The catalytic desulfurization of Wyoming fuel oil
by Oscar H Koski
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering at Montana State College
Montana State University
© Copyright by Oscar H Koski (1951)
Abstract:
The purpose of this investigation was to determine the conditions and contact agents necessary to
reduce the content of Husky Humber 3 fuel oil from 2.1% sulfur to 0.5% sulfur or less.
At atmospheric pressure, the desulfurization effected during a two-hour period by chrome-alumina,
molybdena alumina, cobalt molybdate, acid activated aluminas and acid activated bauxite were
determined on 500 gram samples in a fixed bed reactor at temperatures from 418°C to 422°C space
velocities of 1. and hydrogen rates of 1.74 ft^3 S.T.P. per hr. Of these catalysts, the acid activated
bauxites gave the maximum desulfurization to 1.01% sulfur in the effluent. Consequent investigation
revealed that this was about the maximum obtainable with bauxite or HF activated bauxite« In a
pressure reactor, using 1000 grams of catalyst, desulfurization through destructive hydrogenation was
effected with both cobalt molybdate and molybdena-alumina. Desulfurization to less than 0.5 per cent
sulfur in the effluent is possible with both catalysts.
Desulfurization increases with greater pressures through 500 psig and with larger hydrogen to oil ratios
through 0.76 liters H2 S.T.P. per gram of oil. Regeneration by air oxidation decreases the activity of
both catalysts.
Destructive hydrogenation is the only method investigated which will continuously produce a product
less than O.5 percent sulfur. THE CATALYTIC DESULFURIZATION
OF
WYOMING- FUEL OIL
:
■
by
OSCAR H. KOSKI
A THESIS
S ubm itted t o 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 cien ce in Chemical E n g in ee rin g
at
Montand S ty te C ollege
,==
Approved:
Head
Bozeman, Montana
S eptem ber, 1951
hi i n
K
—2 —
Page
A b s tra c t ................................. ........................................... .........................................................3
I n t r o d u c t i o n .................
...4
E quipm ent, Methods and M a te ria ls ............................... ....................................................8
Equipment ..................................................
8
Methods .....................................
...9
M a te ria ls .....................
.11
Sample C a lc u la tio n s ................................................
,12
R e s u lts and D isc u ssio n o f R e s u lts .............................................. ......................... .. .16
D e s u lf u r iz a tio n C h a r a c t e r i s t i c s o f v a rio u s
c a t a l y s t s a t atm o sp h eric p re s s u re . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 6
The r e l a t i o n s h i p o f p ro c e ss v a r i a b l e s to
d e s u l f u r i z a t i o n w ith b a u x ite .......................................... ................................ ... 17
D e s u lf u r iz a tio n by d e s tr u c ti v e h y d ro g e n a tio n
w ith m olybdena-alum ina and c o b a lt m olybdate
c a t a l y s t s ...................................
.19
Summary .................... ..................... ........................................................ ...............................23
L i t e r a t u r e C ite d ...................
.25
Acknowledgment .............
.26
A p p e n d ix ............................
.27
103000
■ABSTRACT
The purp o se o f t h i s in v e s t i g a t i o n was to d eterm in e th e c o n d itio n s and
c o n ta c t a g e n ts n e c e s s a ry to re d u c e th e c o n te n t o f Husky Humber 3 f u e l o i l
from 2 0\% s u l f u r t o Oe5^ s u lf u r o r le s s «
At atm o sp h eric p r e s s u r e , th e d e s u lf u r iz a ti o n e f f e c t e d d u rin g a tw o^hour
p e rio d by chrom e-alum ina, molybdena a lu m in a , c o b a lt m o ly b d ate$ a c id a c ti v a te d
alum inas and a c id ' a c ti v a te d b a u x ite were d eterm in ed on $00 gram sam ples i n a
f ix e d bed r e a c t o r a t te m p e ra tu re s from AlS0 C to 422°C sp ace v e l o c i t i e s o f 1®
and hydrogen r a t e s o f I 074 f t ^ S0T0P 0 p e r h r . Of th e s e c a t a l y s t s , th e a c id
a c ti v a te d b a u x ite s gave th e maximum d e s u l f u r i z a t i o n to I »01% s u lf u r in th e
e f f l u e n t , C onsequent in v e s t i g a t i o n re v e a le d t h a t t h i s was ab o u t th e maximum
o b ta in a b le w ith b a u x ite o r HF a c t i v a t e d b a u x ite .
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 , d e s u lf u r iz a ti o n
th ro u g h d e s t r u c t i v e h y d ro g e n a tio n was e f f e c t e d w ith b o th c o b a lt m olybdate
and m olybdena-alum ina, D e s u lf u r iz a tio n to l e s s th a n 0 ,5 p e r c e n t s u lf u r
i n t h e e f f l u e n t i s p o s s ib le w ith b o th c a t a l y s t s .
D e s u lf u r iz a tio n in c r e a s e s w ith g r e a t e r p re s s u re s th ro u g h 500 p s ig and
w ith l a r g e r hydrogen t o o i l r a t i o s th ro u g h 0 ,7 6 l i t e r s Hg S 0T0P0 p e r gram
o f o i l o R e g e n e ra tio n by a i r o x id a tio n d e c re a s e s th e a c t i v i t y o f b o th c a t­
a ly s ts O
D e s tr u c tiv e h y d ro g e n a tio n i s th e o n ly method in v e s t ig a te d which w i l l
c o n tin u o u s ly produce a p ro d u c t l e s s th a n 0 ,5 p e rc e n t su lfu r®
INTRODUCTION'
Because o f i t s d e le t e r i o u s e f f e c t s when p re s e n t in e n g in e f u e l s , th e
rem oval o f s u lf u r from p etro leu m d i s t i l l a t e s has re c e iv e d c o n s id e ra b le
a tte n tio n fo r se v e ra l decades.
-Prim ary i n t e r e s t has c e n te re d on th e d e s u l­
f u r i z a t i o n o f g a s o lin e b e ca u se o f th e g r e a t demand fo r i t s u se as a m otor
fu e l.
H ow ever,' common methods f o r th e d e s u lf u r iz a ti o n o f g a s o lin e a re n o t
a p p lic a b le t o th e h e a v ie r d i s t i l l a t e s s m ain ly b ecau se o f th e d if f e r e n c e i n
th e ty p e s o f s u l f u r compounds p r e s e n t.
In g e n e ra l th e s u l f u r p re s e n t in
h e a v ie r d i s t i l l a t e s i s more p re d o m in a n tly th io p h e n ic and hence n o t , re c e p t i v e t o b a u x ite tre a tm e n t /
Also
t h e c o n v e rsio n o f -m e rc ap ta n s -to d i s u l ­
f i d e s ■i s n o t o f any i n t e r e s t in t h e ..p ro d u c tio n .’o f - h e a v ie r •d i s t i l l a t e s s in c e
th e p rim a ry problem i s th e r e d u c tio n o f s u l f u r t o s p e c if ie d l i m i t s .
B ecause o f in c re a s e d u t i l i z a t i o n o f th e d i s t i l l a t e s h e a v ie r th a n g a s­
o l i n e , such a s d i e s e l and j e t engin e f u e l s , a d d itio n a l in c e n tiv e i s p la ce d
on th e developm ent o f p ro c e ss e s c a p a b le o f pro d u cin g co m m ercially a low
s u lf u r p ro d u c t.
The s u p p ly o f low s u l f u r f u e l 'o i l s a re o f p a r t i c u l a r im­
p o rta n c e to our n a tio n a l d e fe n s e , s in c e a t th e h ig h te m p e ra tu re s o f - j e t
en g in e o p e r a tio n t h e o x id a tio n compounds o f s u lf u r w i l l combipe w ith th e
e n g in e m e ta l p ro d u c in g weakness where s t r u c t u r a l s tr e n g th i s o f prim e im­
p o rta n c e .
■
The purpose o f t h i s in v e s t i g a t i o n was t o d is c o v e r th e c o n ta c t a g e n ts
and p ro c e s s e s n e c e s s a ry t o produce a f u e l 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 r c e n t .
A l i t e r a t u r e su rv e y was conducted f o r th e purpose o f in d ic a tin g suc­
c e s s f u l -avenues o f approach to t h i s d e s u lf u r iz a ti o n p ro b lem .
The r e s u l t s
I
5
o f t h i s su rv e y show t h a t a prepond eran ce o f work has been d ir e c te d tow ard
th e d e s u l f u r i z a t i o n o f g a s o lin e s and n a p th a s .
u sed f o r th e d e s u l f u r i z a t i o n a r e a s fo llo w s :
Some o f th e c o n ta c t a g e n ts
b a u x ite , le a d alu m in a, bo ro n
p h o sp h ate on a lu m in a ,■ c h a rc o a l im p reg n ated w ith a lk a li,- asp h ero n c la y s , and
a c o b a lt m olybdate c a ta ly s t*
Among th e a g e n ts used f o r s u l f u r rem oval from
h e a v ie r d i s t i l l a t e s a r e n ic k e l on a lu m in a , copper and n ic k e l on alum ina and
c o b a lt m olybdate*
I t i s e x p ec te d t h a t a com m ercially s u c c e s s f u l c o n ta c t d e s u lf u r iz a ti o n
a g e n t w i l l s a t i s f y th e fo llo w in g c r i t e r i a :
Io
P r a c t i c a l d e s u l f u r i z a t i o n below te m p e ra tu re s o f i n c i p i e n t carbon
to carbon c ra c k in g ,
2,
Long c a t a l y s t l i f e ,
3o
P r a c t i c a l r e g e n e r a tio n ,
4,
R easonable c o s t and a v a i l a b i l i t y .
For a n a ly s is o f th e f i r s t c r i t e r i o n i t sh o u ld be p o in te d o u t t h a t th e bond
e n erg y f o r a carbon to carb o n bond ($ 8 , 6
t h a t f o r a carbon to s u l f u r bond (54.$
i s o n ly s l i g h t l y h ig h e r th a n
I th u s i t would seem e v id e n t
t h a t any th e rm a l c ra c k in g o f th e carb o n t o s u lf u r bond would b e accom panied
by c o n s id e ra b le carbon t o carbon c ra c k in g .
This f a c t i s s u b s ta n tia te d by
d a ta ( 6 ) on th e th e rm a l c ra c k in g o f s u l f u r -stocks where s e v e n ty - f iv e p e rc e n t
o f th e s u l f u r rem ained in th e re s id u e * ..A- d e s u lf u r iz a ti o n a g e n t must be
s e l e c t i v e i n i t s a c tio n i n o rd e r t o e f f e c t •d e s u lf u r iz a ti o n w ith o u t d egrad­
a t i o n o f th e h y d rocarbon m o lecu les o th e r th a n th e s u l f u r c o n ta in in g m o le c u le ,
B ie re a r e two ty p e s o f c o n ta c t a g e n ts w hich a re o f i n t e r e s t in e f f e c t ­
in g t h i s s e l e c t i v e d e s u l f u r i z a t i o n .
One i s th e ty p e o f c o n ta c t a g en t which
o p e ra te s th ro u g h th e medium- o f ch em ical r e a c t i o n , e « g ,: IiiO( 2 ) .
T his ty p e
o f c o n ta c t a g e n t h as th e -in h e re n t -d isad v a n ta g e- ^of- d im in ish in g a c t i v i t y w ith
d e s u l f u r i z a t i o n a cc o m p lish e d , and -thus f r e q u e n t re g e n e ra tio n , i s re q u ire d *
A nother c la s s o f c o n ta c t a g e n ts e f f e c ts - d e s u lf u r iz a ti o n th ro u g h a p ro c e ss
o f d e s tr u c ti v e h y d ro g e n a tio n .
Cawley and H a ll (3 ) d e s t r u c t i v e l y h y d ro g en ated
th io p h e n e arid p henyl m ercap tan w ith-a-m olybdenum d i s u l f i d e c a t a l y s t a t tw erity
atm ospheres o f p re s s u re t o produce hydrogen s u l f i d e -and -a h y d ro c a rb o n .
B yrns e t a l (2 ) r e p o r te d th e d e s u l f u r i z a t i o n o f g a s o lin e h ig h i n s u lf u r w ith
a cobalt-m olybdena-alxim ina c a t a l y s t .
The c h o ic e o f c o n ta c t a g e n ts t o be
u sed i n th e d e s tr u c ti v e h y d ro g e n a tio n o f h ig h s u lf u r s to c k s m ust o f n e c e s s ity
(1 ) have a c ti v e s u l f i d e s as -h y d ro g e n a tio n a g e n ts (molybdenum, tu n g ­
s te n e t c . )
( 2 ) o r form u n s ta b le -s u lf id e s w hich -y ie ld a c tiv e h y d ro g e n a tio n a g e n ts
a t th e te m p e ra tu re s below i n c i p i e n t crack in g *
(3 ) o r h y d ro g e n a tio n a g e n ts which do n o t form s u l f i d e s on c o n ta c t
w ith s u l f u r b e a r in g o i l .
The in h e r e n t d is a d v a n ta g e s o f t h i s p ro c e ss a re -the o p e r a tio n a l c o s ts a s s o c i­
a te d w ith p ro d u c tio n and r e c y c lin g o f la r g e v olum es-of hydrogen in com parison
w ith t h e volume o f o i l t r e a t e d .
S in ce th e -economy o f any p ro c e ss f o r d e s u l­
f u r i z a t i o n i s o f prim e im p o rta n c e , i t i s im p e ra tiv e t h a t t h i s in v e s t i g a t i o n
sh o u ld b e g in w ith th e c h ea p e r c o n ta c t a g e n ts a t th e l e s s ex p en siv e c o n d itio n s
o f o p e ra tio n *
An i n i t i a l s tu d y was made on th e d e g re e o f d e s u lf u r iz a ti o n p o s s ib le
w ith b a u x ite , a c id g a se s w ith b a u x ite , a c id g a se s -w ith a lu m in a , and' m e ta llic
compounds on a lu m in a , a l l a t atm o sp h eric p re s su re *
-7 -
A d d itio n a l work under s u p e r-a tm o sp h e ric c o n d itio n s was done on b a u x ite ?
m olybdena-alum ina, and c o b a lt m oly b d ate.
The e f f e c t s o f p r e s s u r e , .hydrogen
to o i l r a t i o , sp ace v e l o c i t y , te m p e ra tu re and c y c le tim e w ere b r i e f l y i n ­
v e s ti g a te d where th e r e s u l t s in d ic a te d f r u i t f u l s tu d y .
-S EQUIFHEHT, METHODS, MD MATERIALS
EQUIPMENT
Three r e a c t o r s were u sed in t h i s in v e s tig a tio n *
Two w ere d esig n ed
f o r u se a t atm o sp h eric p r e s s u r e and one f o r u se a t su p er atm o sp h eric p re s ­
s u re s up t o n in e hundred pounds p e r sq u a re in c h .
Schem atic diagram s o f th e r e a c t o r s and t h e i r a u x i l i a r y equipment a r e
shown i n F ig u re s I , 2 and 3»
In g e n e r a l d e sig n th e s e u n i t s were i d e n t i c a l .
They w ere c o n s tr u c te d from s t e e l p ip in g j h e a t e d - e l e c t r i c a l l y and in s u la te d
w ith la y e r s o f a s b e s to s ta p e a n d magnesia'-mud.
th r e e - in c h i n t e r v a l s alo n g th e c a t a l y s t b e d .
Thermowells were p la ce d a t
The p re h e a t s e c tio n c o n s is te d
o f e i t h e r ir o n b a l l s o r b e r l s a d d le s , t h e form er b ein g more s u ita b le f o r
good te m p e ra tu re c o n t r o l , b u t h av in g th e d isa d v a n ta g e o f p ro d u cin g poor c o lo r
s t a b i l i t y i n t h e p ro d u c t.
The su p er a tm o sp h eric r e a c t o r , as- shown in F ig ­
u r e I , was c o n s tr u c te d w ith a p a r t i c u l a r e f f o r t f o r s a f e t y o f o p e r a tio n .
C re c e iiu s (4 ) g iv e s an e x c e lle n t d e t a i l e d d e s c r ip tio n o f th e c o n s tr u c tio n
o f th is re a c to r.
A u x ilia ry equipm ent c o n s is te d o f a c a l i b r a t e d m anom eter,
Met t e s t m e te r s , w a te r c o o le d copper tu b e c o n d e n se rs, hydrogen ta n k s w ith
p r e s s u r e r e g u l a t o r s , r e c e iv e r f l a s k s and a l k a l i s c r u b b e rs ,
Ir o n -c o n s ta n ta n
th erm o co u p les w ere u se d i n c o n ju n c tio n w ith a Leads and N o rth ru p in d ic a tin g
p o te n tio m e te r f o r te m p e ra tu re m easurem ent.
-9 -
METHODS .
C o n tro l and m easurem ent o f p ro c e ss v a r ia b le s were conducted a s sum­
m arized i n th e fo llo w in g p a ra g ra p h s :
1 . T em p eratu re;
T em perature was c o n tr o lle d by a d ju s tin g th e in p u t
t o th e Nichrome h e a tin g elem ents w ith a u to -tra n s fo rm e rs >
T em peratures were
m easured w ith Ir o n -c o n s ta n ta n therm o co u p les used in c o n ju n c tio n w ith a Leeds
and N orthrup i n d ic a tin g p o te n tio m e te r *
T em peratures were re a d a t f iv e m in u te
i n t e r v a l s and th e a r ith m e tic a v erag e f o r e v e ry sample p e rio d re c o rd e d ,
2 , Hydrogen r a t e :
The hydrogen r a t e in th e a tm o sp h eric p re s s u re ru n s
was c o n tr o lle d by a d ju s t in g th e r e g u la to r n e e d le v a lv e and m easured w ith a
c a l i b r a t e d m anom eter,
In th e su p er a tm o sp h eric r u n s , hydrogen r a t e was
m easured w ith a wet t e s t m e te r.
C o n tro l o f th e hydrogen r a t e was e x e r c is e d
by a d ju s tin g t h e r e g u la to r o u t l e t p re s s u re i n c o n ju n c tio n w ith a n e ed le
v a lv e a tta c h e d to th e r e g u la to r and t h e r e a c t o r e x i t v a lv e*
At th e b e g in —
n in g o f each r u n , th e r e a c t o r was p r e s s u r e iz e d and th e r e g u l a t o r n e e d le
v a lv e and r e a c t o r e x i t v a lv e a d ju s te d so a s to g iv e th e d e s ir e d r a t e o f
flo w w h ile m a in ta in in g th e r e a c t o r a t o p e ra tin g p r e s s u r e ,
A ru n n in g re c o rd
was made o f th e volume o f e x i t g a se s (H^S f r e e ) and th e hydrogen r a t e o v er
each sam ple p e rio d was d e term in e d from t h e s e d a ta .
A lthough a sm all amount
o f uncondensed hydrocarbon g a se s may be i n th e hydrogen and a p o rtio n o f
th e hydrogen consumed in th e h y d ro g e n a tio n , i t was c a lc u la te d t h a t th e s e
com pensating e r r o r s would n o t in tro d u c e a t o t a l e r r o r o f more th a n 10 p e r­
c e n t i n th e hydrogen r a t e . - B ecause the--hydrogen r a t e d e c re a se d a f t e r th e
ru n commenced due to th e in c r e a s e in r e s i s t a n c e o f th e c a t a l y s t bed and th e
d e c r e a s in g o f p r e s s u r e i n th e hydrogen ta n k , i t was im p o s sib le to f i x a c ­
c u r a t e l y th e hydrogen r a t e a t th e b e g in n in g o f th e r u n .
=>10“
3 , Space v e l o c i t y :
Space v e l o c i t y was a l t e r e d by pump a d ju stm e n ts
and d e term in e d a t t h e end o f each ru n from c a lc u la tio n s in v o lv in g th e w eig h t
o f o i l c h a rg e d 5 th e c a t a l y s t c h a rg e , and t h e o n -stre a m tim e*
4 9 -P re ss u re :
The r e a c t o r p re s s u re d u rin g s u p e r-a tm o sp h e ric ru n s was
c o n tr o lle d by m anual -adjustm ent o f th e r e a c t o r e x i t v a lv e in. c o o rd in a tio n
w ith v i s u a l o b s e rv a tio n o f th e r e a c to r p r e s s u r e g a g e * •
The d e te rm in a tio n o f th e s u lf u r c o n te n t o f th e p ro d u c t and s to c k o i l
and t h e carbon laydown on th e c a t a l y s t was d e term in e d in th e fo llo w in g ways:
(1 ) S u lf u r c o n te n t:
S u lf u r c o n te n t o f t h e in f l u e n t and e f f lu e n t o i l
was d e term in e d by th e lamp s u l f u r m ethod, ( I ) .
In b r i e f , th is
method in v o lv e s t h e com bustion o f a w eighed sam ple o f o i l and th e
a b s o r p tio n o f th e s u l f u r d io x id e produced in a known amount o f base*
The ex cess b a se i s d eterm in ed b y t i t r a t i o n w ith a s u i t a b l e a c id and
in d ic a to r *
(2 ) Carbon laydow n:
Carbon laydown d u rin g -atm ospheric p re s s u re was
d e term in e d by c a t a l y s t w eig h t gain *
T his method i s in h e r e n tly i n
e r r o r due to th e l o s s o f m o is tu re b y th e c a t a l y s t and th e g a in i p
w e ig h t due t o a d s o r p tio n o f o i l .
Though these- f a c t o r s a re compen­
s a t i n g i n e f f e c t , th e l a t t e r i s g e n e r a lly l a r g e r .
Carbon laydown
d u rin g su p er a tm o sp h eric ru n s was d eterm in ed by b u rn in g th e carbon
o f f th e c a ta ly s t- b e lo w 600°C*
The e x h au st g a se s w ere m etered and
a n a ly z e d w ith an o r s a t f o r CO, Og, and COg c o n te n t*
Carbon laydown
was c a lc u la te d from th e m eter r e a d in g s and carb o n c o n te n t o f th e b u rn o f f g a se s a s shown i n th e sam ple c a l c u l a t i o n s »
T h is method te n d s tp
y i e l d h ig h e r r e s u l t s th a n a c t u a l due to th e p re s e n c e o f adsorbed
H2S and o i l on th e c a t a l y s t and t h e o x id a tio n o f t h e m e ta llic
s u l f i d e s to m e ta llic o x id e s and s u l f u r d io x id e » T h is e r r o r can be
lim it e d by c a r e f u l blow down o f th e c a t a l y s t -with hydrogen a t th e end
o f each run*
I t m ight be n o te d h e r e ■t h a t s te a m -s trip p in g o f th e b a u x ite
c a t a l y s t w ith o u t b u rn o ff re d u c ed i t s a c t i v i t y presum ably due to ad so rb ed
w a te r v a p o r« T his phenomenon would p e rh a p s n o t e x h i b i t i t s e l f i f b u rn ­
o f f was conducted a f t e r s t r i p p i n g , s in c e i t would te n d t o remove th e
ad so rb ed w ater*
Materials
T his s tu d y was made e x c lu s iv e ly on a com m ercial g ra d e o f f u e l o i l
a v a il a b le from th e Husky O il Co. o f Cody, Wyoming.
T his p a r t i c u l a r d i s ­
t i l l a t e i s known a s Husky #3 f u e l o i l and h a s th e fo llo w in g p r o p e r tie s :
1.
B o ilin g p o in t ran g e (460-660 oF)
2.
M ean-M olecular w eig h t (C a lc , o f 200)
3.
S p e c if ic g r a v i t y
0.8734
S u lf u r c o n te n t
2.10%
. 4.
5,
A.S.TJM. D i s t i l l a t i o n T a b le -I
A l i s t o f c a t a l y s t s u sed in t h i s s tu d y , to g e th e r w ith i d e n t i f i c a t i o n
codes and th e m a n u fa ctu rin g c o n c e rn , i s g iv e n in T able I I .
T h is l i s t
in c lu d e s a n ic k e l b a u x ite (P o ro c e l) w ith n ic k e l n i t r a t e and decomposing th e
n i t r a t e a t 440°C i n a -stream o f a i r .
hydrogen
The n ic k e l was th e n red u ced w ith
-1 2 -
SAMPLE CALCULATIONS
The c a lc u la tio n s in v o lv e d i n th e d e te rm in a tio n o f space v e l o c i t y ,
hydrogen to o i l r a t i o , and carb o n laydown a r e b e s t d em o n strated by th o se
computed from t y p i c a l r u n s .
The fo llo w in g i s th e d a ta re c o rd e d on one such
ru n .
V - I O .K .,
B .M ,,
J u ly 2 6 , 1951
K ,0>, p . 8?
Run 70
C a t, 1000 g r a s , Harshaws C obalt-M oly,
(Same a s Run 69
No R eg en ,)
Bar 6 4 1 .0
R e a c to r P r e s s ,
S . V. t o be c a l c .
Time
M in,
Samp.
No.
0-30
30-60
60-90
90-120
» 120-150
150-180
I
2
3
4
5
6
300 # /in ^
# S
Avg .
Tempv
0 ,311
0 .348
0.343
0.355
0.333
0.346
400
399
408 403
404
400
Samp,
Wt. 404
428
461
423
433
513
T o ta l e f f l u e n t
2662
O il ch arg ed
O il o u t
2802 grams
2662 grams
T o ta l lo s s e s
140 grams
C
L ite rs
E x it Hg
222393
605
798
980
1131
mmHg,
Temp.
E x it H,
24°C
24°C
24gC
24°C
24°C
24°G
~13“
Loss on Charge
C a lc u la tio n
UG X 100 =
2802
B,
5*0%
C a lc u la tio n o f Space v e l o c i t y
2802 s rm se o i l ch arg ed
3 H rs 6 (lOOO grams c a t . )
A OQ1.
grins , o i l
grm, c a t .
C a lc u la tio n o f a v erag e s u l f u r in e f f l u e n t
Wt6 sample
Wt6 S u lf u r i n E f flu e n t
# S
x
x
x
x
x
x
404
428
461
423
433
513
0,311
0,348
0,343
0,355
0.333
0 ,346
1 .2 5 5
1 ,4 8 9
1 ,5 8 1
1,503
1.443
1 .7 7 5
9.046 grams
Avg6 S u lfu r in e f f » = 2-sPA.6 grams S 6 =
2662 grams e f f . '
De
0 .3 4 0
C a lc u la tio n o f Hydrogen to o i l r a t i o Cavg6)
T6P 6
H2O a t 2 4 °G =
P 6P6
d ry H2
6 18,6
760
x
=
2 2 .4 nurn. -Hg6
6 4 1 .0 — 22»4
C273)
273 +' 24
x
-
6 1 8 ,6 m6m6 Hg6
S S 'g m s . o i l
=
° - 302
L lte rs
srm 6 o i l
E0
C a lc u la tio n
of
B u r n -o ff
S in c e r e g e n e r a tio n o f th e c a t a l y s t on th e ru n from--which th e p re c e e d in g d a ta w ere ta k e n i s n o t w a rra n te d , th e fo llo w in g d a ta were s u b s t i t u t e d
from a n o th e r r u n 0
( P lo tte d F ig , 1A)
15
30
60
90
120
1 2 ,5
3 7 .5
75
H
XJl
O
D ata:
225
300
1 0 ,0
1 4 .7
1 5 .1
1 3 .2
6 .0
1 .5
3 .4
2 .3
2 .4
2 .5
1 .0
0
0 .2
0 .5
0 ,5
1 .1
1 0 .0
1 5 .2
1 3 .4
1 7 .0
1 7 .6
1 5 .7
7 .0
1 .5
Time M inutes
5
L i t e r s E f f lu e n t
by A n a ly sis
s '
CO
°2
T o ta l CO + CO2
(T o ta l V ol. E f f lu e n t i n L i t e r s (CO2 + CO) b y)
( g r a p h ic a l i n t e g r a t i o n o f F ig , 1 a
)
T em perature = 24°C
Wt, Carbon
Burned o f f
_
_ ^ 0I l i t e r s
V0P 0HgO = 2 2 ,4 P r e s s , = 639
(6 3 9 -2 2 ,4 )
ToO
x
273
273 + 24
x 3 6 ,1 = 1 4 .4 grm s. Cbh
* C o rre c tio n f o r V,P» o f HgO n e c e s s a ry s in c e g ases a re m etered w ith
w et t e s t m eter
CO + CO2 CONTENT (LITERS)
2 0
O __________________________ ____________ _________________________ _____________ I___
O
IOO
200
300
LITERS
EXHAUST GAS
F ig . IA P lo t o f B u rn -o ff Data
RESULTS MD DISCUSSION
•
De 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 v a r io u s c a t a l y s t s a t atm o sp h eric
p re ssu re *
T able I I I and F ig u re s 4 , $ , and 6 p r e s e n t th e - d e s u lf u r iz a ti o n c h a r­
a c t e r i s t i c s o f a c id a c ti v a te d b a u x ite 5 a c id a c ti v a te d a lu m in a 3 chromealum ina j m olybdena-alum ina# Harshaws c o b a lt m olybdate and Union O il Go*
c o b a lt m o ly b d a te .
These t e s t s were co n d u cted a t a tm o sp h eric p r e s s u r e , a
sp ace v e l o c i t y o f 1*083 grams 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, av erag e
ru n te m p e ra tu re s from 40? to 422°C, a hydrogen r a t e o f 1*74 f t ^ S,T*P» p e r
h o u r, and an on stre am tim e o f two h o u rs on f i v e hundred gram sam ples o f th e
c a t a l y s t s a s i d e n t i f i e d i n T able II*
i s found i n F ig u re 3*
A sch em atic diagram o f th e a p p a ra tu s
The charged o i l , which i s s ta n d a rd -throughout t h i s
s tu d y , c o n ta in s -2*10$- s u lf u r *
I t may be n o te d t h a t th e m e ta l o x id e-alu m in a
c a t a l y s t s [F ig* 6 ) e x h ib it a c h a r a c t e r i s t i c d e c lin e i n a c t i v i t y w ith on­
stre a m tim e*
As w ith th e work o f Haas ( $ ) , t h i s i s a p p a r e n tly due t o th e
i
fo rm a tio n o f m e ta llic - s u lf id e s - * ■■ The -b e st d e s u lf u r iz a ti o n was o b ta in e d w ith
m olybdena-alum ina which gave an a v e ra g e e f f l u e n t o f 1*08 p e r c e n t s u lfu r*
The a c id a c t i v a t e d alum ina c a t a l y s t exhibits--low - i n i t i a l a c t i v i t y w ith
th e HCL a c ti v a te d alum ina y ie ld in g th e b e s t r e s u l t s * ( F ig . $)*
The a c id
a c t i v a t e d b a u x ite c a t a l y s t s ( F ig . 4 ) y i e l d a b o u t-th e -sa m e o v e r a ll r e s u l t
w ith t h e HF a c ti v a te d b a u x ite e x h ib itin g - 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 and
th e HCL a c ti v a te d b a u x ite th e h i g h e s t - f i n a l a c t i v i t y .
BF3 a c ti v a te d b a u x ite
gave a p ro d u c t o f good c o lo r s t a b i l i t y w h ile th e - o th e r s d id n o t .
The maxi­
mum o v e r a l l d e s u l f u r i z a t i o n f o r t h i s group was -obtained w ith a c id a c ti v a te d
b a u x ite , w ith t h e e f f l u e n t o i l c o n ta in in g an av erag e o f 1*01 p e r c e n t s u l f u r
f o r t h e tw o -h o u r p e r io d .
“■17“
The r e l a t i o n s h i p o f ‘p r e s s u r e , hydrogen r a t e , te m p e ra tu re and space
v e l o c i t y t o d e s u lf u r iz a ti o n w ith b a u x ite *
The d a ta r e l a t i v e t o th e e f f e c t o f hydrogen r a t e on th e d e s u lf u r iz a ti o n
o f t h i s o i l a t a tm o sh p eric p re s s u re may be found in T able IV s
o f th e r e s u l t s o f th e s e s i x r u n s , r e f e r t o F ig , 7»
For a p l o t
T his p l o t shows no d i s T
c e rn a b le e f f e c t o f hydrogen r a t e from r a t e s o f zero to 1 ,7 4 f t ? S0TePe p e r
h o u r»
The r e l a t i o n s h i p s e x i s t i n g betw een te m p e ra tu re and d e s u lf u r iz a ti o n w ith
b a u x ite c a t a l y s t a t sp ace v e l o c i t i e s o f 4 ,1 and I gram o f o i l p e r gram o f
c a t a l y s t p e r hour a r e p re s e n te d i n T able V and F ig , 8 ,
T his p l o t in d ic a te s
t h a t th e same d e s u l f u r i z a t i o n can be o b ta in e d a t b o th sp ace v e l o c i t i e s in
th e v i c i n i t y o f 440°C.
S in c e te m p e ra tu re and c o n ta c t tim e may be c o n sid e re d
a s a com posite v a r i a b l e , i t i s odd t h a t a t th e -same te m p e ra tu re two v a lu e s
o f c o n ta c t tim e sh o u ld y i e l d th e same r e s u l t u n le s s th e r e a c t i o n went t o
c o m p le tio n .
T hus, i t i s in d ic a te d t h a t ab o u t h a l f th e s u l f u r p re s e n t in
th e o i l i s r e c e p tiv e to b a u x ite t r e a t m e n t , ■ The -maximum d e s u lf u r iz a ti o n ob­
ta in e d was su ch as to y ie ld a p ro d u c t s l i g h t l y over one p e r c e n t s u l f u r .
The e f f e c t o f sp ace v e l o c i t y on d e s u lf u r iz a ti o n w ith a HF a c tiv a te d
b a u x ite and w ith b a u x ite a lo n e i s g iv e n in T ables VI and V I I ,
p h i c a l l y p r e s e n ts t h i s r e l a t i o n s h i p .
F ig , 9 g ra ­
I t may be n o te d , by in s p e c tio n o f t h i s
p l o t , t h a t convergence o f b o th space v e l o c i t y cu rv es to y i e l d a p ro d u c t o f
s l i g h t l y l e s s th a n one p e r c e n t s u l f u r a t z e ro space v e l o c i t y i s in d ic a te d .
The sp ace v e l o c i t i e s ra n g e from 8 ,2 t o 0 ,2 5 grams 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.
In th e o r y , th e d is c u s s io n o f th e p re c e d in g a p p lie s h e re a l s o .
-1 8 -
Maximum d e s u lf u riz a - tio n sh o u ld be o b ta in e d a t th e lo n g e s t c o n ta c t tim es o r
■
lo w e st sp ace v e l o c i t i e s .
I
T his i s s u b s ta n tia te d by th e r e s u l t s .
The e f f e c t o f p r e s s u r e on d e s u l f u r i z a t i o n can be d e term in e d from th e
r e s u l t s o f two ru n s on f r e s h b a u x ite c a t a l y s t a t a tm o sp h eric and 500 p s ig
■
a s re c o rd e d i n T able V I I I ,
s l i g h t l y n e g a ti v e .
.
,
.
'
:i
The e f f e c t o f p re s s u re i s shown t o be o n ly
The im p lic a tio n drawn from t h i s f a c t i s t h a t th e p o r tio n
o f th e d e s u l f u r i z a t i o n ta k in g p la c e u n d er b a u x ite tr e a tm e n t i s p r im a r ily o f
an i r r e v e r s i b l e n a t u r e «
The p a re n t h y d ro carb o n m olecule c o n ta in in g s u l f u r
y ie ld s a c o n d e n s ib le p ro d u c t i n th e b o i l i n g p o in t ran g e o f 196°F to 660°F
and hydrogen s u l f i d e and o th e r gaseous p ro d u c ts n o t l i q u e f i e d i n a w a te r
c o o led c o n d e n se r«
I t m ight be added t h a t r e c y c le o f t h e o i l red u ced th e s u l f u r c o n te n t
t o a minimum o f s l i g h t l y l e s s th a n one p e r c e n t.
T his s u b s t a n t i a t e s th e
d a ta on sp ac e v e l o c i t y v e rs u s d e s u l f u r i z a t i o n (F ig , 9 ) w here th e e f f e c t o f
i n f i n i t e c o n ta c t tim e o r z e ro sp ace v e l o c i t y showed a minimum o f s l i g h t l y
l e s s th a n one p e rc e n t s u lf u r in th e e f f l u e n t .
R ecycle o i l w ith a s u l f u r
c o n te n t o f 1 .1 p e r c e n t was t r e a t e d w ith a n ic k e l im p reg n ated b a u x ite (8$ )
I
I
I
N ic k e l) w ith th e r e s u l t o f o n ly 0,022 grams o f s u lf u r removed p e r gram o f
n ic k e l.
R e g e n e ra tio n o f t h i s c a t a l y s t b y s u c c e s s iv e a i r o x id a tio n and r e ­
d u c tio n w ith hydrogen f a i l e d .
D e s u lf u r iz a tio n was th e n e q u a l t o t h a t ob­
ta in e d by r e c y c lin g o v er b a u x ite .
A c o r r e l a t i o n betw een d e s u lf u r iz a ti o n and p er c e n t t o t a l lo s s on o i l
charged was com piled from th e r e s u l t s o f 17 ru n s on b a u x i t e , a c id a c ti v a te d
b a u x i t e s , and alum ina c a t a l y s t s .
(T ab le IX , F ig , 1 0 ) .
The ru n s w ere con­
d u c ted a t atm o sp h eric p r e s s u r e over a ra n g e o f space v e l o c i t i e s o f 0 ,5 to
j
8 .2 grams 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 te m p e ra tu re ra n g in g
!
“
from 350° to 450°Ce
19
"
I t can be deduced t h a t d e s u lf u r iz a ti o n to a p ro d u ct
„ o f s l i g h t l y o v e r one p e rc e n t s u l f u r w i l l in v o lv e a t o t a l l o s s ' o f s l i g h t l y
o v er 5 p e r c e n t f o r b a u x ite and from 6 to 9 p e r c e n t f o r a c id a c tiv a te d
b a u x ite s »
These lo s s e s in c lu d e carbon laydown and uncondensed g a se s .
B a u x ite in s e v e r a l tw o-hour ru n s shows no c a t a l y s t w eig h t g a in which was
a m easure o f carbon laydow n.
D e s u lf u r iz a tio n th ro u g h d e s tr u c ti v e h y d ro g e n a tio n w ith m o ly b d en a-alumina and c o b a lt m olybdate c a t a l y s t s .
The mechanism o f th e e lim in a tio n o f th e s u lf u r compounds n o t r e c e p tiv e
t o b a u x ite tre a tm e n t may be proved t o be one o f h y d ro g e n a tio n »
Through th e
e x c lu s io n o f hydrogen o r th e h y d ro g e n a tio n c a t a l y s t d e s u lf u r iz a ti o n i s
m arkedly d e c r e a s e d .
(See T able V III)
The r e l a t i o n s h i p e x i s t i n g betw een d e s u lf u r iz a ti o n and te m p e ra tu re was
o b ta in e d from th e d a ta o f th r e e ru n s on molybdena alum ina c a t a l y s t and
p l o t t e d in F ig , 11 from th e in fo rm a tio n i n T able Xe
These w ere s u b je c t t o
l i m i t a t i o n s in p r a c t i c a l u se a s a r e f e r e n c e b ecau se o f th e numerous f a c t o r s
a ffe c tin g - r e s u l t s ,
These f a c t o r s w i l l be d is c u s s e d l a t e r .
T his curve was
found u s e f u l 5 however <, in th e d e c is io n to in v e s t ig a te th e e f f e c t s o f o th e r
p ro c e ss v a r ia b le s in th e neighborhood o f Zj-OO0 C5 s in c e a l a r g e in c re a s e i n
d e s u l f u r i z a t i o n i s n o t in d ic a te d w ith in c r e a s in g te m p e ra tu re s .
From g e n e r a l
c o n s id e r a tio n s 5 a minima sh o u ld be o b ta in e d i n th e p l o t o f d e s u lf u r iz a ti o n
v s . te m p e ra tu re on an o v e r a l l a v erag e o f lo n g p e rio d r u n s 9 s in c e th e carb o n
laydow n and co n seq u en t d e a c tiv a tio n o f th e c a t a l y s t w ould, a t some p o i n t ,
be g r e a t e r th a n th e in c re a s e d d e s u l f u r i z a t i o n o b ta in e d b y r a i s i n g th e tem­
p e r a tu r e .
S in c e te m p e ra tu re and hydrogen t o o i l r a t i o b o th a f f e c t carbon
=SO =
laydown as shown in T able I l 5 h ig h e r te m p e ra tu re s m ay b e u sed in c o n ju n c tio n
w ith h ig h e r hydrogen to o i l r a t i o s w ith o u t p r o h ib i tiv e carbon laydow n.
An in d ic a tio n o f th e e f f e c t o f p re s s u re on th e d e s u lf u r iz a ti o n e f f e c te d
w ith a molybdena-alu m in a c a t a l y s t i s shown in T able X II and i n F ig u re 12»
The d a ta was s e le c te d from ru n s a f t e r f i v e and s i x r e g e n e r a tio n s to l i m i t
th e e f f e c t o f r e g e n e r a tio n .
In s p e c tio n o f F ig , 13 (Runs SO5 S l 5 and 825
T able X III ) s u b s t a n t i a t e th e r e s u l t s o f F ig , 1 2 , s in c e a g r e a t e r in c re a s e
i n d e s u l f u r i z a t i o n i s r e a l i z e d th a n can b e ex p ected from t h e d if f e r e n c e i n
hydrogen t o o i l r a t i o ,
A lso5 th e d e d u c tio n t h a t th e mechanism i s one o f
h y d ro g e n a tio n i s in p a r t s u b s ta n tia te d by th e f a c t t h a t in c re a s e d p re s s u re s
g iv e in c re a s e d d e s u l f u r i z a t i o n ,
However5 from g e n e r a l c o n s id e r a tio n s , th e
e f f e c t o f p re s s u re in c r e a s e sh o u ld a ls o te n d t o r e v e rs e th e e lim in a tio n o f
hydrogen s u l f i d e u n le s s t h e r e a c tio n i s o f an i r r e v e r s i b l e n a tu r e .
The
e f f e c t o f h ig h e r hydrogen to o i l r a t i o s sh o u ld te n d t o m inim ize t h i s nega­
tiv e e ffe c t of p re ssu re .
The e f f e c t o f hydrogen to o i l r a t i o s upon d e s u lf u r iz a ti o n w ith a m olybd en a-alu m in a and a c o b a lt m olybdate c a t a l y s t i s in d ic a te d i n F ig , 135 which
was p l o t t e d from th e d a ta o b ta in e d from 14 ru n s a t te m p e ra tu re s in th e v ic ­
i n i t y o f 400°G and space v e l o c i t i e s from 0*764 to I 6O ll grams 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, a s p re s e n te d i n T able X III*
L in e s a re drawn
th ro u g h th o s e p o in ts w hich a r e b e s t s u ite d f o r com parison w ith r e s p e c t to
th e number o f r e g e n e ra tio n s on th e c a t a l y s t p re c ed in g th e r u n , and th e h i s ­
t o r y o f th e c a t a l y s t ,
"Wild" r e s u l t s w ere o b ta in e d from ru n s 8 0 , 8 1 , 82
(T ab le X III ) u s in g h ig h hydrogen to o i l r a t i o s .
b y th e d if f e r e n c e in th e h i s t o r y o f th e c a t a l y s t ,
T his i s a p p a r e n tly caused
In e lu c i d a tio n o f t h i s
—2 1 =
rem ark 5 i t must be p o in te d o u t t h a t th e c a t a l y s t which produced th e s e r e s u l t s
(Runs 8 0 , 8 1, and 8 2 , T able X III ) was n e v e r exposed to low hydrogen to o i l
r a t i o s o r te m p e ra tu re s i n e x cess o f 410 C»
I t may be th e o r iz e d t h a t i n t h e
ru n s a t low hydrogen to o i l r a t i o s (Run $51 e tc * ) th e -fo r m a tio n o f a more
a c ti v e molybdenum s u lp h id e to o k p la ce *
S in ce b o th hydrogen t o o i l r a t i o s
and te m p e ra tu re s were d i f f e r e n t f o r th e two t e s t s on f r e s h molybdena—alum­
in a c a t a l y s t a t 300 p s i g ’ (Runs 57 and 8 6 ) T able X I I I , th e p r e c is e re a so n f o r
th e v a ria n c e in a c t i v i t y i s n o t known*
From t h e d a ta on ru n s 60, 7 0 , and 71
T able X I I I , i t sh o u ld be n o te d t h a t t h e c o b a lt m olybdate c a t a l y s t e x h ib ite d
a p e rio d o f in c re a s e d a c t i v i t y d u rin g th e second th r e e h o u r run*
T his a ls o
may be a t t r i b u t e d t o th e fo rm a tio n o f a h ig h ly a c ti v e molybdenum s u lf id e *
I f t h i s i s t r u e , i t would le n d cred en ce t o th e assu m p tio n t h a t an a c ti v e
molybdenum s u lp h id e i s formed a t a b o u t 400°C and a t low hydrogen to o i l r a t i o s *
In th e o r y , t h e h y d ro g e n a tio n sh o u ld be d eterm in ed by hydrogen p r e s s u r e
alone*
One may th e n wonder a t th e in c re a s e d d e s u l f u r i z a t i o n e f f e c te d w ith
h ig h e r hydrogen t o o i l r a t i o s *
T his f a c t i s b e s t e x p la in e d by th e d e d u c tio n
t h a t th e h y d ro g e n a tio n and e lim in a tio n o f hydrogen s u l f i d e from th e p a re n t
hydro—carb o n m olecule i s r e v e r s i b l e r e a c t i o n and t h u s , t h e h ig h e r hydrogen
t o o i l r a t i o s te n d t o s h i f t th e e q u ilib riu m tow ard th e p ro d u c tio n o f th e
h y d ro carb o n and hydrogen s u l f i d e by rem oving and d i l u t i n g t h e hydrogen s u l­
fid e *
S in c e b a u x ite w i l l remove t h a t p o r ti o n o f th e s u l f u r , i t m ight be
found f e a s i b l e t o b a u x ite t r e a t th e o i l p re v io u s to -h y d ro g en atio n t o re d u c e
th e s u l f u r compound c o n c e n tra tio n a n d , c o n sq u e n tly re d u c e th e hydrogen to
o i l r a t i o s n e c e s s a ry f o r a g iv e n d e s u lf u r iz a ti o n *
A lso , t h e e f f ic ie n c y o f
th e h y d ro g e n a tio n m ight be improved b y c o n c e n tra tin g th e s u l f u r b e a rin g
-2 2 -
p o r tio n o f th e o i l th ro u g h s o lv e n t e x t r a c t i o n follow ed b y b a u x ite tre a tm e n t
and h y d ro g e n a tio n * '
The e f f e c t o f r e g e n e r a tio n by a i r o x id a tio n can be deduced from a s tu d y
o f Fig* 1 3 o
C obalt m o ly b d ate, a f t e r one r e g e n e r a tio n , th o u g h v a s tl y more
a c t i v e in a f r e s h c o n d itio n , approach es th e a c t i v i t y o f m olybdena-alum ina„
The e f f e c t o f r e g e n e r a tio n on m olybdena-alum ina can be a s c e r ta in e d by fo llo w ­
in g th e code g iv e n on Fig* 1 3 .
v i t y o f th e c a t a l y s t .
In g e n e r a l, r e g e n e r a tio n d e c re a s e s th e a c t i ­
'
The t o t a l l o s s on o i l ch arg ed f o r b o th m olybdena-alum ina and c o b a lt
m olybdate i s in th e ran g e o f from 4*5 to 6 p e r c e n t.
However, i n re v ie w ,
th e lo s s e s w ith b a u x ite a lo n e , a re a ls o i n t h i s ra n g e .
The la b o r a to r y d a ta from which th e p re v io u s f ig u r e s and t a b le s were
com piled i s p re s e n te d in T able XIFe
"
2 3 *=
SUMMARY
One may j u s t l y c r i t i c i z e some o f th e d e d u c tio n s and d is c u s s io n p re ­
s e n te d in th e r e s u l t s a s n o t b e in g su p p o rte d by a s u f f i c i e n t b u lk o f data*
These w ere in c lu d e d , how ever, w ith th e hope t h a t th e y may be o f a s s is ta n c e
to th o s e who c o n tin u e th e work upon t h i s d e s u lf u r iz a ti o n problem*
Of th e t e s t s a t atm o sp h eric p re s s u re on a c id a c tiv a te d a lu m in a , chrom ea lu m in a , m olybdena-alum ina, c o b a lt m olybdate and a c id t r e a t e d b a u x ite s , t h e
a c id t r e a t e d b a u x ite s gave th e lo w e st o v e r a l l d e s u lf u r iz a ti o n f o r th e tw oh o ur p e rio d and were u nique in th e f a c t t h a t a c t i v i t y was f a i r l y un ifo rm
th ro u g h o u t th e t e s t .
D e s u lf u r iz a tio n w ith b a u x ite o r . HF a c ti v a te d b a u x ite re a c h e s a maximum
where th e e f f l u e n t o i l c o n ta in s a p p ro x im a te ly one p e rc e n t s u l f u r .
A tte n d an t
lo s s e s a re 5*2 p e rc e n t w ith b a u x ite and 6 to 9 p e rc e n t f o r HF and b a u x ite .
C ontinuous d e s u l f u r i z a t i o n th ro u g h d e s tr u c ti v e h y d ro g e n a tio n t o a p ro d u ct
lo w er th a n 0 ,5 p e rc e n t s u l f u r f o r p e rio d s in .e x c e s s o f n in e h o u rs a t space
v e l o c i t i e s o f one i s p o s s ib le w ith b o th c o b a lt m olybdate and m olybdenaa lu m in a ,
The r e s p e c tiv e hydrogen t o o i l r a t i o s and p r e s s u r e s a r e (8 ,3 l i t e r s
H2 S 0TeP . p e r gram o f o i l and 300 p s ig f o r c o b a lt m o ly b d ate) and (0 ,6 3 l i t e r s
H2 SeTeP , p e r gram o f o i l and 500 p s ig f o r m o ly b d en a-alu m in a).
The e f f e c t
o f th e fo llo w in g - f a c t o r s on 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 p ro d u c t f o r
a m olybdena-alum ina c a t a l y s t .- i s summarized a s fo llo w s ;
p r e s s u r e s ■— d e c re a s in g th ro u g h 500 p s ig
te m p e ra tu re s — d e c re a s in g th ro u g h 430°C„
. _ -z- l i t e r s HpS0T0P ,
Hydrogen t o o i l r a t i o n — d e c re a s in g th ro u g h 0 ,7 b
gram o f o i l
=»2Z).<"
r e g e n e r a tio n by an o x id a tio n — in c r e a s e s
s u l f i d i n g o f c a t a l y s t — d e c re a s e s
The t o t a l lo s s e s on o i l charged a r e a l l i n th e ra n g e o f from 4»5 to
8 p e r c e n t3
. I n .c o n c lu s io n , d e s t r u c t i v e h y d ro g e n a tio n i s th e o n ly p ro c e s^ i n v e s t i ­
g a te d which w i l l c o n tin u o u s ly produce an o i l w ith a s u lf u r c o n te n t l e s s tfyan
0 o5 p e r c e n t«
«»
25
”
LITERATURE CITED
(1 )
AeS6TeH, S ta n d a rd s on P etro leu m P ro d u c ts and L u b r ic a n ts , American
S o c ie ty f o r T e s tin g M a te r ia ls ^ P h ila d e lp h ia , p« 272 ( l 9 4 l )
(2 )
B yrns, .A, C ,, B ra d le y , .¥« E , , and. L e e , Me W6, Lnde Eng* Chem6
l i , 1160 (1943)
(3 )
CawlSy, C* Me, and H a l l , Ce C6, . J e Soce Chem6 In d , 6 2 , 116-19 (1943)
(4 )
C r e c e liu s , R6 L 6, .M6 S 6 T h e s is , Montana S ta te C o lle g e , (1949)
( 5)
H aas, P , , M6 S6 T h e s is ; Montana S t a t e C o lle g e , (1951)
(6)
S achanen, A6, "C onversion o f P etroleum " (T ex t)
R ein h o ld P u b lis h in g C o ,, Mew Y ork, P6 216 2nd E d itio n (1948)
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 o f Cody, Wyoming, who spo n so red t h e w ork on t h i s problem and fu r n ­
is h e d th e f u e l o i l u sed th ro u g h o u t th e i n v e s t i g a t i o n .
*=
27
—
APPENDIX
T ab le I
T able I I
T able I I I
D ata on D e s u lf u r iz a tio n C h a r a c te r is tic s o f
T able 17
D e s u lf u r iz a tio n v s . Hydrogen R ate (
T ab le V
D e s u lf u r iz a tio n v s . T em perature ( b a u x i t e ) . . , , «»*33
T able VI
D e s u lf u r iz a tio n v s . Space V e lo c ity ( b
T ab le V II
D e s u lf u r iz a tio n v s . Space V e lo c ity (HF and b a u x i t e ) . 34
T ab le V I I I
D ata on th e E echanism o f D e s u l f u r i z a t i o n .. . . . . . . . . . . . . . . . . * 3 5
b
a
u
a
x
u
i
x
t
e
i t e
)
«33
) , 34
T able IX
T a b le X
D e s u lf u r iz a tio n v s . T em perature ( m o l y b d e n a - a l u m i n a ) ,37
T able XI
Carbon Laydown v s . Tem perature and Hydrogen to O il R a t i o . . . 37
T ab le X II
D e s u lf u r iz a tio n v s . P re s s u re (m o ly b d en a-alu m in a). . . . . . . . . *.38
T able X I I I
C o r r e la tio n o f D e s u lf u r iz a tio n w ith Hydrogen
tO Oxl RatXOn e t c « • e * * e * * # e * » e e e » e » * » * * e * * * *
* * ® * » * e
* , e e e e e '
T ab le XIV
A c o m p ila tio n o f L a b o ra to ry D ata b y Run N u m b e r . . . . . . . ......... «40
F ig . I
Diagram o f h y d ro g e n a tio n equipm ent f o r su p ert-atm o sp h eric
WOrk e o e o a e e e
e e
********^3
*
*
*
*
*
*
*
*
»
*
*
*
*
»
*
*
*
*
»
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
F ig . 2
Diagram o f a tm o sp h eric system f o r c a t a l y t i c d e s u lf u r iz a ti o n
F ig . 3
Diagrain f o r c o n tin u o u s a c id a c t i v a t i o n o f c a t a l y s t . . . . . . . , . 5 5
F ig . K
P lo t o f d e s u l f u r i z a t i o n v s . o n -s tre a m tim e f o r a c id
a c ti v a te d b a u x ite c a t a l y s t s . . , . . » . . # . . . . . . . . . . . » » . . » •
• ♦ « « • » 5 6
F ig . 5
P lo t o f d e s u l f u r i z a t i o n v s . o n -stre a m tim e f o r
m e ta llic -o x id e -a lu m in a c a t a l y s t s and a c id a c t i v a t e d
F ig . 6
P lo t o f d e s u l f u r i z a t i o n v s . o n -stre a m tim e f o r m e t a l l i c o x id e alum ina c a t a l y s t s and c o b a lt m olybdate c a t a l y s t s , 5 8
oceSdm
-F ig , 7
P lo t o f hydrogen r a t e v s - d e s u l f u r i z a t i o n w ith b a u x i t e •« » » * ,.5 9
F ig* 8
P lo t o f te m p e ra tu re v s . d e s u l f u r i z a t i o n w ith b a u x i t e . . . . . . . . . 6 0
Fig* 9
P lo t o f Space V e lo c ity v s . D e s u lf u r iz a tio n w ith
HF and b a u x i t e .
..................
«6l
Fig* 10
P lo t o f % l o s s on c h arg e v s , d e s u l f u r i z a t i o n . ............................... ..6 2
.F ig . 11
P lo t o f te m p e ra tu re v s . d e s u l f u r i z a t i o n w ith
m olybdena-alum ina. . . . . . . . . . . . . . . . . . . .
................ • ........... ..» .6 3
Fig* 12
P lo t o f R e a c to r p r e s s u r e v s . d e s u lf u r iz a ti o n w ith
m olybdena-alum ina................»64
Fig* 13
P lo t o f hydrogen to o i l r a t i o v s . d e s u l f u r i z a t i o n
w ith m olybdena-alum ina and c o b a lt m o ly b d ate. . . . . . . . . . . . . . . . . . 6 5
-2 9 TABLE I
Ai S1T1M. D i s t i l l a t i o n Data
P e rc e n t
F i r s t drop
5^
10
20
30
40
50
60
70
80
90
F in a l Temp.
% R ecovery
% S u lf u r
Feed O il
B au x ite
T rea te d
HF
+
B au x ite
T reatm ent
460°F
500
518
534
546
556
566
576
586
600
621
660
196°F
348
450
500
526
540
552
564
576
590
614
662
180°F
340
442
496
522
538
550
562
574
588
610
660
98
2 .0 4
98
1.055
98
1 .0 2 5
Molybdena
Alumina
196°F
365
438
492
513
538
548
562
576
592
6 l6
658
97
0.465
C obalt
M olybdate
2l6°F
406
460
506
518
540
551
564
579
591
616
66l
9 8.5
0 .3 9
-3 0 -
TABLE I I
CATALYSTS
C a ta ly s t
B a u x ite (P o ro c e l)
Alumina
Chrome-alumina
M olybdena-alum ina
C obalt-m olybdate (H)
C obalt-m olybdate (U)
N ic k e l-B a u x ite
I d e n t i f i c a t i o n Code
SB
Al
Cr
Mo
Co
-
2446 - 51
0104 . T 1 /8 »
0202T
l/8 "
0602T
1 /8 "
Mo - 0201T 1 /8 "
Producer
P o ro ce l Corp.
Harshaw Chemical Co.
Harshaw Chem ical Co.
Harshaw Chem ical Co,
Harshaw Chemical Co.
Union O il Co.
Made in L a b o ra to ry
-3 1 TABLE I I I
DESULFURIZATION CHARACTERISTICS OF VARIOUS
CATALYSTS AT ATMOSPHERIC PRESSURE
S.V . = 1.083
C a ta ly s t
500 Grams
H- R ate - 1 ,7 4
^
gram c a t . h r .
On-Stream
Time (Min)
Avg, % S u lf u r
in E f f lu e n t
Avg. Temp,
uC
B a u x ite
+
HF
0
30
60
90
-30
- 60
- 90
- 120
0 .9 2
0 .9 9
1 .0 5
1 .0 8
427
410
412
412
B a u x ite
+
HCL
0
30
60
90
-30
- 60
- 90
- 120
1 .0 3
1 .0 3
0.951
0 .9 5
425
408
404
405
B a u x ite
+
BFo
J
0
30
60
90
-30
- 60
- 90
- 120
1 .0 0
1 .0 1
1 .0 1
1 .0 1
420
418
409
404
M olybdenaAlumina
0-30
30 - 60
90 - 120
0.83
1 .0 1
1 .1 6
411
414
416
HCL
+
Alumina
0
30
60
90
-30
- 60
- 90
- 120
1 .1 3
1 .0 9
1 .1 4
1 .1 8
415
433
427
412
Alumina
+
HF
0
30
60
90
-30
- 60
- 90
- 120
1 .3 6
1 .2 3
1 .2 5
1.23
425
427
417
420
ChromeAlumina
0
15
30
90
-15
- 30
- 60
- 120
1 .1 2
1 .1 9
1 .2 4
1 .315
405
413
414
407
HR.
D ata From
Run
#34
#36
#51
#48
#37
#38
#49
-3 2 TABLE I I I
D E SU L FU R IZ A T IO N
(C O N T IN U E D )
C H A R A C T E R IST IC S OF VARIOUS
CATALYSTS AT ATMOSPHERIC PRESSURE
S.V . = 1.083 grams o i l
gram C a t. h r .
H0 R ate = 1 .7 4 f t 3 S eTeP.
HR.
C a ta ly s t
500 Grams
O n -S tream
Time (Min)
Harshaws
C obalt
M olybdate
0-15
35-30
30 - 60
60 - 90
90 - 120
0.975
1.054
1 .10 2
1.115
1 .28 2
403
417
415
412
416
Union O il
C obalt
M olybdate
0
15
30
60
90
0.813
0.892
1 .1 7 4
1 .19 7
1 .3 0 7
391
398
412
418
418
-15
- 30
- 60
- 90
- 120
Avg. % S u lf u r
in E f f lu e n t
Avg, Temp.
^ c "
D ata From
Run
#56
#55
-33'
TABLE IV
DESU LFU R IZ A T IO H V S .
% S u lf u r
In E f f lu e n t
1 .0 6
1 .0 4
1.046
1.089
1 .0 1
1 .0 4
Ho R ate
F t3 S. T. P .
H r.
0
1 .7 4
0 .3 5
0 .7 0
0
1 .7 4
HYDROGEN RATE (B A U X IT E )
Temp. 0C
Space V e lo c ity
Grams O il
Grams C a ta ly s t H r.
412
404
412
412
406
404
1 .0 8
1 .0 8
0.989
0.991
1 .0 8
1 .08
40-2
43-2
53-2
54-2
41-1
43-2
TABLE V
DESULFURIZATION VS. TEMP. (BAUXITE)
% S u lf u r
In E f f lu e n t
1 .1 1
1 .0 7
1.075
1 .1 1
1.455
1 .1 8 2
Temp. 0C.
360
400
412
417
362
416
Ho R ate
Ft3 S. T. P .
H r.
0
1 .7 4
0 .3 5
0 .7 0
0 .7 0
0 .7 0
Space
V e lo c ity
1.083
1.083
0.989
0 .9 9 1
4 .1
4 .1
D ata From
Run Sample
D ata From
Run Sample
40-3
43-a v g .
5 3 -av g .
5 4 -av g ,
61-2
61-3
-
34
table
D E SU L FU R IZ A T IO N V S .
S u lf u r
In E f f lu e n t
%
0.975
1.075
1 .1 1
1.122
1.33
-
VI
SPA C E V EL O C IT Y (B A U X IT E )
S p ace V e l o c it y
Grams O il
Gram C a t a ly s t H r.
Temp.
°c.
R a te
Ft3 S .T .P .
A verage o f
Run Sam ple
H r.
416
407
417
416
407
1 .0 7
0.989
0.991
4 .1
8 .2
1 .7 4
0 .3 5
0 .7 0
0 .7 0
0 .7 0
# 3 1 -1 ,2 ,3
53-avg
54-avg
# 6 1 -1 ,3
#62-avg
TABLE V II
DESULFURIZATION VS. SPACE VELOCITY (BAUXITE + HF)
% S u lfu r
In E f f lu e n t
1 .0 5
1 .1 1
1 .0 1
1.296
1.59
1 .6 1
Space V e l i c i t y
Grams O il
Grams C a ta ly s t H r.
0.221
1 .0 7
1.083
3 .9 5
6 .9 8
6 .7 7
Temp.
°c
393
407
415
466
451
394
Ho R ate
F t3 S .T .P .
H r.
1 .1
1 .7 4
1 .7 4
2 .5
2 .5
2 .5
Average o f
Run Sample
#30-avg
# 3 1 -4 ,5 ,6
#34-avg
# 2 8 -1 ,2 ,3
# 2 8 -4 ,5
#27-a v g
TABLE V I I I
data on determination of mechanism of desulfurization
catalyst
GAS
USED
C obalt
M olybdate
CE.
B au x ite
Molybdena
Alumina
4
H2
H2
None
GAS LITERS S .T .P .
OIL
GRAM OIL
% SULFUR
H EFFLUENT
REACTOR
PRESSURE
PSIG
SPACE VEL.
GRAMS OIL
GRAMS CAT. HR.
AVG. TEMP.
£C
AVG
OF
RUN
0.312
0.302
1 .4 5 2
0 .3 4 0
300
300
0.805
0.934
403
402
#76
#70
0.268
0.0927
1 .2 2 0
1 .0 8
500
ATM
1.156
1 .0 8
399
399
#67
# 43
0.346
0.465
1 .0 6
300
300
0.949
0 .9 5 0
392
383
#58
#60
XX XXX
-3 6 table
D ESU L FU R IZ A T IO N V S .
% SULFUR
IN EFFLUENT
1 .0 7
1 .1 1
1 .1 6
1 .2
1 .2 1
1 .3 1
1 .3 3
1 .0 1
1 .0 4
1 .0 5
1.443
1 .0 1
1 .0 1
1.13
1 .2 7
1 .0 2
1.23
% LOSS
ON CHARGE
5.25
4 .5
2 .4 9
3 .6 2
3 .7 2
2 . 8?
3 .3 2
5.92
7.83
8 .3 8
3 .8 1
6 .8 3
7.66
7 .7
1 .8 5
8 .4 5
3 .1 5
IX
%
_L O SS
ON CHARGE
CATALYST
B a u x ite
B a u x ite
B a u x ite
B a u x ite
B au x ite
B au x ite
B au x ite
B a u x ite + HF
B a u x ite + HF
B a u x ite + HF
B a u x ite + HF
B a u x ite + BFo
B a u x ite + BF^
HCl + Alumina
HF + Alumina
Molybdena Alumina
Chrome-Alumina
RUN
NUMB]
#43
#54
#41
#44
#61
#42
#62
#34
#31
#30
#28
#52
#51
#37
#38
#48
#49
-3 7 table
X
DESULFURIZATION VS. TEMPERATURE
MOLYBDENA-ALUMIMA CATALYST
Temp.
OC
322
333
340
383
393
397
404
432
427
435
% S u lf u r
In E f f lu e n t
1 .3 7 9
1 .3 0 4
1 .3 3 7
0.756
0 .7 0 9
0.665
0.656
0.568
0.573
0 .5 9 4
Ho L i t e r s S .T .P .
0~
Gram O il
R e a c to r
P ress.
0 .1 6 8
0.201
0.1715
0 .307
0 .2 8 1
0 .2 8 0
0 .271
0 .198
0.206
0 .177
Space V e l.
Data o f
Grams O il
Run
Gram C a ta ly s t H r. Sample
300
300
300
300
300
300
300
300
300
300
0 .9 4 5
0 .9 4 5
0.945
0 .926
0.926
0.926
0 .9 2 6
0 .9 2 7
0 .9 2 7
0 .9 2 7
59-4
59-1
59-2
63-2
63-3
63-4
63-5
57-avg
57-2
57-3
TABLE XI
DATA ON CARBON LAYDOWN VS. TEMP.
HYDROGEN OIL RATIO
^Carbon Laydown
On Charge
8 .3
1 .915
4 .3 7
0 .957
T em perature
OC
432
330
383
399
Ho L i t e r s S .T .P .
0
Gram O il
Run
Number
0 .198
0.1775
0
0.778
#57
#59
#60
#64
.3 »
TABLE X I I
DESULFURIZATION VS. PRESSURE MOLYBDENA ALUMINA
P re s s u re
PeSeI eA.
% S u lf u r
In E f f lu e n t
H0 L i t e r s S .T .P .
0~
Gram O il
1 2 .2
312.
$12.
1 .0 8
0.734
0.583
0.108
0.278
0.244
R ea c to r
P ress.
P .S .I .G .
0
300
$00
Space V e l.
Data
Grams O il
Of
Grams C a t. H r. Run
Samp]
1.083
0 .9 2 4
1 .0 1 1
#60
#64
#66
TABLE X I I I
CORRELATION OF D ESU L FU R IZA T IO N WITH HYDROGEN TO O IL R A T IO AND E 1 T .
Fh
<
U
M olybdena
Alumina
Harshaws
C ob alt
M olybdate
Is
Sg
H
E-i
I
O
CO
%
O
E
I
a
if!
%@ @
B
if
W lO
CO
CO
REAC
PSIG
E-i
PE-<
COrf
COO
0.198
0.346
0.294
0.284
0.441
0.433
0.244
0.633
0.760
0.568
0.465
0.683
0.734
0.583
0 .472
0.583
0.387
0.328
432
392
395
399
399
402
399
397
398
0 .9 2 7
0.949
0.926
0.924
0.947
0.764
1 ,011
0.991
0.812
300
300
300
300
300
500
500
500
500
0.312
0.302
0.326
0.517
0.192
0.396
0 .340
0.398
0.363
0.530
409
402
404
405
405
1 .0 1
0.934
0.954
0.943
0 .951
300
300
300
300
300
I.MCO a
I
ill
a
H
En
Eh
C.
§
a
o
CO
W
w co
H
Eh
<
sip i §
I sIIi
cr\a :s M
I
SE
0
I
I
I
4
5
0
6
6
0
0
3
3
3
3
3
3
3
0
0
0
3
3
3
3
3
I
I
O
O
O
O
O
O
I
I
O
O
I
2
O
I
#57
#58
#63
#64
#80
#65
#66
#82
#81
#69
#70
#71
#79
#78
TABLE X IV
TABULATED RESULTS FOR RUHS
E-H S
0 -1 5
I
7 9 6 ,0
1 ,6 1
399
2 .5
847
0-20
20-40
40-60
60-73
73-83
I
2
*3
4
5
6 11.2
622
629.4
703.7
6 38.7
1 .3 1
1 .2 8
448.5
481
470
468
435
2 .5
2 .5
2 .5
2 .5
2 .5
3332
29
0-20
I
422
1 .09 5 410
1 .7 4
30
0-30
30-60
60-110
110-160
160-200
200-250
I
2
3
4
5
6
2 5 .5
3 5 .9
6 8 .0
66.5
59.0
7 8 .2
1 .05 5
1 .05 5
1 .0 4
1 .0 4
1 .0 4 5
1.105
1 .1
1 .1
1 .1
1 .1
1 .1
2 .5
g
ii
28
g
§
<3
CO
1 .5 1
1 .6 7
H EL.
g •
< a.
u @
O E-I
401
389
383
991
387
394
§
g
k
O
co PO
co cb
d
O
v iB
6 .2
HR.
E-i
EC
S
gI
I
I zla I
>
Eh S
CO <
M CO
d cb
EH O
C y clo cel
3 .8 1 C yclocel
C y clo cel
3 6 1 .0
3 6 1 .0
3 6 1 .0
3 6 1 .0
3 6 1 .0
3 6 1 .0
8 .3 8 C yclocel
I
S
e tis
MOO
a
g
g g
I s s
I
HF
Gas
6 .7 7
Rxm d is c o n tin u e d .
Incom plete condens a tio n "U ndersized"
condenser
HF
3 .9 5
3 .9 5
3 .95
6.9 8
6.9 8
C a ta ly s t same as
Run 27.
No cra ck in g
e v id e n t a t 470° C
HF
Gas
1.08
C at. check
HF
Gas
0.221
E f f . o f h ig h H2
r a t e checked
?
TABLE X I V
(C O N T IN U E D )
TABULATED RESULTS FOR RUNS
I
&
<
§
ii
O
O
EH S
88
CO
fa
EC
31
0-30
30-6 0
60-90
90-120
120-150
150-175
I
2
3
4
5
6
1 9 4 .2
232
249.1
233.2
254.9
229.2
0.93
0 .9 4
1.055
1 .1 2
1 .1 0
1 .1 0
413
422
413
404
410
415
1 .7 4
1 .7 4
1 .7 4
1 .7 4
1 .7 4
1 .7 4
32
0-30
30-60
I
2
191.5
1 72,2
1 .0 2
1.025
407
407
1 .7 4
0 .8 4
396
1 .7 4
1512
7.83
I
9
o
9
U
I
&
<
riS
MOO
< • •
8 8 8
C yclocel
None
None
None
HF
Gas
Same
1.0 7
C y clo cel
same as
31
HF
1.038
10-30
mesh
c y c lo c e l
HF
Gas
F resh Cat
10-30 mesh
G asket le ak a g e
ru n d is c o n tin u e d
33
0-30
I
34
0-30
30-60
60-90
90-120
I
2
3
4
243.1
261.9
271.9
276.5
0 .9 2
0 .9 9
1 .0 5
1 .0 8
427
410
412
412
1 .7 4
1 .7 4
1 .7 4
1 .7 4
1120
5.9 2
10-30
mesh
c y c lo c e l
HF
Gas
35
0-25
25-40
I
2
200
142
1 .0 0
0 .9 6
427
423
1 .7 4
1 .7 4
3 62.9 5.75
10-30
mesh
C y clo cel
HF
Gas
1.038
Run d is c o n tin u e d
1.083
C a t. same as
Run 33
1.083
R ecycle o i l
o f 1 .1 $ s u lf u r
used f o r fe e d o i l
TABLE X IV
(C O N T IN U E D )
TABULATED RESULTS FOR RUNS
3
Run N<
I
Sg
E- S
•
S
g
ICO
^pq i§2
.
I
g
I
.
O
O SEH
C CO
tiC^
IO
.
COW
EC
OS<
H cti
I
§ 0
I s
I l
5
ti
O
TAO
1 7 .9
0-30
30-60
60-90
90-120
I
2
3
4
204.7
200.2
230.5
253.5
1.03
1.03
0 .9 0
0 .9 5
425
408
404
405
1 .7 4
1 .7 4
1 .7 4
1 .7 4
1083
0-30
30-60
60-90
90-120
I
2
3
4
216.5
249.5
252.7
281.0
1.13
1 .0 9
1 .7 4
1083
1 .1 8
415
433
427
412
33
0-30
30-60
60-90
90-120
I
2
3
4
239.5
265
232.5
301
1 .3 6
1 .2 3
1 .2 5
1.23
425
427
417
420
1 .7 4
1 .7 4
1 .7 4
1 .7 4
1073
1 .8 5
39
0-30
30-60
60-100
I
2
3
245
2 64.8
3 6 8.9
1 .9 5
1 .8 8
1 .9 9
426
431
410
None
1 .7 4
379
0
0-60
60-120
120-160
I
2
3
444.5
454.5
2 73.0
0 .8 9
1.0 6
1 .1 1
410
412
360
None
36
37
40
7 .7
O u~\
S
goo
<< • .
C
Cti ti)
Cti
CLO, O
HCL
10-30
mesh
Gas
C y clo cel
1.083
HCL
1.083
Alumina
I
Cti
F resh c a t .
Jr
No coke on c a t .
No c ra ck in g
e v id e n t as h ig h
a s 434°C
Alumina
HF
None
None
None
1.083
S te e l b a l l s o f
p re -h e a t s e c tio n
a lo n e 542 g r s .
O iljAir
HF
1421
1 1 .2
C y clo cel None
1.083
Run d is c o n tin e d
due to blow o u t
Cause o f high
lo s s
TABLE XTV
TABULATED RESULTS FOR RUNS
-p
1068
2.4 9
C y clo cel
None
1.083
42
0-30
30-60
60-120
120-180
I
2
3
4
218
280
530.5
555.0
1.125
1 .3 2
1 .3 9
1 .4 1
408
408
408
404
1 .7 4
1 .7 4
1 .7 4
None
1620
2 .8 ?
Same
None
1.083
0-30
30-60
60-120
120-150
I
2
3
4
222
250.5
518.5
2 8 2 .7
1 .0 8
1 .0 4
1 .7 4
1 .7 4
1 .7 4
1 .7 4
1344
1 .0 9
396
404
400
400
44
0—60
60-120
120-180
I
2
3
4 6 6.5
542.0
510.5
1 .2 3
1 .1 9
1 .1 7
405
401
402
1 .7 4
1 .7 4
1 .7 4
1574
45
0-10
10-20
20-30
30-40
40-50
50-60
60-80
I
2
3
4
5
6
7
42
75
84
82
80
83
204
0 .3 0
0 .6 1
0 .7 9
0 .8 4
393
394
396
398
394
393
391
1 .7 4
721
43
0 .9 5
Remarks
Space V e l.
O r. O il
O r. C a t. Hr
None
1 .7 4
1 .7 4
® Ph
-P E-i
.
CO
Ph
6
0)
E-I
% Lo$s o f
Charge
406
409
398
£
d
O
O
O il Charge
1 .0 1
1 .1 5
1 .3 3
% S u lf u r
228.5
271.5
542.5
Sample Weigl
In grams
I
2
3
Sample No.
0-30
30-60
60-120
Time In te rv z
M inutes
41
Run
No.
A c tiv a te d
With
*
C a ta ly s t
500 grams
I-I
58? gm o f
c a t a l y s t & coke
removed
5.25
C y clo cel
None
1.083
F resh c a t .
3 .6 2
Same
None
1.083
9 .9
NiNO3
on
C yclocel
None
1,083
C at. removed
Wt. 527 gm.
C at. was 0.69
mols o f NiNO3
absorbed in 500 gm o f
c y c lo c e l. C at. th e n
h e a te d 2 h r s . a t 440°C
in a i r stre a m , th en
reduced w ith Hg 1.10%
S in fe e d .
&
1
TABLE X H
(CONTINUED
TABULATED RESULTS FOR RUNS
o*
3
S
<D
3
o> I
S
I
a?
«
.
t o CL,
IH
-P
< g.
I
*0
CO Q>
HC^
I
ii
CO
46
O-IO
10-30
30-55
55-78
I
2
3
4
49
0 .7 9 370
202
0 .9 7 395
223
433
226. 5 0 .9 0 415
1 .7 4
735
4 .7 4
500
c y c lo c e l
N ic k el im preg.
c y c lo c e l
47
0-20
20-40
40-60
60-90
I
2
3
4
0 .8 1
114
172. 5 0 .9 7
1 7 0 .0
311. 0 1 .0 1
412
415
410
398
1 .7 4
847.5
9.4 5
Same
(Run 45)
0-30
30-60
60-90
90-120
I
2
3
4
213
255
253
286
0 .8 3
1 .0 1
411
414
415
416
1 .7 4
1100
8 .4 7
500
m oly-alum ina
0-15
15-30
30-60
60-90
90-120
I
2
96
123
247
250
268
1 .1 2
1 .1 9
1 .2 4
405
413
419
412
1 .3 1 5 407
1 .7 4
1016
3 .1 5
500
chrome
alum ina
dW
48
49
I
3
4
5
VL
1 .1 6
U
d
O
ffl
O E-I
^ a
VL 6
3 5
< is
H
i
S
I 0.0.
I
co 6 6
t§
1.083
R ecycle o i l i n a t
1.1% S u lf u r
r
1*083 C at. re g e n e ra te d
from Run 46 by b u rn in g
o f f and re d u c tio n w ith
hydrogen. R ecycle o i l
in a t 1.1% S.
1.083
C at. w t. grm
= 20 gm.
1.083
No coke on c a t .
No c a t . w t. g a in
TABLE XIV (CONTINUED)
TABULATED RESULTS FOR RUNS
-p
I
Q>
j
-P
CL
S
i ra
o i
iCl A
rO
5rrt 6
g
td 8
O irx
gg
-=C
d
O
413
421
420
418
414
1 .7 4
1011
1 .8
420
418
409
404
1 .7 4
993
7 .6 6
500 g r .
C y clo cel
fre sh
1 .7 4
542
6 .8 3
1 .0 4
413
413
418
500 g r .
c y c lo c e l
fr e s h
3 8 .2
4 3 .6
46.1
51.9
1.036
1.046
1 .1 0 5
1.112
402
412
408
407
0 .3 5
1 9 7 .7 1 0 .1
7 9 .2
8 1 .2
109.6
108.4
1.076
1.089
1 .1 0 4
1 .1 7
423
412
421
412
0 .7 0
50
0-15
15-30
3 0 -6 0
60-90
90-120
I
2
3
4
5
97
123
230
248
275
0-30
30-60
60-90
90-120
I
2
3
4
200
229
236
252
0-30
30-60
60-90
I
2
3
158
179
168
0-30
30-60
60-90
90-120
I
2
3
4
0-30
30-55
55-90
90-120
I
2
3
4
54
jj
6
^ ^
£C K 3
I
CO
53
•
<H
O Eh
I l
EW2
52
I
d
n
TA
Pw
<DiH
<5
3 &
t.
-q I
O
§ o*
« S
51
0)
1 .7 9
1 .8 8
1 .9 0
1 .0
1 .0 1
1 .0 1
0 .9 7
I? d
S
O <D
CM-P P
3 9 6 .2
4 .5
(—•
500 g r .
John M an v ille
C at.
100 g r .
c y c lo c e l
200 g r .
fre s h
c y c lo c e l
BF3
. £
©
> 3 -3
S00
nj • •
(H P P
CO O C5
1.083
a
S
®
CU
No c a t . vrt. g a in
jVt
1 .0 8
Good c o lo r
1
s t a b i l i t y o f pro d u ct
0 .7 2 0 BF3 tr e a te d o i l
i n . R esin formed was
f i l t e r e d o u t. Good
c o lo r s t a b i l i t y o f
0 .9 8 9 p ro d u c t
No c a t a l y s t w t.
g a in . P re h e a t s e c t , gained
i s b e r l sa d d le s
0.991
C a t. l o s t 3 .5 g r .
in w t. P re h e a t s e c t , gained
0 .5 g r . W ater o f f c a t . e s t .
2 -5 grins.
T A B L E D (C O N T IN U E D )
I
-P
©
i
i
'g .
S
5
CO
M
t> •
^ s*
a
O ©
O E-i
Ph
© Eh
■p CO
§
CO
I C
CO -H
0-15
15-30
30-60
60-90
90-120
I
7 8 .2
117
235.3
263
2 3 5 .7
0.813
0.892
1 .174
1 .1 9 7
1 .307
391
398
412
418
418
1 .7 4
0-15
15-30
30-60
60-90
90-120
I
100
114
238.5
246
266
0.975
1 .054
1.102
1.115
1.282
403
417
415
412
416
1 .7 4
I i
Bh a
2
3
4
5
2
3
4
5
TA
©
faO
&
6
tQ
ro ©
m bo
d
O
JB
ta . 0
1045
11.05
1051
8 .2
-p g
W CD
I s
P O
© UN
O
O
©
-P
.L
P P
<O -H
g
500 g r .
3 /1 6 " c o b a lt
m olyb.
" Union O il Co"
500 g r .
C obalt
inolyb.
(lia r shaw)
pace Ve]L.
r . O il
r . C a t. H r.
TABULATED RESULTS FOR RUNS
CO O O
1.046
1.0 5
TABLE X I V
(C O N T IN U E D )
CATALYTIC DESULFURIZATION OF jf3 FUEL OIL
O
6
g
fl $
®
A
-P
1 1
*
Ico
<D S
° &
S
y
CO
I
TA
CO
bO
5 &
O §
O EH
* B
c o
^ g ®
© v
S i
M g
KrxfH
S g
O
H
©
O
b TWH
e
+3
o
cd ® .
A CO
hC
O ©~ .
U i
I
1000 g r . 0.927
molyb.
Alumina
300
Molyb.
Alumina
300
0-15
15-30
30-45
45-60
I
2
3
4
1 2 4 .5
209:8
1 7 6 .0
2 41.1
0.357
0:573
0.594
0.653
427
427
435
440
3 .8 0
3 .1 9
2.7 3
2.1 3
0-15
15-30
30-45
45—60
I
2
3
4
126.5
227.5
224
208
0.368
0.545
0 .420
0.486
382
377
401
406
5.78
5.38
5:22
5.53
9 .6
0-15
15-30
30-45
45-60
I
2
3
4
HO
214
225
360
1 .3 0 4
1 .3 3 7
1.498
1.379
333
340
326
322
3 .1 6
2 .7 0
2 .6 5
2.6 5
3 .8 1
1.915
Molyb.
Alumina
0.945
300
6 36.7
0-15
15-30
30-45
45-60
I
2
3
4
68
164
204
440
0.916
1.014
1.189
1.129
377
391
382
383
0
O
0
O
7 .8
4 .3 7
Molyb.
Alumina
0 .95
300
635.2
0-15
15-30
30-60
I
2
3
169
222
399
0.992
1.455
1.182
417
362
416
0.3 3
0 .33
0.3 3
3 .7 2
Atm.
631.6
1 8.9
2 .6 5
0.949
633.7
I
7 6 .8 g r . carbon
by b u rn -off
c a lc .
639.6
-O
T
C yclocel 4 .1
200 gms.
TABLE X I V
(C O N T IN U E D )
CATALYTIC DESULFURIZATION OF £3 FUEL OIL
i
I
S s
4->
So
WS
1 1
E-I si
i
0
a.
I
CO
I
-H
I M
a> I
S C
CO eH
C
O
I
I
CO
TA
> •
0 0
O EH
0) •
-P C
CN•
K H
S <D
to.
. a)
1Oj 6
OC
E-i O
62
0-15
15-30
30-60
I
2
3
190
211
399
1.259
1.393
1.352
413
400
4H
0.165
0.165
0.165
3 .3 2
63
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
366
418
412
436
446
589
O.424
0.756
0.709
0.665
O.656
0.812
404
383
393
397
404
393
5.5 0
4 .7 3
4 .3 4
4 .3 2
4 .1 7
4 .2 0
0.665
64
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
353
468
424
446
430
490
0.765
0.653
0.772
0.724
0 .7 3 0
0 .768
400
398
392
402
401
400
4 .5 0
4 .5 0
4 .8 0
4 .4 3
4 .8 0
2.63
65
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
28?
232
354
378
413
519
0 .401
0.309
0.448
0.485
0.581
0.503
404
406
401
399
401
404
5.41
5.63
5 .9 8
4 .8 3
5.73
5.43
og
42 S 4>
td S
Vlh4 O
mI
!>> 6
cd O
OH
C yclocel
100 gms
rH
<D
^
0
cd
P<
CO
QXN
6 5 g
"o
<d <u •
O fn
CB (L H
<u
O M
8 .2 7
Atm.
636
N. D. Molyb.
Alumina
0.926
300
639.6
5.8 7
0 .957
0 .924
300
640.3
4 .8 1
No
Molyb,
Regen. Alumina
0.764
500
640.9
Molyb.
Alumina
to
A)
4
TABLE X I Y (C O N T IN U E D )
CATALYTIC D ESU L FU R IZA T IO N OF A
FUEL O IL
I—i
cd ra
> 0)
U -P
£
0)
a
•
S
d
CO
TA
W
t> =
0-30
30-60
60-90
90-120
I
2
3
4
413
464
409
647
0 .614
0 .5 2 4
0.649
0.548
399
406
393
398
0-30
30-60
I
2
335
600
1 .122
1 .319
368
335
0-30
30-60
60-90
90-120
120-150
I
2
3
4
5
413
524
508
585
699
1 .1 6 7
1.219
1 .272
1 .6 4 0
1 .4 6 2
69
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
517
647
318
372
444
508
70
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
404
428
461
423
433
513
S i
66
67
68
Time
In te
Mint
I
«, §
a A
I C
CO "H
O ®
O H
2 g
« <'I
CNe
mH
3 .6 2
^ 8 «
rH ^ bO
-p $ &
0)
Ss-S-S
m |g
S i
I
o ^q
-P CO-H
O CO
• COtc
i
J l a
Cti
4 .4
No
Regen,
Molyb. 1 .0 1 1
Alumina
500
637.1
2 .9 8
2 .9 8
9 .5 1
No
Regen.
C y clo cel 1.033
500
639.1
407
402
396
395
397
5.83
6 .1 7
6 .6 8
5.33
5.42
5 .7
C y clo cel 1 .1 5 6
500
637.1
0.553
0.603
0.241
0.228
0.241
0 .330
416
404
415
404
413
402
6,4 8
5.52
4 .9 0
4 .9 7
5.03
4 .6 0
7.43
0.311
0 .348
0.343
0.355
0.333
0.346
400
399
408
403
404
400
5.53
4 .2 7
5.28
4 .8 1
4.5 3
3 .7 7
5 .0
3 .3 6
4 .2 6
4 .7 2
No
Regen.
T
No
Regen.
C obalt
Molyb.
No
Regen.
C obalt
Molyb.
1 .0 1
300
0.934
300
638,2 Space V e l.
d u rin g t h i s
ru n v a r ie d due
to pump. See sam ple vrt.
641
O
S
td
C
o
i> 0)
Q)
U -P
d
I
CO
0-30
I
2
30-60
60-90
3
90-120 4
120-150 5
150-180 6
71
Time
Inte
Minu
Run
No.
H
+3
^o) Ia
%
<h
It
£
379
407
488
472
363
590
0.332
0.477
0.462
0.339
0.439
0.356
407
403
404
404
405
403
4.9 3
3 .7 3
3 .8 2
6.63
1 .9 6
1 0 .1
5.73
5.34
bfl
£ A
O ®
OH
Iti-S
Ph
=cnH
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
3 4 1 .0
4 1 4 .0
3 8 7 .0
4 24.5
3 9 0 .5
452.5
2409.5
0.0355
0.053
0.0289
0.0186
0.046
-
417
401
404
399
402
401
4 .7
4 .4 2
4 .3 2
4 .5 2
4 .0 7
4 .2
73
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
444
504
4 68.5
498
493
Lost
0.0661
0.0442
0.0322
0.0296
0.0300
406
404
407
403
412
395
4 .8 7
4 .8 ?
4 .4 5
4 .6 5
6 .5 2
5 .1
74
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
4 89.5
5 03.0
558
521
540.5
489.5
3101.5
0.0544
0.0511
0.043
412
421
406
396
405
404
5 .1
5.02
4.3 6
3 .7 8
4 .3
3 .5 2
72
0.0453
i Hb O
-P W f3
8 .7 2
C
OC »
,O g M
Si-S-S
•
-P CO
H ^
3 8
V3.1-4 0 O H
No
Cobalt
Regen. Molyb.
H
>
0)
I
•CO
©CM
-PM-H
O M\
C
d © e
© O ,0
Cd (L H
E
III
©
M
.Mffi
O M
Remarks
TABLE XIV (CONTINUED)
CATALYTIC DESULFURIZATION OF A FUEL OIL
0.954
300
640
Cobalt
Molyb.
No
Regen.
0.849
300
6 4 2 .7
Cobalt
Molyb.
No
Regen.
1.058
300
638.1
#1 o i l
Cobalt
Ffolyb .
No
Regen.
1.133
300
6 40.8
#1 o i l
#1 o i l
I
vn
?
TABLE X IV
( GQNT P jB E D )
CATALYTIC D ESU L FU R IZA T IO N OF
£
^P ^
S
d
6
a
-P Q
CO B
t>a b e
H
cd O
-P Q
cd O
O 1—I
I0)
OMN
©
Jh 0
5 .85*
6.7 6
5.82
6 .4 8
6 .3
5.92
7.63
C obalt 1.066
Molyb.
No.
Regen.
gas
4 .5 5 *
4 .5 0
4 .1 2
3 .9 2
3 .3 3
3 .6 0
7.2 8
C obalt 0.805
Molyb,
No
Regen.
CH^ Gas
300
6 3 8 .4
1 .619
424
396
398
400
402
400
3 68.5
469.5
4 6 8 .0
521.0
1827.0
1.196
1 .282
1 .1 9 8
1.196
404
401
401
404
3 .3 6 *
3 .0 4
2 .9 6
2 .5 7
2.8 7
C obalt 0.942
Molyb.
No Regen.
C% gas
300
6 3 9 .2
I 3 4 8 .0
2 411.5
3 4 5 6 .0
4 4 9 6 .5
5 4 53.0
6 521.5
2686.5
0 .534
0.716
0.627
0.464
0.476
0.427
409
404
404
405
405
404
3 .7 7
1 .5 7
2.5 3
4 .1 4
4 .3 0
3 .3 8
5.97
C obalt 0.951
Molyb.
R eg en erated
300
638.6
I C
CO *H
CO
VL
0.265
0.261
0.271
0 .370
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
248
346.5
3 81.5
403.5
388.5
4 7 2 .0
2240.0
1.147
1 .442
77
0-30
30-60
60-90
90-120
I
2
3
4
78
0-30
30-60
60-90
90-120
120-150
150-180
-
0.382
-
1 .602
-
•
O ©
O E-i
-P co <fl
.O
Jh
Cd
O
S
O
TJ
t>.
Cd
V ti-4
ho
.C
O
C
O
O
&
CO
ra
&£
3 60
-P
. m to
O
O CO
0) O
s
I l i
to A S
to
300
6 36.5 #1 o i l CH,
s u b 'd f o r Hg
389
397
405
402
401
403
I
CO
I
I 450.5
2 510.0
3 4 8 9 .0
4 522.5
5 531.0
6 4 5 6 .7
2959.7
76
fl)
* 8 ©
iHbO
0)
0-30
30-60
60-90
90-120
120-150
150-180
75
•
Jsi
O IL
H_ Ral
I ./ m i i
Time
Inte
Mint
Run
No.
Id ro
_ t ®
& FUEL
#3 O il
Regen. f o r
20 h r s . to
g iv e a c a lc u la te d
213.5 gm. C
#3 O il
1—
I
Cd Q
-P O
Cd O
OH
O
Cd
A
CO
<D
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
414.5
443.5
4 3 9 .0
541.7
4 4 2 .0
5 1 5 .?
2706.2
0.317
0.382
—
0.309
0.454
0.372
410 9 .6 7
404 8 .95
403 7 .0 0
407 7.6 5
401 7.8 5
405 1 1 .7
4 .1 8
C obalt 0.943
Molyb.
No Regen.
300
639.6
80
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
4 0 9 .0
4 6 1 .0
406.5
4 32.5
4 7 4 .0
485.5
2668.5
0.508
0 .5 8 0
0.616
0.544
0 .660
0.590
406
406
392
401
389
399
5.13
6 .1
9.0 5
7 .46
8 .7 0
8 .2 5
6.03
Molyb. 0.945
Alumina
300
641.1
SI
0-30
30-60
60-90
90-120
120-150
150-180
I 339
2 363
3 3 7 7 .5
4 379
5 366
6
2267.5
0.496
0.202
0.391
0.239
0.412
0.257
399
411
398
403
387
394
1 4 .2
6 .1
1 1 .9
14 .6
8 .2
1 1 .9
6 .8
Molyb. 0.812
Alumina
No. Regen.
500
637.4
82
0-30
30-60
60-90
90-120
120-150
150-180
I
2
3
4
5
6
381
4 40.5
466.5
490
483
0.461
0 .284
0.474
0.350
0.435
0.336
395 8 .5 5
406 9 .3 5
389 1 0 .7 0
401 8 .1 6
392 1 3.85
398 1 2 .1 0
5.88
Molyb. 0 .991
Alumina
No Regen.
6 4 0 .1
<2>
I
2802.0
© e
£
<
O
O
.
e<
g
©
EH
=SjH
% Carboi
Laydown
on ch g .
79
Run
No.
CO
Baro
P re s s u r
mm. Hg.
©
R e a c to r
P re s s u r
lb ./in .
:
©CN
8
T o ta l %
Loss on
Charge
0
+3 CO
% S u lfu r
Cl
FUEL O I L ,
Sample k
i n Grams
:P
Time
In te rv a l
M inutes
*
o
(C O N T M jB D )
Remarks
TABLE X I T
CATALYTIC D ESU L FU R IZA T IO N OF # 3
3.
n
H
Diagram o f H ydrogenation Equipment f o r S u p er-atm o sp h eric Work
I
VO
I
EXHAUST
/. H2 TANK
R. C O N D E N S E R (WATER)
Z REGENERT I ON AIR 10. T H E R M O W E L L S
3. BLOWOUT DISK $
//• WET T E S T M E T E R
EXHAUST
IZHIGH P R E S S U R E
4. UNION
PUMP
I Z J E R GUSON GAGE
5. HEAT E X C H A N G E
PACKI NG
/4 OIL R E S E R V O l O
6.
CATALYST
IS I N S U L A T I O N
7. HEATING COILS
8.
PRE3SURE GAGE
-5 4 -
>
M ANOM ETER
BERL
Np
TANK
6
S
R£ 3 /3 TANCE
C O IL S
CATALYST
BELL O W S
PUMP
CONDENSER
RECEIVING
TL A SK
ATMOSPHERIC REACTOR
F ig . 2
Diagram o f A tm ospheric System f o r C a ta ly tic D e s u lf u r iz a tio n
I
-5 5 -
H
A. ORIFICE FLOWMETER
B. INSULATION
C. H2O COOLED
CONDENSER
D. THERMOWELLS
E.
BALL BEARINGS
EXHAUST
F CATALYST
G. FLANGE
FIGURE 3.
REACTOR SYSTEM FOR HF ACTIVATED CATALYST
OIL
EFFLUENT
IN
SULFUR
O N -ST RE A M TIME IN MINUTES
F ig . 4
P lo t o f D e su lfx iriz a tio n v s . On-Stream Time For
Acid A c tiv a te d B auxite C a ta ly s ts
CURVE: A
MOLYBDENA- ALUMINA
HCL - ALUMINA
C
HF - A L U M I N A
D
CHROME - ALUMINA
% SULFUR
IN E F F L U E N T
OIL
B
ON-STREAM
TIME IN MINUTES
F ig . 5 P lo t o f D e s u lf u riz a tio n v s . O n-stream Time For
M e ta llic -o x id e -a lu m in a C a ta ly s ts and Acid
A c tiv a te d Alumina C a ta ly s ts
SULFUR IN EFFLUENT
OIL
CURVE! A- MOLYBDENA ALUMINA
B- UNION c o b a l t MOLYBDATE
C- HARSHAW'S "
"
D- CHROME ALUMINA
ON-STREAM
F ig . 6
TIME
IN MINUTES
P lo t o f D e s u lf u r iz a tio n v s . O n-stream Time f o r
M e ta llic -o x id e alum ina c a t a l y s t s and
C o b alt M olybdate C a ta ly s ts
CATALYST
SULFUR
IN E FFL U E N T OIL
BAUXITE
HYDROGEN RATE
F ig .
7
P lo t
of
H yd rogen R a te v s .
FT* S .T . P . /H R
D e s u lfu r iz a tio n
w ith
B a u x ite
c a ta lyst
2.0
1.5
----------C U -------------------------------------- O
-------------- ---------------
v-s 4 .l H R -1 ____
' W - I
LJD - *
V 'I I H l
G
W
oTZ
-
60-
SULFUR IN EFFLUENT OIL
bauxite
0.5
)
TEMPERATURE
F ig . S
°C
P l o t o f T em perature v s . D e s u l f u r i z a t i o n w ith B a u x ite
*
BAUXITE
o
-T9-
% SULFUR IN EFFLUENT OIL
BAUXI TE+HF
SPACE
F ig .
9
P lo t
of
S p ace V e lo c ity
VELOCITY IN HR
v s.
D e s u lfu r iz a tio n
w ith
HF a n d B a u x i t e
SULFUR IN EFFLUENT OIL
O — BAUXITE
® — ACID-GAS+BAUXITE
® — ALUMINA BASE CAT.
■®—@r
O
l
2
3
4
5
% LOSS
F i g . 10
P lo t o f
6
7
8
9
ON OIL CHARGED
%
L o ss on Charge v s . D e s u l f u r i z a t i o n
I
IO
MOLYBDENA-ALUMINA CATALYST
AT
300
P.S.I.G.
OIL
NUMBERS INDICATE
SUM
OF
REGENERATIONS
“ £9”
SULFUR IN EFFLUENT
PREGEEDING
THE
TEMPERATURE
F ig .
11
P lo t o f
T e m p e r a tu r e v s .
D e s u lfu r iz a tio n
°C
w ith
M o ly b d e n a - a l u m i n a
MOLYBDE NA- ALUMINA
AT
300
CATALYST
P.S.I.G.
-V9**
SULFUR IN EFFLUENT OIL
NUMBERS INPICATE THE SUM OF
PRECEEWNG REGENERATIONS
REACTOR PRESSURE IN LBS PER SO.IN. ABS.
F i g . 12
P lo t o f R e a c to r P r e s su r e v s . D e s u l f u r i z a t i o n w ith M olybdena-alum ina
IN EFFLUENT OIL
O MOLYBDENA-ALUMINA
©
"
"
® COBALT MOLYBDATE
3 0 0 P.S.I.G.
500
"
300
"
NUMBERS INDICATE THE SUM OF REGENERATIONS
PRECEEDING THE RUN.
LETTERS INDICATE NO. OF 3'HR RUNS PREVIOUS,
A«0, B *l, C«2.
SULFUR
-S 9-
WITHOUT REGENERATION.
O
CO
o
CO
O
HYDROGEN TO OIL RATIO
LITERS Ht (S.T.R) PER GRAM OF OIL
F ig , 13
P lo t o f Hydrogen t o O il R a tio v s . D e s u lf u riz a tio n
With M olybdena-alum ina and C obalt M olybdate
{
M O N TA N A S T A T E U N IV E R SIT Y L IB R A R IE S
762 10056678
103000
WH** --------- -------______
K848c
K° ? S ’ c o t t iy v io a esu l ---arimUon
o f Wyoming f u e l o i l —----------
DATE
—[
I
"
I S S U E D TO
N 378
K 8 4 8 c ,
co jp
&/
~ v
‘,miis
103000
.
2.