l y s t s u c c e s s f u lly d e s u lf u r iz e d a No. I f u e l o i l from 1 .0 9 p e rc e n t
s u l f u r to l e s s th a n 0 .5 p e rc e n t s u l f u r w h ile d e s u lf u r iz a ti o n o f No. 3 f u e l
o i l was u n s u c c e s s fu l as t h e p ro d u c t o i l had from 1 .1 to 1 .9 p e rc e n t s u lf u r
i n 100 hours o f o p e r a tio n .
•With th e knowledge t h a t pu re hydrogen was n o t n e c e s s a ry f o r s u c c e s s fu l
d e s u l f u r i z a t i o n , .J . R. H a rtw ig -(9 ) and F . 0 . S ilv e y (10) d ir e c te d t h e i r
e f f o r t s tow ard th e u se o f a n e f f l u e n t gas ( 8 9 .1 p e rc e n t hy d ro g en , 3 .5
p e rc e n t m ethane, 1*5 p e rc e n t e th a n e , 2 .5 p e rc e n t p ro p a n e , and 3 .5 p e rc e n t
p ro p y le n e ) from a c a tfo rm in g u n i t f o r a d e s u lf u r iz a ti o n atm o sp h ere.
H artw ig (9 ) s tu d ie d t h e e f f e c t o f gas r e c y c le on d e s u l f u r i z a t i o n w ith gas
consum ption b e in g th e m ain o b j e c t i v e .
The r e s u l t s w ith a molybdenum o x id e
c a t a l y s t were 140 SCF/bbl o f o i l and 250-300 SCF/bbl o f o i l f o r pure
hydrogen gas and c atfo rm in g gas r e s p e c tiv e ly ^
S ilv e y (10). r e p o r te d t h a t b o th c o b a lt m olybdate and molybdenum o x id e
gave s u c c e s s f u l d e s u l f u r i z a t i o n r e s u l t s when u sed i n c o n ju n c tio n w ith
c a tfo rm in g gas f o r th e d e s u l f u r i z a t i o n atm o sp h ere.
The s tu d ie s were c a r r i e d o u t a t 500 p s ig 415°C and a l i q u i d space
y e lic ity of I .
The c o b a lt m olybdate c a t a l y s t showed a c o n s id e ra b ly h ig h e r
a c t i v i t y and lo n g e r c a t a l y s t l i f e th a n .t h e molybdenum oxide, c a t a l y s t „
\
A fte r 480 h o u rs o f c a t a l y s t on stream tim e , S ilv e y found t h a t th e c r i t i c a l
hydrogen c o n te n t (minimum amount o f hydrogen n e c e s s a ry to produce an o i l
w ith a s u l f u r c o n te n t l e s s th a n 0 ,5 p e rc e n t) was a p p ro x im a te ly 83 p e rc e n t
by volum e.
The d a ta o b ta in e d by K oski ( $ ) , Munro ( ? ) , and G reen (8 ) p e rm itte d
developm ent o f a p ro c e ss t o d e s u lf u r iz e H usky's Ho. 3 f u e l o i l .
D ata by
H artw ig (9 ) and S ilv e y (lO ) supplem ented by p re v io u s d a t a , were th e b a s is
I
f o r th e d e sig n o f a d e s u l f u r i z a t i o n p la n t c o n s tr u c te d a t Cody, Wyoming.
The prim e purpose o f t h i s r e s e a r c h was t o c o n tin u e t o g a th e r d a ta so
t h a t a com parison may be made o f H arshaw 's (Harshaw Chemical Company)
molybdenum o x id e c a t a l y s t , Ikirshaw 's c o b a lt m o ly b d ate, and Union O i l 's
c o b a lt m olybdate w ith r e g a rd s to c r i t i c a l hydrogen c o n te n t, and c a t a l y s t
a c t i v i t y a f t e r re p e a te d r e g e n e r a tio n s .
In a d d itio n to t h i s r e s e a r c h , p re lim in a ry r e s e a r c h was c a r r ie d o u t on
th e d e s u lf u r iz a ti o n o f o i l s from th e C o n tin e n ta l O il Company r e f i n e r y
and th e Farm ers Union C e n tra l Exchange r e f i n e r y a t B i l l i n g s , and L a u re l,
M ontana, r e s p e c t i v e l y .
The d e s u l f u r i z a t i o n atm osphere was to- be an
e f f l u e n t w aste gas from each o f t h e t w o ( r e f i n e r i e s .
C onoco's o i l f o r
*
}
d e s u l f u r i z a t i o n s tu d ie s was t h e i r crude tow er overhead h a v in g a g r a v ity
Cf 4 3 .6 ° A .F .I . a t 60°F , an I .B .P . ( i n i t i a l b o ilin g p o in t) o f l3 8 0F , an
E . Be (end p o in t) o f 620oF , and c o n ta in in g 0 ,8 7 4 p e rc e n t s u l f u r .
The
d e s u l f u r i z a t i o n was to be such t h a t th e overhead d i s t i l l a t e o f 350-375GF
end p o in t would c o n ta in n o t more 0 .1 w e ig h t p e rc e n t s u l f u r w h ile t h a t
p o r tio n o f th e f r a c t i o n rem ain in g would c o n ta in n o t more th a n 0 ,2 5 p e rc e n t
s u lfu r,
C onoco's gas f o r th e d e s u lf u r iz a ti o n atm osphere was made up o f
-
10 -
35»6 p e rc e n t hydro gen, 9 .2 p e rc e n t n itr o g e n , 3 2 .0 p e rc e n t m ethane, 7 .8
p e rc e n t e th y le n e , 1 0 .1 p e rc e n t e th a n e , and 5 .3 p e rc e n t propane p lu s .
Farm ers U n io n 's o i l s were a No. I b u rn e r o i l and a d i e s e l f u e l .
The
b u rn e r f u e l had a g r a v ity o f 4 1 .4 ° A .P.-I. a t 60°F , an I .B .P . o f 334°F , an
E . P . o f 5340F , and a s u l f u r c o n te n t o f 0 .6 0 0 w eig h t p e r c e n t.
The d i e s e l
f u e l had a g r a v i t y o f 3 4 .2 ° A .P .!„ a t 60°F , an I .B .P . o f 406oF , an E .P . o f
606°F, and a s u l f u r c o n te n t o f 1 .2 8 w eig h t p e r c e n t.
The gas f o r d e s u lf u r ­
i z a t i o n was t o be s im ila r t o w aste gas stre a m o f f from Farm ers U n io n 's
c a t a l y t i c c ra c k in g u n i t .
T his gas was made up o f 1 0 .5 p e rc e n t hydrogen,
1 3 .9 p e rc e n t n itr o g e n , 2 7 .9 p e rc e n t m eth an e, 1 5 .5 p e rc e n t e th a n e , and th e
rem ain in g g a se s b e in g hydrogen s u l f i d e , carb o n d io x id e , carb o n monoxide.
Oxygen, e th y le n e , and some C y s and
's .
“’l l "
EQUIPMENT
A sch em atic flo w diagram o f t h e d e s u l f u r i z a t i o n u n i t i s i l l u s t r a t e d
i n F ig u re I ,
The u n i t may be d iv id e d in to two p a r t s , th e gas r e c y c le
s e c tio n and th e r e a c t o r and condenser s e c tio n *
F ig u re 2 i s a d e ta i le d
w orking draw ing o f t h e r e a c t o r and condenser s e c tio n ,
c The gas r e c y c le s e c tio n c o n s is te d o f a su rg e v e s s e l , a com pression
v e s s e l , and a fe e d v e s s e l .
two gas c y l i n d e r s „
The su rg e and com pression v e s s e l s were number
The fe e d v e s s e l was a number one gas c y lin d e r .
The p ip in g u sed i n th e u n i t was l / 8- in c h s t a i n l e s s s t e e l h ig h p re s s u re
tu b in g e x c e p t f o r th e r e a c t o r s e c tio n and th e re c o m p re ssio n o i l l i n e s o f
th e gas r e c y c le sy ste m .
i n F ig u re 2 .
The p ip in g f o r th e r e a c t o r s e c tio n i s i l l u s t r a t e d
The p ip in g f o r th e o i l l i n e s o f th e gas r e c y c le system i s
o f l / 8-in c h sc h e d u le 40 b la c k ir o n p ip e .
D uring th e f i r s t p a r t o f t h i s r e s e a r c h , a two c y lin d e r H ills-M cCanna
h ig h p re s s u re p ro p o r tio n in g pump was u sed a s th e com pression pump.
pump had a c a p a c ity o f f o u r g a llo n s p e r h o u r.
T his
The p r e s e n t pump i s a Pesco
■gear pump c a p a b le o f pumping .2 .5 g a llo n s p e r m inute c o n tin u o u s ly a t 1200
p s ig ,
The r e a c t o r p r e s s u r e was m a in ta in e d a t a r e l a t i v e l y c o n s ta n t v a lu e by
means o f a M ason-N eilan s m a ll voltime a i r - t o - c l o s e back p r e s s u r e v a lv e .
T his p r e s s u r e r e g u la to r was c o n tr o lle d by a F ish e r-W iz ard p ro p o r tio n a l
c o n tro lle r.
C u rre n t was s u p p lie d t o th e th r e e r e a c t o r h e a tin g c o i l s by th r e e
1 2 0 -v o lt a u to tr a n s f o r m e r s .
Alundum b a l l s were used a s a p re h e a t m ed ia.
The r e a c t o r te m p e ra tu re was m easured w ith ir o n - c o n s ta n ta n th erm o co u p les i n
«*3.2=»
c o n ju n c tio n w ith a L eed s-N o rth ru p i n d ic a tin g p o te n tio m e te r„
MATERIALS
C a ta ly s ts f o r t h i s r e s e a r c h were H arshaw 's c o b a lt m o ly b d ates Union
O il Company's c o b a lt m olybdate and Harshaw1s molybdenum o x id e .
The d a ta
f o r th e s e c a t a l y s t s a re p re s e n te d i n T able I*
O ils from Husky O il Company, Cody, Wyoming5 C o n tin e n ta l O il Company,
B i l l i n g s , M ontana; and Farm ers Union C e n tra l Exchange, L a u r e l, M ontana,
were u sed i n th e r e s e a r c h r e p o r te d h e r e in .
I n s p e c tio n d a ta f o r th e s e o i l s
can be found i n Table I I .
G ases u sed i n th e r e c y c le system w ere th e fo llo w in g f o u r :
1.
Methane
2 . . C atform ing gas
3.
C o n tin e n ta l O il Company w aste gas
k»
Farm ers Union C e n tra l Exchange w aste gas
A ll g a se s were o b ta in e d from The M atheson Company, E a s t R u th e rfo rd ,
New J e r s e y .
The co m p o sitio n o f th e c a tfo rm in g gas was 8 9 .0 p e rc e n t hydrogen,
3 .5 p e rc e n t m ethane, 1 .5 p e rc e n t e th a n e , 2 .5 p e rc e n t p ro p a n e , and 3 .5
p e rc e n t p ro p y le n e .
The c o m p o sitio n o f Conoco®s w aste gas was 3 5 .6 p e rc e n t hydrogen, 9 .2
p e rc e n t n itr o g e n , 3 2 .0 p e rc e n t m ethane, 7 .8 p e rc e n t e th y le n e , 1 0 .1 p e rc e n t
e th a n e , and 5 .3 p e rc e n t propane p lu s .
The co m p o sitio n o f Farm ers U n io n 's w a ste g a s , w ith m o d if ic a tio n , was
1 8 .3 p e rc e n t h y d ro g en , 2 4 .2 p e rc e n t n itr o g e n , 4 8 .6 p e rc e n t m ethane, 4 .2
p e rc e n t carbon m onoxide, and 4 .7 p e rc e n t carb o n d io x id e .
-13-
METHODS
The d e s u l f u r i z a t i o n u n i t was p u t in to o p e ra tio n by a p p ly in g e l e c t r i ­
c i t y to th e h e a tin g c o i l s .
D uring th e h e a tin g -u p p e r io d 3 g as flo w was
s t a r t e d and th e r e a c t o r p re s s u re was m a in ta in e d a t th e d e s ir e d o p e ra tin g
p re s s u re (500 p s ig o r 800 p s i g ) „
When th e c a t a l y s t te m p e ra tu re reach ed
)
320- 340° C th e o i l flo w was s t a r t e d and th e sp ace v e l o c i t y was a d ju s te d to
th e p ro p e r r a t e .
D ata was ta k e n as soon a s th e o i l flo w was s t a r t e d .
The p ro d u c t o i l was c o lle c te d i n and allo w ed t o d r ip slo w ly from th e
s ig h t g la s s (s e e F ig u re I ) a t th e bottom o f th e c o n d en se r.
The p ro d u c t
o i l was c o l l e c t e d i n a o n e - l i t e r E rlenm eyer f l a s k where any d is s o lv e d
g a se s co u ld f l a s h o f f t o p a ss on t o a c a u s tic s c ru b b e r ( to remove hydrogen
s u l f i d e ) and a gas m e te r.
The o i l sample was removed from th e o n e - l i t e r
f l a s k once e v ery e ig h t h o u rs .
A nalyses o f each c o lle c te d o i l sample were
made o f t h e g r a v ity as ° A .B .I. and s u l f u r c o n te n t a s w eig h t p e r c e p t. • The
g r a v ity was checked b y a h y d ro m e te r.
The s u l f u r a n a ly s is o f each sample
was made by th e lamp method (1 2 ) .
In th e o p e ra tio n o f th e u n i t th e r e c y c le gas was m etered th ro u g h th e
fe e d gas ro ta m e te r (s e e F ig u re I ) t o th e r e a c t o r .
From th e r e a c t o r th e
gas p assed th ro u g h th e c o n d en ser and back p re s s u re v a lv e and was c o lle c te d
i n ' th e su rg e and com pression v e s s e ls up t o a p re s s u re o f 400 p s ig .
At t h i s
p r e s s u r e th e com pression v e s s e l was i s o l a t e d from th e s u rg e v e s s e l and th e
com pression pump s t a r t e d .
The pump fo rc e d o i l in to th e com pression v e s s e l
and th e o i l fo r c e d th e r e c y c le gas ov er in to th e fe e d v e s s e l .
Compression
was sto p p ed when th e gas p re s s u re i n th e fe e d c y lin d e r re a c h e d 600 p s ig o r
when th e o i l appeared i n th e s ig h t g la s s a t th e to p o f th e com pression
(
-14>
c y lin d e r .
To com plete th e com pression c y c le th e o i l was d ra in e d back to
th e com pression o i l r e s e r v o i r and makeup gas was added t o th e com pression
and su rg e v e s s e ls to b rin g th e p re s s u re up t o an a r b i t r a r y v a lu e o f 250
p sig p w h ile th e fe e d c y lin d e r was a t a p re s s u re o f 600 p s ig .
R ecycle gas sample's w ere ta k e n from a b le e d - o f f v a lv e lo c a te d on th e
downstream s id e o f th e back p re s s u re v a lv e .
The r e c y c le gas was c a u s tic
s c ru b b e d , m e te re d , and c o lle c te d i n e i g h t - l i t e r g la s s sample b o t t l e s .
-15'
SAMPLE CALCULATIONS
T y p ica l D ata From a S h o rt D u ra tio n Rxm
H0 Co Hooper9 A., H a rris
FUH-3
Jan u a ry 27- 28, 1954
O il? Husky No. 3 f u e l o i l 2 9 ,7 ° A .P ,I . and 2.176 % S .
R ecy cle G as; Farm ers Union "=^17% Hg
C a ta ly s t: 100 grams (n o t r e g e n e ra te d from FUR-2)
Union O i l 's C obalt M olybdate 3 / l6 "
Sample
No.
I
2
3
4
5
T o ta l
Hours
8
16
24
32
40
'
Sample
W eight
Grams
P e rc e n t
S u lf u r
749
751
746
791
.740
3777
0.945
1 .1 8 0
1 .2 1 0
1 .2 7 5
' 1 .260
Average
C a ta ly s t
Temp °C.
416
411
414
416
416
L i t e r s STP
Makeup
Gas
83.5
9 1 .8
55.6
55.6
60
346.5
L i t e r s STP
B le e d o ff
Gas
1 8 .4
1 4 .6
15.3
1 8 .9
14 .6
8 1 .8
O il i n 3831 grams
C a lc u la tio n , o f Average Space V e lo c ity
(3631 grams o i l c h arg ed )
- nc_
_ , ,,
(100 grams c a t a l y s t )(4 0 h r ) = Go957 Srams 0W S ram c a t a l y s t / h r
C a lc u la tio n o f Average Gas Consumption
T o ta l l i t e r s STP makeup gas
T o ta l l i t e r s STP b le e d o f f gas
T o ta l l i t e r s STP consumed
3 46.5
8 1 .8
2 6 4 .7
(2 6 4 .7 l i t e r s consumed) : lOOO grams
,
3831 grams o i l i n
k ilo g ra m ~
l i t e r s consumed
k ilo g ram o i l
. o i l a t 2 9 .7 ° A .P .I . = 7.309 I b / g a l
6 9 .1 l i t e r s / I ffe3
7.309 l b
kgm
I 28.316 l i t e r s
gal
_ 6 9 .1 l i t e r s
kgm
4 2 .0 g a l
bbl
f 4 .9 1 ft^-kgmA
^ lit e r s - b b l / = 3 4 0 ft3 /b b l
0.4536 kgm )
lb
J
-16-
C a ic u la tio n o f W eight P e rc e n t Loss o f O il
Charge o i l
E f f lu e n t o i l
.54
3831
383I grams
3777 grams
54 grams
1 .4 1 #
C a lc u la tio n o f Grams o f S u lf u r Removed p e r Kilogram o f Charge O il
(Sample No, 2)
751
0.9859
O r ig in a l S c o n te n t
F in a l S c o n te n t
Charge o i l
761 grams
2.176 #
1.180 %
(7 6 1 ) (0 ,0 2 1 7 6 )-(7 6 l ) (0.01180)1000 gm
761 grams
kgm
= 9 .6 grams S/kgm charge o i l
(2 .1 7 6 -1 .1 8 0 )1 0
-17-
DISCUSSION OF RESULTS
As. s t a t e d b e f o r e , th e purpose o f t h i s re s e a rc h was to c o n tin u e to
g a th e r d a ta so t h a t a com parison co u ld be made o f Harshaw1S molybdenum
o x id e c a t a l y s t , Harshaw1s c o b a lt m olybdate, and Union O i l 's c o b a lt m olybdate
w ith re g a rd t o c r i t i c a l hydrogen c o n te n t and c a t a l y s t a c t i v i t y a f t e r r e p e a t­
ed r e g e n e r a tio n s „
In a d d itio n t o t h i s w ork, some p r e lim in a ry r e s e a r c h was c a r r ie d o u t on
th e d e s u l f u r i z a t i o n o f f u e l o i l s from th e C o n tin e n ta l O il Company r e f i n e r y
a t B i l l i n g s , M ontana, and th e Farm ers Union C e n tra l Exchange r e f i n e r y a t
L a u r e l, M ontana.
The e x p e rim e n ta l ru n t o o b ta in d a ta on th e c r i t i c a l hydrogen c o n te n t
f o r Harshaw1s c o b a lt m olybdate c a t a l y s t , d e s ig n a te d Co-Mo-0201-T-3/ 1 6 u
(s e e Table I f o r c o m p o s itio n ), was c o b a lt m olybdate Run GMR-20
This ru n
fo llo w e d c o b a lt m olybdate Run CMR-I (10) w ith o u t r e g e n e r a tio n o r shutdown?
c o n se q u e n tly th e t o t a l hours o f p ro d u c in g s p e c i f i c a t i o n o i l o r o f su c c e ss­
f u l d e s u l f u r i z a t i o n ( s u l f u r c o n te n t l e s s th a n 0 .5 w eig h t p e rc e n t o f
e f f l u e n t o i l ) a re th o s e t o t a l ho u rs on stre am f o r Run CMR-I, 864 h o u rs ,
p lu s th e h o u rs o f Run CMR-2, 704 h o u rs , g iv in g a t o t a l o f 1568 h o u rs .
The
c o n d itio n s f o r t h i s ru n a r e a te m p e ra tu re o f 415°C, a sp ace v e l o c i t y o f
1 .0 and a gas r e c y c le r a t e o f 7500 f t ^ / b b l . .
The d a ta c o lle c te d from CMR-2 a r e ta b u la te d i n T ab les I I I and 17 and
i l l u s t r a t e d i n F ig u re s 3 and 4«
T able V i s a t a b u l a t i o n o f d a ta o f e v e ry f i f t h o i l sam ple from Run
CMR-I ( 1 0 ) .
This d a ta i s i l l u s t r a t e d i n F ig u re 5»
F ig u re 5 i l l u s t r a t e s
t h a t th e c a t a l y s t was n o t r a p i d l y lo s in g i t s a c t i v i t y , in d ic a tin g t h a t th e
c a t a l y s t was i n a r e l a t i v e l y stablfe s t a t e .
W ith t h i s knowledge th e n , th e
d e g re e o f d e s u l f u r i z a t i o n would depend t o a g r e a te r e x te n t on th e amount
o f hydrogen p r e s e n t i n th e re c y c le gas th a n on th e r e l a t i v e a c t i v i t y o f th e
c a t a l y s t and a c r i t i c a l hydrogen gas d e te rm in a tio n would b e more r e p r e s e n t­
a t i v e o f th e minimum amount o f hydrogen n e c e s s a ry in a r e c y c le gas .to
produce s p e c i f i c a t i o n o i l .
In o rd e r t o d e term in e th e c r i t i c a l hydrogen c o n te n t, m ethane was added
to th e r e c y c le g a s .
Gas sam ples w ere ta k e n p e r i o d i c a l l y and a n a ly s e s were
made f o r t h e v a rio u s c o n s ti tu e n ts o f th e r e c y c le g a s .
A .ta b u la tio n o f th e
d a ta o b ta in e d from gas sam ple a n a ly s e s i s i n T able Ii7.
F ig u re s 3 and 4 in d i c a t e t h a t th e c r i t i c a l hydrogen c o n te n t f o r
Harshawj S c o b a lt m olybdate c a t a l y s t d e s u lf u r iz in g H usky's Ho. 3 f u e l o i l
(2 .1 7 6 p e rc e n t s u l f u r ) a f t e r 1568 hours o f o p e ra tio n a t 4 1 5 °C ., 1 .0 space
v e l o c i t y and a gas r e c y c le r a t e o f 7500 f t 5 / b b l i s betw een 30 and 40 p e r­
c e n t hydrogen.
This i s c o n s id e ra b ly l e s s th a n 83 p e rc e n t minimum f o r a
16 p e rc e n t molybdenum, o x id e c a t a l y s t a f t e r 480 h o u rs o f o p e r a tio n and under
th e same c o n d itio n s ( 1 0 ) .
From t h i s com parison th e n , i t may be concluded
t h a t H arshaw 1S c o b a lt m olybdate i s a s u p e r io r c a t a l y s t i n t h a t i t r e q u ir e s
l e s s hydrogen t o f a c i l i t a t e s u c e s s f u l d e s u lf u r iz a ti o n o f H u sk y 's No. 3 f u e l
o il.
The c a t a l y s t a c t i v i t y Runs C A R -1,2,3j4 were c a r r ie d o u t ‘to o b ta in d a ta
so t h a t a com parison w ith re g a rd s to c a t a l y s t a c t i v i t y , a f t e r re p e a te d
r e g e n e r a tio n s o f H arshaw "s c a t a l y s t s molybdenum o x id e and c o b a lt m o ly b d ate,
I
and Union O i l 's c a t a l y s t c o b a lt m olybdate c o u ld be made. The d a ta f o r
th e s e fo u r ru n s a r e ta b u la te d i n T a b le s V I, V II, V I I I , and IX .
“i9“*
I-
The c a t a l y s t a c t i v i t y Buns GAR—I and 3 were s t a r t e d a t a te m p e ra tu re
o f 4i5°C (779°F) f o r 24 h o u rs .
The te m p e ra tu re was th e n in c re a s e d as
fo llo w s s
Second 24-hour p e rio d
T h ird 24-hour p e rio d
F o u rth 2 4 -h o u r p e rio d
F i f t h 24-hour p e rio d
S ix th 24-hour p e rio d
425°C
435°C
445°C.
470°C
495°C
(797°F)
(815°F)
(833°F)
(878°F)
(923°F)
A fte r th e s i x t h 24 -h o u r p e rio d th e c a t a l y s t was b u rn ed o f f .
The o i l
ch arg e t o th e r e a c t o r was Husky^s vacuum heavy gas o i l w ith a s u lf u r
c o n te n t o f 3*18 w eight p e r c e n t.
The space v e l o c i t y and r e c y c le r a t e was
s e t a t 1 .0 gram o f o i l p e r gram c a t a l y s t p e r h o u r, and 7500 f t ^ / b b l o f
o i l re s p e c tiv e ly .
Run CAR-1 was on H arshaw 's molybdenum o x id e c a t a l y s t , d e sig n a te d
M o -0 2 0 3 -T -l/8 ".
The ru n was c a r r ie d o u t as- o u tlin e and a f t e r th e 24-hour
p e rio d a t 495°C th e c a t a l y s t was b urned o f f (r e g e n e r a te d ) and th e stu d y
was c o n tin u e d a s Run CAR-2 a t a te m p e ra tu re o f 495°0..
The 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 was g r e a t e r th a n t h a t from th e end o f CAR-1.
I t was
th e n co n cluded th a t, r e g e n e r a tio n had b een in co m p lete a t b e s t , and a second
r e g e n e r a tio n was s t a r t e d .
D uring th e second r e g e n e r a tio n , th e c a t a l y s t
re a c h e d a te m p e ra tu re o f over 900° C5 c o n se q u e n tly a p o r tio n o f i t was
s in te re d .
■Run CAR-3 i s a c a t a l y g t a c t i v i t y s tu d y o f Union O i l 's c a t a l y s t c o b a lt
m olybdate 3 / l 6 " .
.T his s tu d y was ru n a t th e same c o n d itio n s o f CAR-1.
A f te r t h e s i x t h 24-hour p e rio d a t 495°C, th e c a t a l y s t was re g e n e ra te d and
Run CAR-4 was begun a t 4950 C.
F ig u re s 6 and 7 i l l u s t r a t e th e d a ta ta k e n from Runs CAR-1 and 3 .
1
•20«
F ig u re 6 i l l u s t r a t e s t h a t Union O il.' s c o b a lt m olybdate i s a more a c ti v e '
I
d e s u lf u r iz a ti o n c a t a l y s t th a n i s th e molybdenum oxide*
F ig u re 7 b e t t e r
i l l u s t r a t e s t h a t th e c o b a lt m olybdate c a t a l y s t i s a s u p e r io r d e s u lf u r iz a ti o n
c a ta ly s t.
F ig u re 7 shows t h a t th e c o b a lt c a t a l y s t removes more s u lf u r a n d
rem ains a c ti v e lo n g e r th a n does molybdenum oxide*
S tu d ie s would have been c a r r i e d o u t on Harshawr s c o b a lt m o ly b d ate, b u t
co rresp o n d en ce from th e Harshaw Chem ical Company s t a t e d t h a t t h e two
c a t a l y s t s , Harshaw rs c o b a lt m olybdate and Union O i l 's c o b a lt m o ly b d ate, had
th e same com position*
W ith th e knowledge t h a t d e s u l f u r i z a t i o n o f H usky's No* 3- f u e l o i l from
2.176 w eig h t p e rc e n t s u l f u r to l e s s th a n 0*5 p e rc e n t s u l f u r i s p o s s ib le
Trdth H arshaw 's c o b a lt m olybdate c a t a l y s t and a r e c y c le gas c o n ta in in g l e s s
th a n 40 p e rc e n t h y drogen, p re lim in a ry r e s e a r c h was c a r r ie d o u t on o i l s from
th e C o n tin e n ta l O il Company and Farm ers Union C e n tra l Exchange*
The
r e c y c le gas was t o be a w aste gas c o n ta in in g hydrogen from each company's
re fin e ry .
The o i l from Conoco's r e f i n e r y a t B i l l i n g s , M ontana, was a crude
tow er overhead sam ple i d e n t i f i e d as No. B i 987.
The g r a v i t y and s u lf u r
c o n te n t o f t h i s o i l was 4 3 .1 0A*B.I* and 0*874 p e rc e n t s u l f u r ( f o r ASTM
d i s t i l l a t i o n d a ta s e e T able I I ) *
The w a ste gas stre a m from C onoco's r e f i n e r y was composed o f 35*6
p e rc e n t h y d ro g en , 9 .2 p e rc e n t n itr o g e n , 23*0 p e rc e n t m ethane, 7*8 p e rc e n t
e th y le n e , 1 0 .1 p e rc e n t e th a n e , 2 ,8 p e rc e n t p ro p y le n e , 2 .0 p e rc e n t p ro p a n e ,
and 0*5 p e rc e n t b u ta n e p l u s .
y
The gas m ix tu re u sed f o r th e d e s u l f u r i z a t i o n atm osphere was e s s e n t i a l -
(
”
21
“
I y th e same as th e above m ix tu re e x ce p t t h a t th e p ro p y le n e 5 p ro p a n e , and
b u ta n e s p lu s w ere a l l lumped to g e th e r a s 5«3 p e rc e n t
p lu s*
The o i l was t o be d e s u lf u r iz e d to a p o in t such t h a t an overhead
d i s t i l l a t e o f 350“375°F end p o in t would have a s u lf u r c o n te n t o f n o t o v er
0*1 p e rc e n t and t h a t o f th e rem ain in g p o r ti o n o f th e p ro d u c t c o n ta in n o t
more th a n 0*25 p e rc e n t s u lfu r*
The d a ta c o lle c te d from re s e a rc h on Conoco !s o i l i s ta b u la te d in
T ab le X and XI*
The d a ta may be summarized a s fo llo w s :
Average c a t a l y s t te m p e ra tu re = 77S°F (v a ry in g from 775-782°F)
Average l i q u i d sp ace v e l o c i t y = 0,955 gm o il/g m c a t a l y s t / h r
(v a rry in g from 0*862 to 1 , 04)
R e a c to r p re s s u re = 500 p s ig
Average g as r e c y c le r a t e = 8700 f t ^ / b b l o i l (v a ry in g from 7880
to 9600 f t 3 / b b l )
I n i t i a l hydrogen c o n te n t o f r e c y c le gas = 35*6 volume p e rc e n t
F in a l hydrogen c o n te n t o f re c y c le gas = l e s s th a n 30 p e rc e n t
T o ta l h o u rs on stre am = 128 hours
Average re c y c le gas consum ption = 250-300 f t ^ / b b l o i l
O il y i e l d = 95»4 w e ig h t p e rc e n t
O il y i e l d = 9 6 ,2 volume p e rc e n t
Charge o i l p r o p e r tie s ;
°A»P*I* = 4 3 ,1 a t .60°F
P e rc e n t s u l f u r = 0*874
P ro d u ct p r o p e r t i e s :
C om posite, 0AeP . I , = 4 3 ,5 a t 60°F
C om posite, p e rc e n t s u l f u r = 0*124
C om posite, I„ B ,P , = 139°F
F r a c tio n b o ilin g <365°F. 36*5 w eig h t p e rc e n t o f p ro d u c t
a
it
n
4 1 .0 volume p e rc e n t o f p ro d u ct
if
Ii
< Ii
0 ,0 3 7 p e rc e n t s u lf u r
F r a c tio n b o i l i n g 7365°F
6 1 ,5 w eight p e rc e n t o f p ro d u c t
Il
H
y Il
5 9 .0 volume p e rc e n t o f p ro d u ct
"
it
Ii
0 .1 9 p e rc e n t s u l f u r
F ig u re 8 i l l u s t r a t e s how d e s u l f u r i z a t i o n p ro g re sse d d u rin g th e Conoco
ru n as c a t a l y s t o n -stre a m tim e in c re a se d *
T able X II i s a ta b u l a t i o n o f a n a l y t i c a l d a ta o f a com posite sample o f
th e d e s u lf u r iz e d Conoco o i l .
The a n a l y t i c a l work was done by C o n tin e n ta l
~22,"
O il Company p e rs o n n e l a t Ponca C ity , Oklahoma,
T his T able i s included, w ith
t h i s t h e s i s f o r re c o rd p u rp o se s o n ly .
Runs FUR-1 and 2 a re re s e a rc h on th e d e s u lf u r iz a ti o n o f Farm ers Union
C e n tra l Exchange o i l u t i l i z i n g a w aste g a s , stre am from Farm ers U nion’s
r e f i n e r y as th e hydrogen so u rc e n e c e s s a ry f o r a d e s u lf u r iz a ti o n atm o sp h ere.
The c a t a l y s t u sed f o r d e s u l f u r i z a t i o n was Union o i l s c o b a lt m olybdate 3 /1 6 ” ,
The w aste g as c o n ta in e d 1 0 ,5 p e rc e n t hydrogen, 1 3 ,9 p e rc e n t n itr o g e n ,
2 7 ,9 p e rc e n t m ethane, 15»5■p e rc e n t e th a n e , and th e re m a in in g g ases b e in g
hydrogen s u l f i d e , carb o n d io x id e j carbon m onoxide, oxygen, e th e y le n e , and
some C3 's and C^?s ,
T his gas i s to o low i n hydrogen to b e o f g r e a t v a lu e
f o r u se i n d e s u l f u r i z a t i o n so i t was th o u g h t t h a t i f t h i s gas m ix tu re were
p r e s s u r iz e d to 800 p s i g , and c o o led to l e s s th a n SO0F a l l hydrocarbons
h ig h e r th a n and in c lu d in g e th a n e would be condensed and c o u ld b e removed
from th e o th e r g a s e s .
Removal o f th e s e h y d ro carb o n s would b rin g th e hydro­
gen c o n te n t up t o 1 8 ,3 p e rc e n t and a t a p r e s s u r e o f 800 p s ig th e p a r t i a l
p re s s u re o f th e hydrogen would b e a b o u t 146 p s ig ,
This com pares to th e
Conoco gas a t 500 p s ig and 3 5 ,6 p e rc e n t h y d ro g en , th e p a r t i a l p re s s u re o f
which i s a b o u t 1?8 p s i g .
From t h i s , th e n , th e r e c y c le g as m ix tu re used i n
d e s u lf u r iz in g Farm ers U nio n ’s o i l s c o n ta in e d i n i t i a l l y 1 8 .3 p e rc e n t hydro­
g e n , 2 4 .2 p e rc e n t n itr o g e n , 4 8 .6 p e rc e n t m ethane, 4 .2 p e rc e n t carbon
m onoxide, and 4 .7 p e rc e n t carb o n d io x id e .
The Farm ers Union o i l s t h a t were to be d e s u lf u r iz e d c o n ta in e d 0,600
p e r c e n t s u l f u r and 1 ,2 8 p e rc e n t s u l f u r .
The d e s u lf u r iz a ti o n s tu d ie s on
th e s e o i l s w ere l i s t e d a s Farm ers Union Run FUR-1 and 2 , r e s p e c t i v e l y .
Run FUR-3 i s a d e s u l f u r i z a t i o n o f H usky’s No, 3 f u e l o i l u s in g Farm ers
•=23~
Union r e c y c le g a s .
The d a ta from FUR-I, 2 , and 3 a re ta b u la te d i n T ables
X I I I 5 XIV5 XV5 and XVI.
These ru n s w ere made c o n s e c u tiv e ly on th e same
c a t a l y s t w ith o u t r e g e n e r a tio n .
An a n a ly s is o f th e r e c y c le gas f o r hydrogen c o n te n t was n o t p o s s ib le
a s th e r e c y c le gas c o n ta in e d n itr o g e n and gas a n a ly s is a r e made i n a low
te m p e ra tu re m i c r o - s t i l l w ith th e p o t' and head b e in g c o o led w ith l i q u i d
n itr o g e n a t i t s b o ilin g p o in t a t 640 mm Hg.
B o ilin g l i q u i d n itr o g e n a t
a tm o sp h eric p r e s s u r e c an n o t condense gaseous hydrogen o r n itr o g e n a t
a tm o sp h eric p re s s u re and th e g a se s come o f f a s a m ix tu re . The r e s u l t s o f
•)
gas a n a ly s e s p e r ta in in g to th e Farm ers Union s tu d ie s a re l i s t e d i n T able
.
XVI.
In Farm ers Union Run FUR-1 th e s u l f u r c o n te n t was re d u c ed from 0.600
p e rc e n t s u l f u r t o a v a ry in g p e rc e n t o f 0 .0 6 2 to 0.109 p e rc e n t s u lf u r w ith
Union O i l 's c a t a l y s t c o b a lt m olybdate 3 /1 6 " d u rin g 93 h o u rs o f o p e r a tio n .
The c o n d itio n s w ere a s fo llo w s ;
Tem perature
P re s s u re
R ecycle r a t e
4X5°C
800 p s ig
IO 5OOO and 6000 f t ^ / b b l
I t sh o u ld be n o te d t h a t .when th e r e c y c le r a t e was changed from IO 5OOO
f t ^ / b b l t o 6000 f t ^ / b b l th e s u l f u r c o n te n t v a r ie d from a r e l a t i v e l y
c o n s ta n t v a lu e o f 0 . 0?6 p e rc e n t t o a r e l a t i v e l y c o n s ta n t v a lu e o f 0 .104
(s e e T able X I I I ) 5 in d ic a tin g t h a t d e s u l f u r i z a t i o n f o r t h i s ru n was more
d ependent on th e number o f hydrogen m o le c u les p re s e n t p e r u n i t o f tim e th a n
th e c o n ta c t tim e o f th e hydrogen m o le c u le .
T his i s u n d e rs ta n d a b le because
th e r e c y c le gas i s d e f i c i e n t i n hydrogen and in c r e a s in g th e v e lo c i ty o f
th e gas o v e r th e c a t a l y s t bed would a ls o in c r e a s e th e number o f hydrogen
—24“
atoms a v a il a b le f o r r e a c t i o n t o hydrogen s u l f i d e p e r u n i t o f tim e .
F ig u re
9 i s an i l l u s t r a t i o n o f how d e s u l f u r i z a t i o n p ro g re s se d d u rin g FhR-I a s on
stre a m tim e in c r e a s e d .
The d e s u lf u r iz a ti o n s tu d y on Farm ers Union o i l c o n ta in in g 1 .2 8 p e rc e n t
s u l f u r was d e s ig n a te d FUR-2.
XIV.
The d a ta ta b u la te d f o r t h i s ru n i s i n Table
The t o t a l tim e o f th e ru n was 6$ h o u rs .
D e s u lf u r iz a tio n was from
1 .2 8 p e rc e n t s u l f u r i n th e c h arg e o i l to a v a ry in g v a lu e from 0.421 to
0 .5 3 4 p e rc e n t s u lf u r i n th e e f f l u e n t o i l .
b e in g ab o u t 0 . 47? p e rc e n t s u l f u r .
The com posite s u l f u r p e rc e n t
In o rd e r to a c h ie v e t h i s d e s u lf u r iz a ti o n
i t was n e c e s s a ry t o r a i s e th e r e c y c le r a t e from ab o u t 6000 f t ^ / b b l f o r th e
f i r s t h a l f o f th e ru n to a b o u t 9000 f t ^ / b b l f o r th e l a s t p a r t o f th e ru n .
T h is in d ic a te s t h a t th e hydrogen c o n te n t o f th e gas was r a p i d l y becoming
le a n e r as an in c re a s e o f r e c y c le r a t e from 6000 t o 9000 f t ^ / b b l d id n o t
even m a in ta in th e same d e g re e o f d e s u l f u r i z a t i o n a s was en co u n tered a t th e
f i r s t p a r t o f th e r u n .
O ther th a n r e c y c le r a t e , FUR-2 was ru n a t th e same
c o n d itio n s as FUR-1.
The ta b u la te d d a ta i n T able XV a r e from Farm ers Union Run FUR-3.
T his
ru n fo llo w e d FUR-2 , and was o p e ra te d a t th e same c o n d itio n s e x c e p t t h a t th e
c h arg e o i l was H usky’s No. 3 f u e l o i l (2 .1 7 6 p e rc e n t s u l f u r ) .
The e f f l u e n t
o i l f o r t h i s ru n c o n ta in e d from 0.945 t o 1 ,2 7 5 p e rc e n t s u l f u r .
C o n cu rren t­
l y w ith th e p re c e d in g r e s e a r c h , a s tu d y was made on d e s u lf u r iz in g a b le n d
o f H usky's k e ro sen e d i s t i l l a t e and l i g h t gas o i l w ith an a c ti v a te d b a u x ite
c a t a l y s t ( C y clo cel Sb-2446=51) ■> The b le n d o i l c o n ta in e d about 0 ,8 p e rc e n t
s u lfu r.
The p ro d u c t c o n ta in e d l e s s th a n 0 ,5 p e rc e n t s u l f u r .
from t h i s s tu d y a r e l i s t e d i n T ables XVII and X V III.
The d a ta
The Run i s d e s ig n a te d
—25™
LMR-I (from Husky a t L lo y d m in ste r9 Canada) .
i n T able X V III.
The d a ta on th e b len d o i l a r e
T able XIX c o n ta in s d a ta from an A.S.T.M . d i s t i l l a t i o n o f
a com posite sample o f th e d e s u lf u r iz e d o i l .
T his d e s u lf u r iz a ti o n s tu d y was ru n a t atm o sp h eric p r e s s u r e and w ith
no r e c y c le g a s .
The c a t a l y s t te m p e ra tu re and space v e l o c i t y was 400°C
and I gram o il/g r a m c a ta ly s t/h o u r r e s p e c t i v e l y .
Dfcen 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 i l re a c h e d 0 .5 p e rc e n t
s u l f u r , th e u n i t was s h u t down and th e c a t a l y s t was re g e n e ra te d by a i r
b u rn o ff.
The. c a t a l y s t was re g e n e ra te d tw ic e ,
A p lo t o f th e s u l f u r r e ­
moved v e rs u s th e h o u rs o f o p e ra tio n i s i l l u s t r a t e d i n F ig u re 1 2 .
Three
c u rv e s a r e p l o t t e d , th e f i r s t curve i s d e s u lf u r iz a ti o n w ith new. c a t a l y s t ,
th e l a s t two c u rv e s a re d e s u l f u r i z a t i o n w ith re g e n e ra te d c a t a l y s t .
This
g rap h i l l u s t r a t e s t h a t r e g e n e r a tio n does e f f e c t c a t a l y s t l i f e betw een
r e g e n e r a tio n s .
g e n e r a tio n .
The i n i t i a l a c t i v i t y o f t h e c a t a l y s t in c re a s e d a f t e r r e ­
-26-
SUMAEY
The r e s u l t s o f th e r e s e a r c h r e p o r te d h e r e in may be summarized as
f o llo w s ;
1.
The c r i t i c a l hydrogen c o n te n t f o r H arshaw 's c o b a lt m olybdate
c a t a l y s t , C o-M o-0201-T -3/l6", d e s u lf u r iz in g H u sk y 's Noe 3 f u e l
o i l ( 2*176
p e rc e n t s u l f u r ) a f t e r 1$6S h o u rs o f o p e ra tio n a t 41$ o c ,
Space v e l o c i t y o f I eG and a gas re c y c le r a t e o f 7500 f t ^ / b b l i s
betw een 30 and 40 volume p e r c e n t,
2,
H arshaw 's c o b a lt m olybdate c a t a l y s t , Co-Mo-0201-T-3/ 1 6 n, i s
s u p e r io r to H arshaw 's molybdenum o x id e c a t a l y s t , M o -0 2 0 3 -T -l/S ",
i n t h a t i t has a g r e a t e r a c t i v i t y and lo n g e r c a t a l y s t l i f e .
3,
A fte r 128 hours o n -s tre a m , an o i l from C o n tin e n ta l O il Company
h av in g g r a v i t y and s u l f u r c o n te n t o f 43 «1 0Ai Pe-Ie and 0,874 p e r­
c e n t s u l f u r r e s p e c t i v e l y , was d e s u lf u r iz e d i n an atm osphere o f
r e c y c le gas c o n ta in in g l e s s th a n 35 p e rc e n t hydrogen t o y ie ld an
e f f l u e n t o i l c o n ta in in g 0,142 p e rc e n t s u l f u r , 'The c o n d itio n s o f
d e s u l f u r i z a t i o n w ere as fo llo w s :
R e a c to r p re s s u re = 500 p s ig
Average g as re c y c le r a t e = 8?00 f t ^ / b b l o i l (v a ry in g from
7880-9600 f t 3/ b b l )
Average c a t a l y s t te m p e ra tu re = 7.78 (v a ry in g from 775-782°F )
Average sp ace v e l o c i t y = 0 ,9 5 5 gm o ll/g m c a t a l y s t / H r . .
(v a ry in g from 0 ,8 6 2 to 1 , 04)
4.
O ils from Farm ers Union C e n tra l Exchange c o n ta in in g 0 ,6 0 0 and
1 ,2 8 p e rc e n t s u l f u r were d e s u lf u r iz e d i n a d e s u lf u r iz a ti o n
atm osphere c o n ta in in g l e s s th a n 18 p e rc e n t hydrogen t o l e s s th a n
0,109 and 0 ,5 3 4 p e rc e n t s u l f u r r e s p e c t i v e l y .
The t o t a l h o u rs o f
*”27*”
d e s u l f u r i z a t i o n f o r th e o i l s c o n ta in in g 0 .6 0 0 and 1*28 p e rc e n t
s u l f u r w ere 93 and 65 ho u rs r e s p e c tiv e ly ,,
5.
R e g e n e ra tio n o f a c ti v a te d b a u x ite c a t a l y s t ( C y clo ce l Sb-2446-51)
d e c re a se d th e c a t a l y s t l i f e , b u t seemed to in c r e a s e th e i n i t i a l
c a ta ly s t a c tiv ity .
LITERATURE CITED
(I)
H atch , L»- R0, P e tro leu m R e f in e r , 3 2 , No, 6 , 105 (1 9 5 3 ).
-(2)
N elso n , •¥. E 0, -PETROLEUM REFINERY ENGINEERING,■ .McGraw-Hill Book
Company, I n c . , New Y ork, N„ Y ., T h ird E d itio n (1 9 4 9 ).
(3 )
H aas, -P0 A ., M0 S . T h e s is , M ontana S ta te C o lle g e , ,(1 9 5 1 ),
.(4)
C o y k en d all, J . W., M. 8 . T h e s is , Montana S ta te C o lle g e , (1 9 5 1 ).
(5 )
K o sk i, 0 , J . , M. S 0 T h e s is , Montana S ta te C o lle g e , (1 9 5 1 ),
(6 )
F is c h b a c h , R . . J . , . M 0 S , T h e s is , Montana S ta te C o lle g e , (1 9 5 2 ),
(7 )
Munro, B0 L 0, M0 S 0 T h e s is , M ontana S ta te C o lle g e , (1 9 5 2 ).
(8)
G reen , Ke J , , M0 S . T h e s is , Montana S ta te C o lle g e , (1 9 5 2 ),
(9 )
H artw ig , J 0 R „, M0 S„ T h e s is , Montana S ta te C o lle g e , (1 9 5 3 ),
(10) S ilv e y , F 0 C0., Me -S0 T h e s is , Montana S ta te C o lle g e , .(1953.),
( I I ) H a r r is , A0,. M0 S . -T hesis, Montana S t a t e . C o lle g e , (1 9 5 4 ),
(12) A0S 0T0M ..STANDARDS ON PETROLEUM AND LUBRICANTS, American S o c ie ty f o r
T e s tin g M a te r ia ls , P h i l a d e l p h i a , (1 9 4 1 ),
ACKNOWLEDGMENT
The a u th o r acknow ledges, w ith th a n k s , th e c o u rte s y o f th e Husky O il
Company who sp o n so red t h i s r e s e a r c h ,
'The c o o p e ra tio n o f D r. -Lloyd B erg, H0 -A. S a n e r, and L 0 G0 M ay field ,
th e f a c u l t y , and M rs. Howard Dean, th e s e c r e t a r y , o f t h e Chemical E n g in eer­
in g D epartm ent, i s g r a t e f u l l y acknow ledged.
APPENDIX
page
T able I
C om position and I d e n t i f i c a t i o n o f C a ta ly s t U sed, . ,
« 30
T ab le I I
Charge O il In s p e c tio n D ata ...........................
.
31
T able I I I
T a b u la te d D ata from C obalt M olybdate Run GMR-2 , » •,
.
32
T able IV
Gas A nalyses D ata f o r Run C M R -2,.................. .... . . . .
.
35
T ab le V
T ab u lated D ata from C obalt M olybdate Run CMR-I * , .
.
36
T able VI
T a b u la te d D ata
from C a ta ly s t A c tiv ity Run CAR-Ii , ,
.
37
T able V II
T a b u la te d D ata
from C a ta ly s t A c tiv ity Run CAR-2, , „
.
38
T able V III
T ab u lated D ata
from C a ta ly s t A c tiv ity Run CAR-3,
. ,
.
39
T able IX
T ab u lated D ata
from C a ta ly s t A c tiv ity Run CAR-4• , »
.
40
T able X
T ab u lated D ata from C o n tin e n ta l O il Run Conoco-I , *
.
41
T able XI
Gas A nalyses D ata f o r Run Conoco-I
.
42
T able X II
A n a ly tic a l D ata on C o n tin e n ta l O il Company's Crude
Tower Overhead O i l , Sample No, B i 987» . , ,
.
43
T ab le X III.
T ab u lated D ata from Farm ers Union Run FUR-1,
.
44
Table XIV
T ab u lated D ata from Farm ers Union Run FUR-2.
.
45
T able XV
T ab u lated D ata from Farm ers Union Run FUR-3•
.
46
T able XVI
Gas A nalyses D ata f o r Run FUR-1, 2 and 3 <> ,
.
47
T able XVII
T ab u lated D ata from L lo y d m in ste r Run LMR-I ,
.
48
T able X V III O il B lending D ata f o r L lo y d m in ste r Run LMR-I
.
50
T able XIX
T a b u la te d D ata from L lo y d m in ste r Run LMR-I ,
.
50
F ig u re I
Schem atic Flow Diagram o f D e s u lf u r iz a tio n U n it . , . . .
51
F ig u re 2
D e ta ile d Drawing o f R e a c to r and Condenser S e c tio n . . . .
52
F ig u re 3
P e rc e n t S u lf u r i n E f f lu e n t O il and P e rc e n t Hydrogen
i n R ecycle Gas vs O n-Stream Time f o r C obalt
M olybdate C a t a ly s t, Run CMR-2.
53
.
-29-
APPENDK
page
F ig u re 4
F ig u re 5
E f f e c t o f Hydrogen C ontent in ,R e c y c le Gas on th e
S u lf u r C ontent i n E f f lu e n t O il f o r C obalt
M olybdate C a t a ly s t, Run CMR-2, ........................... . . . . . .
54
E f f e c t o f On-Stream Time on S u lf u r Removal f o r
C obalt M olybdate C a t a ly s t, Run CMR-I (1 0 )„ . . . . . . .
55
F ig u re 6
E f f e c t o f C a ta ly s t T em perature on D e s u lf u r iz a tio n . . . .
Run CAR-1 and 3
F ig u re 7
E f f e c t o f On-Stream Time bn S u lfu r Removal ...........................57
Run CAR-1 and 3
F ig u re 8
E f f e c t o f On-Stream Time on S u lf u r Removal f o r
C obalt M olybdate C a t a ly s t, Run Conoeo-1 . . . . . . . . .
58
E f f e c t o f On-Stream on S u lf u r Removal f o r
C obalt M olybdate C a t a ly s t, Run FUR-1 . ...................... ....
59
E f f e c t o f On-Stream Time on S u lf u r Removal f o r
' C obalt M olybdate C a ta ly s t Run FUR-2 . . . . . . . . . .
60
E f f e c t o f On-Stream Time on S u lf u r Removal f o r
C obalt M olybdate C a ta ly s t FUR-3. . . . . . . . . . . . . .
6l
E f f e c t o f R e g e n e ra tio n on S u lf u r Removal f o r
A c tiv a te d B au x ite ( C ycloc e l ) C a ta ly s t Run LMR-I. . . . .
62
F ig tire 9
F ig u re 10
F ig u re 11
F ig u re 12
56
"30*"
TABLE I
COMPOSITION AND IDENTIFICATION OF CATALYSTS WSED '
Run No.
C a ta ly s t and
C om position
LMR-I
Cy1CloGel
100$ B au x ite
Id e n tific a tio n
Code
. Sb-2446-51
C a ta ly s t
M anufacturer
P o ro c e l Gorp.
OMR-2
C o b alt M olybdate
9 .5 $ MoOo ‘
3 .0 $ CoOT .
5 .0 $ -SiO2
2 . 0$ G ra p h ite
8 0 .5 $ Al2O3
C o-M o-0201-T -3/l6"
Harshaw Chemical
Company
Conoco-I
C o b alt M olybdate
9 .5 $ -MoOo
3 .0 $ CoO
5 .0 $ SiO2
2 . 0$ G ra p h ite
80.5$ Al2O3
O0-M0-O20I - T - 3/ 1 6 "
Harshaw Chemical
Company
U nion O il Co. C obalt
M olybdate 3 /1 6 "
Harshaw Chemical
Company
FUR-1,2 & 3
C obalt M olybdate
9 .5 $
3 .0 $
5 .0 $
2cQffo
8 0.5$
CAR-3 & 4
MoOo
CoO
SiO2
G ra p h ite
A l2O3
C obalt M olybdate
t
Union O il Co C obalt
M olybdate 3 /1 6 "
Harshaw Chemical
Company
MO-0203-T-1/8"
l 60—A—2—I
Harshaw Chemical
Company
9 .5 $ MoO3
3 . 0$ -CoG
5.0$- SiO2 '
2 .0 $ G ra p h ite
80o5$ Al2O3
CAR-1 & 2
Molybdenum Oxide
16$ MoO3
79$ Al2O3
5$ SiG2
TABLE I I
CHARGE OIL INSPECTION DATA
S m
W CO
3 0 .6
33 »0
32.6
38.2
3 6 .8
ASTM D i s t i l l a t i o n
0F , 640 mm Hg
I 0B0P..
425
5 K
504
10
520
20 .
536
30
548
40
558
50
567
60
575
70
584
80
594
611
90
62$
95
E0B0
652
R ecovery, Vbl % 99.0
R e sid u e , Vol %
0 .8
L o ss, Vol %
6.2
Wt. I ' S .
2.176
252
300
351
372
393
294
390
415
449
471
490
508
526
543
565
594
627
649
99.0
0 .5
0.5
0.9<
294
403
427
451
Q $x0) OS
SA
O=Sfc
CO
O ft
s i
308
469
330
371
394
484
500
514
413
427
442
530
550
424
436
449
459
460
*=•«=■
581
610
642
475
497
■ti
Cti
© CDJfctO to
",Ga
0 %
O Jh
O © ft
• C
iS iB w
IA
•H
CQ 1—I jr-\
cd © cd
-H
CO
»
•H
H
O
I
IA
CQ 1—I r H
O
Cd
CQ
cd
§ 5 #
O
E-c CO
ft O to
M
4 3 .6
41.0
33.8
334
359
406
,
470
#
372
490
503
8
. 138
———
236
389
410
492
UO
G ra v ity . oA .P6I e, 60°F;
Ii
•
. -P
co
•H
■Q
O
CDO
C
so
O=Sfc
co
O ft
-H
OH
O
mso
cti=?fc
CS „
&
J §
^ CO
d
0 to
Os
Cl IA
D e sig n a tio n ;
ra
ITO
.
-P
■f—
■—
»
422
■=**«■
■riu.mp
573
520
514
528
620
535
99.0
99.'^
99.0
0.5
0.5
0.5
0.5
0.5 • 0.5
0.975
0.551
0.623 0.874
402
415
427
442
457
475
500
520
534
99.0
I
0
0 .6 0 0
«3
rya c©
d
22.66
515
524
532
540
550
558
566
574
606
99.0
I
0
1 .2 8 0
3 .1 8
“
32
“
TABLE III
TABULATED. DATA FROM COBALT' MOLYBDATE RUBL-CMR-Z
C a t a ly s t:
CO“Mo"0201“ T“3 /1 6 11
IOO grams (u n re g e n e ra te d -fro m CMR-I*)
P re s su re s $00 p s ig
O ii:
Husky No. 3 f u e l o i l , 2 9 .7 ° A .P .I . an^ 2.18% S
R ecycle Gass C atform ing gas (See Table IV)
Y ield s
97.46 W eight %
3 3 .8 °A * P .I.
103 Volume %
0.309 % S
* R esearch by S ilv e y (1 0 )
Samp
No.
I
2
3
4
5
6
7
8
9
1 0.
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
T o ta l
Hours
8
16
24
32
40
48
56
64
72
80
88
779
779
777
780
777.
779
779
779
783
1 .003
1 .0 3 2
1 .015
1.003
1 .0 1 2
1 .0 0 2
0.985
1 .0 1 0
0.984
0 .9 7 0
7150
7010
7060
7150
7080
7200
7270
7100
7300
7400
7200
7450
96
780
779
780
779
0 .980
7350
136
144
777 ■
770
780
0.955
0.980
7520
152
160
168
176
184
192
200
27
28
216
224
232
240
248
256 .
32
779
104
112
120
128
208
31
779
0.996
0.967
0.967
0.984
26
29
30
Cat Temp Space Vel R ecycle
0F Av.
gms/gm/hr F t3 /b b l
778
779
766
780
780
781
781
779
781
781
779
781
1 .0 7 0
0.973
0.990
0.946
0.972
7360
7300
7330
6795
7320
7200
7660
7400
Av Gas Y ie ld
Consump Gms
F t3 /b b l O il
0
0
779
800
35.4
35.3
80.9
186.5
787
3 5 .1
777
35.2
318
786
778
765
3 5 .0
253
329
362
319
345
310
352
354
332
321
298
313
310
313
313
814
I .013
1 ,0 0 4
7130
294
7150
280
779
1 .016
7360
286
7420
7150
279
7375
7100
830
755
768
734
310
780
760
764
6990
7325
'
294
7400
0.980
0.975
750
750
763
760
740
330
0.975
I .003
783
762
753
773
336.2
1 .0 5 0
0.,975
0.975
P ro d u ct
A .P .I .
273
274
264
.279
0 .154
0.143
0 .144
0.145
"
3 5 .2
35.1
35.6
35.6
35.7
35.6
35.7 35.7
35.6
35.2
35.2
35.2
34.8
3 4 .8
P ro d u ct
%S
-
0.165
0 .148
0.160
0 .157
0 .2 0 8
'
0.210
0.220
0 .2 4 2
0.238
0.254
0.312
0.316
0.348
0.299
3 4 .3
3 4 .4
3 4 .5
0 .3 0 2
0 .3 1 4
0 .3 1 4
0.301
0.286
34.5
0.290
3 4 .5
34.8
757
787
780
756
756
779
34.5
0.288
0 .3 1 4
34
3 4 .1 0
34
0.292
0.319
761
757
788
34.1
34.2
34.1
0.310
.
0.337
0.342
0.333
—3 3 ”
TABLE I I I (con t»d ) '
Samp
No.
T o ta l
Hours
Cat Temp
°F Av 0
Space Vel
gms/gm/hr
R ecycle
F t3 /b b l
779
781
1 .002
779
1 .0 0 1
I . 010
7180
7200
7120
7120
7250
6840
33
264
272
34
280
35
288
36
296
37
38
304
312
39
320
40
328
41
42
336
43
344
352
44
45 . 360
46
368
47 . 376
48
384
392
49
400
50
408
51
52
416
53
424
432
54
440
55
56
448
456
57
58
464
472
59
60
480
6l
488
777
780
780
776
778
781
62
496
778
63
64
504
512
779
780
66
67
68
69
70
Tl
72
73
74
520
528
782
779
777
781
779
779
781
777
781
781
780
779
777
779
778
781
779
778
777
779
536
779
779
544
552
778
779
560
568
576
779
779
584
781
777
592 .
779
0.990
0.984
1 .049
1 .0 2 1
1 .0 3 1
1 .0 2 2
1 .0 1 6
1 .005
1.020
1 .0 0 0
0 .990
1 .0 2 0
1 .0 1 2
1 .0 2 0
1 .0 1 0
1 .0 1 2
1 .0 2 0
0.992
1 .0 0 5
0.985
0 .992
0.978
0.962
1 .0 0 1
0 .988
0 .9 6 0
1 .0 0 0
0 .991
0 .988
w-wee.*.
0 .8 8 ?
0 .905
0 .9 0 8
0.959
1 .0 1 8
1 .0 0 0
1 .0 3 0
I.O36
1.038
7030
Av Gas Y ie ld
Consump Gms
F t^ /b b l O il
268
777
767
776
782
762
813
793
800
25.8
270
260
261
269
261
265
P ro d u ct
A .-P.I.
34.2
3 4 .1
P ro d u ct
$ S
0.322
0.298
34.2
34.2
0 .3 0 8
3 4 .1
0 .3 0 8
0.346
33.9
34.0
0.307
0.355
0.327
7000
7020
7070
7150
7040
7190
7380
7050
251
250
252
255
7105
249
794
3 3 .9
7005
7110
7100
7050(7300
7200
7250
7240
7350
7450
7160
798
34.0
0 .3 1 8
791
3 3 .8
794
799
33.9
33.9
0.341
0.297
777
788
771
778
3 3 .8
8160
246
243
240
240
244
247
244
243
238
236
231
240
241
244
246
240
240
236
0.312
0.322
0.323
0.332
0.330
0.327
0.332
7810
7780
235
230
7260
7460
7200 •
7250
7260
Hauua
796
789
26?
259
258
781
794
775
775
799
.
228
225
229
, 228 .
6980
' ■228
6950 A
224.
7520
7080
7210
7040 "
766
754
785
774
752
784
3 4 .0
34.0
33.8
33.7
33.8
33.7
33.8
33.9
0.338
0.295
0 .3 2 0
0.296
0 .2 6 2
33.8
33.8
33.9
0.288
3 3 .8
3 3 .9
0.279
0 .2 4 8
33.8
33.8
33.9
33.9
0.255
0.294
0.273
0.292
776
3 3 .8
0.280
774
518
691
704
707
33.8
33.9
0.268
0.282
0.236
746
792
779
3 4 .9
35
34.9
0.233
0.233
3 4 .9
0 .2 5 1
801 .
806.
34.7
34.5
34.6
34.6
0.256
0.269
0.272
809 -
3 4 .6 .
0.272
0.284
TABLE III (cont'd)
Samp
No.
T o ta l
Hours
75
76
77
78
79
80
81
600
608
82
93
84
85
86
8?
88
616
624
632
640
648
656
664
672
680
688
696
704
Cat Temp
°F Av,
777
778
780
779
781
779
779
778
779
781
779
779
781
777
Space Vel
gms/gm/hr
R ecycle
F t3 /b b l
1 .0 1 2
I . 064
1 .0 1 5
1 .0 5 0
1 .0 2 1
1.043
1 .0 2 2
1 .0 2 2
1 .0 1 7
714Q
6770
7HO
0.959
6860
7060
6920
7050
7050
7520
0.952
7490
7690
7560
7560
0 .9 6 0
7460
0 .977
0 .9 6 7
I
Av Gas Y ie ld
Consump Gms
F t3 /b b l O il
225
230
237
787
830
790
233
229
818
227
224
224
222
222
220
216
220
220
795
813
P ro d u ct
A .P .I ,
34.5
34.4
33.8
33.9
33.7
33.5
33.6
33.7
33.6
33.7
P ro d u ct
%S
0.306
0.356
0.401
0.439
0.498
. 741
3 3 .6
748
0 .4 9 8
0 .5 0 0
0.517
0.547
0 .5 0 0
0.516
0 .5 2 0
0 .5 1 4
33.7
0.586
796
797
792
746
760
3 3 .8
752
33.7
-3 5 -
TABLE IV
GAS ANALYSES DATA FOR RUN CMR-2
Charge g a s :
C atform ing g a s , &)% Hg; 3>5% CHjlj 1*5% C2H6 ;
2 .5 $ C3H8 ; 3 05$ C^H6 ( a n a ly s is by M atheson Co,-)
C orresponding O il
Sample No,
Hour on
Stream
S ta rt
cttUta
6
IS
64
76
79
82
$3
48
144
512
60S
632
656 .
664
C orresponding O il ' R ecycle Gas A n aly sis
Sample % S
% GH4
$ C2+
$ H2
0.153
0 .1 4 8
0.295
0 .2 6 8
0.356
0 .498
0 ,5 1 7
0 .5 4 7
8 4 ,1
66.9
4 9 .1
51 .2
49
3 5 .0
3 5 .0
3 9 .0
1 3 .3
3 1 .4
4 6 .9
4 0 .2
3 8 .9
51.5
5 6 .0
5 1 .0
-
2 .6
1 .7
3 .2
2:3
1 2 .1
1 3 .5
9 .0
1 0 .0
-36
TABLE V
TABULATED DATA FROM COBALT MOLYBDATE RUN CMR-]>
FOR FIGURE 3
Sample No*
I
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
&5
90
95
100
105
108
T o ta l
Hours
% S u lfu r
In E f f lu e n t
O il
8
40
80
120
160
200
240
280
320
0*098
360
0.135
400
0.156
0 .0 3 5
0 .0 9 8
0.087
0.102
0.078
0.079
0.062
440
0.139
0 .1 5 1
480
520
0.103
560
600
640
680
720
760
800
840
858
0 .1 0 4
0.115
0.128
0.130
0 .0 8 0
0.062
0 .0 8 9
0 .1 4 1
0 .1 2 2
0.113
^'R esearch by F e Ce •S ilv e y (10)
Grams S u lfu r
Removed p e r
Kilogram
E f f lu e n t O il
2 0 .2 0
21.40
22.22
2 0 .9 0
20.72
20.85
2 1 .0 0
2 1 .1 4
2 1 .1 2
2 0 .4 0
20.32
2 0 .2 0
2 0 .6 2
20.62
2 0 .6 0
2 0 .4 8
2 0 .4 8
20.97
2 0 .8 7
2 0 .8 7
20.36
20.52
20.65
“37"
TABLE VI
TABULATED DATA FEGM CATALYST ACTIVITY RIM CAR-1
C a ta ly s ts Mo-02 Q3-T-1/G11
/
lOO grams (new)
Pressure; 500 p sig
O ils
Husky vacuum heavy gas o i l , 3„18$ S
R ecycle g a s: C atform ing gas (a p p ro x im a te ly 6 0 .5 # H9 )
Y ie ld s
97 w eight % (sam ples 1 -1 0 i n c l . )
96 w eig h t % (sam ples l l -13 in c l.-)
93 w eig h t % (sam ples 14-16 i n c l . )
89 w eight % (sam ples 17-19 i n c l . )
Samp
No.
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
T o ta l
Hours
7
15
23
31
39 '
47
55
63
71 .
79
8?
95
103
111
119
127
135
143
. 151
Cat Temp
0F Av.
777
781
777
779
801
795
799
816
810
816
837
830
335
379
874
336
928
923
9 io
Space Vel
gms/gm/hr
R ecycle
F tV b b l
0.815
0.946
0.906
0 .9 7 2
1.039
0 .960
0.995
1.013
0.955
0 .995
1 .0 7 7
0 .984
8080
7980
3340
7780
7320
7820
7620
7470
7930
7570
7060
7670
■— * -
1.013
1 .0 3 6
1 .026
0 .944
0.965
1 .0 1 2
7470
7310
7360
8030
7820
7470
Av Gas Y ie ld
Consump Gms
' F tV b b l O il
125
184
167
175
184
189
246
248
253
260
256
248
245
248
248
236
235
226
632
734
704
• 754
806
745
773
786
741
773
828
765
P ro d u ct
A .P .I .
2 9 .9
2 6 .4
2 6 .1
2 6 .1
26 .6
2 6 .6
2 6 .8
2 7 .1
2 6 .2
2 5 .3
2 8 .0
27.3
1
■iiulmi 1
rm m
754
770
763
679
695
729
2 9 .0
2 8 .1
2 8 .6
31#
2 9 .5
2 9 .1
P ro d u ct
%S
1 .6 8
1 .5 4
1 .5 1
1 .4 8
1 .4 2
1 .4 0
1 .2 4
1 .2 6
1 .2 5
1 .3 9
I .2 7
1 .3 7
1 .6 8
1 .6 4
1 .7 7
1.-73
1 .9 2
2 .08
2 .3 0
. -3 8 TABLE VlI
TABULATED DATA FROM CATALYST ACTIVITY RUN CAR-2
Mo-0203-T-l/B"
IOO grams (re g e n e ra te d from CAR-1)
P r e s s u r e : $00 p s ig
O il:
Husky vacuum heavy gas o i l , 2 2 .7 0AePeI . , 3.18% g .
R ecy cle Gass C atform ing gas (a p p ro x im a te ly 60.$% Ho)
Y ield s
89 w eig h t %■
C a ta ly s t:
Samp T o ta l
No. ■ Hours
1
2
3
8
16
24
Cat Temp Space Vel
°F Av.
gm s/gm /hr
936
921
919
0 .9 4 0
0 .9 9 8
0 .9 5 4
R ecycle
F t^ /b b l
8380
7570
7930
Av Gas Y ie ld
Consump Gms
F t3 /b b l O il
P ro d u ct
A .P .I .
P ro d u ct
% 8.
670
29.4
2.$7
711
68
2 7 .7
2 4 .4
2 .7 2
—
=•39=*
TABLE VIIi
TABULATED DATA FROM CATALYST ACTIVITY RUM CAR-3
C a ta ly s ts
Union O il Co1Se C obalt M qlybdate - 3 /1 6 "
iOO grams (new)
P re s s u re s
500 p s ig
O il:
Husky vacuum heavy g as o i l , 2 2 ,7 0AoP0I 0, 3 ,1 8 % Se
R ecycle Gas: C atform ing gas (a p p ro x im a te ly 6 0 .5 $ Hc,)
Y ields
9 7 .5 w eig h t % ( sam ples 1 -1 2 in cl,* )
9 7 .0 w eig h t % (sam ples 13-15 in c l,-)
96 w eig h t % (samples,- 16-18 in c l,.)
91 w eig h t % (sam ples 19-21 i n c l , )
Samp
No,
T o ta l
Hours
I
2
3
4
5
6
7
8
.9
10
11
12
13
14
15
16
17
18
19
20
2l
11
19
27
35
43
51
59
67
75
83
91
99
107
115
123
131
139
147
155
163
171
Cat Temp
0F Av,
Space Vel
gms/gm/hr
R ecycle
F t3 /b b l
0 ,827
9160
793.5
643
784
779
777 ,
774
796
796
800
814
813
0 .820
0.883
0.903
0.871
1 .0
0.983
0.975
0.993
0.993
D ™e a
eacac=»
831
834
835
880
879
878
926
921
921
0 .9 4 8
0 .930
0.949
0 .939
0.936
0.932
0 .9 6 6
0.913
0 .9 5 8
= = »
9220
8550
8390
8550
7570
7720
7620
7620
am a
7980
7980
8130
7980
8030
8080
8080
7830
8280
7930
Av Gas Y ie ld
Consump Gms
F tV b b i O il
283
262
208
2 l5
216
251
295
239
215
215
212
227
225
230
220
230
222
218
2 l0
203
2 l0
646
407
640
689
703
780
782
766
762
775
775
428
736
722
734
721
719
716
702
664
684
P ro d u ct
A .P .I .
2 9 .0
2 8 .1
2 9 .4
2 7 .7
2 7 .4
2 7 .2
2 7 .9
2 7 .8
2 8 .0
2 8 .6
2 8 ,4
Produi
%8
0.575
0 .6 7 0
O.585
0.796
0.871
0.990
0.895
0.875
0.850
0 .844
O.896
5
* M=*C=e
2 8 .5
2 8 .$
2 8 .4
3 0 .3
2 9.3
2 9 .6
3 0 .5
2 9 .5
2 8 .1
O.96O
0.973
IoO l
1 .1 5
1 .2 8
i .4 0
1 .6 7
1 .9 9
2 .1 1
TABLE IX
TABULATED DATA FROM CATALYST ACTIVITY RUH CAR-4
C a t a ly s t:
,
P ressu re;
G il;
R ecycle Gas:
Y ie ld :
Samp T o ta l
Ho.
Hours
6
0 ,
I
14
2
22
30
3
4
46
5
6
54
62
7
8
70
78
9
f
Union O il G o 's. C obalt M olybdate 3 /1 6 "
100 grams (regenerated fromCAR-3)
500 p s ig
Husky vacuum heavy g as o i l , 22„7 0AePe-Ie, 3 .1 8 % Se
C atform ing gas (a p p ro x im a te ly 60*5% Hg)
96.3 w e ig h t %
C at Temp
°F Ave
900
928
922
917
924
920
908
924
919
920
Space V el
gms/gm/hr
R ecycle
Ft-3Zbbl
0.860
0.898
G.915
0.915
0.920
0.925
0.891
0.933
0.925
8460
8090
7940
7950
7900
7880
8160
7800
7800
Av Gas Y ie ld
Cohsump Gms
F t3 /b b l O il
0
3 2 .2
6 6 .1
130.6
146.5
167.4
166.2
190.4
198
687
719
734
733
736
740
713
746
740
P ro d u ct
A .P .I .
3 0 .5
2 9 .4
29.2
28.8
28.6
2 7 .5
2 8 .4
2 8 .2
2 7 .7
P ro d u ct
%S
1 .3 2
1 .0 6
1 .2 9
1 .4 5
1 .64
1 .7 2
1.92
2.08
2 .2 8
2.43
-A l-
TABLE X
TABULATED DATA FBOM CONTINENTAL OIL RUN CONOCG-I
C ataly st-:
Co-M o-020l-T-3 /1 6 11
100 grams (new)
P ressu re:
$00 p s ig
O il:
C o n tin e n ta l O il Co’s , jsample No,, B i 987
43»1 0AeP eI , and 0 ,8 7 4 % S , (See T able I I )
R ecycle Gas: Conoco w aste gas (See. T able XI)
Y ie ld :
95»4 w e ig h t %
Samp
No,
i
2
3
4
5
6
7
8
9
10
11
12
13
14
15
T o ta l
Hours
16
24
32
40
48
56
64
72
80
88
.96
104
112
120
128
Cat Temp
°F Av,'
■
Space Vel R ecycle
gms/gm/hr F t^ /b b l
Av Gas Y ield
Consump Gms.
F t3Zbbl O il
775
0 ,8 8 0
9330
290
779
0.938 .
0,927
8880
243
720
209
269
668
294
319
345.
659
679
772
323
784
775
780
777
775
781
77&
776
780
777
778
782
778
780
0,875
0,862
0 ,888
1 ,0 1
1 ,0 2
1 ,0 2
0 ,972
0.963
1.03
1 ,0 4
0.955
0.938
8880
■9470
9600
9330
8900
8120
8120
856O
8560
7970
7880
8600
8800
'
302
306
306
305
278
259
239
P ro d u ct
AeP-,1,
673
4 4 .1
708
43.6
43.8
784
742
735
786
798
730
715
4 3 .6
4 3 .3
4 3 .5
4 3 .7
4 3 .6
4 3 .6
4 3 .7
4 3 .7
4 3 .7
4 4 .8
4 5 .0
4 4 .9
P ro d u ct
# S
0 ,1 3 8
0.140
0,146
0,144
0,129
0,122
0.144
0.146
0.142
0,138
0 .134
0.157
0.158
0.163
0.146
TABLE XI
GAS ANALYSES DATA FOR RUN CONOCOCorresponding Nature
O il Sample Noe
Of
Sample
I
Charge*
Gas
Vent
Gas
R ecycle
Gas
R ecycle
Gas
5
.11
Hpe on
Stream
% N2+H2
%E
———
=”=■
35«6
22
='"=
——
. 48
” =
92
34*4
30 e8
-x- A nalyses by Matheson Company
-X-X-
CHj^ p lu s higher compounds
$ C2H4
^ ^2
% OH4
9.2
3 2 .0
7.8
1 0 .1
5.3
2 4 .9
6
40.2
28.9
48
65.6**
^ 02%
B”” e“
% C2+
2 0 .4
% C3+
TABLE X II
ANALYTICAL DATA OF COMPOSITE SAMPLE FROM CONTINENTAL OIL' COMPANY rS
DESULFURIZED CRUDE TOMER OVERHEAD OIL SAMPLE NO. B i 937*
■gg
B illin g !
C ataly t:
D esulftu
S tra ig h i
G asolim
N Pd
Sample No.
G ra v ity ,°A P I
D i s t i l l a t i o n , °F
IBP
#
6547
I
O
E-i
f
h
I
6547
A=I
43.6
69.9
103
141
30#
203
234
234
332
40#
372
164
172
180
50#
60#
70#
' 30#
90#
95#
409
187
453
433
194
201
210
223
234
20#
§
A
139
10#
Q1
522
566
590
152
.
E .P . ’ 612"
258
R ecovery #
98.0
99.0
1 .0
R esidue #
0 .7
T o ta l S u lfu r Wt % 0.1470.03
M ercaptan C ontent
Wfc. %
0 .0 0 0 ?
-
I
I
8
rS
d ®h
CL
g
O
f t
S g
S 1S'
cxj >
6547
A=2
& §
O
f O
O
P,
^ I
O
O
ft-
TS
O
A
cn >
? &
O
P 1
VX|5
'J e
© fi
0
•P
CO cH
CD
CO Cs O >
6547
A=4
A-A
4 4 .6
344
352
354
357
338
361
364
366
370
374
382
388
38.5
410
424
426
431
435
439
443
447
453
459
470
478
A-5
32.3
507
522
525
122
172
190
210
226
240
534
252
538
542
269
347
554
0 .0 0 3 0 .1 2
0 .06
0 .2 8
-
-
—
—
59.2
528
530
532
560
331
356
500
409
575
99.0 99.0 99.5 99.0
0.8
0 .7
1.0
9.5
-
gCL,
ft
6547 6547 6547
A=3
52 .2
260
269
272
277
282
288
292
296
301
310
322
ft
^ g
m O
FQ
282
294
312
323
347'"
99.5
0.5
to
q ft©
.
•H
-P
4 I
cd Tf -=5 -=Il
© d© CYftM
^ O VXIA
ft Y T
©NO VO
iH rH
©
P
QtS.'fcQ
CO
4f\ ir\.
CDrH • • »
•H eO
H VCs-X -CYN
O
I
-S
W
.
0"
f t
O Ph p
&
0 0 cd
PQno >
6547
A=B
6547
A=C
6547
A—6
4 1 .4
35,8
29.1
352
421
443
449
368
372
381
387
iCo
I
457
466
395
475
484
402
411
422
■■■•ew
495
507
521
437
456
468
494
99.0
0.003
1 .0
0 .0 4
0.004
«
Z
^ A n a ly tic a l work done by C o n tin e n ta l O il Company, Ponca C ity , Oklahoma
338
549
565
99.6
1 .0
0.16
ew ew e-
***=
“ 44“
TABLE XIII
TABULATED DATA FROM FARMERS UNION RUN FUR-1
C a ta ly st;
Union O il G o's. Cobalt Molybdate 3 /1 6 ,T
( P re v io u s ly u sed f o r S t a t i s t i c a l Runs ( l l ) )
P ressu re;
800 p s ig
O il:
Farmers U n io n 's, 4 1 .0 0AePeI . and 0.600. % S (See Table I I )
R ecycle Gas: Farmers U nion's w aste gas (See Table XVl)
Y ie ld :
97«5 w eig h t % (e s tim a te d )
Samp
No.
I
2
3
4
5
6
7
8
9
10
11
12
T o ta l
Hours
5
13
21
29
37
45
53
6l
69
77
85
93
Cat Temp
°F Av.
760
781.5
775.5
779
780
778
765.5
781
776
775.5
782.5
777
Space Vel
gms/gm/Hr
6.896
0 .9 1 5
0.919
0 .940
0 .9 0 8
0 .9 0 8
0 .895
0 .859
0.893
0 .9 5 8
0 .9 6 0
R ecycle
F t3 /b b l
10030
9850
9800
9560
9900
9560
10130
10530
6500
6110
6110
Av Gas Y ie ld
Consump Gms
F t3 /b b l O il
223
587
566
432
444 •
384
323
297 .
103
447
374
663
714
716
733
708
708
698
669
697
747
748
P ro d u ct
A .P .I .
4 1 .6
‘4 1 .6
4 1 .6
4 1 .6
4 1 .6
4 1 .4
4 1 .5
4 1 .5
4 1 .5 ■
41*4
4 1 .4
P ro d u ct
%8
0 .0 6 8
0 .0 6 4
O.O65
0 .0 6 2
0 .0 6 4
0 .0 8 0
0 .0 7 5
0.076
0 .1 0 4
0.104
0.109
TABLE XI#
TABULATED DATA FROM FARMERS UNION RUN FUR-2
C a ta ly st;
Union O il G o's. Cobalt Molybdate 3 /1 6 11
lOO grams (p r e v io u s ly used fo r FUR-1
and S t a t i s t i c a l Runs ( l l ) )
Pressure;
800 p slg
0 il:
Farmers U n io n 's, 33»8 0AeP -.!. and I »280 % S 6
(See Table I I )
R ecycle Gas; Firmers U nion's w aste gas (See Table XVl)
Y ie ld ;
9 7 .5 w eight % (estim a ted )
Sarap
No.
I ,
2
*3
4
5
6
7
8
9
T o ta l
Hours
I
9
17
25
33
41
49
57
65
Cat Temp
0F Av6
Space Vel
gms/gm/hr
784.5
780
—mn.
748
782
777
0.848
0.984
0.959
0.985
0.994
0.988
0.986
777
767.5
779
780
0.926
^Sample 3 - power o f f Ig h rs, .
R ecycle
F t3 /b b l
Av Gas Y ie ld
Consump Gms
F t3 /b b l O il
P ro d u ct
A6B6I 6
. ■-
6460
7060
6100
9380
9140
8900
9090
9120
P ro d u ct
%S
0.436
500
722.3 3 5 .6
629
6 6 1 .0 ; '3 4 .3
0 .4 2 1
0 .5 3 0
497
202
137
104
176
234
767.0
747.5
769
774.5
35.3
35.4
35.1
O.425
0 .4 7 0
3 5 .0
0.508
771
35.0
O.525
769
3 5 .0
0.534,
0.450
TABLE XE.
TABULATED DATA FROM FARMERS UNION RUN FUR-3
C a ta ly s t;
Union O il Coi Se C obalt M olybdate 3/16".
lOO grams ( p r e v io u s ly u sed f o r FUR I & 2
and S t a t i s t i c a l Runs ( I l ) )
P ressu re:
800 p s lg
O il:
Husky No. 3 f u e l o i l , 2 9 . T 0A0EeI e and 2 .1 7 6 % S .
R ecycle Gas: Farm ers U n io n 's w aste gas (See T able XFI )
Y ie ld :
9 8.59 w eig h t % ■
Samp
No.
T o ta l
Hours
*1
2
3
4
5
8
16
24
32
40
Cat Temp
dF Av.
780
772
776.5
779.5
780
Space Vel
gms/gm/hr
0 .950
0.952
0.945
1 .0 0 2
0 .938
R ecycle
F t3 /b b l
9460
9400
9500
8920
9520
Av Gas Y ie ld
Consump Gms
F t3Zbbl O il
420
459
393
351
340
, 749
751
746.
791.3
740
P ro d u ct
A .P ..I.
3 1 .9
3 1 .5
31.5
3 1 .4
3 1 .7
•“"Sample I had s m a ll p e rc e n ta g e o f Farm ers Union F u el O il
P ro d u ct
# S
0.945
1 .1 8 0
1 .2 1 0
1.275
1.260
“47“
,TABLE XVI
GAS ANALYSES DATA FOR RUNS FUR-1, 2 , & 3
Charge G as:
U8.6% CH4 , 4 .2 # CO, 4 .7 # GO2 , 1 8 .3 # H2 and 2 4 .2 # N2
(A n a ly sis by M atheson Company)
N atu re o f Sample
Vent gas (77 h o u rs)
# n2+h2
# CH4
# G2E4
# C2Ea
64 .6
6 .7
7 .3
8 .7
R ecy cle gas a t end
FUR-2 & s t a r t o f FUR-3
2 8 .1
4 4 .5
rrumwn
R ecy cle gas a t end
o f FUR-3
25.3
6 2 .1
# C2 F
1 2 .7
2 6 .3
1 2 .6
__rr.
—4 8 -
. .
TABLE XVII
TABULATED DATA FROM LLOYDMIMSTER RUM LMR-I
C a ta ly s t:
C y clo ce l ( a c tiv a t e d b a u x i t e ) , Sb-2446-51
i.OO grams (new)
P ressure::
A tm ospheric (1 2 ,4 p s ia )
R ecycle G as: None
Y ie ld :
9 8 ,5 w eig h t %
Samp T o ta l
Mo, ' -Hours
(O il:
0
I
2
3
4
5
6
7
B
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Cat Temp
0F Av,
Space V el
gm s/gm /hr
R ecycle
F t-V b b l
Efflu­
e n t Gap
F t3 /b b l
Y ie ld
Gms
O il
P ro d u ct
A»P 01*
P ro d u ct
%8
Husky b le n d 3 4 .1 0AePeI . , 0,850 S 0 (See T able X V II'I)
3
11
1 .0 8 1
123
852
754
1 .1 1 0
19
749
131
875
2?
0 .9 4 8
751
129
747
762
6 7 .2
35 ;
0.989
778
43
753
0.945
4 7 .5
744
47.0
757
51.
1*049
824
(O il: Husky, b le n d , 3 4 ,0 ° A ,P ,I , and 0.783 # S .)
1.072
59
755
52*3
845
1 .052
67
32.6
755
829
1 .0 7 0
75
753
30.7
843
1 .0 1 8
802
83
754
28.3
808
91
1 .0 2 5
2 8 .3
753
99
747
1 .005
25.4
793
2 4 ,0
1 ,0 1 0
107
743
795
1 .0 0 1
2 2 ,6
115
754
787
123
1 .0 0 0
2 2 .0
788
746
(O il: Husky, b le n d , 3 3 ,9 0AePeI 0 and 0.823 % S .)
1 ,0 1 0
752
131
22.6
795
752
20.6
131
0.994
783
REGENERATION
762
762
147
0.967
65.3
758
61.4
155
0.951
749
58.6
163
0,945
745
757
4 8 .0
756
171
0.965
759
760
0.970
179
46.5
764
187
756
0.932
4 2 .7
734
32.6
0.929
195
732
753
752
203
0.947
37.9 . 745
( O il: Husky, b le n d ., 3 3 .8 qA » P ,I, and 0,807 ^ S1. )
211
752
3 1 .2
0.943
744
219
732
.754
P.929
29.3
REGENERATION
227
752
0.973
3 6 .0
766
35.1
3 4 .8
3 4 .7
34.6
34.6
3 4 .5
3 4 .5
34.5
34.5
34.5
34.5
0.384
0.397
0.432
0.449
0.459
0,502
0,425
0 .4 2 0
0.437
0 .4 4 2
P.453
3 4 .3
3 4 .2
3 4 .4
3 4 .4
" 0 .5 0 5
3 4 .2
3 4 .3 .
0 ,5 1 0
O.522
34.6
34.6
34.5
34.5
0.330
0.339
0,365
0 ,3 6 2
34*4
3 4 .4
0.390
0.380
34.5
0 .4 0 0
0.443
3 4 .4
3 4 .3
0 .455
0.413
0.470
34.3
0 .4 6 7
0 .500
3 5 .0
0.347
"49—
TABLE X Y H lcont *(3.)
TABULATED DATA FROM LLOYDMINSTER RUN LMR-I .
Samp
Noo
31
32
33
34
35
36
37
38
39
40
41
42
43
44
T o ta l C at Temp
Hours 0F Ave
Space V el
gms/gm/hr
(O il: Husky, b le n d .
235
749
756
243
750
251
259
763
267,
751
275
753
283
756
. 291
754 .. . •
(O il: Husky, b le n d .
299
759
307
757
315
757
323
753 '
752
331
339
753
R ecycle
F t- y b b l
E f f l u - Y ie ld
e n t Gas Gms
F t3 /b b l O il
3 3 .8 0AePeI e and 0 .8 0 7 % S.O
0.81?
9 5.0
643
0.672
4 6 .6
528
3 2 .6
468
0.595
1.408
6 2 .0
1110
0 .990
57.0
779
0.990
53.3
779
1 .158
4 5 .6
913
1 .1 5 0
906
45.6
34.3 0AePeI . and 0.754 # S e-)
1 .0 7 2
54.3
844
1 .136
50.9
895
862
1 .0 9 4
38.9
22 .6
1.189
936
606
6.769
1 3 .4
1 .1 7 8
928
13.9
P ro d u ct
AeP eI e
P ro d u ct
%S
3 4 .8
3 4 .8
3 4 .7
3 4.5
3 4 .4
3 4 .4
34.5
3 4 .5
0.342
0.354
0.380
0.352
0.376
0.372
0.374
0.377
3 4 .7
3 4 .6
3 4 .7
3 4 .6
3 4 .5
3 4 .4
0.385
0.393
0.453
0.478
0.466
■ 0.534
-5 0 -
TABLE m i l
OIL BLENDING DATA FOB LLGYDMINSTEB BUN LMB-I
E f f lu e n t
O il Samp No.
Source of. Blend
O i l , H usky’s Samp
No.
1 -6 i n e l .
7-15 "
16-26 "
2 7 -3 8 "
3 9 -4 4 »
L eG0O0
L.G .O .
L0G0O0
L.G.O.
L.G .O .
598
601
661
601
601
# By w t.
L0G0O0
^ By -wt.
K0 D.
& K.D.
& K0D0
& K0D0
& K0D0
&'K0Do
597 7 1 .7
. 2 8 .3
600 6 0 .7
3 9 .3
600 6 0 .7
3 9 .3
600 6 0 .7
3 9 .3
600 More K0D0 added to
s t r e t c h o i l b le n d
and s t i l l n o t v a ry to o f a r
from 0 ,8 % S i n blend*
G ra v ity % S i n
0A0-P0I 0 Blend
a t 60°F ■Oil
3 4 .1
3 4 .0
3 3 .9
3 3 .8
3 4 .3
TABLE XIK- '
TABULATED DATA FBOM LLOYDMINSTEB BUN LMB-I ■
A0S 0T eM. D i s t i l l a t i o n on LME-I Composite o f E f f lu e n t O il
( O il l e f t a f t e r s m a ll p o r tio n s w ere removed f o r a n a ly s e s )
G ra v ity °A.-P0I 0 a t 60°F
IBP
5 cc
10
20
30
40
50
60
70
80
90
95
E0P 0
Becovered
Efesidue
Loss .
3 4 ,3
277°F
362
380
404
425
442
460
471
488
514
548
582
601
9#
1 .8
0 .1
0 .8 5 0
0.733
0.823
0 80
0 .754
. ?
TO FHAA/e/Slf
Figure I .
O/l /A/
--------- AIO BiIJtAIdFF
'-• A W A /O lI M
AAIII
Schematic Flow Diagram o f D e su lfu r iz a tio n U nit
/-W A T IA IG COUX
/ CATAiYST
/-O V Si/lA T IO II
AACA PACSSUAE
VAlVE
CAVSTfC
SCAtfBACA
OH
. SAMPLE
52-
J0 VEN J
/"
O A //O N
(AMLf E N D )
I “x Z I mA / A E
CAA
BOAEO FOR
J P/PE
=3 —^ our
z " P IP E THERMO-
G P S
TO S U R G E
O ESSEL
/J
x /6
"P /P E
TO
\
I N R P P T O P ,A 4 fO O L E , A N D
b o t t o m
s e c t
E A C H W /T H
PRESSU RE
P /P E
/C
/ ONS OE REACTOR
j e r g u s o n
S /G N T G L A S S
3 3 ' R E A L fE O
N IC H R O A A f W IR E -0 .0 /6
CONTROLLER
O U fR fL O N
0 /A .
,/-X 2 “
/
S E L L N E //.
J ~ U A L .U C
NOTE:
L A U
/a 6
/0 0 0 R SL
P /P E
/S
f
SCH EO . SO
E X C E P T N O T E O O T H E R * //S E
N IP P L E '
2
/ “ U N / O N fcV,
A LL
A R E
P /P E
F /T T /N O S
2 0 0 0 A S J UNLESS
IfE A M L f E l/ij} \
NOTEO
C O N N E C T TB
O N O E W fA
3 /NSU LATE REACTOR
W f 3 " 8 5 % AOA<SNCSY/f
HffiCTOR
F ig u re 2 .
OTH ER W IS E
-N E fO L E V A L U E
C O N Q fN S fR
D e ta ile d Drawing o f R ea c to r and Condenser S e c tio n
p e a c e N T Hi mz r e c y c l e g a s
W T PERC EN T $ I # EFFLU£AJT
400
HOUHS ON S T R E A M
F ig u re 3 . P e rc e n t S u lfu r i n E f flu e n t O il and P e rc m t
Hydrogen in R ecycle Gas v s . O n-S trean Time f o r C obalt
I b ly b d a te C a ta ly s t, Run CMR-2
PERC EN T S >vy EF FLU E N T OiL
54-
a/
---------------4 0 --------------- 5 0 -------------- 60 ---------------7 0 ----------------00
PERCENT A ; M/ RECYCLE GAS
Fifrxire 4 . E f f e c t o f Hydrogen C ontent in R ecycle Gas on th e
S u lf u r C ontent in E f f lu e n t O il f o r C obalt M olybdate C a ta ly s t,
Run CMR-2
GtfAAfS S tf£ M Q V £ 0 P £ /f K tL Q Q fiA M C tM tfG f OtL
H O O tfS OH S T tfC tfM
F ig u re 5.
E f f e c t o f On-Stream Time on S u lfu r Removal f o r C obalt
'it
P E ffC E N T S (N E F F L U E N T OIL
i
4 2 0 --------- 4 3 0
4 6 0 -------- 4 7 0 ---------- 4 6 0 ---------- 4 9 0
CffZ ffL V S T T E M P E ffffT U R E - e C
I
F ig u re 6 . E f f e c t o f C a ta ly s t T em perature on D e s u lf u r iz a tio n , Run CAR I and 3
Molybdenum Oxide C a ta ly s t ■ o
C obalt M olybdate = x
I
vn
?
F ig u re 7 . E f f e c t o f On-Stream Time on S u lf u r Removal, Run CAR I and 3
Molybdenum Oxide = o
"
C obalt Molybdate - x
a
HOUftS QH STR EAM
F ig u re 8 , E f f e c t o f On-Stream Time on S u lf u r Removal f o r C obalt
M olybdate C a t a ly s t, Run C0N0C0-1
GJMAts S f t EA/K)\/£Q P fftK iL O G ftA ftf CJJftftGE Oft.
59'
HOOftS OAj S TftEftM
F ig u re 9 . E f fe c t o f On-Strearn Time on S u lfu r Removal
f o r C obalt M olybdate C a t a ly s t, Run FUR-1
M A M S S # £ M Q V £ Q P £ # K fL O G fiA M C H A R G E O ft
- 60-
HAORS ON S TREAM
F ig u re 1 0 . E f f e c t o f On-Stream Time on S u lf u r
Removal f o r C obalt M olybdate C a ta ly s t,
Run FUR-2
GRAMS S R£MOV€D P M XtLOCAAM
CHARGf OfL
-6 1 -
-------------- 2 4 -----------HOOAS OH STAfAAA
F ig u re 1 1 . E f f e c t o f On-Stream Time on S u lfu r Removal
f o r C obalt M olybdate C a t a ly s t, Run FUR-3
OAL
GR/jMS S R eu o ya o P£R KILOGRAM CHARGf
b
/—i.
O
Co
C ri
WOMRf AM STRfAM
F ig u re 1 2 . E f f e c t o f R eg e n e ra tio n on S u lf u r Renoval f o r A ctiv ated
B au x ite ( C y c lo c e l) C a t a ly s t, Run LKR-I
MONTANA STATE UNIVERSITY LIBRARIES
3
762 100 4356 7
N578
_ | H766c
cop. 2
Hooper, Howard C
3^ 6
110375
%
6oy>Z
MAY I I '58
1^ T T w t
U 0375t e e n e