Use and regeneration of nickel oxide for desulfurization of fuel oil
by Paul A Haas
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 Paul A Haas (1951)
Abstract:
The use of nickel oxide in the presence of hydrogen for the desulfurization. of a fuel oil and the
regeneration of spent nickel catalyst was investigated. The effects of temperature, space velocity,
physical condition of catalyst, recycle, and hydrogen rate were studied. Spent catalyst was treated by
various methods and the materials produced tested for activity as desulfurization catalyst.
The desulfurization unit consisted of an adjustable rate oil feed pump, a combination preheater and
reactor, a condenser system, an exhaust system, and an arrangement for collecting and recycling the oil.
A fluid regenerator for the oxidation of spent catalyst with air was also constructed The nickel oxide
acted as a chemical reagent to combine with the sulfur in the oil to produce nickel sulfide©
Temperature proved not to be an important variable for this process© Less than 50 per cent of the
nickel oxide present in any of the catalyst tested was converted to nickel sulfide before the
desulfurization reaction ceased# This cessation of activity was not due to mechanical blocking of the
catalyst pores as the conversion to nickel sulfide was no greater for powdered nixkel oxide than for
nickel oxide pellets# The amount of desulfurization depended on the contact time and seemed to be
independent of whether this contact time was obtained by one pass at a low space velocity or several
recycles at a higher space velocity© The hydrogen rate was not an important variable although high
hydrogent rates reduced the amount of desulfurization.
The hydrogen reduced some of the nickel oxide to free nickel.
Free nickel is an active desulfurization agent under the conditions used and may have been the
desulfurization agent for this process© The oxidation of nickel sulfide with air produced nickel sulfate
which had no activity as a desulfurization agent. Nickel oxide prepared by decomposition of nickel
hydroxide and nickel carbonate precipitated from solutions could not be activated with air or hydrogen
to produce an active desulfurization catalyst. USE MD EEGEIpiRATI OE OF EIOKEL OXIDE FOR DESULFURIZATION OF FUEL OIL
P a u l Ac'' Haas
(
A THESIS
S u b m 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 eg ree o f
M aster o f S cien ce i n Chem ical E n g in ee rin g
at
Montana S ta te C o lle g e
Approved;
Head, M ajor D epartm ent
^ e a n , G raduate D iv is io n
Y
Bozeman, Montana
Ju n e, 1951
1 V,*
■•a u
h l i ? ?
y
i i z .u.
-
2
-
T able o f C o n ten ts
Page No
A b s tra c t .................................................................................................
3
I n tr o d u c tio n ....................................................................... . . . .
h
Equipm ent, M ethods, and M a te ria ls
The Com parison U n i t ..............................................................
7
The F lu id R e a c to r System
9
. ............................................
P rocedure f o r Com parison U nit . ..........................
12
P ro ced u re f o r F lu id R e g e n e ra tio n ...................................
l),
A n a ly tic a l M e t h o d s .............................................................
15
P ro ced u re f o r Chem ical R e g e n e ra tio n ...........................
16
M a te ria ls ...................................................................................
18
Methods f o r C a lc u la tio n s . . . . . . .
...............................
19
Thermodynamic C a lc u la tio n s .........................................................
21
R e s u l t s ...........................................
P)|
Summary
31
................................................................................................
A cknow ledgm ent..........................
33
L i t e r a t u r e C ite d
.............................................................................
3b
Appendix
.
35
..
.
.
.
IOOSuO
I
»
^
ABSTRACT
The use o f n ic k e l oxide i n th e p re se n c e o f hydrogen f o r t h e 'd e ­
s u lf u r iz a tio n . o f a f u e l o i l and th e re g e n e r a tio n o f sp en t n ic k e l c a t­
a l y s t was in v e stig a te d © The e f f e c t s o f ' te m p e ra tu re „ space v e l o c i t y ,
p h y s ic a l c o n d itio n o f c a t a l y s t , r e c y c le , and hydrogen r a t e w ere s tu d ­
ied© Spent c a t a l y s t was t r e a t e d by v a rio u s methods and th e m a te r ia ls
produced t e s t e d f o r a c t i v i t y a s d e s u l f u r i z a t i o n c a ta ly s t©
The d e s u l f u r i z a t i o n u n i t c o n s is te d o f an a d ju s ta b le r a t e o i l feed
pump, a co m b in atio n p r e h e a te r and r e a c t o r , a co n d en ser system , an
e x h au st sy stem , and an arrangem ent f o r c o l l e c t i n g and r e c y c lin g th e
o i l © A f l u i d r e g e n e r a to r f o r th e o x id a tio n o f sp en t c a t a l y s t w ith
a i r was a ls o c o n s tru c te d
The n ic k e l oxide a c te d a s a ch em ical re a g e n t to combine w ith
th e s u l f u r i n th e o i l t o produce n ic k e l su lfid e© Tem perature proved
n o t to be an im p o rta n t v a r ia b le f o r t h i s process©
Less th a n 50 p e r
c e n t o f th e n ic k e l oxide p re s e n t i n any o f th e c a t a l y s t t e s t e d was
c o n v e rte d t o n ic k e l s u l f i d e b e fo re th e d e s u l f u r i z a t i o n r e a c tio n ceased#
T his c e s s a tio n o f a c t i v i t y was n o t due t o m ech an ical b lo c k in g o f th e
c a t a l y s t p o re s a s th e c o n v e rsio n t o n ic k e l s u lf id e was no g r e a te r f o r
powdered n ix k e l oxide th a n f o r n ic k e l oxide p e lle ts #
The amount o f d e s u l f u r i z a t i o n depended on th e c o n ta c t tim e and
seemed t o be indep en d en t o f w h eth er t h i s c o n ta c t tim e was o b ta in e d by
one p ass a t a low space v e lo c i ty o r s e v e r a l re c y c le s a t a h ig h e r space
v elo city © The hydrogen r a t e was n o t an im p o rtan t v a r ia b le a lth o u g h
h ig h hydro g en t r a t e s reduced th e amount o f d e s u lf u r iz a tio n #
The hydrogen reduced some o f th e n ic k e l oxide t o f r e e n ic k e l#
F ree n ic k e l i s an a c tiv e , d e s u l f u r i z a t i o n a g e n t u n d er th e c o n d itio n s
used and may have b een th e d e s u l f u r i z a t i o n a g en t f o r t h i s process©
The o x id a tio n o f n i c k e l .s u l f i d e w ith a i r produced n ic k e l s u lf a te
w hich had no a c t i v i t y as a d e s u l f u r i z a t i o n agent© N ick el oxide p re ­
p a re d by d eco 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 re ­
c i p i t a t e d from s o lu tio n s could no t be a c ti v a te d w ith a i r o r hydrogen
t o produce an a c tiv e d e s u l f u r i z a t i o n c a ta ly s t©
•
U
-
I).
»
In trod u ction
The p re se n c e of s u l f u r i n f u e l o i l i s o b je c tio n a b le and th e
amount o f s u lf u r may have an im p o rtan t e f f e c t on the- v a lu e o f th e
o i l c,
A h ig h s u lf u r o i l te n d s to be c o rro s iv e to th e equipm ent in
w hich i t . i s han d led and u sed ; and when th e o i l i s b u rn e d , th e s u lf u r
d io x id e produced may form s u lfu ro u s a c id w ith th e w a te r o f Combusione
The s u lfu ro u s a c id may be f u r t h e r o x id iz e d t o s u l f u r i c a c id .
In creasin g demand fo r o i l has lead t o th e in creased production
and use o f high s u lfu r crudes such as th o se produced in th e West
T exas, Eocky Mountain, and C a lifo r n ia , a r e a s,
A fu e l o i l produced from
th e se crudes may be o f very good q u a lity except fo r i t s s u lfu r co n ten t<,
An econom ical method o f reducing th e
amount o f su lfu r in such o i l •
w ith ou t ad v ersely a ff e c tin g th e oth er q u a lit ie s would be v a lu a b le „
The s u lfu r in o i l may be p resen t as fr e e s u lfu r , hydrogen s u l­
f i d e , mercapt&ns, th io e t h e r s , d i s u l f id e s , th iop h an es, or th io p h en es<>
The fr e e s u lfu r or hydrogen s u lfid e can be removed by d i s t i l l a t i o n
or washing8 » The exact nature o f th e o th er su lfu r compounds present
in any given sample o f o i l i s u s u a lly hard to determ ine» .Mabery. (7)
c a rr ie d out some o f th e e a r l i e s t in v e s tig a tio n s in t h is f ie ld ,.
When
a crude i s fr a c tio n a te d , th e s u lfu r g e n e r a lly appears in g r ea ter
co n cen tra tio n in th e high er b o ilin g f r a c t io n s » Thus, a s tr a ig h t run
fu e l o i l or gas o i l w i l l co n ta in a high er percentage o f s u lfu r than a
s tr a ig h t run g a so lin e or naphtha from th e same crude*
A ls o , th e s u l­
fu r compounds in th e h ig h er b o ilin g fr a c tio n s are g e n e ra lly more s ta b le
Jl
I
«» 5 **
and h a rd e r to rem ove»
The l a r g e s t p a r t o f th e s u lf u r i n th e f r a c tio n s
t o i l i n g above th e g a s o lin e range from a h ig h s u lf u r crude seems t o be
p re s e n t i n c y c lic compounds,
M o K ittric k ( 8 ) found t h a t th e s u lf u r in . a
naphtha from a crack ed C a l if o r n ia Midway cru d e was m o stly th io p h e n ie ,
There a r e many p ro c e ss e s f o r removing s u l f u r from g a s o li n e .
V a ri­
a tio n s o f a c id o r a l k a l i w ashing and v a rio u s c a t a l y t i c d e s u lf u r iz a ti o n
p ro c e ss e s a re th e most commonly u s e d ,
'However, most o f th e s e p ro c e sse s
a re n o t s a t i s f a c t o r y f o r removing s u l f u r from f u e l o i l .
The use of sul=>
f u r i c a c id f o r removing s u lf u r from f u e l o i l o b ta in e d from a h ig h s u lf u r
cru d e i s im p r a c tic a l because o f h ig h a c id consum ption and h ig h o i l l o s s .
The p ro c e ss e s in v o lv in g c a u s tic w ashing a re e f f e c t i v e on m e rc a p ta n s, b u t
have l i t t l e e f f e c t on c y c lic s u lf u r compounds.
D e s tru c tiv e hydrogena­
t i o n i s e f f e c t i v e in rem oving th e s u lf u r compounds, b u t i s an expensive
p ro c e ss.
C a t a ly ti c d e s u l f u r i z a t i o n w ould seem to be th e m ost prom ising
p ro c e ss f o r com m ercial u s e .
C a ta ly tic methods u s u a lly remove th e s u lf u r
by c o n v e rtin g i t t o hydrogen s u l f i d e .
The a d d itio n o f hydrogen may
make a c a t a l y t i c - d e s u lf u r iz a tio n 'p r o c e s s more e f f e c t iv e and may reduce
.
th e amount o f u n s a tu r a tio n o f th e p ro d u c t,
M ickel compounds o r f r e e n ic k e l a re a c ti v e c a t a l y s t s f o r many r e ­
a c ti o n s ,
Me H, Gwynn (5) (U) has p a te n ts on th e p r e p a r a tio n and use o f
c a t a l y s t s f o r th e h y d ro fin in g o f o i l s .
These co n cern th e u se o f- b la c k
o x id e s , p a r t i c u l a r l y n ic k e l o x id e , w ith hydrogen f o r th e d e s u lf u r iz a ­
t i o n o f h y d ro carb o n d i s t i l l a t e s .
The n ic k e l o r n ic k e l compounds may be
c a t a l y s t s a c tin g t o remove th e s u lf u r a s hyd ro g en s u l f i d e , o r may be
re a g e n ts a c c o rd in g t o th e fo llo w in g r e a c tio n :
1 1 1JI
_
6
-
+ 3RSE + I4B 2 — ^ IlH2 O + 3NiS + 3EB
H e r e a f te r , th e d e s u lf u r iz a tio n , a g e n ts c o n ta in in g n ic k e l w i l l "be re~
f e r r e d t o a s c a t a l y s t w ith o u t th e im p lic a tio n t h a t th e y do no t change
c h e m ic a lly d u r in g ' th e p r o c e s s , i * e , , th e te rm nn ic k e l c a t a l y s t " w i l l
r e f e r to a m a te r ia l w hich may a c t as a t r u e c a t a l y s t o r as a chem ical
re a g e n t#
T his in v e s t i g a t i o n was concerned w ith th e use and re g e n e r a tio n o f
n ic k e l c a ta ly s ts '# . The e f f e c t s o f te m p e ra tu re , space v e l o c i t y , phys­
i c a l c o n d itio n o f th e c a t a l y s t , r e c y c le , and hydrogen r a t e w ere in ­
v e s tig a te d #
F u r th e r i n v e s t i g a t i o n o f a v a r ia b le was d is c o n tin u e d
when i t was f e l t th e r e s u l t s in d ic a te d t h a t
u n te s te d v a lu e s o f th e
v a r ia b le would n o t g iv e b e t t e r d e s u lf u r iz a tio n #
H ickel compounds are not cheap and th e d e s u lfu r iz a tio n o f a
f u e l o i l w ith n ic k e l c a t a ly s t would be p r a c tic a l only i f th e w eight
o f o i l d e su lfu r iz e d per weight- o f c a t a ly s t were high#
As part o f
t h i s in v e s t ig a t io n , spent c a t a ly s t was tr e a te d by various methods and
th e products te ste d , t o determine t h e ir a c t i v i t y as d e s u lfu r iz a tio n
c a t a ly s t s .
I
The Comparison Unit
Figure I i s a drawing of th e apparatus c a lle d th e Comparison.
U n ito
The comparison u n it was designed so th a t various c a t a ly s t s
could he t e s t e d under s p e c if ie d co n d itio n s o f tem perature, space
v e l o c i t y , hydrogen r a te , and q u antity o f o il*
The o i l was recy cled
and samples could be tak en when d e s ir e d ,
.
The r e a c t o r body was a p ie c e o f 25 mm g la s s tu b in g w ith th e
fem ale s e c tio n o f a 29/l|.2 ground g la s s t a p e r j o i n t on th e to p and
th e m a le . s e c tio n o f a 35/25 b a l l j o i n t on th e botto m .
le n g th in c lu d in g j o i n t s was ab o u t 17 in c h e s ,
The t o t a l
A g la s s therm ow ell
s tu c k up in to th e r e a c t o r w ith i t s opening ab o u t Ig- in c h es above th e
bottom j o i n t .
An ir o n - c o n s ta n ta n th erm ocouple was used w ith a
Leeds and N orthrup p o te n tio m e te r c a li b r a t e d d i r e c t l y i n d e g re es
C e n tig ra d e ,
The r e a c t o r body was mounted i n an 11 in c h le n g h t of
1-g- in c h s ta n d a rd s t e e l p ip e ,
The p ip e was wrapped w ith a s b e s to s
ta p e and th e n w ith a h e a tin g c o i l t h a t had a maximum o u tp u t o f 750
w a tts a t 150 v o l t s ,
t o th e c o i l
4 V a ria c was u sed t o c o n tr o l th e v o lta g e in p u t
and th u s c o n tr o l th e te m p e ra tu re o f th e r e a c t o r .
The
u n i t was in s u la te d w ith a n o th e r la y e r o f a s b e s to s ta p e .and a s b e s to s
mud.
W ith th e method o f assem bly u se d , th e g la s s r e a c to r co u ld be
re p la c e d when damaged w ith o u t d is tu r b in g th e h e a tin g c o i l .
The male s e c tio n o f a 29 /^2 g la s s t a p e r j o i n t was necked down
f o r th e hydrogen feed l i n e and p ro v id e d w ith a s id e arm i n l e t f o r th e
o i l fe e d .
The hydrogen su p p ly was a c y lin d e r p ro v id ed w ith a p re s s u re
- 8 r e g u la to r and n e e d le v a lv e „
th e hydrogen r a t e was m easured w ith a
c a l i b r a t e d g la s s o r i f i c e and manometerD
The low er j o i n t o f th e r e a c t o r was clamped t o a g la s s w a te r cooled
c o n d en ser about 15 in c h es Io n g 6
T h is co n d en ser was co n n ected t o an
■ice co o led f in g e r con d en ser by means o f a b a l l j o i n t s
A sto p co ck
was p ro v id e d t o ta k e o f f sam ples o r t o remove w a te r t h a t condensed w ith
th e o i l s
The condensed o i l flow ed o u t a s id e arm th ro u g h a n o th e r
sto p c o c k in to a g ra d u a te d 5OO ml s e p a ra to ry fu n n e l used a s an o i l r e s ­
e r v o ir s
A tu b e w ith i t s low er end n e a r th e bottom o f th e s e p a ra to ry
fu n n e l was p ro v id e d f o r blow ing i n a i r f o r m ixing th e o i l s
The b o t­
tom o f th e o i l r e s e r v o i r was co n n ected t o th e o i l pump th ro u g h a
th re e -w a y sto p co c k used to ta k e Samples0
A H e rk le -K o rff ty p e b e l ­
lows pump was u s e d 0 S t a i n l e s s s t e e l tu b in g o f l / 8 in c h o u ts id e diam­
e t e r was used f o r th e o i l fe e d I i n e e
The uncondensed gases p a sse d th ro u g h th e ic e cooled co n d en ser
t o th e e x h a u st I i n e 0 A cadmium c h lo rid e b u b b le r was used f o r some
runs t o t r a p th e EgS g iv en o f f « A w et t e s t ; g a s m eter was u sed in
th e e x h a u st I i n e 0 A sm all s e p a ra to ry fu n n el# n o t shown in F ig u re 1#
was p u t in th e e x h a u st l i n e t o t r a p e n tra in e d liq u id s n o t removed by
th e ic e cooled c o n d e n se r«
The m a te r ia l c o lle c te d was re tu rn e d t o th e
■o i l r e s e r v o i r th ro u g h a l i n e connected from th e bottom o f th e sep a ra ­
t o r y fu n n e l.
The F lu id R e a c to r System
A u n it was c o n s tr u c te d t o i n v e s t ig a te th e p o s s i b i l i t y o f reg en ­
e r a tin g th e n ic k e l c a t a l y s t by o x id a tio n w ith a i r i n a f l u i d reg en ­
e ra to r,,
Two g la s s f l u i d r e a c to r s w ere o b tain ed , and one o f them s e t
up i n th e system shown' Si "Figure 2 0- When th e g lass, r e a c to r f a i l e d
from th e rm a l s t r a i n s , a m e ta l r e a c to r was c o n s tru c te d from s ta n d a rd
p ip e n ip p le s and re d u c in g c o u p lin g s and used w ith th e same a i r p re h e a te r and c a t a l y s t fe e d system s *
The f l u i d r e a c to r s were c o n s tru c te d a cc o rd in g t o d e sig n s modi­
f ie d from p la n s o b ta in e d from th e P h i l l i p s P etro leu m Companyo The
r e a c to r s had c y l i n d r i c a l u p p er s e c tio n s 12 to l j in c h e s long and 2^
t o 3 in c h es i n d ia m e te r .
The c e n te r s e c tio n s were 20 t o 25 in c h es
lo n g and ta p e r e d t o th e c y l i n d r i c a l low er s e c tio n s w hich were 6
in c h e s lo n g and l e s s th a n one in c h in d ia m e te r.
wound
in t u r n w ith a s b e s to s ta p e , th e
la y e r
o f a s b e s to s t a p e ,
The r e a c to r s were
h e a tin g c o i l s , and a second
A c o i l w ith a r e s is ta n c e o f 22 ohms and a
maximum o u tp u t o f 750 w a tts a t 130 v o lts was used f o r h e a tin g th e
g la s s
re a c to r.
The m e ta l r e a c t o r used a s im ila r h e a tin g c o i l on th e
ta p e r e d p a r t o f th e r e a c t o r and a HO
on t h e ‘up p er p a r t o f th e u n i t .
ohm, 230 v o l t , 600 w a tt c o i l
These h e a tin g c o ils were used w ith
V a ria c s to c o n tr o l th e h e a t in p u t to -the r e a c t o r .
S in g le therm o­
w e lls e x te n d in g in to th e m iddle o f th e r e a c t o r w ith t h e i r openings
n e a r th e to p s o f th e re a c to r s -w e re u s e d .
s u la te d w ith p ip e i n s u l a t i o n ;
and a s b e s to s mudi
The g la s s r e a c to r was in ­
th e m e ta l r e a c to r w ith m agnesia s la b s
The e x i t a t th e to p o f th e f l u i d r e a c to r was con­
10 -
n e c te d to an e x h au st I i n e c
. The feed in g o f c a ta ly s t in to th e r ea c to r was done in batch es by
an a ir I n je c to r 6
The c a t a ly s t hopper was a p ie c e o f I inch, standard
pipe connected t o th e sid e arm o f a sm all t e e w ith a reducing coupling®
A ir , c o n tr o lle d by a n eed le v a lv e , flowed s tr a ig h t through th e te e in ­
t o th e reactor®
The c a t a ly s t hopper was capped t o prevent th e lo s s of
a ir and provided w ith a bypass t o e q u a liz e th e a ir pressure above and
below th e catalyst®
The bottom o f th e r e a c t o r was co n n ected t o a t e e w ith th e com­
b u s tio n a i r l i n e connected to one arm of. th e t e e and a thermowelli n s t a l l e d . i n th e other®
The a i r l i n e was wrapped w ith a s b e s to s ta p e
and a 22 ohm, 750 w a t t , 130 v o lt h e a tin g c o i l , and th e n co v ered w ith
a s b e s to s mud in su la tio n ®
The a i r r a t e was c o n tr o lle d w ith a n e ed le
v a lv e and m easured w ith a c a li b r a t e d g la s s o r i f i c e and manometer®
The m e ta l t o g la s s c o n n e c tio n s were made w ith g ly c e r in and l i t h a r g e
j o i n t s w h e rev e r th e te m p e ra tu re s w ere to o h ig h f o r ru b b e r hose®
The a i r p r e h e a te r was an o ld r e a c t o r f i l l e d w ith s t e e l scrap
and b a l l bearings®
The r e a c t o r body was a 2li in c h le n g th o f 3 in c h
s ta n d a rd p ip e w ith a cap w elded on th e low er end and h a l f o f a fla n g e f i t t i n g on th e u p p er end®
The o th e r h a l f o f th e fla n g e f i t t i n g had a
n ip p le and a cap ta p p e d f o r th e a i r in le t®
e r end was ta p p e d f o r th e e x i t line®
The cap w elded on th e low­
The r e a c to r was wound w ith a s­
b e s to s ta p e and h e a tin g c o i l s , and covered w ith m agnesia s la b and
a s b e s to s mud in s u la tio n ®
Two 750 w a tt, 130 v o l t , 22 ohm h e a tin g c o ils
and
one HO ohm/ 600 w a t t , 260 v o l t h e a tin g c o i l were used w ith Var=
la c s to c o n tr o l th e heat input to the a ir preheater*
Thermowells o f
>
1/k- inch standard pipe were welded in th e r ea c to r at p o s itio n s i}.$ S8,
and 12 in ch es from th e bottom .
Iron and constantan thermocouples were used w ith a Leeds and
JMorthrup p oten tiom eter t o measure tem peratures*
was c a lib r a te d d ir e c t ly in degrees Centigrade*
The poten tiom eter
=> 12 «=
Procedure fo r Comparison. Unit
Ao
General Procedure fo r Runs
TIie s t a in le s s s t e e l screen used as a packing support in- the re­
a c to r was in se r te d in th e r ea c to r from th e bottom ,
A two inch la y er
o f l / 8 in ch diam eter f i s h sp in es was used in th e rea cto r below the
c a ta ly s t e
Twenty grams o f c a ta ly s t were used fo r each run*
The space
above th e c a t a ly s t t o th e top j o in t was f i l l e d w ith f i s h sp in es*
The
r ea c to r system was assembled as shown in Figure I , th e g la s s jo in ts
lu b r ic a te d w ith stopcock grease and clamped, and th e V ariac turned oh*
The d e sire d amount o f o i l was weighed out and put in th e o i l reservoir*
The pump was s e t at approxim ately th e d e sire d ra te and primed by pump­
in g th e b ello w s by hand*
The w ater t o th e condenser was turned on and
th e fin g e r condenser f i l l e d w ith i c e .
A fter th e rea cto r had reached
th e operating tem perature, th e o i l pump and a stop watch were start®
ed*
The hydrogen pressure reg u la to r and n eed le v a lv e were s e t t o give
th e manometer reading corresponding to th e d esired hydrogen rate*
The tem perature and hydrogen r a te were checked freq u en tly, during
runs and kept a t th e d e sire d values*
The fin g e r condenser was kept f u l l
o f ic e and e x ce ss liq u id w ater siphoned b u t. . The o i l was kept mixed bybubbling a ir through a tube extendin g in to th e o i l rese rv o ir *
Samples
were tak en from th e three®way stopcock in th e lin e between th e o i l
r e s e r v o ir and th e pump.
The w eigh ts o f th e samples were recorded
along w ith th e tem peratures and volumes in d ic a te d by th e gas m eter fo r
runs where th e gas meter was used*
-
13
» "
At th e end o f a ru n , th e o i l was d ra in e d th ro u g h th e th re e -w ay
sto p co c k and weighed*
A f te r th e r e a c t o r had c o o le d , i t was d is a s ­
sembled from th e system and em p tied e
The c a t a l y s t was s e p a ra te d from
th e pack in g m a t e r i a l , w eighed, and s to re d i n a sample b o ttle *
The
space v e lo c i ty was determ ined by w eig h in g th e amount o f o i l pumped i n
a m easured
le n g th o f tim e by th e pump a t th e .s e ttin g used f o r th e
ru n .
B*
D e ta ils o f P ro ced u res f o r I n d iv id u a l Runs •
The r e a c to r was p re p a re d f o r Run 3 by p o u rin g th e powdered C at-
■a l y s t over l / 8 in c h d ia m e te r f i s h s p in e s f i l l i n g h a l f o f th e r e a c t o r ,
A p lu g o f g la s s wool was. u sed i n th e bottom o f th e re a c to r *
The
■p re s s u re d rop was to o la r g e u s in g t h i s arrangem ent and re p e a te d ly
blew lo o s e th e ground g la s s t a p e r j o i n t a t th e to p o f th e r e a c t o r .
The charge f o r Run b was p re p a re d by w e ttin g I4.O grams o f l / l 6 in ch
d ia m e te r f i s h s p in e s w ith o i l and m ixing them w ith 20 grams o f powd­
e re d c a t a l y s t * T h is method o f c a t a l y s t su p p o rt was s u c c e s s f u l and was
I
used f o r th e o th e r runs w ith powdered c a t a l y s t .
The h ig h hydrogen r a t e u sed i n Run 6 blew p a r t o f th e c a t a l y s t
in to th e c o n d e n se r.
Run 7 was a tte m p ted u s in g a p lu g o f g la s s wool
to . p re v e n t th e lo s s o f c a t a l y s t , b u t th e p re s s u re drop th ro u g h th e
r e a c t o r was to o g r e a t , ■Run 8 was s u c c e s s f u lly made a t th e c o n d itio n s
o f Run 7 , u s in g g la s s h e lic e s i n p la c e
o f th e g la s s wool plug*
- T k P rooedure f o r F lu id R e g e n e ra tio n
■
F l u i d i z a t i o n was s tu d ie d i n th e u n ja c k e te d g la s s r e a c to r a t
room te m p e ra tu re o
P a r t i c l e s la r g e r th a n 60 mesh d id n o t f l u i d i z e
w e ll w h ile c a t a l y s t lo s s e s i n th e e x h a u st g ases ."became s e r io u s w ith
c a t a l y s t p a s s in g a 200 mesh screen*
A w ide ran g e o f a i r -v e lo c itie s
gave good f l u i d i z a t i o n w ith o u t la rg e lo s s e s w ith 60 t o 100 mesh c a t­
a ly s t p a rtic le s *
B efore s t a r t i n g a ru n , th e fe e d was p u t i n th e c a t a l y s t fe e d
hopper*
The a i r to th e p r e h e a te r was tu rn e d on and a d ju s te d t o th e
d e s ir e d r a te *
The V a ria c s w ere tu rn e d on and a d ju s te d u n t i l th e
f l u i d r e a c t o r and th e a i r e n te r in g th e f l u i d r e a c to r w ere a t th e
o p e ra tin g te m p e ra tu re *
a ir *
The c a t a l y s t was fe d in to th e r e a c t o r w ith .
The a i r ra te , and te m p e ra tu re were k e p t a t c o n s ta n t v a lu e s f o r
th e d u r a tio n o f th e run*
Then th e a i r and V a ria c s w ere sh u t o ff*
A fte r th e f l u i d r e a c t o r had c o o le d , th e b ottom c o n n e c tio n was lo o sen ­
ed, and t h e p ro d u c t o f th e ru n removed*
The fe e d hopper was checked
t o in s u re t h a t a l l th e c a t a l y s t had been fe d in to th e r e a c t o r a t th e
s t a r t o f th e run
15
- .
A n a ly tic a l Methods
The s u lf u r c o n te n ts o f th e sam ples o f o i l were d eterm in ed by .
th e lamp s u l f u r method as d e s c rib e d i n th e ASTM manual o f s ta n d a r d s o
(2 )
Four s e t s o f a p p a ra tu s were u sed w ith w a te r a s p ir a to r s t o p ro v id e
s u c tio n f o r ,a ir f o r com bustion*
doors t o p re v e n t e r r o r s from
The a i r su p p ly was o b ta in e d from o u t­
1HCls H2S 9 o r o th e r g ases w hich m ight
be p re s e n t i n th e la b o r a to r y a ir *
A pproxim ately two m illi e q u iv a le n ts
o f sodium c a rb o n a te s o lu tio n w ere u sed f o r each d e te r m in a tio n . • Modi­
f i e d m ethyl orange in d ic a to r was u s e d .
A ll o f th e samples f o r th e
lamp s u l f u r d e te rm in a tio n s were d r ie d w ith calciu m c h lo rid e and f i l ­
te re d .
Standard q u a n tita tiv e methods were used fo r a n alyses o f th e c a t­
a ly s ts .
Efickel was determ ined by th e volum etric cyanide method.
The s u lf a t e s were determined by th e standard gravam etric p r e c ip ita ­
t i o n as barium s u l f a t e .
The volum etric b enzidine method fo r s u lfa te
was found t o be s a t is f a c t o r y fo r the s o lu b le s u lfa te e x tr a c te d w ith
a w ater le a c h .
S u lfid e s were ox id ized t o s u lf a t e s and determined grav-
a m e tr ic a lly .
The ASTM d i s t i l l a t i o n p ro ced u re f o r l i g h t hydrocarbon f r a c tio n s
( I ) was a p p lie d t o sam ples o f o i l t o o b ta in th e d i s t i l l a t i o n d a ta
ta b u la te d i n T able V.
The s p e c if ic g r a v i t i e s o f th e s e sam ples were
d eterm in ed w ith a W estphal b a la n c e .
.
-
2.6
' P ro ced u re f o r Chem ical R e g e n e ra tio n '
The chem ical re g e n e r a tio n o f n ic k e l c a t a l y s t was c a r r ie d ou t by
two s im ila r
m ethods„
One method in v o lv e d th e p ro d u c tio n o f n ic k e l
hydroxide and th e o th e r •in v o lv e d n ic k e l carbonate© '
The- i n i t i a l s te p was th e d is s o lv in g o f sp en t n ic k e l c a t a l y s t i n
acid©
IWien n i t r i c a c id was u s e d , foam ing was bad and brown o x id es o f
n itr o g e n w ere g iv e n off©
H y d ro c h lo ric a c id gave a more m oderate re -
■action w ith l e s s fuming©
P a r t o f th e c a t a l y s t was ground u p , b u t i t
was found t h a t t h i s was n o t n e c e s sa ry f o r solution©
The s o lu tio n s
o f n ic k e l c h lo rid e and n ic k e l n i t r a t e w ere f i l t e r e d t o remove carb o n
s i l i c a and o th e r in s o lu b le m aterial©
A s o lu tio n o f n ic k e l n i t r a t e and n ic k e l c h lo rid e was made a lk a ­
l i n e w ith sodium hydro x id e t o p r e c i p i t a t e n ic k e l hydroxide©
A s o lu ­
t i o n o f n ic k e l n i t r a t e was made a lk a lin p w ith p o tassiu m c a rb o n a te t o '
p r e c i p i t a t e n ic k e l carbonate©
Both p r e c i p i t a t e s were volum inous and
seemed t o c o n ta in la r g e p e rc e n ta g e s Of w a te r © The p r e c i p i t a t e s were
f i l t e r e d and washed w ith water©
The f i l t e r cakes were mixed w ith w a te r
t o form uniform S lu r r ie s w hich
were allo w ed to sta n d 12 h o u rs © These
I
s l u r r i e s w ere f i l t e r e d and th e f i l t e r cak es washed w ith water© The
n ic k e l hydro x id e was d rie d 2l% ho u rs i n an oven a t Il(X)-i 6 o°C © The
d r ie d m a te r ia l was' p a r t l y b la c k and p a r t l y green©
The h y d ro x id e was
formed in to l / 8 in c h d ia m e te r p e l l e t s by th e Harshaw Chem ical Company©
The n ic k e l, c a rb o n a te was d r ie d 2I4. h o u rs a t IO ^-IlO 0C© The n ic k e l
J.
17
“
h y d ro x id e p e l l e t s and th e d rie d n ic k e l c a rb o n a te f i l t e r cake w ere
a c ti v a te d and t e s t e d i n th e com parison u n it as d e s c rib e d i n T ab le I I 0
18
-
M aterials
The o i l u sed f o r a l l th e d e s u l f u r i z a t i o n runs was a s t r a i g h t ru n
f u e l o i l w hich was r e f in e d from a Wyoming crude a t th e HusTcy'O il
Compaiy r e f i n e r y i n Cody, Wyoming,'
in c lu d e d i n T able V0
In s p e c tio n d a ta f o r t h i s o i l a re
The o i l was l i g h t c o lo re d w ith a s u l f u r c o n te n t
o f s l i g h t l y o v er two p e rc e n t and an' av erag e m o le c u la r w eig h t o f about
200o WorTc done a t th e Husky O il Company l a b o r a t o r i e s . in d ic a te d t h a t
th e s u l f u r i n t h i s o i l was n e a r ly a l l in ' th e form o f th e homologues
o f th io p h e n e and th io p h a n e ,
Removal o f JO p e r c e n t o f th e o i l by ex­
t r a c t i o n w ith s u lf u r .d io x id e removed 75 p e r c e n t o f th e s u l f u r .
About
0 ,7 p e r c e n t s u l f u r seemed t o be th e minimum o b ta in a b le by t h i s m ethod.
Reagent grade ch em icals w ere used f o r th e a n a l y t i c a l work and f o r
th e chem ical r e g e n e r a tio n o f th e n ic k e l c a t a l y s t ,
Hydrogen was ob­
ta in e d i n c y lin d e r s from th e N a tio n a l C y lin d e r Cas Company,
Most o f the fr e sh c a ta ly s t was manufactured .by the Harshaw Chem­
i c a l Company,
Some samples were prepared by M» H, Cwynn ( j ) (J^)6
.Spent c a ta ly s t and some samples o f regenerated c a ta ly s t were obtained
from th e Husky O il Company,
A ll o f the c a ta ly s t was in th e form of
l / 8 in ch diam eter p e l l e t s when r e c e iv e d .
-
19
Methods fo r 'C a lc u la tio n s .
The c a t a ly s t and o i l lo s s e s "were c a lc u la te d on the "basis o f the
in p u ts t o th e runs,,
A n eg a tiv e c a t a ly s t lo s s in d ica ted an in crea se
in w eight "by th e c a ta ly s t*
cubic f e e t per hour*
The hydrogen r a te s are given in standard
The volumes in d ic a te d by th e wet t e s t m eter dur­
in g c a lib r a tio n s were corrected fo r p r e ssu r e , tem perature, and th e
vapor pressu re o f water*
ured by w eight*
The.amounts o f c a t a ly s t and o i l were meas­
A ll space v e l o c i t i e s were th e r e fo r e expressed as
grams o f o i l per gram o f c a t a ly s t per hour*
. S u lfu r balan ces were made fo r th e runs on th e comparison u n it
t o c o rr e ct fo r th e e f f e c t s o f lo s s e s and fo r th e o i l removed fo r
samples*
The o i l lo s s e s were d is tr ib u te d as eq u a lly as p o s s ib le
over th e tim e in te r v a ls fo r a run*
A co rrected w eight o f o i l fo r
th e end o f each tim e in te r v a l was obtained by su b tra ctin g th e w eight
o f th e sample and th e d is tr ib u te d lo s s *
The d iffe r e n c e between th e
w eigh ts o f s u lfu r a t th e beginning and the end o f a tim e in te r v a l
(based on th e same w eight o f o i l ) was considered to be the amount o f
s u lfu r removed during th a t in te r v a l*
The t o t a l amount o f su lfu r
removed during a run was ta b u la ted in Table I I I as grams o f su lfu r
removed per gram o f c a ta ly s t*
The q u a n tita tiv e c a lc u la tio n s were o f th e type o r d in a r ily used
fo r th e methods o f a n a ly s is employed*
The c a lc u la tio n s fo r th e lamp
s u lfu r determ inations were o f th e fo llo w in g forms
'
*x> 20
(ml o f Na2CO^KN o f BagI y )
<D
(meq» o f Ba2CO^)
(ml o f HGI ) (ET o f HG!)
s
(mego o f EC l)
D iffe re n c e
-
(meg0 o f S)
(mego o f 8 ) (l<,6 0 )
W te o f o i l burned
s
P e rc e n t S i n o i l
"B" s ta n d s f o r n o rm a lity , "ml" f o r m i l l i l i t e r s , and "meq0" f o r m i l l i e q u iv a le n ts o
*21
«°
Thermodynamic C a lc u la tio n s
The d a ta i n T able I wene c o lle c te d and u sed to make thermodynamic
c a lc u la tio n s f o r v a rio u s r e a c tio n s in v o lv in g : n ic k e l compounds,,
o f th e v a lu e s o f
A E a re from Lange (6 )„
from Hougen and W atson ( 5 ) .
Most
Many o f th e v a lu e s o f S a re
The Bureau o f Mines B u lle tin Ho. Ifih (9)
was used f o r some v a lu e s , p a r t i c u l a r l y f o r th e v a lu e s f o r n ic k e l com­
pounds®
The v a lu e s o f
c u la te d .
and
f o r th e r e a c tio n s l i s t e d were c a l -
The c a lc u la tio n s w ere made to see w h eth er th e s e r e a c tio n s
w ere therm odynam ically p o s s ib le a t v a rio u s tem peratures®
The accu racy
d e s ir e d d id n o t r e q u ir e c a lc u la tio n s t o com pensate f o r v a r i a t i o n s i n
S and
AH w ith te m p e ra tu re »
The v a lu e s f o r ..AS. a t 298°K and
a t 291°K w ere u sed i n th e fo rm u la s;
AF
s
T
A H - -TAS
s
3SE. ■
$ri0 ( s ) +
AHf
_58oll
s
?298 ?
9 ,2 0
-± L ,
IETg-
H2 (g ) — ^
O
51.23
m
Cb) *
( g )>.'
O
-57®8
7 o l2
T.
HE
AH
!4.5 «13
=
51°K
.. AS
s
»
0 .6
= 1 1 .8 2
- 220% •
A h «195.6
Tm,
2 3 .2
'.
=
2100oK
as
. 9 2 .8 6
-s ■ISOO0C
AH
-
Co
« s (s)
AHp
»20*14
S
18.0
3/2 Og
+
CO
-20*4
S
18.0
■ F298
F.®
AHp
S
=
38,700
5 3 .4
6 3 .8
As
s
4 9 .8
Tqe
- 4 .8
s
' 4 9 .1 5
- 5 8 .4
9 .2 0
-
SOO0Co
AH S
AS s
15.6
7 .0 4
2200°% s 1900°C.
+
4 5 .1 3
:
+ 11Ss (S)
-— ^
Tw
23.l l
44oo°c
S
. '7 =12
s 13,500
=
' AH
0
31.23
F " S 16,400
=298
4 7 oo°%
104 O2
M (s)
0
AS =
5 9 .2 4
Tme = 1070°%
^ (g )
s i S ( S ) ■ * ■ H2G(s )
-20*1).
-5 7 .8 0
18*0
+
9.20
2 3 .2
AHp
THE "
AH S 108.92
cF
CO
' -58Ui
sT
Eo
- 70.92
-102,000
«216*0
F298
« '5 8 .4
9 .2 0
^ 0(S)
• S
+ SOg (g)
73.55
HiSO1 , ■s — ^
Ms) •
AHf
—-B*- ^ ( S )
0
F298 '
Do
22
M (g )
- 4 .8
4 9 . 15.
n e g a tiv e °%
AH s' +15.00
* AS S - 4 .7 8
R e s u lts
For th e f i r s t r u n s , c h a rg e s o f lj.20 grams o f o i l and 20 grains o f
c a t a l y s t w ere s e l e c t e d .
T h is amount o f o i l was a p p ro x im a te ly th e cap­
a c i t y o f th e o i l r e s e r v o i r and c o n ta in e d ap p ro x im ately th e amount o f
s u l f u r t h a t would be r e q u ir e d f o r com plete c o n v e rsio n o f 20 grams o f
n ic k e l oxid e t o n ic k e l s u l f i d e by a q u a n t i t a t i v e r e a c t i o n .
W ith th e
space v e lo c i ty o f 2 0 ,9 s th e o i l was c y c le d over th e c a t a l y s t about
once p e r h o u r.
The e f f e c t s o f te m p e ra tu re w ere in v e s tig a te d by Runs I and 2 ,
eThe te m p e ra tu re o f 6 75°F u sed f o r Run 2 was c lo s e to th e maximum t h a t
j •
co u ld be used w ith o u t e x c e s s iv e c r a c k in g . W hite fumes due to c ra c k in g
were o bserv ed a t 625°F f o r Runs 1 0 , 11, and 18*
t i o n f o r Run 10 (se e T able Y)
The ASTM d i s t i l l a ­
d id n o t show th e low f i r s t drop temp­
e r a tu r e t h a t would in d ic a te th e p re se n c e o f l i g h t s from c rack in g *
The
d e s u l f u r i z a t i o n seemed to be indep en d en t o f te m p e ra tu re a t 625°F and
above,
S in ce th e p ro c e ss does n o t ta k e p la c e a t room te m p e ra tu re , "
th e r e i s some te m p e ra tu re range below 6250F w here th e d e s u lf u r iz a ti o n
does depend on te m p e ra tu re ,
A te m p e ra tu re o f 625°F was s e l e c t e d . f o r
th e o p e ra tin g te m p e ra tu re f o r th e i n v e s t i g a t i o n o f o th e r v a r i a b l e s .
E f f e c tiv e d e s u l f u r i z a t i o n seemed to have alm ost c ea sed a t about
1,53 p e r c e n t s u lf u r i n th e o i l a t th e end o f s ix hours f o r Runs I and
2*
Runs 5 and 6 , made w ith s m a lle r amounts o f o i l , showed t h a t th e
n ic k e l c a t a l y s t could low er th e s u l f u r c o n te n t o f th e o i l below t h i s
-
v a lu e o
25
-
P e rso n n e l a t th e HusTsy O il Company la b o r a to r ie s w ere a b le to
o b ta in o i l w ith a s low a s 0*1 p e r c e n t s u l f u r from la r g e q u a n t i t i e s
o f n ic k e l c a t a l y s t and th e f u e l o i l used f o r t h i s in v e s tig a tio n *
The
use o f a cadmium c h lo r id e b u b b le r i n th e e x h au st l i n e showed t h a t
v e ry l i t t l e o f th e s u l f u r removed from th e o i l was g iv e n o f f as hydro­
gen ' s u lfid e *
th e
E x am in atio n o f th e sp e n t c a t a l y s t from ru n s showed t h a t
n ic k e l o x id e was c o n v e rte d to n ic k e l s u lfid e *
The n ic k e l oxide was
a chem ical re a g e n t r e a c tin g alm ost q u a n t i t a t i v e l y w ith th e s u l f u r com­
pounds i n th e o i l *
As a chem ical re a g e n t,o n e gram o f n ic k e l oxide
would r e q u ir e (52)/(58*69+ 16) o r 0 J 4.3 grams o f s u lf u r f o r com plete
c o n v e rsio n to n ic k e l s u lf id e *
On Runs I and 2 , made w ith p e lle te d
pure n ic k e l o x id e , th e c a t a l y s t removed l e s s th a n 30 p e rc e n t o f t h i s
t h e o r e t i c a l amount o f s u l f u r b e fo re e f f e c t i v e d e s u l f u r i z a t i o n sto p p ed *
The c a t a l y s t used i n Run 17 was a p p ro x im a te ly 70 p e r c e n t
o x id e »
n ic k e l
I t removed s u lf u r e q u iv a le n t t o ^5 p e r c e n t co n v ersio n , o f
th e n ic k e l
oxide p r e s e n t t o n ic k e l s u lf id e b e fo re th e ru n was ended *
H ick el s u lf id e has a l a r g e r m o le c u la r volume th a n n ic k e l oxide*
I t m ight have b een 'p o s s ib le f o r th e n ic k e l s u l f i d e m e c h a n ic a lly to
b lo c k th e p o re s o f th e c a t a l y s t and th u s p re v e n t th e n ic k e l o x id e i n
th e c e n te r o f th e p e l l e t s from coming i n c o n ta c t w ith th e o il*
was checked i n Runs 5 . &&d b by u sin g 66 t o 200 mesh c a ta ly s t*
This
T his
m a te r ia l was p re p a re d by g rin d in g pure n ic k e l oxide p e l l e t s w ith a .
m o rta r and p e s tle *
The f i n a l r e s u l t s w ere alm o st i d e n t i c a l f o r
p e l l e t e d and powdered c a ta ly s t*
The powdered c a t a l y s t exposed no more
«= 26 <«»
active m aterial to the o i l than the p e lle t s e
Run 9 was made with a space v e lo c ity of approximately h a lf of
the value used for previous runs.
The r esu lts indicated that the
actual to ta l contact time determined the amount of desulfurization,,
For Runs 5 and 9s approximately the same resu lts were obtained byputting the o il through once at one space v elo city or by putting i t .
through twice in the same length of time at double the space velocity,,
The maximum space v elo c ity that could be investigated was lim ited by
the preheater section of the reactor,
The minimum amount of heating
and cooling would be required i f a space v elo city low enough to give
the desired desu lfu rization in - one pass were used.
The space velocity
of 20.9 used for the f i r s t runs was alsp used for Run 10 and there­
a fte r , so the runs would have the same basis for comparison. With
th is space velocity# the o i l was cycled over the catalyst at le a st
once per hour.
At the Husky Oil Compary laboratories, a space v elocity
o f 0.2 was used with the feed o i l used for th is in vestigation to
obtain nine volumes of o i l per volume of ca ta ly st with the sulfur con­
ten t _of the o i l below 0.5 per cent.
This amount of desulfurization
corresponds to the removeI of le s s than 0.1 gram of sulfur per gram o f c a ta ly st.
The a ir bubbler used to mix the o i l in the o il reservoir was
not in sta lled u n til Run 3»
Therefore, when the samples were taken
for Runs I and 2 , they may not have been tru ly representative of the
o il.
Samples taken without mixing might have had higher su lfu r contents
27
th a n th e t r u e a v erag e s b ecause th e d e s u lf u r iz e d o i l from th e r e a c to r
te n d e d t o form la y e r s on to p o f th e o i l a lre a d y in th e r e s e r v o ir *
The l a r g e s t amounts o f s u l f u r w ere removed- d u rin g th e f i r s t two tim e
p e rio d s f o r a l l r u n s e
P a r t o f t h e s u l f u r in th e o i l was easy t o r e ­
move and i t would be removed f i r s t « The a c t i v i t y o f th e n ic k e l c a t­
a l y s t dropped o f f as i t was p a r t i a l l y c o n v erted t o n ic k e l s u lfid e *
The co m b in atio n o f h ig h c a t a l y s t a c t i v i t y and e a s y t o remove s u l f u r
compounds caused th e h ig h i n i t i a l r a t e s o f d e s u lf u r iz a tio n *
The grams
o f s u lf u r removed p e r gram o f c a t a l y s t was low er f o r runs made w ith
s m a lle r amounts o f o i l as shown by com parison o f Puns 5' th ro u g h 9»
w ith puns I s 2 , and U.0 A p p a ren tly p a r t o f th e c a t a l y s t was a c tiv e
enough t o d e s u lf u r iz e some o f th e s u lf u r compounds, 1b u t co u ld n o t
remove th e s u l f u r from th e more r e f r a c t o r y compounds l e f t a f t e r p a r­
t i a l d e s u lf u r iz a tio n *
I t would seem t h a t a scheme o f c o u n te r-
c u r r e n t d e s u l f u r i z a t i o n u s in g p a r t i a l l y s p e n t c a t a l y s t on f r e s h o i l
and f r e s h c a t a l y s t on p a r t i a l l y d e s u lf u r iz e d o i l would have ad v an t­
ages.
The h ig h hydrogen r a t e s used i n Runs 6 and 8 seemed to reduce
th e amount o f d e s u lf u r iz a tio n *
S in ce tihe n ic k e l o x id es a re n o t ac­
t i v e u n le s s th e y a re t r e a t e d w ith h y d ro g en , th e r e should be an o p t*
Imum r a t e betw een no hydrogen and th e h ig h r a t e used f o r Runs 6 and 8 *
.
The d isa d v a n ta g e of th e h ig h hydrogen r a t e was p ro b ab ly t h a t i t c a r . .
—
•
e
—
- -
-
- *•
••
••
— , ■• .
,»
-
■
r i e d th e o i l th ro u g h f a s t e r and red u ced th e a c tu a l c o n ta c t tim e*
"
The
hydrogen r a t e o f about 2*5 SCF o f hydrogen p e r hour used f o r m ost of
28
th e ru n s was 10 t o 15 tim e s th e q u a n t i t a t i v e amount o f hydrogen t h a t
would be re q u ire d f o r com plete d e s u l f u r i z a t i o n a c c o rd in g t o th e f o l ­
low ing r e a c tio n ;
MO + ESH + Hg ------H2O +
EH
+
HiS
• I t was' n o tic e d , t h a t c a t a l y s t removed from a c o ld r e a c to r a f t e r
a ru n became h o t when f i r s t exposed to a ir «
I t was a ls o n o tic e d t h a t
a l l u sed c a t a l y s t was a t t r a c t e d by a magnet <, Hone o f th e f r e s h c a t a - '
y
\
l y s t s had t h i s p r o p e r ty „
F u r th e r in v e s t ig a ti o n s showed t h a t a magnet
a t t r a c t e d f r e s h c a t a l y s t h e a te d w ith h y d rd g en , b u t had no e f f e c t on
f r e s h c a t a l y s t h e a te d i n a ir *
The s tr e n g th o f t h i s a t t r a c t i o n 'd e ­
c re a s e d a f t e r th e c a t a l y s t had b een o u t o f th e r e a c to r f o r a few .day's*
These o b s e rv a tio n s le d to th e c o n c lu s io n t h a t some o f th e n ic k e l
oxide was reduced t o f r e e n ic k e l by th e hydrogen*
therm odynam ically p o s s ib le *
Such a r e a c tio n i s
(See thermodynamic c a l c u l a t i o n s ) „
Eun
1 2 3 made w ith HOP H ydrogenation C a t a l y s t , in d ic a te d t h a t f r e e n ic k e l
was an a c tiv e d e s u l f u r i z a t i o n a g en t u n d er th e c o n d itio n s used*
Hydro­
gen a lo n e was n o t e f f e c t i v e -in rem oving s u lf u r under t h e same co n d i­
tio n s *
The n ic k e l c a t a l y s t was n o t a n a c ti v e d e s u lf u r iz a ti o n ag en t
u n t i l i t had b een t r e a t e d w ith hydrogen*
■
The removal o f OolO gram
. o f s u lf u r p e r gram o f c a t a l y s t by th e HOP H ydrogenation c a t a l y s t
I
compares fa v o ra b ly w ith th e 0*112 and
0*113 grams o f s u l f u r p e r gram
o f c a t a l y s t removed by th e p u re n ic k e l ox id e i n Euns I and 2*
From
t h i s , i t would seem t h a t f r e e .n i c k e l produced by th e re d u c in g a c tio n
o f hydrogen may be th e a c ti v e d e s u l f u r i z a t i o n a g en t when n ic k e l oxide
f
29
~
c a ta ly s t i s used*
Thermodynamic c a lc u la tio n s were made fo r variou s r e a c tio n s which
might be used to convert n ic k e l s u lfid e to n ic k e l oxide or fr e e n ic k e l<,
The treatm ent o f n ic k e l s u lf id e w ith hydrogen or steam to produce hy­
drogen s u lfid e and f r e e , n ic k e l or n ic k e l oxide are b oth thermodynam­
i c a l l y unfavorable*
C a lc u la tio n s a ls o show th a t th e o x id a tio n o f n ic k e l
s u lf id e w ith oxygen could produce e ith e r n ic k e l s u lfa t e or su lfu r
d io x id e and n ic k e l o x id e 0 The n ic k e l s u lf a t e i s sta b le a ft e r i t is
formed and could not be decomposed by h eat excep t a t tem peratures th a t
would
s in t e r th e c a ta ly s t*
Runs 15» l6» 19» 2 0 , and 21 showed th a t
n ic k e l s u lfa t e had no a c t iv it y as a d e s u lfu r iz a tio n c a t a ly s t .
l 6 , 19» 20 and 21 are e s s e n t ia ll y d u p lic a te s o f Run 15*
Runs
In th e c a t­
a ly s t s t e s t e d , th e n itik e l s u lf id e had been converted t o n ic k e l s u l­
fa te by o x id a tio n w ith oxygen d ilu te d w ith n itr o g e n , steam , and/or
s u lfu r dioxide*
Some a c tiv e m a te r ia l should have been l e f t in th e
spent c a t a ly s t b efo re o x id a tio n , but th e regenerated p e l l e t s showed no
sig n s o f a c t iv it y fo r removing s u lf u r .
H ickel oxide can be,prepared by therm al decom position o f n ic k e l
hydroxide, n ic k e l carb on ate, or n ic k e l n itr a te *
and n ic k e l carbonate-are in so lu b le in water*
Both n ic k e l'hydroxide
N ickel s u lf id e can be
put in to s o lu tio n by d ig e s tio n w ith a cid s or by o x id a tio n to n ic k e l
s u lfa t e which i s w ater solu b le*
As part o f t h i s in v e s t ig a t io n , spent
c a ta ly s t w as' put in s o lu tio n w ith hyd rochloric and n it r i c acids*
N ick el hydroxide and n ic k e l carbonate were p r e c ip ita te d from th e se
-
30
s o lu tio n s , f i l t e r e d , w ashed, a n d .d rie d *
posed to n ic k e l oxide b y h e a t.
-
The p r e c i p i t a t e s w ere decom­
A c tiv a tio n was c a r r ie d o u t a t h ig h and
low te m p e ra tu re s i n stre am s o f a i r o r h y d ro g en ,
TSTone o f th e
m a te r ia ls
produced w ere a c tiv 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 ,
/
A ru n was made in t h e f l u i d r e g e n e r a to r a t JbO0C f o r one hour w ith
a i r as th e f l u i d i z i n g g a s .
The fe e d was 60 to 100 mesh sp e n t c a t a l y s t ,.
Uo odor o f s u lf u r d io x id e was n o tic e a b le i n th e e x i t g a s ,
IVhen sam ples
o f th e p ro d u c t w ere d is s o lv e d i n h y d ro c h lo ric a c id , th e odor o f hydro­
gen s u lf id e co u ld be d e te c te d ^ b u t th e amount g iv e n o f f was s m a llo
#
The s u l f a t e e x tr a c te d from th e p ro d u c t w ith a h o t w a te r le a c h was
.
c a l l e d s o lu b le s u l f a t e and th e s u l f a t e r e q u ir in g d ig e s tio n w ith a c id
f o r s o lu tio n was c a lle d in s o lu b le s u l f a t e .
was 7 ,2 0
The p ro d u c t o f t h e ru n
p e r c e n t s o lu b le s u l f a t e and J 0SJ p e r c e n t in s o lu b le s u l f a t e .
T h is would co rre sp o n d to 2l|.,2 p e r c e n t '■n ic k e l s u l f a t e i f a l l th e s u l­
f a t e w ere i n th e form o f n ic k e l s u l f a t e ,
The t o t a l s u l f a t e c o n te n t
o f th e s p e n t c a t a l y s t u sed as feed was u n d er one p e r c e n t.
u c t o f th e ru n on th e f l u i d re g e n e ra to r was
The prod­
5 3 oh p e r c e n t n ic k e l and
1 9 p e r c e n t m a te r ia l in s o lu b le i n 1-1 h y d ro c h lo ric a c id .
r
Summary
There i s a c o n s id e ra b le ran g e o f te m p e ra tu re , 600 to 675°F,
w here t h e d e s u l f u r i z a t i o n i s ' ind ep en d en t o f te m p e ra tu re e
The m axi= '
mum te m p e ra tu re t h a t can be used i s lim ite d by c ra c k in g s
The n ic k e l oxide d e s u lf u r iz e s by a c ti n g as a chem ical re a g e n t
combining w ith th e s u l f u r in th e o i l to produce n ic k e l s u l f i d e .
A ll o f th e sam ples o f c a t a l y s t t e s t e d became in a c t iv e when l e s s th a n $0
p e r c e n t o f th e n ic k e l oxide p re s e n t was c o n v e rte d to n ic k e l s u l f i d e .
T h is c e s s a tio n o f a c t i v i t y was n o t due t o m ech an ical b lo c k in g o f the.
c a t a l y s t p o r e s , b u t m ust have been due t o p a r t o f th e n ic k e l oxide
b e in g i n an in a c t iv e form .
The e x is te n c e o f in a c tiv e forms o f n ic k e l
oxide was d e m o n strated when n ic k e l oxide p re p a re d by ch em ical methods ■
was found i n e f f e c t i v e a s a d e s u l f u r i z a t i o n c a t a l y s t .
The d e s u l f u r i z a t i o n depends d i r e c t l y on th e t o t a l c o n ta c t tim e
and seems to be in d ep en d en t o f w h eth er t h i s c o n ta c t tim e was o b ta in e d
by one p a ss a t a g iv e n space v e lo c ity o r s e v e r a l re c y c le s a t a h ig h e r
space v e l o c i t y .
The co m b in atio n o f h ig h i n i t i a l c a t a l y s t a c t i v i t y and
easy t o remove s u l f u r compounds caused a h ig h r a t e o f d e s u l f u r i z a t i o n
a t th e s t a r t o f a ru n w hich r a p id ly dropped o f f u n t i l th e rem ain in g
n ic k e l oxide"was i n e f f e c t i v e i n removing th e r e f r a c to r y s u l f u r com­
pounds w hich w ere l e f t i n th e o i l .
The 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 ce p t t h a t
h ig h hydrogen r a t e s c a r r ie d th e o i l th ro u g h f a s t e r and th u s reduced th e
-
32
-
c o n ta c t tim e o ' The hydrogen r e a c te d w ith n ic k e l o x id e t o produce some
fre e n ic k e le
F ree n ic k e l was an a c ti v e d e s u l f u r i z a t i o n a g en t u n d er
th e c o n d itio n s used and. may have b een th e a c ti v e d e s u l f u r i z a t i o n ag en t
fo r t h i s p ro c e sso
The o x id a tio n o f n ic k e l s u lf id e w ith a i r produced n ic k e l s u lf a te ,
w hich had no a c t i v i t y as a d e s u lf u r iz a ti o n a g en t * S ie k e l oxide p r e - ■
p a re d by d e c o 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 re ­
c i p i t a t e d from s o lu tio n s co u ld n o t be a c ti v a te d w ith a i r o r hydrogen
t o 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 0
L i.
-
33
-
Aoknowledgment
The a u th o r acknow ledges th e c o u rte s y o f th e Husky O il Company
who su p p o rte d th e r e s e a r c h program u n d er w hich t h i s work was c a r r ie d
o u to
The Husky O il Company a ls o s u p p lie d th e f u e l o i l used as feed
s to c k and f u r n is h e d in fo rm a tio n t h a t com plim ented th e d a ta c o lle c te d
fo r th is th e s is e
I
3b
-
L i t e r a t u r e C ite d .
(1)
ASTH STANDARDS, P a r t 5 (I9b9)
D 86-i|6
(2)
.ASTM STANDARDS ON PETROLEUli PRODUCTS AND LUBRICANTS, 272,
D 90-ii.l-T (191+1)
(3)
G--Wynn3 Mo Ho
Uo S 0 P a te n t 2 ,0 7 3 ,5 7 8 - March 9 , 1937•
(If.)
Gwynn, Mo Ho
UoS0 p a te n t 2 ,1 7 ^ ,5 1 0 - O ctober 3> 1939»
(5)
Hougen , 0* Ae and W atson, Ko Mo CHEMICAL PROCESS
PRINCIPLES Vole I I , John -Wiley & Sons, I n e .
New Y ork3 No Yo 19U7
(6)
Lange, No'A, HANDBOOK' OF CHEMISTRY,"Sixth E d itio n ,
Handbook P u b lis h e r s , I n c e Sandusky3Ohio3 19^6
(7)
M abery3 Co Fo
(8)
(9)
Am. Chem. J 6 .13 232
. M c K ittrio k 3 De S .
In d . E n g r. Chem.
(1891)
21. 585-592 (1929)
U n ited S ta te s B ureau o f Mines B u l l e t i n No. b jb ( 19Ul)
-
35
-
C o n te n ts o f Appendix
Page Wo.
F ig u re I .
Com parison TJni t . . . . . . . . . . . . . . .
F ig u re 2«
F lu id R e a c to r System
T able .I .
Thermodynamic D ata . .................. . . . . . . .
38
T able I I . '
Type of C a ta ly s t TJsed for Runs . . . . . . .
39
...............................
3^
37
T able I I I . O p e ratin g C o n d itio n s f o r Runs on th e .. .
Com parison TJnit
...................... »
lf.0
T able TV9
S u lf u r B a la n c e s. . . . . . . . . . . . . . .
lj.1
T able V0
I n s p e c tio n D ata f o r Samples o f O il . . . . .
fj.8
f t
B
EXHAUST
-H2O
A.
WET TEST GAS METER
B.
INSULATION
C.
ORIFICE FLOWMETER
D.
H2O COOLED CONDENSER
E.
ICE COOLED
F.
THERMOWELL
G.
CONDENSER
INCH PIPE
H.
CATALYST
I.
PACKING
FIGURE
I.
COMPARISON
UNIT
37
EXHAUST
LINE
A. THERMOWELLS
B. NEEDLE VALVES
C. ORIFICE FLOWMETER
D. CATALYST FEED SYSTEM
E. FLUID REACTOR
F. INSULATION
FIGURE 2
FLUID REACTOR SYSTEM
38
-
TABLE I
THERMODYNAMIC DATA
EIemeirb^or
Compound
S ta te used
a s B a sis
n f BOlt3K
k ilo -c a l,
gm-mol
s SgetoK
H2
(g)
O
31.23
Ni '
(s)
O
7 .1 2
(g)
O
.
4 9 .0 3
SgO
(g)
-5 7 .8 0
4 5 .1 3
S2S
(g)
- 4 .8
Ni (OH)2
(s)
-1 2 9 .8
15. ■
NiO
(a)
- 5 8 .4
. 9.20
NiS
(a)
-2 0 .4
1 8 .0
NiSO4
(a)
-2 1 6 .0
2 3 .8
SOg
(g)
SO3
(g)
°2
•
-7 0 .9 2
-1 0 4 ,2
' 49.15
5 9 .2 4
6 3 ,8
T iB L I i i - TYPE -OF CiTiLYST USED FOR RUES.
Runs LTsed Catalyst
PSyiical.,
Condition
Remarks
1 ,2 ,9
Pure EiO
1/8" p e lle ts '
"Obtained from Harshaw Chemical Co,
3 thru 8
Pure EiO
60 to 200 mesh
P e lle ts obtained from the Harshaw Chemical Co,
were ground up.
IO
Ei(OH)S
1/8" pellets"
Activated with Hg",at 625 0Fo
11
Ei(OH)2
-i/8" p e lle t's
Activated with Eg at 820°Fo
12 '
HOP Hydrogena­
tio n Catalyst
13
Ei(OH)2
1/6" p e lle ts
Dried at 750°C, then activated with Hp at290°F,
1%
Ei(OH)2
1/8" p e lle ts
Activated with Hg at 550°F®
18
Ei(OH)2
l/8" p e lle ts
Activated with a ir for'
15,16
Regenerated
Catalyst
1/8" p e lle ts
1 9 ,2 0 ,2 1
The EiS in spent catalyst had been "oxidised to
EiSOi o These" samples were obtained from the
Husliy Oil Compary =
17
EiO and F ille r
’i/8" p e lle ts
A frbsh catalyst prepared by M= H.- Gmyhn and
activated w ith Hg="
22
EiC 0 ,
Irregular Lumps Activated w ith a ir for b hours at 8250F= The ■
. green' lumps of EiC0? were converted to a
friab le black powder by actIvatiotie
1/6" p e lle t s
Obtained from Universal Oil Products Company
b
hours at 825° F»
ho
■TABLE I I I - O p eratin g C o n d itio n s fo r . Runs on th e Comparison ."Ohit.
C a ta ly s t
Run WtY in P e rc e n t
No. grams
Loss
O il Eeed
WtY In P e rc e n t
grams
L oss
Hydrogen
R a te Y n ’
f t^ /h o u r
SjDiaee
V e lo c ity
Cm o f >S
Removed •
p e r gm o f
C a ta ly s t
20
8 .7 0
420
4.3 5
2.4 1
20 .9
2
20 '
9.58
420
2.4 5
2 .5 1
2 0 ,9
0.1135
4
20
15,65
440
5 .4 8
2 .4 7
2 0 .4
0.1135
5
20
1 4 .0 1
167
0 .8 1
2 .6 9
2 0 .9
0.0725
. 6 ■ 20
2 5 .0
167
2 .1 0
1 1 .8
2 0 .9
0.0470
8.
20
1 6 .5
167
' 19.7
1 2 ,4 .
2 0 .9
0.0640
9
20
1 5 .0
167
2 8 .3
1 .3 8
10
20
1 2 .0
420
27.2
11
20
1 4 .5
- 420
12
20
=4. 0
13
20
14
15
. I
.
0.1115
0.0590
9.14
2 .6 3
2 0 .9
0.0150
5 .3 2
2 .5 8
2 0 ,9
0.0145
420
9.87
2 .5 8
2 0 .9
0.1000
9 .0
420
1.0 7
2 .5
2 0 .9
0.0280
20
1 3 .0
420
.6.32
2 .5
. 20.9-
0.0105
20
7 .0
, 420
2 .5 7
2 .5
20 .9
0.0205
—0 .4 5 .
420
2 .6 2
2 .7 8
2 0 .9 .
0.0165
16 ' 20
17
20
-9 .2 5
420
3 .8 9
2 .5
2 0 .9
.
18
20.
1 6 ,0
420
11.05
2 .5 1
20 .9
0.0145
19
20
1 0 .0
420
’ 2.26
2 .5
20 .9
0.0065
20
20
1 2 ,0
420
5 .3 5
2 .5 7
20 .9
0,0080
21
20
1 0 .0
420
6.95
2 .4 7
2 0 .9
0.0265
22
20
1 1 .0
420
5 .3 2
2 .5
2 0 .9
0.0105 ■
0.1375
TABLE IV - SULFUR •BALANCES
Bun
Ho,
I
Average
B ea e to r
Temp0
' i n 0F
625
Wt0 i n grams
Time
C o rre c tio n s
P e rc e n t
B efore
in
W t o' o f
Hours. S u lf u r "C o rre ctio n
S u lf u r Sample Losses
O il
420
O
I
2
3
1.92
.1.70
420
1 063
370
8.78
8.06
6x,54
6.03
b
1.53
355
. 5=43
326
4=97
4=73
3
-.6T a ils
2,09
Io53
1.525
1.52
385
34o
311
5.20
420
8.78
3
.385
3 • 370
3
355
346
3"
326
'3
• 3 , 311
299
.7*40
.
32
12
12
12
11
12
12
Wto i n grams
A fte r
. C o rre c tio n
O il
S u lfu r.
'
6.29
■ 5.74
5,20
4.99
4.74
4.54
S u lf u r
Bembved
D uring' Time
I n te r v a l
0.72
0.86
0.26
O.36
0.02
OoOl
2.23
2
675
O
I
- 25
b
5
6
T a ils
h
625 ■
2*09
1.91
420
ii
7
1.64
1.60
399
389
6.85
6.54
6.22
6.04
358
5=71
5=50
10
I
2
-
9.20
7.59
7.22
6.62
-9'
6
10
6
9
6.29
5.94
10
7
6
6
1.59 - 380
A.55
369
1.536
2.09
1.725
2
3
1.70
1.62
1.595
1.57
44b
44o
425
409
.394
378
9
7
Io
9
408
. I
2
■I
2
408
O
T a ils
8.78
8.03
1 068
I
4
420
420
-
.
399
389
380
.369
8.78
-7.80"
6=70
6 .3 8
0.16
6.08
Oo16
0o04
348
5.87
3,55
5.35
44o
9.20
.425
7.33
6.95
6.39
6.03
5.82
358
409
394
378
371
0.75
0=95
0.16
0.Q5
2.27
1 060
O o ll
0.33
OolO
■0o09
TABLE IV = SULFUR BALANCES ( C o n t in u e d )
Wto in grams
Corrections irt. in grams
Average Time
"After
in
Percent
Before
Bun Beactbr
Correction Wt 0' of
Temp,• Hours Sulfur
No,
Correction
'In 0F
Oil
Sulfur Sample ' Losses O il
•
Sulfur
5 . ‘ 625
0
2,09
I »616
0,5
I
1,59
lohb
2
3
1,27
.1,25
b:
1,20
i.175
5
6
167
167
l6l
155
3.1:9
167
2.23
Ikl
ibo
6
6
8
1=88
7
1.72
133
1 .6 0
6 .
8
I
0
7
0
125
2.75
' 2.56
1.1:7
'0
0
0
■0
161
155
11:7
IbO
133
125
118'
3.b9
2.65
2 obi
Sulfur
Bemoved
During "Time
Interval
o.Tb
0.09
2.13
0.2b
1.78
l . 6b
1=50
0.06 .
O.ob
1.39
0,03
0.25
i.b5
6
625 .
2.09
1.61:5
0
:0,5
I
1.58
.1,51
1,2
*
167
3.1:9
167 , 2.75
159 . 2.52
151
2.28
7
I
■7
I
I
7
167
159
151
11:3
3.1:9
2 .6 2
2.38
2 .16
o.7b
0.1 0
oqo
0 . 9b
8
625
G
2,09
1.76
0 ,5
1
2
1 065
1.52
ij+o
3
k
5
6
■
1,33
1,26
1.22
167 .
167
156
1I4.6
133
119
105
89
3.1:9
2.9b
2.57
2.22
1.86
1=58'
1-33
1.07
8
.
7
8
9
9
Io
7
.
3
3
5
5
5
6
6 -
167
156
m
133
119
105
89
76
3»b9
2.7b
2 .b i.
2.02
1.67
0.55
0.17
0.19
0.16
0.09 '
1 .bo
1.1 2
0.07
0.9 3 ■ 0.05
TABLE IV - SULFUR BALMCES- ( C o n t in u e d ) .
Run
Ho
9
Average ■' Time
R ea c to r
in
Temp0
Hours
i n °F
625
0
I
2!
3
h
5
6
P e rc e n t
S u lf u r
. 2,09
1 067
1.565
1, 5 1 .
C o rre c tio n s
Wt0 i n grams
B efore
C o rre c tio n W t0 o f
O il
S u lf u r Sample Losses
167
167
151
138
Ick 2 5
123
1 .5 7
109
90
lo29
3 .to •
2.79
2 .3 6
2.08
1.75
1 .to
1.16
"’
IO
7 '
.9
8
13
7
6
’
6 •
6
6
6
6
.
Wt0 in grams
A f te r
C o rre c tio n
O il
S u lf u r
167
151
138
123
'109
90
77
S u lf u r
Removed
D uring Time
I n te r v a l
3^9
2 .5 2
2 o16
OolO
1.86
1.55
I .23
0.99
0.08
Ooll
0 .1 6
0 .0 6
OoOl
1.18
Sr
lb
625
0
1
2
-P
k
5
6
2 .0 9
.2001+5
. 2.015
2.02
2.02
2.02
2.02
.Wo
1+20'
590
362
355
307
280
8.78
8.6 0
7.86
7.31
6.77
6.21
5.65-
12
9
9
9
9
10
«
18 19
18
19
18
19
1+20
590
362
335
307
' 280
251
8.78
7.98
7.31
6o.77
6.21
5.65
5.07
O0I 8
0,12
*.*»<**#
w—ww
---0 .3 0
ii
625
0
1
2
2,09 '
2.01+5
2,02
1+20
1+20
599
8.78
8.6 0
8.05
10
9
11
11
1+20
399.
579
8.78
8.16
7.6$
«»•»«»«»
0.18
0.11
0o29
TABLE-IY - SBLEUB BALANCES (C ontinued)
Average
Run R eacto r
Ho o Tempo
i n ®F.
12
13
' 625
527
Time
in
Hours
0
I
2
3
Ir
5
6
0
I
2
3
P e rc e n t
S u lf u r
Wto i n grams
B efore
C o rre c tio n
O il . S u lf u r
L20
L20
C o rre c tio n s
Vft0 o f
Sample
-10-725
1065
I .65
106I
1-39
ko3
388
370
356
339
8 o78
7-7L
6.95
6<,Lo
6.11
5-73
5-39
2,09
2.00
1,975
1,955
L20
L20
Lio
Loi
8.78
8.Lo
9
8.10 . 8
8 .
7.8L
2 „09
loSlf.
10
8
11
7.
XO
11
L osses
7 •
7
7
7
7
6
I
I
•I
Wt- in grams
A fte r
C o rre c tio n
O il
S u lf u r
L20
L03
38.8
370
356
339 .
321
8.78
7-L2
6069
'6.11
5.87
5«If5
5-10
L20
Lio
Loi
392
8.78
8.20
7.92
7.66
S u lfu r
Removed
During Time
I n te r v a l
1. 0L
0.L7
0.29
a*="""=
0. 1L
0.06
2.00
0.38
0.10
0.08 .
O.56
Hr
527
0
I
2 .
3
h
5
6
2^09
2o0k
2.0L
2o0k
2.0L
2 .Ol^
2, OL
L20
L20
L07
393
.379
36L
352
8.78
8.57
8.31
8.02.
7.71
7-L3
7.19
9
10
TO
io
8
15
u.
if
5
If
If
L20
L07,
393
379
36L
352
333
8.78
0.21
8.31
8.02
7.73
' 7 .Li
7.19
6.80 .
*■ o r .
—r e . C r f S
TABLE 17 - SULFUR BALAECES ( C o n t i n u e d )
Run
Ho.
Average Time
R e a c to r i n
Temp0 Hours
i n 0Fo '
625
15 .
G
I
2i09
2.03
2
2 o03
3
k
5
'
P e rc e n t
S u lf u r
6
2 .0 2
2
.0 2
.
2.015
1.99
Wto i n grams
B efore
C o rre c tio n
O il
S u lf u r
Mo
Mo
Mb
C o rre c tio n s
W t. o f
Sample
W t. i n grams
A fte r
C o rre c tio n
O il
S u lf u r
L osses
8,7 8
.8.53
8.29
8 .0 0
396
385
37U
.7.79
7.5U
7 . 21+
36 b
1+20
10
10
10
9
9
12
2
2
.
1+08
396
385.
371+
561+
350
I
2
I
2
S u lf u r
Removed
’ D uring Time
I n te r v a l
8.78
0 .25
8.29
8 . Ol+
7.79 ■ OaOb
7.56
0 .02
.7.34
'
Q0IQ
6.97
' oo+i
16
625
0
1
2
3
h
5
2.09
2.035
2 ,0 5
2 .0 2
2 .0 2
2 .0 1
Mq
Mo
M9
8.7 8
.
398
.8,55
8.32
8.05
.386
375
7 .8 0
7.5U
1+20
9
9
10
9
10
2
2
2
2
2
1+09
398
386
375
363
8.78
8 . 3I+
8.09
7.80
0.23
0 .0 2
0 .0 4
7 .5 8
7 .3 0
0 .0 4
0.33
17
625'
0
I
2 .
"3 k
5
~~6~-
T a ils
2.09 . '7+20
1.7^
S20
1.69
^oL
391
579
367
357
3Wt
1.605
lo55
iJ iS
lo b b
lo b o
8.78
7 .3 1
6 .8 3
6 .2 7
5 .8 8
5*b3
5 o ib
4,81
1+20
8.78
3
Mb
3
2
391
7.0 3
6 .6 0
<
*»<
0
13
10
. 10
9
8
10
12
3
2
3
-
'
379
367
357
6.09
5.69
3bb
4,95
332
5 .2 8
4 .6 5
10+7
0 .2 0
Q.33
0.21
0.26
0 .1 4
0 .1 4
2.75
TABLE TJ - SULFUR BALANCES ( C o n t i n u e d )
Wt i in grams
Average Time .
Before 1
in
'
Percent
Run Reactor
Correction
’
Hours
Sulfur
Mo. Temp.
Oil ; Sulfur
' i n .5F0
18
62$
0
2 ,0 9
2.02
2.02
2.02
2.02
2.02
I
2
3
k
5.
Corrections Tft0 in grams
"After
Correction
Wt.' of
Sample
Losses O il,
Sulfur
8.78
8.1:9
8.12 ■
i|.20
h2D
b02
7 .7 8
7.2 a
385
567
3^8
7.05
•
1:20
9
8
9
10
8
9.
9
9
9
9
1:02
385
367
324.8
331
8.78
8.12
0.29 '
7.78
a fe ifle re e
7 . 1a
w eeee*.
7.05
6.69
625
0
2 „0l|.
I
2.015
2.015
2.015
2.01
2
3
h
.
Ij.20
b20
14.08
399
388
•
-
0.29
-
19
Sulfur
Removed
During'"Time
Interval
8.57
8.1:6
8.22
8.01:
7.80
** '
9
7
8
10
3
2
3
1^0
1:08
8.57
399
388
-8.01:
• 2 ■ 376
8.22.
7.82
7.56
0.11
W O O f lo o e
.
o rev eacD
0.02
0.13
20
62$
6
2.0^
k20
I
2 . 0I4.
2
3
2.05
1|.08
2.015 ■ 395
2.005 38L
2.00
372
b
5
1^20
8.57.
8.57
8.29
7.96
7.70 .
Iobk
9
10
8
■ 9
9
.3
3
3
3
3
k2Q
boe
■ 8.57
8.33,
e a a a A ee e-
372
8,02
7.71:
7.2:6
O0OI4.
36O
7.20
0.02
395
381:
b.oi:
6*06
0 . 1%
'
TABLE 17 - SBLFBH BALANCES (Continued)
Run
No.
21
22
Average
R e a c to r
Temp6
. i n 0Fe
625
625
T M e'
in
Hours
0
I
2 '
5
If.
0 .
i
2
3
h
5
6
Wto i n grams
P e rc e n t
B efore
S u lf u r .C o rre c tio n
S u lf u r
O il
2 . Oli
2*02
2*00 ■
2*00
2*00
2 *0L
1 .9 7
1*92
1 .9 2
1 .9 1
1 .91
1 .9 1
420
lf.20
k05
589
37^
li20
lf.20
UoU
393
38U
375
361
8*57
• 8.U9
BoiO
7*78
7.U.6
8 .5 7
8*28
7*76
7*55 •
7.3U
7.1 3
6*90
C o rre c tio n s
Wt * o f
Sample
.Losses
8
8
"9
ib
7
8
7
7
Wt * i n grams
A fte r
C o rre c tio n
O il
S u lf u r
U20
U05
389
.373
356
8 .5 7
8*18
7*78
7,U6
7 .1 2
-
-
U-20
iU
9'
■ 6
9
9
9
2
2
3
2
3
2
hoh
395
' 38U373
361
350
8*57
7*96.
7*55 .
7*3.8
7 .1 5
6*90
6*69
S u lf u r
Removed
D uring TMe
In te rv a l
0*08
0*08
2222'
0*16
a0*29
0*20
OoOlf-
0.53
a
-10
TABLE, V »
O rig in o f
Sample
-
INSPECTION DATA FOE SAMPLES OF OIL
Feed
O il
Run 2
______
Run IO
_____
Run 17
______
100
h90
508
528
5ho
552
562
572
583
598
620
658
ASTM D i s t i l l a t i o n s - T em peratures Ln- 0F „
1|60
500
518
53k
5k&
556
566
576
58& .
6ob
620
660 •.
b38
b9b
5 io
530
5b2
553
565
573
58^
600
618 •
661
1^60
U98
520
53.2
■5bb
556
566
576
586
602
622
658
# R ecovery •
98
98. .
' 98
98
B aro m etric
P re s s u re i n '
mm o f Hg.
638
Skl
658
F i r s t Drop
5#
20#
3#
,W
50#
6 o# i ■
70#
. 8C^ ■
90#
End P o in t
S p e c if ic G ra v ity
# S in sample
6I1I
..
■0*868
0*868
2*05
1*51+
■
,
0*873
0*861}.
2*02
I 9IlO
' F req u e n t checks on th e s u l f u r c o n te n t o f th e fe e d o i l were
madeo The "values v a r ie d from 2<,10 t o 2*07 f o r runs I th ro u g h 18* A
v a lu e o f 2 *09- was u sed f o r a l l th e s u l f u r B alan ces f o r th e s e runs *
V alu es o f 2*01). t o 2*06 w ere obtained, f o r th e : feed o i l used, f o r runs
19 th ro u g h 22* The s u l f u r b a la n c e s f o r th e s e runs w ere made u sin g
RoOli as t h e s u l f u r c o n te n t o f th e fe e d o il*
'U
$
100900