Catalytic hydrogenation of shale oil coker distillate
by Glenn A King
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering
Montana State University
© Copyright by Glenn A King (1955)
Abstract:
This investigation was made to determine the applicability of four catalysts to the hydrogenation of a
650° F.E.P. shale oil coker distillate. Two preliminary studies were made on an 850° F.E.P. coker
distillate to determine the optimum operating conditions.
The catalysts investigated were? (1) Harshaw's molybdenum oxide/ Mo-0203-T-l/8", promoted with
indium, (2) Harshaw's molybdenum oxide promoted with palladium, (3) Peter Spence & Sons', Ltd.,
cobalt molybdate, 5/32 in., graphite base, and (4) Harshaw'S cobalt molybdate, Co-Mo-0201-T-l/8". A
Union" Oil Company cobalt, molybdate catalyst was used in the two preliminary studies. The indium
and palladium promoted catalysts were prepared in the laboratory at Montana State College.
The "investigations were conducted in a bench-scale pilot plant unit. The preliminary runs showed that
an operating pressure of 1000 psig. was more conducive to a successful hydrogenation process
for"shale oil coker distillate than was a pressure of 500 psig. Conditions used in the catalyst studies
were a reactor pressure of 1OOOpsig., a space velocity of 1.0 gms. of oil per gm„ of catalyst per hour,
and the recycle gas rate was 7500 cu. ft. of 65 percent hydrogen, 35 percent methane, per bbl. of oil"
charged. The temperature was raised from 725° F. to 925° F, in increments of 50° F. every 24 hours
during each catalyst study. The average run length for each catalyst was 120 hours of on-stream
operation plus a 24-hour lineout period at the beginning of a series of runs and an eight-hour lineout
period between temperature increments.
The Spence cobalt molybdate catalyst was found to give "better nitrogen and sulfur removal than the
other three catalysts investigated. Palladium molybdate and Harshaw's cobalt molybdate were effective
catalysts, with the palladium giving the indication that it might be used,, effectively at higher
temperatures than the other catalysts. The indium catalyst gave good yields, 92.5 weight percent of the
charge at 875° F., but had poor denitrogenization properties. CATALYTIC HmO.GSN.ATIDJ5...DE...SHALE....OIL
QOKER DISTILLATE)
by
GLENK A. KING
A THESIS
S u b m itte d to th e G ra d u a te 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 r e q u ir e m e n ts
f o r th e d e g re e o f
M a s te r o f S c ie n c e i n C h em ical E n g in e e rin g
at
M ontana S ta t e , C o lle g e
A pproved:
Bo z e m a n ,.,.M o n tan a
S e p te m b e r, 1955
M31?
K
- 2TABLE OF CONTENTS
ABSTRACT...........................................................................................................................................
3
I
I n t r o d u c t i o n ....................................................................................................................
4
II
E quipm en t, M ethods, and M a te r i a ls ..................................................................
10
III
A.
E q u ip m e n t.....................................................................................................................10
B.
M e th o d s .......................
C.
M a t e r i a l s .....................................................................................................................17
13
D is c u s s io n o f R e s u l t s .................................................................................................. 19
A.
D e te rm in a tio n o f th e Optimum O p e ra tin g C o n d itio n s ....................
19
B.
H arshaw 1s Molybdenum Oxide C a t a l y s t Prom oted w ith Indium . .
21
C.
H arshaw 1s Molybdenum Oxide C a t a ly s t Prom oted w ith
P a l l a d i u m .....................................................................................................................22
D.
P e t e r Spence &S o n s,
E.
H arsh aw 1s C o b a lt M olybdate C a t a l y s t .......................................................
F.
ASTM D i s t i l l a t i o n D ata f o r th e 875° F. Run f o r Each C a ta ly s t 26
L t d . , C o b a lt M olybdate C a t a l y s t . . . .
23
2$
IV
S u m m ary ...................................................................................................................................27
V
A cknow ledgm ent.....................................................................................................................29
VI
L i t e r a t u r e C i t e d ................................................................................................................30
V II
A ppendix..................................................
................................. .......................31
114897
ABSTRACT
T his i n v e s t i g a t i o n was made t o d e t e m i h e th e a p p l i c a b i l i t y o f f o u r
c a t a l y s t s " t o th e h y d ro g e n a tio n o f a 6 50° F .E .P . s h a l e " o i l " c o k e r d i s t i l ­
la te .
Two p r e lim in a r y s t u d i e s w ere made on an 850° F .E .P . c o k e r d i s t i l ­
l a t e t o d e te rm in e th e optimum o p e r a t in g c o n d i t i o n s .
The c a t a l y s t s i n v e s t i g a t e d were"? ( I ) H arshaw t s molybdenum o x i d e /
M o -0 2 0 3 -T -l/8 11, prom oted w ith in d iu m , (2 ) HarshawTs molybdenum' o x id e p r o ­
m oted w ith p a l l a d i u m ," ( 3 ) P e t e r Spence & S o n s ’, L t d . , c o b a l t m o ly b d a te /
5 /3 2 i n . , g r a p h it e b a s e ,- and" (4") "H arshaw t s c o b a lt m o ly b d a te , Co-M o-0201-T1 / 8 ” . A U n io n "O il Company c o b a lt, m o ly b d ate c a t a ly s t" w a s u s e d i n th e two
p r e li m i n a r y s t u d i e s . T h e "indium and p a lla d iu m prom oted c a t a l y s t s w ere p r e ­
p a re d i n th e l a b o r a t o r y a t M ontana S t a t e C o lle g e .
The i n v e s t i g a t i o n s w ere c o n d u c te d i n a b e n c h - s c a l e . p i l o t p l a n t ,u n i t .
The p r e li m i n a r y fu n s showed t h a t an o p e r a t in g p r e s s u r e o f 1000 p s ig . was
more c o n d u civ e t o a s u c c e s s f u l h y d r o g e n a tio n p r o c e s s f o r " s h a l e " o il c o k e r
d i s t i l l a t e th a n was a p r e s s u r e o f "500 p s i g . C o n d itio n s u s e d i n th e c a t a ­
l y s t s t u d i e s w ere a r e a c t o r p r e s s u r e o f I O O O p s ig ., a sp a c e v e l o c i t y o f
1 .0 gras, o f o i l p e r gm„ o f c a t a l y s t p e r h o u r , and th e r e c y c le g as f a t e was
7500 c u . f t . o f 6"5 p e r c e n t h y d ro g e n , 35 p e r c e n t m e th an e, p e r b b l . o f o i l "
c h a rg e d . The "te m p e ra tu re was f a i s e d fro m 725° F . t o 925° F , i n in c re m e n ts
o f 50° F . e v e r y 24 h o u fs d u r in g each c a t a l y s t s tu d y . T h e " a v e ra g e ru n
le n g th f o r eac h c a t a l y s t was 120 h o u rs o f o n -s tre a m o p e r a t io n p lu s a 24h o u r l i n e o u t p e r io d a t th e b e g in n in g o f a s e r i e s o f ru n s >and an e i g h t h o u r l i n e o u t p e r io d b etw een te m p e r a tu r e in c re m e n ts .
The 'S pence c o b a l t m o ly b d ate c a t a l y s t was fo u n d " to g iv e " b e t t e r n i t r o ­
gen and s u l f u r , fem o v al th a n th e o t h e r t h r e e c a t a l y s t s i n v e s t i g a t e d . . P a l l a ­
dium m o ly b d ate an d H arshaw t s c o b a l t m o ly b d a te w ere e f f e c t i v e c a t a l y s t s ,
w ith t h e p a lla d iu m g iv in g th e i n d i c a t i o n t h a t i t m ig h t be used,, e f f e c t i v e l y
a t h ig h e r te m p e r a tu r e s th a n th e o th e r c a t a l y s t s . The in d iu m c a t a l y s t gave
good " y ie ld s , 9 2 .5 w eig h t p e r c e n t o f th e c h a rg e a t 875° F . , b u t had p o o r
d e n itro g e n iz a tio n p r o p e r tie s .
-4 -
I
INTRODUCTION
The i n v e s t i g a t i o n o f o i l s h a le a s a p o s s i b le s o u r c e ' o f com m ercial
f u e l s h as b een c a r r i e d on. by th e B ureau o f M ines o f th e U n ite d S ta t e s
D epartm ent o f th e I n t e r i o r s in c e a b o u t 1 9 2 5 .
how ever, v e r y l i t t l e
From 1929 u n t i l 1944
i n v e s t i g a t i o n was c o n d u c te d b e c a u se o f th e e v e r
i n c r e a s i n g s u p p ly o f p e tro le u m .
I n A p r il o f 1 9 4 4 , th e S y n th e tic L iq u id
F u e ls A ct was p a s s e d by th e 7 8 th C ongress f o r th e p u rp o se o f i n v e s t i g a t i n g
p o s s i b l e s o u rc e s o f l i q u i d f u e l s w ith w hich t o su p p lem en t th o s e d e r iv e d
from p e tro le u m .
The p a s s a g e o f t h i s a c t was prom pted by t h e h eav y w artim e
co n su m p tio n o f f u e l s w hich s e e m i n g ly 'th r e a te n e d t o d e p l e te t h e n a t i o n 's
o il re se rv e s.
I t was e x te n d e d when p e a c e tim e demands f o r o i l and o i l
p ro d u c ts s u rp a s s e d p eak re q u ire m e n ts o f W orld War I I .
In 1943 t h e con­
su m p tio n o f l i q u i d f u e l s was 1 .7 b i l l i o n b a r r e l s w h ile i n 1953 i t had
in c re a s e d to 3 b i l l i o n b a r r e ls p e r y e a r.
I t i s t r u e t h a t s u p p ly h a s managed t o k eep p ace w ith t h i s demand,
b u t o n ly th ro u g h im p o rts o f more and m o r e , o i l .
o n e - h a l f b i l l i o n b a r r e l s o f o i l i n 1953«
These im p o rts ap p ro ac h ed
T h is f a c t a lo n e j u s t i f i e s th e
g o v e rn m e n ta l a p p r o p r i a t i o n s t o th e B u reau o f M ines so t h a t new s o u rc e s o f
f u e l s may be. opened up t o l e s s e n th e n a t i o n 's dependence on o th e r
c o u n t r i e s f o r ;i t s f u e l s .
O il s h a le can be d e f in e d a s a com pact la m in a te d ro c k o f s e d im e n ta ry
o r i g i n w hich c o n ta in s s o l i d o rg a n ic m a t t e r c a l l e d " k e r o g e n ," t h a t w i l l y i e l d
o i l upon d i s t i l l a t i o n .
I t i s i n t e r e s t i n g t o n o te t h a t th e word p e tro le u m
i s d e r iv e d from two L a t in w o rd s, p e t r a and o leu m , w hich mean ro c k and o i l ,
re s p e c tiv e ly .
Thus p e tro le u m means "ro c k o i l . "
The d e r i v a t i o n o f t h i s
-5 -
word p lu s th e f a c t t h a t o i l s h a le was known t o e x i s t and was u se d a s e a r l y
a s 1694 i n E ngland and S c o tla n d g iv e s an i n d i c a t i o n o f how lo n g th e
know ledge o f o i l s h a le p re c e d e d th e d is c o v e r y o f w hat i s now known a s
p e tro le u m .
The o r i g i n o f o i l s h a le i s b e l ie v e d t o be q u i t e s i m i l a r t o t h a t o f
c o a l.
Beds o f o rg a n ic m a t t e r , v e g e ta b le s p o r e s , p o l l e n , a l g a e , s h e l l s o f
m in u te c r u s ta c e a n s , e t c . , w ere d e p o s ite d a t th e b o tto m o f l a k e s .
U pheaval
o f th e la k e b o tto m fo llo w e d by e r o s io n have l a i d b a re th e v a s t s t r a t i f i e d
seam s o f o i l s h a l e .
The f i e l d s o f o i l s h a le t h a t a p p e a r t o be th e m ost p ro m is in g f o r
co m m ercial e x p l o i t a t i o n i n th e U n ite d S t a t e s a r e th o s e lo c a t e d i n C o lo ra d o ,
Wyoming, and U ta h .
T h is i s th e G reen R iv e r f o r m a tio n .
T h is fo rm a tio n i s
a p p ro x im a te ly 1 7 ,0 0 0 s q . m i. i n a r e a o f w hich 9200 s q . m i. a r e i n Wyoming,
5200 s q . m i. a r e i n U ta h , and th e re m a in d e r i s in C o lo ra d o .
The C olo rad o
p o r ti o n o f th e fo r m a tio n h a s b een th e m ost th o r o u g h ly i n v e s t i g a t e d .
E s tim a te s o f p a r t l y b lo c k e d and i n f e r r e d s h a le f o r t h i s a r e a i n d i c a t e t h a t
a 500- f o o t - t h i c k m e a su re , a s s a y in g 15 g a l . p e r t o n , c o n ta in s a p o t e n t i a l
r e s e r v e o f 494 b i l l i o n b a r r e l s o f s h a le o i l .
The lo w e r segm ent o f t h i s
m e a su re , c a l l e d th e Mahogany le d g e , i s up t o 90 f e e t t h i c k and a v e ra g e s 30
g a l. p er to n .
T his r e p r e s e n t s an e s tim a te d r e s e r v e , i n p l a c e , o f 126
b i l l i o n b a r r e l s o f s h a le o i l .
In t h i s zone a l o n e , th e p o t e n t i a l s h a le o i l
r e s e r v e i s ab o u t f o u r tim e s th e known p e tro le u m r e s e r v e o f t h i s c o u n try .
D e s p ite t h i s l a r g e . r e s e r v e , d ev elo p m en t o f o i l s h a le r e s o u r c e s h a s n o t been
o f com m ercial i n t e r e s t b e c a u se i t was f e l t t h a t o i l c o u ld n o t be p ro d u ced
a s c h e a p ly by m in in g o i l s h a le a s from th e n o rm al p e tro le u m c ru d e s o u rc e s
—6 —
and t h a t th e p e tro le u m r e s e r v e s w ere q u i t e a d e q u a te .
As a r e s u l t o f th e S y n th e tic L iq u id F u e ls A ct, th e B ureau o f M ines was
e n a b le d to s e t up a d e m o n s tr a tio n m ine a lo n g w ith r e t o r t i n g and r e f i n i n g
f a c i l i t i e s n e a r th e s m a ll m o u n tain tow n o f R i f l e , C o lo ra d o .
A lthough t h i s
v e n tu re c a n n o t be c l a s s i f i e d a s a co m m ercial o n e, many c o m p a n ie s, among
w hich a r e some o f th e l a r g e r o i l co m p a n ie s, have begun t o e x p r e s s an
i n t e r e s t i n th e p o s s i b i l i t i e s o f u t i l i z i n g o i l s h a l e .
U nion O il Company,
i n p a r t i c u l a r , i s s a i d t o have made c o n s id e r a b le p r o g r e s s to w a rd s
c o m m e rc ia liz in g o i l s h a le a s a f u e l s o u r c e ( 3 ) .
The B u reau o f Mines a l s o
h a s many c o o p e r a tiv e a g re e m e n ts w ith f ir m s o t h e r th a n o i l com panies and w ith
v a r io u s c o l l e g e s and u n i v e r s i t i e s , among w hich i s Montana S t a t e C o lle g e .
A lthough i n d u s t r y h a s b een slo w t o s e e th e p o s s i b i l i t i e s o f o i l from s h a l e ,
th e e n g in e e r in g and c o s t d a t a w hich th e B u reau o f M ines h a s o b ta in e d from
t h e i r r e s e a r c h d u r in g th e p a s t s e v e r a l y e a r s , b o th a t R i f l e and a t th e s h a le
o i l l a b o r a t o r y i n L a ra m ie , lo o m in g , i s a v a i l a b l e f o r i t s u s e .
One o f th e b i g g e s t p ro b lem s o f th e B ureau o f M ines h a s b een t o d e v e lo p
a s a f e , eco n o m ic a l m ethod o f m in in g o i l s h a l e .
In o r d e r t o pro d u ce o i l
from s h a le e c o n o m ic a lly , th e m in in g s t e p h as t o be e x tre m e ly e f f i c i e n t .
I t h a s b e e n known f o r y e a r s t h a t th e m in in g c o s ts i n s u r f a c e w o rk in g s a r e
l e s s th a n i n u n d e rg ro u n d m in e s .
The aim o f th e d e m o n s tra tio n m in e,
t h e r e f o r e , h a s been t o l i t e r a l l y ta k e a q u a r r y u n d erg ro u n d and ad o p t a s
many s u r f a c e m in in g te c h n iq u e s a s p r a c t i c a b l e t o u n d e rg ro u n d c o n d i t i o n s .
The B ureau o f M ines h a s d e v e lo p e d su ch a m ethod o f u n d e rg ro u n d m in in g ,
c a l l e d t h e room and p i l l a r m ethod, and hav e found t h a t 75 p e r c e n t o f th e
o i l s h a le c o u ld be s a f e l y rem oved le a v in g th e o th e r 25 p e r c e n t t o s e rv e
1
a s p i l l a r - t y p e r o o f s u p p o r ts .
U sing th e room and p i l l a r ty p e m in in g
m eth o d , a m o n th ly a v e ra g e s h a le p r o d u c tio n up t o 165 to n s p e r m a n - s h if t
a t an a p p ro x im a te c o s t o f $ 0 .5 0 p e r to n h a s b een a t t a i n e d ( 9 ) .
This
r e p r e s e n t s ab o u t 25 tim e s th e p r o d u c tio n o f th e a v e ra g e A m erican c o a l
m in e r.
Much o f th e r e s e a r c h t h a t h a s b een co n d u c te d on th e r e t o r t i n g o p e r­
a t i o n h as b een t o d e v e lo p a c o n tin u o u s ty p e r e t o r t .
was f i r s t b eg u n , a b a t c h - ty p e r e t o r t was u s e d .
When th e o p e r a tio n
A c o n tin u o u s r e t o r t i n g
p r o c e s s , c a l l e d t h e g a s -c o m b u s tio n p r o c e s s , h a s b een d e v e lo p e d and h as
ta k e n t h e p la c e o f th e o ld NTU r e t o r t a t th e d e m o n s tra tio n m in e.
In t h i s
p r o c e s s , th e o i l s h a le i s r e t o r t e d a s a downward moving bed h e a te d by an
a s c e n d in g s tre a m o f h o t co m b u stio n g a s e s .
The co m b u stio n g a s e s a r e
g e n e r a te d by b u rn in g r e c y c le d p r o d u c t g a s and c a rb o n a c e o u s r e s id u e from
th e r e t o r t e d s h a le d i r e c t l y i n th e s h a le b e d .
By c o n t r o l l i n g th e r a t e
o f c o o l in g , th e s h a le o i l v a p o rs a r e co n d en sed w ith in th e r e t o r t a s a
fo g o r m is t i n th e g a s s tr e a m .
T hus, s h a le o i l i s removed fro m th e s h a l e "
bed i n a l i q u i d s t a t e and can be r e c o v e re d w ith o u t f u r t h e r c o o lin g o r
c o n d e n s a tio n .
T h is f a c t b r in g s o u t a d i s t i n c t ad v a n ta g e f o r th e gas
c o m b u stio n r e t o r t o v e r o t h e r r e t o r t s ; e g . , i t r e q u ir e s no w a te r i n an
a r e a w here w a te r i s e x tre m e ly s c a r c e .
The c ru d e from th e r e t o r t h a s b een g iv e n some o f th e more common
p e tro le u m tr e a tm e n ts su ch a s c o k in g , v i s b r e a k i n g , f r a c t i o n a t i o n , th e rm a l
c r a c k in g , c a t a l y t i c c r a c k in g , h y d r o g e n a tio n , and a c i d t r e a t i n g .
The f u e l s
o b ta in e d from th e s e p r o c e s s e s a r e c h a r a c t e r i z e d by a h ig h gum c o n t e n t,
h ig h d e g re e o f u n s a t u r a t i o h , h ig h s u l f u r and n it r o g e n c o n t e n t , p o o r c o lo r
-S -
s t a b i l i t y , and an o f f e n s iv e o d o r s u g g e s tiv e o f p y r i d i n e „
A g a s o lin e and
d i e s e l f u e l , w hich w ere a c t u a l l y u se d i n a tr u c k and a t r a i n , have been
o b ta in e d - b y th e rm a l c r a c k in g and s u l f u r i c a c i d t r e a t i n g , b u t th e y i e l d
was t o o p o o r t o s u g g e s t u t i l i z i n g t h a t p ro c e d u re f o r a co m m ercial p r o c e s s .
In r e c e n t y e a r s , s e v e r a l p r o c e s s e s i n p e tro le u m te c h n o lo g y have b een ■
d e v e lo p e d t h a t a r e o f i n t e r e s t in t h e i r a p p l i c a t i o n t o s h a le o i l .
The
p o ly fo rm p r o c e s s , c a t a l y t i c c r a c k in g , and c a t a l y t i c h y d ro g e n a tio n a r e
t h r e e o f t h e p r o c e s s e s t h a t a p p e a r t o be p ro m is in g .
The p o ly fo rm p r o c e s s
em ploys t h e p r i n c i p l e o f c r a c k in g n a p h th a and h e a v i e r o i l s i n a d m ix tu re
w ith v a r y in g am ounts o f c h e a p , g a se o u s h y d ro c a rb o n s su ch a s th e p ro p a n e s
and b u ta n e s .
C a t a l y t i c c r a c k in g i s a p r o c e s s f o r c o n v e r tin g p e tro le u m
f r a c t i o n s i n th e g a s o i l b o i l i n g ra n g e i n t o g a s o lin e and o th e r lo w e r
b o i l i n g h y d ro c a rb o n s .
The two p r o c e s s e s may be com bined t o form a p r o c e s s
c a l l e d c a t a l y t i c p o ly fo rm in g .
The e f f e c t s o f t h i s p r o c e s s on s h a le o i l
w ere i n v e s t i g a t e d by C r e e e liu s ( 6 ) .
He d e te rm in e d t h a t h ig h e r y i e l d s o f
g a s o li n e w ere o b ta in a b le th ro u g h t h i s p r o c e s s th a n from th e rm a l c r a c k in g ,
c h e m ic a l t r e a t m e n t , e t c . , b u t t h a t th e q u a l i t y o f th e p r o d u c ts was n o t
m a t e r i a l l y im proved o v e r o t h e r m ethods o f r e f i n i n g s h a le o i l .
The
minimum gum c o n t e n t , i n p a r t i c u l a r , was s t i l l to o g r e a t .
I t h a s b een s u g g e s te d by v a r io u s r e s e a r c h e r s on s h a le o i l and th e
p r o d u c ts o b ta in e d t h e r e o f , t h a t th e k e y t o t h e i r i n s t a b i l i t y m ig h t be th e
p re s e n c e o f n i t r o g e n . - They f e e l t h a t n i t r o g e n e i t h e r t a k e s p a r t i n o r
p o s s i b l y c a t a ly z e s t h e gum fo rm in g r e a c t i o n s .
The o b v io u s answ er t o
s o lv in g su ch a p ro b lem i s rem o v al o f th e n i t r o g e n .
The B ureau o f Mines
and o th e r s have d e m o n s tra te d t h a t by t h e u s e o f d e s t r u c t i v e c a t a l y t i c
-9 -
h y d r o g e n a tio n , e g . , te m p e r a tu r e s above 850° F . and p r e s s u r e s o f 1000 p s i g .
o r g r e a t e r i n th e p r e s e n c e o f h y d ro g e n , b o th n it r o g e n and s u l f u r can be
e s s e n t i a l l y rem oved from th e p r o d u c t.
The f a c t t h a t th e u s u a l m ethods o f t r e a t i n g p e tro le u m do n o t a p p e a r
e c o n o m ic a lly a p p l i c a b l e t o t h e r e f i n i n g ' o f s h a le o i l , le d th e a u th o r t o
i n v e s t i g a t e th e p o s s i b i l i t i e s o f a m ild ty p e c a t a l y t i c h y d ro g e n a tio n
p ro c e ss.
The i n v e s t i g a t i o n was i n i t i a t e d by d e te r m in in g th e optimum
o p e r a t in g c o n d i t i o n s .
Once th e s e c o n d i tio n s w ere e s t a b l i s h e d , a s tu d y o f
th e e f f e c t s o f s e v e r a l d i f f e r e n t c a t a l y s t s on th e m ild h y d ro g e n a tio n o f
a 6 50° F .E .P . c o k e r d i s t i l l a t e was m ade.
p r e p a r a t i o n s a r e d e s c r ib e d on page 1 7 .
The c a t a l y s t s u se d and t h e i r
“ 10—
II
EQUIPMENT, METHODS, AND MATERIALS
A EQUIPMENT
A sc h e m a tic d ia g ra m o f th e u n i t i s ' shown i n F ig u re I .
The u n i t can be
d iv id e d i n t o two m ain p a r t s : ( I ) th e r e a c t o r s e c t i o n and ( 2 ) th e r e c y c le gas
s e c tio n .
The r e a c t o r s e c t i o n c o n s is te d o f a fe e d s y ste m , th e r e a c t o r , and th e
sa m p lin g f a c i l i t i e s .
The f e e d was pumped from a r e s e r v o i r th ro u g h l / S i n .
ID h ig h p r e s s u r e s t a i n l e s s s t e e l tu b in g i n t o th e to p o f th e r e a c t o r by a
H ills-M cO anna C hem ical P r o p o r tio n in g Pump.
The flo w r a t e o f th e pump was
a d j u s t a b l e t o any d e s i r e d r a t e up t o 1 .0 2 g a l ./ m i n . a t .2900 p s i .
The r e a c t o r .was made from an 18 i n . le n g th o f 2^ i n . s c h e d u le 80,
a u s t e n i t i c , s t a i n l e s s s t e e l p ip e and was d e s ig n e d t o o p e r a te a t a m ax i­
mum p r e s s u r e o f 3000 p s i . w ith a s a f e t y f a c t o r o f 1 0 .
I t was c lo s e d a t
eac h end by a s p e c i a l l y d e s ig n e d s c re w -ty p e f i t t i n g w hich was m achined
h e r e a t M ontana S t a t e C o lle g e ; h o w ev er, b e c a u se o f d i f f i c u l t y i n o b ta in ­
in g a s a t i s f a c t o r y s e a l , b o th ends w ere e v e n t u a ll y w eld ed p e rm a n e n tly in
p la c e .
T hree n ich ro m e h e a t in g c o i l s , each a p p r o x im a te ly 33 f e e t lo n g ,
w ere bead ed an d w rapped aro u n d th e r e a c t o r w hich had f i r s t b een w rapped
w ith a s b e s to s t a p e .
A n o th er l a y e r o f a s b e s to s ta p e c o v e re d t h e c o i l s t o
p r o t e c t th em a g a i n s t th e m ag n esia mud l a y e r w hich p ro v id e d th e n e c e s s a r y
in s u la tio n .
The t o p o f th e r e a c t o r was f i t t e d w ith th e n e c e s s a r y f i t ­
t i n g s , v a l v e s , e t c . t o p ro v id e f o r fe e d g a s i n l e t , o i l i n l e t , o i l f e e d ­
l i n e b le e d , vacuum l i n e c o n n e c tio n , b lo w o u t- d is k e x h a u s t sy ste m , and
th e rm o w e ll.
The th e rm o w e ll was made from a le n g th o f
i n . s e a m le s s ,
-1 1 -
s c h e d u le 80 , s t a i n l e s s s t e e l p i p e .
I t f i t t e d i n t o t h e to p o f th e r e a c t o r
and a llo w e d f o r th e l o c a t i n g o f t h r e e th e rm o c o u p le s a t an y d e s i r e d p o in t
a lo n g t h e v e r t i c a l a x i s o f th e r e a c t o r .
At t h e b o tto m o f th e r e a c t o r , a c o n d e n s e r was c o n n e c te d by means o f a
3 / 4 i n . s c h e d u le 80 u n io n .
Below th e c o n d e n s e r was f i t t e d a sam ple r e ­
s e r v o i r w hich was a s h o r t le n g th o f 2 i n . s c h e d u le 80 p ip e c lo s e d a t b o th
ends by c a p s w elded i n p l a c e .
The cap s w ere ta p p e d f o r l / 2 i n . p ip e .
C onnected t o th e r e s e r v o i r a s shown i n F ig u re I , was a J e rg u s o n s i g h t g l a s s
fo r liq u id le v e l c o n tro l.
From t h i s J e rg u s o n th ro u g h a v a l v e , th e sam ple
was drawn o f f a s d e s i r e d i n an 800 m l. E rlen m ey e r f l a s k .
The n o n -c o n -
d e n s a b le g a s e s c o n ta in e d i n th e sam ple w ere p a s s e d th ro u g h a s e r i e s o f
t h r e e c a u s t i c wash b o t t l e s and m e te re d th ro u g h th e wet t e s t m e te r b e f o r e
b e in g v e n te d .
P r e s s u r e i n th e r e a c t o r was m a in ta in e d by u se o f a M aso n -N eilan a i r t o - c l o s e v a lv e w hich was c o n t r o l l e d by a F is h e r-W iz a rd p r o p o r t i o n a l con­
tro lle r.
The pow er f o r h e a t in g th e r e a c t o r was f u r n is h e d by two 260 v o l t ,
3 amp P o w e r s ta ts and one 130 v o l t , 7 .5 amp P o w e r s ta t.
T em p eratu re s w ere
re a d d i r e c t l y from a L e e d s-N o rth ru p i n d i c a t i n g p o te n tio m e te r c o n n e c te d t o
t h e th e rm o c o u p le s , and a d ju s tm e n ts o f t h e P o w e rs ta ts w ere made a c c o r d in g ly .
The r e c y c le g as s e c t i o n c o n s is te d o f a s to r a g e c y l i n d e r , c o m p re ssio n
c y l i n d e r , f e e d g as c y l i n d e r , makeup g a s c y l i n d e r w ith r e g u l a t o r , r o t a ­
m e te r s , a re c o m p re s sio n s y ste m , and th e n e c e s s a r y v a l v e s , f i t t i n g s , and
tu b in g .
The s u rg e o r s to r a g e c y l i n d e r c o l l e c t e d th e g a s e s w hich had
p a s s e d th ro u g h t h e r e a c t o r and s to r e d th em u n t i l tim e t o reco m p ress them
back t o th e f e e d c y l i n d e r .
Rec o m p re ssio n was acc o m p lish e d by pumping o i l
”
12
-
from th e o i l r e s e r v o i r i n d i c a t e d in F ig u re I , th ro u g h a P e sc o h ig h p r e s s u r e ,
g e a r - ty p e pump i n t o th e b o tto m o f th e co m p re ssio n c y l i n d e r .
The p ip in g in
t h e re c o m p re s s io n sy stem was done w ith l/& i n . s c h e d u le 80 p ip e and f i t t i n g s .
-The P esco pump was c a p a b le o f d e l i v e r i n g 4 .5 gpm. a t 2800 RPM and 1200
p s i.
The pump was d i r e c t l y c o u p le d a t a 3 . 2 : 1 p u l l e y r a t i o t o a Powr-
K r a f t I h p . r e p u l s i o n - i n d u c t i o n - t y p e e l e c t r i c m o to r.
H igh p r e s s u r e
s t a i n l e s s s t e e l t u b i n g , f i t t i n g s , and v a lv e s w ere u s e d i n th e r e c y c le
g a s sy ste m .
The v a lv e s w ere Hoke #321 n e e d le v a lv e s w ith b lu n t s p i n d l e s .
The
ro ta m e te r s w ere B rooks High P r e s s u r e I n d i c a t i n g R o ta m e te rs and were
eq u ip p e d w ith a num ber o f d i f f e r e n t w e ig h t f l o a t s w hich a f f o r d e d a
f a i r l y w ide ra n g e o f flo w r a t e s .
Flow th ro u g h th e r o ta m e te r s was con­
t r o l l e d by two Hoke m e te r in g v a l v e s .
The r e a c t o r h e a t c o n t r o l P o w e r s t a ts , p r e s s u r e c o n t r o l l e r , p r e s s u r e
g a g e s , r o ta m e te r s , pump s w i tc h e s , and p r i n c i p a l o p e r a tin g v a lv e s were
m ounted on a p a n e l b o a rd t o a f f o r d q u ic k and e f f i c i e n t o p e r a t io n o f th e
u n it.
-1 3 -
B
I.
METHODS
C a t a ly s t C hangeover
In o r d e r t o c h a rg e f r e s h c a t a l y s t to th e r e a c t o r , i t was ta k e n down
from i t s o p e r a t i o n a l p o s i t i o n w ith in th e u n i t , i n v e r t e d , and th e u sed
c a t a l y s t and th e alundum b a l l s w ere rem oved.
The u se d c a t a l y s t was
s c re e n e d t o s e p a r a t e i t from th e alundum b a l l s , p a r t o f w hich w ere th e n
r e p la c e d i n th e r e a c t o r t o s e rv e a s p r e h e a t m e d ia.
O ne-hundred grams
o f new c a t a l y s t was p la c e d i n th e r e a c t o r and enough a d d i t i o n a l alundum
b a l l s w ere ad d ed t o c o m p le te ly f i l l i t .
A . c i r c u l a r w ire s c r e e n , th e s i z e
o f th e o p en in g th ro u g h w hich t h e c a t a l y s t and alundum b a l l s w ere ad d ed ,
was u s e d t o s u p p o r t th e c o n te n ts o f th e r e a c t o r .
The r e a c t o r , ch arg e d w ith
f r e s h c a t a l y s t , c o n ta in e d a p r e h e a t s e c t i o n o f ab o u t t e n in c h e s , a c a t a l y s t
b ed a p p ro x im a te ly 1 .5 in c h e s i n d e p th , and a b o u t 3 in c h e s o f b o tto m s u p p o rt
f o r th e c a ta ly s t bed.
A f te r th e c a t a l y s t ch an g e o v er was c o m p le te d , th e
r e a c t o r was r e p la c e d w ith in th e u n i t ,
2.
S ta rt-u p
The u n i t was p la c e d i n t o o p e r a t io n by a p p ly in g c u r r e n t t o th e h e a t ­
in g c o i l s .
When th e te m p e r a tu r e o f t h e c a t a l y s t bed re a c h e d ab o u t 600°
F . , th e r e a c t o r was e v a c u a te d and t h e r e c y c le g as flo w was s t a r t e d .
The
r e a c t o r was th e n p r e s s u r i z e d by a d j u s t i n g th e b a c k - r e s s u r e ' v a lv e and th e
flo w o f o i l was s t a r t e d .
The d e s ir e d l i q u i d - h o u r l y - s p a c e v e l o c i t y was s e t
on th e H ills -M c Ganna pump by tim in g th e f lo w o f o i l from a g ra d u a te d r e s e r ­
v o i r w ith a s to p w a tc h .
A f te r th e sp a c e v e l o c i t y was a d j u s t e d t!he r e a c t o r
was a llo w e d t o l i n e o u t f o r 24 h o u rs b e f o r e th e ta k in g o f d a t a was b eg u n .
i
—1 4 —
The o i l i n th e r e s e r v o i r was d r a in e d down t o th e i n d i c a t e d m ark on th e
sam ple J e rg u s o n ; th e f e e d r e s e r v o i r was f i l l e d , and th e f e e d b o t t l e was
w eighed i n o r d e r t h a t a w e ig h t b a la n c e m ig h t be ta k e n a t th e end o f th e
ru n .
3-
R ecy c le Gas P ro c e d u re s
Makeup g as was p r e p a r e d h e r e a t th e l a b o r a t o r y by m e te r in g th e d e­
s i r e d q u a n t i t i e s o f h y d ro g en and m ethane th ro u g h t h e .makeup r o ta m e te r
i n t o th e c o m p re ssio n c y l i n d e r .
g ases f o r t h i s p u rp o se .
The r o ta m e te r had b een c a l i b r a t e d w ith b o th
The makeup g as ra n g e d from 65 p e r c e n t h y d ro g en ,
35 p e r c e n t m ethane t o 1 0 0 .p e r c e n t h y d ro g e n .
The d e s ir e d r e s u l t was t o
m a in ta in th e c o m p o s itio n o f th e g as p a s s in g o v e r th e c a t a l y s t bed a s
n e a r 65 p e r c e n t h y d ro g en a s p o s s i b l e .
A p e r i o d i c ch eck on th e c o m p o s itio n o f th e r e c y c le g as was made a t
th e b e g in n in g o f th e s e r i e s o f ru n s an d a t th e end o f each r u n .
A sam ple
o f th e r e c y c le g as was ta k e n by d i s p l a c i n g w a te r i n a tw o - g a llo n , i n v e r t e d ,
g l a s s b o t t l e w ith g as from th e f e e d g as c y l i n d e r .
T h is g a s was a n a ly z e d
i n th e lo w -te m p e ra tu re f r a c t i o n a t i o n u n i t i n th e l a b o r a t o r y .
T his
a n a l y s i s i s d e s c r ib e d l a t e r in t h i s s e c t i o n .
The f e e d g as which, h ad p a s s e d th ro u g h t h e r e a c t o r was c o l l e c t e d i n
t h e s u rg e and c o m p re ssio n c y l i n d e r s .
When th e p r e s s u r e i n th e fe e d
c y l i n d e r had d ro p p e d t o a p p r o x im a te ly 100 p s i g . above th e r e a c t o r
o p e r a tin g p r e s s u r e , th e c o l l e c t e d g as was r e tu r n e d t o th e f e e d c y l in d e r
by re c o m p re s s in g i t .
To a c c o m p lish t h i s , th e co m p re ssio n ta n k was
i s o l a t e d from th e sy stem and th e re c o m p re s s io n pump was s t a r t e d .
When
e q u a l p r e s s u r e s w ere r e a c h e d , t h e v a lv e b etw een t h e co m p re ssio n and fe e d
-1 5 -
ta n k s was opened and th e c o m p re ssio n c o n tin u e d .
When t h e co m p re ssio n
c y l i n d e r was c o m p le te ly f i l l e d w ith o i l , th e pump was s to p p e d , and th e
v a lv e betw een i t an d t h e f e e d c y l i n d e r was c l o s e d .
The v a lv e betw een
th e co m p re ssio n ta n k and th e o i l r e s e r v o i r was o p en ed , and when th e
p r e s s u r e s i n t h e su rg e o r s to r a g e ta n k and c o m p re ssio n ta n k w ere e q u a l­
i z e d , th e v a lv e c o n n e c tin g th e two was o p en ed .
The p r e s s u r e i n th e two
c y l i n d e r s was u se d t o d r iv e th e o i l b ack i n t o i t s r e s e r v o i r , th u s com­
p l e t i n g th e re c o m p re s sio n c y c l e ,
4o
S am pling th e P ro d u c t
A sam ple o f th e p ro d u c t was ta k e n e v e ry e i g h t h o u r s , t h r e e sam ples
m aking u p a r u n ,.
The e i g h t —h o u r sam ple was a c o m p o site o f 't h e f o u r
tw o -h o u r sam p les on w hich th e API g r a v i t i e s w ere ta k e n .
At th e tim e o f
sam ple t a k i n g , th e sam ple was d r a in e d down t o th e i n d i c a t e d m ark on th e
sam ple J e rg u s o n and w e ig h e d .' The f e e d r e s e r v o i r was f i l l e d , and th e
c h a rg e b o t t l e was w eighed a l s o .
The sam ple w e ig h t and th e c h a rg e w eig h t
w ere re c o rd e d on th e d a ta s h e e t p r o v id in g a w eig h t b a la n c e f o r th e r u n .
5.
Shut-dow n
The u n i t was s h u t down by s to p p in g th e o i l fe e d pump and s h u tti n g o f f
th e P o w e rS ta ts t o th e r e a c t o r .
R ecy c le g a s flo w was c o n tin u e d u n t i l th e
r e a c t o r was c o o le d t o a b o u t 25Q° F .
A ll i n t e r c o n n e c t in g v a lv e s t o th e
r e a c t o r and betw een t h e 'c y l i n d e r s w ere c lo s e d a f t e r th e g a s flo w c e a s e d .
The a i r s u p p ly t o t h e c o n t r o l l e r was s h u t o f f , an d th e p r e s s u r e was b le d
from th e l i n e s le a d in g to t h e b a c k - p r e s s u r e v a lv e .
Once t h e c o n t r o l v a lv e
was i n o p e r a t i v e , t h e r e a c t o r p r e s s u r e was v e n te d , th u s c o m p le tin g t h a t
s e r ie s o f ru n s.
-1 6 -
6 «,
A n aly ses
The a n a ly s e s p e rfo rm e d i n th e s t u d i e s w ere n i t r o g e n and s u l f u r d e t e r ­
m i n a tio n s , ASTM d i s t i l l a t i o n s , and API g r a v i t i e s on th e p r o d u c t; and lo w te m p e r a tu r e d i s t i l l a t i o n s t o d e te rm in e t h e c o m p o sitio n o f th e r e c y c le g as
sa m p le s .
The n i t r o g e n c o n te n t o f each sam ple was d e te rm in e d by u s e o f th e
s ta n d a r d K je ld a h l a n a l y s i s f o r n it r o g e n a s s e t up by Boyd G u th rie e t a l .
( I ) f o r s h a le o i l and i t s f r a c tio n s .- -
D e te rm in a tio n o f th e s u l f u r c o n te n t
o f e a c h .s a m p le was made by u s e o f th e L am p -G rav im etric m e th o d , D 90-50T ,
e s t a b l i s h e d by t h e A m erican S o c ie ty f o r T e s tin g M a te r i a ls ( 2 ) .
The ASTM
d i s t i l l a t i o n p r o c e d u r e , D 8 6 -5 4 , was a l s o ta k e n from t h a t s o u r c e .
D e te r ­
m in a tio n o f th e s p e c i f i c g r a v i t y o f t h e p r o d u c t was done w ith a W estf a l l B a la n c e .
C o n v ersio n o f s p e c i f i c g r a v i t y t o 0API was acc o m p lish e d
w ith th e e q u a tio n ,
0API = 1 4 1 .5 / s . g . - 1 3 1 .5 .
The g as a n a l y s i s equipm ent c o n s i s t e d o f a w e l l - i n s u l a t e d f r a c t i o n a t i n g
colum n i n w hich c o n d e n s a tio n o f th e low b o i l i n g c o n s t i t u e n t s o f th e g as
was a c c o m p lish e d by t h e u s e o f l i q u i d n i t r o g e n .
The o v e rh e a d d i s t i l l a t e
was c o l l e c t e d ,and-.m easured . in "thb""'va:^Bf '-'sta te ' 'u n d erp ro d u ced ' p r e s s u r e .
U sing t h i s m eth o d , t h e am ounts o f h y d ro g e n , m e th an e, e th a n e , and p ro p a n e ,
i f a n y , p r e s e n t i n t h e sam ple w ere d e te r m in e d .
-1 7 -
G MATERIALS
. The m a t e r i a l s u se d f o r t h e h y d r o g e n a tio n s t u d i e s w ere a 650° F . and
an 850° F„ E .P . s h a le o i l c o k e r d i s t i l l a t e , h y d ro g e n , m e th a n e , and v a r io u s
c a ta ly s ts 0
The B ureau o f M ines s u p p lie d t h e c o k e r d i s t i l l a t e s , th e p r o p e r t i e s
o f w hich a r e fo u n d i n T a b le I 9
The h y d ro g en u se d f o r th e s e s t u d i e s was o b ta in e d from t h e D tiitm ore
Oxygen Company i n S a l t Lake C it y , U ta h 9
M atheson Company o f J o l i e t , I l l i n o i s . .
The m ethane was s u p p lie d by th e
The g as w ith t h e d e s i r e d c o m p o sitio n
o f h y d ro g en an d m ethane was made up h e r e a t th e l a b o r a t o r y .
The c a t a l y s t s i n v e s t i g a t e d w ere a c o b a lt- m o ly b d a te m a n u fa c tu re d by
t h e Harshaw C hem ical Company, a c o b a lt- m o ly b d a te made by P e t e r Spence &
S o n s, L t d . , and two c a t a l y s t s made up h e r e a t th e l a b o r a t o r y ; H arshaw 1s
molybdenum o x id e c a t a l y s t p ro m o ted w ith ( I ) in d iu m and ( 2 ) p a lla d iu m .
The code l e t t e r s and c o m p o s itio n s o f th e c a t a l y s t s may be fo u n d in T a b le .I I 9
The two c a t a l y s t s p re p a re d h e r e w ere made a s f o l l o w s :
N ine grams o f m e t a l l i c in d iu m was d is s o lv e d i n 50 c c . o f c o n c e n tr a te d
n i t r i c a c id .
The r e s u l t i n g s o l u t i o n was e v a p o ra te d t o a b o u t 10 c c . , and
enough w a te r was added t o make th e volum e up t o 60 c c ,
T h is s o l u t i o n was
ad d ed t o 100 gram s o f Harshaw M o -0 2 0 3 -T -l/8 11 p e l l e t i z e d molybdenum o x id e
c a ta ly s t.
T h i r t y - t h r e e c c . o f th e n i t r a t e was ta k e n up i n th e f i r s t
im p re g n a tio n .
17 c c .
The c a t a l y s t was d r ie d and g iv e n a seco n d im p re g n a tio n o f
I t was a g a in d r ie d and th e n re d u c e d f o r e i g h t h o u rs a t 4 0 0 -4 5 0 ° C.
i n an a tm o sp h ere o f h y d ro g e n .
I t was e s tim a te d t h a t 7 .5 gram s o f e le m e n ta l
—1 8 —
in d iu m was added t o 100 gram s o f th e c a t a l y s t s u p p o r t.
An a c id s o l u t i o n (1 2 ,5 c c . o f c o n c e n tr a te d n i t r i c a c i d and 1 7 .5 c c .
o f w a te r ) o f p a lla d iu m n i t r a t e
(3 .5 gram s) was im p re g n a te d i n 100 grams
o f Harshaw- M o -0 2 0 3 -T -l/8 " molybdenum o x id e c a t a l y s t .
The prom oted c a t a ­
l y s t was d r i e d s lo w ly a t a b o u t 60° C. i n a i r , and th e n re d u c e d in . a
h y d ro g en atm o sp h ere a t 3.59° G. f o r e i g h t h o u r s .
I t was e s tim a te d t h a t 1 .6
grams o f p a lla d iu m was added t o IQO gram s o f th e c a t a l y s t s u p p o r t .
L
-1 9 -
III
DISCUSSION OF RESULTS
A f te r t h e d e s ig n and c o n s t r u c t i o n work on th e u n i t was f i n i s h e d , a
s e r i e s o f shakedown ru n s w ere made t o t e s t i t .
Only a few m in o r c o r­
r e c t i o n s w ere n eed ed t o re a d y th e u n i t f o r th e s t a r t o f t h e h y d ro g e n a tio n
s tu d ie s .
A.
D e te r m in a tio n o f t h e Optimum O p e ra tin g C o n d itio n s
The f i r s t s t u d i e s , ru n s I th ro u g h 1 0 , w ere aim ed a t d e te rm in in g th e
e f f e c t o f te m p e r a tu r e and p r e s s u r e on th e h y d ro g e n a tio n o f an 850° F .E .P .
coker d i s t i l l a t e .
Runs w ere made a t b o th $00 p s i g . and 1000 p s i g . t o d e­
te rm in e th e e f f e c t s o f p r e s s u r e on th e h y d ro g e n a tio n p r o c e s s .
The r e s u l t s
o f th o s e ru n s a r e shown i n T a b le s I I I and IV and F ig u r e s 2 and 3 . . The
c o m p o s itio n s o f th e r e c y c le g as a r e shown i n F ig u re s 8 an d 9 .
The i n i t i a l
te m p e r a tu r e was 725° F 0 a t w hich f o u r tw o -h o u r sam p les w ere c o l l e c t e d and
c o m p o site d a f t e r API g r a v i t i e s w ere r u n on each o n e .
u se d a s a q u ic k check on t h e a c t i v i t y o f t h e c a t a l y s t .
The g r a v i t i e s w ere
They w ere p l o t t e d
v e r s u s o n -s tre a m ti m e , and th e s lo p e o f th e l i n e gave an i n d i c a t i o n o f t h e
c a ta ly s t a c tiv ity .
T h ree o f th e e i g h t - h o u r co m p o site sam p les made up a r u n ,
and n i t r o g e n and s u l f u r a n a ly s e s w ere p e rfo rm e d on each s a m p le .
At th e end
o f eac h 24 h o u r s , th e te m p e r a tu r e was in c r e a s e d $0° F . and a n o th e r ru n was
m ade.
■
The l a s t ru n was made a t 92$° F . , th u s c o m p le tin g t h a t s tu d y .
c a t a l y s t u s e d was H arshaw t s c o b a l t m o ly b d a te , C o -M o -0 2 0 1 -T -3 /l6 ,t.
The
The
s p a c e v e l o c i t y was 1 . 0 , an d th e r e c y c l e g as r a t e was 7500 e u . f t . / b b l . ( 6 $
volume p e r c e n t h y d ro g e n ).
I t was fo u n d t h a t th e 1000 p s i g . p r e s s u r e was more c o n d u civ e t o n i t r o ­
—2 0 -
gen and s u l f u r rem o v al th a n t h e lo w e r p r e s s u r e ,
A t- 1000 p s i g . th e s u l f u r
c o n te n t o f th e 850° FeEePo c o k e r d i s t i l l a t e was red u ce d t o a minimum v a lu e
o f 0 ,0 8 7 w e ig h t p e r c e n t .
T his com pared t o a minimum s u l f u r c o n te n t o f
0 ,3 9 w e ig h t p e r c e n t when t h e ch a rg e s to c k was t r e a t e d a t 500 p s ig .
minimum v a lu e i n eac h c a s e was o b ta in e d a t 875° F .
The
The minimum n it r o g e n
c o n te n t f o r th e 1000 p s i g . ru n was 0 .8 5 w e ig h t p e r c e n t and o c c u rre d a t
875° F . , w h ile th e minimum f o r th e 500 p s i g . ru n was 1 .6 8 3 w eig h t p e r c e n t
o c c u r r in g a t 825° F .
O ver th e e n t i r e ra n g e o f te m p e r a tu r e s i n v e s t i g a t e d
t h e 1000 p s i g . s tu d y gave b e t t e r r e s u l t s th a n d id th e s tu d y a t 500 p s i g .
F ig u r e s 2 and 3 i l l u s t r a t e th e c o r r e l a t i o n betw een c a t a l y s t a c t i v i t y
and s u l f u r and n i t r o g e n c o n te n t f o r th e 500 p s i g . and th e 1000 p s i g ,
s tu d ie s , re s p e c tiv e ly .
They showed d e f i n i t e l y t h a t th e d e n i t r o g e n a tio n
and d e s u l f u r i z a t i o n p r o p e r t i e s o f th e c a t a l y s t d ro p p ed o f f a s i t was de­
a c tiv a te d .
F o r b o th s t u d i e s i t was n o ti c e d t h a t th e a c t i v i t y l e v e l o f th e
c a t a l y s t rem ain ed f a i r l y c o n s ta n t w ith i n a ru n a t a g iv e n te m p e r a tu r e , and
t h a t i t in c r e a s e d w ith a r i s e i n te m p e r a tu r e up t o 925° F,.
r a p id d e a c t i v a t i o n o c c u r r e d .
At t h a t tim e a
F ig u r e s 8 and 9 show t h a t d u r in g th e 925° F .
ru n t h e hyd ro g en c o n te n t o f th e r e c y c le g a s d ro p p ed o f f r a p i d l y .
I t was
s u s p e c te d t h a t t h i s e f f e c t was cau sed by a g r e a t l y i n c r e a s e d hydrogen
co n su m p tio n a t t h a t h ig h te m p e r a tu r e .
The d e c re a s e i n h y d ro g en c o n te n t
c o u ld p o s s i b l y have h ad a b e a r in g on t h e r a p id d e a c t i v a t i o n o f th e c a t a ­
l y s t , b u t i t was b e l ie v e d t h a t m ost o f t h e d e a c t i v a t i o n o c c u rre d a s a
r e s u l t o f th e in c r e a s e d c a rb o n la y -d o w n 'o n th e c a t a l y s t due t o in c r e a s e d
c r a c k in g a t 925° F .
On th e b a s i s o f t h e d a ta o b ta in e d from t h e above s t u d i e s , i t was
-2 1 -
e o n c lu d e d t h a t a 1000 p s i g e o p e r a tin g p r e s s u r e was more co n d u c iv e t o th e
s u c c e s s f u l h y d ro g e n a tio n o f a s h a le o i l c o k e r d i s t i l l a t e th a n was a p r e s ­
s u r e o f 500 p s i g . , and t h a t t h e optimum te m p e r a tu r e a p p e a re d t o be 8750 p .
T h e ..e ff e c ts t h a t f o u r d i f f e r e n t c a t a l y s t s had on t h e h y d ro g e n a tio n
o f a 650° F .E .P . s h a le o i l c o k e r d i s t i l l a t e w ere i n v e s t i g a t e d i n an
e f f o r t t o u n c o v e r a s u i t a b l e c a t a l y s t w ith w hich t o t r e a t s h a le o i l and
i t s fra c tio n s .
The c a t a l y s t s u s e d w e re : ( I ) H a rsh a w 's molybdenum o x id e
c a t a l y s t prom oted w ith indium ,, (2 ) H arsh aw 's molybdenum o x id e c a t a l y s t
prom oted w ith p a lla d iu m , (3 ) a g r a p h i t e b a se c o b a l t m o ly b d ate c a t a l y s t
o b ta in e d from P e t e r Spence & S o n s, L t d . , and (4 ) H arshaw ’ s c o b a l t m olyb­
d a te c a t a l y s t .
B.
H a rsh a w 's Molybdenum Qxide C a t a l y s t Prom oted w ith Indium
The s e r i e s o f ru n s fro m 12 th ro u g h 16 w ere made u s in g th e indium
m o ly b d ate c a t a l y s t .
The ru n s w ere made on th e 650° F .E .P . co k e r d i s t i l ­
l a t e u s in g a p r e s s u r e o f 1000 p s i g . , sp a c e v e l o c i t y o f 1 . 0 , r e c y c le gas
r a t e o f 7500 c u . f t . / b b l . , and te m p e r a tu r e s b e g in n in g a t 7 2 5 ° F . and g o in g
t o 925° F. by 50° F . i n c r e a s e s e v e ry 24 h o u r s .
c h a rg e s to c k a r e shown i n T able I .
7 and F ig u re 4 .
The p r o p e r t i e s o f th e
R e s u lt s o f th e ru n s a r e shown i n T able
The c o m p o s itio n o f th e r e c y c le g as d u r in g th e ru n s i s
shown i n F ig u re 1 0 .
In F ig u re 4 i t can be n o ti c e d t h a t t h e a c t i v i t y o f t h e c a t a l y s t i n ­
c r e a s e d w ith each te m p e r a tu r e in c r e a s e up t o th e s t a r t o f t h e ru n a t
925° F .
At t h a t tim e a r a p id d e a c t i v a t i o n o c c u rre d and was due i n p a r t
t o th e h ig h te m p e r a tu r e e f f e c t on th e c a t a l y s t 5 h o w ev er, i n F ig u r e 1 0 ,
th e r e c y c le g as c o m p o sitio n f o r t h a t r u n , ru n 1 6 , i s shown t o h av e d ro p p ed
from a b o u t 65 p e r c e n t' h y d ro g en t o 40 p e r c e n t h y d ro g e n .
T his was p ro b a b ly
-2 2 -
c a u s e d by an in c r e a s e i n th e hy d ro g en co n su m p tio n r a t e .
The makeup g as
a t t h e tim e was o n ly a p p ro x im a te ly 65 p e r c e n t h y d ro g e n , s in c e i t was n o t
known t h a t th e r a t e a t w hich h ydrogen was consumed w ould in c r e a s e t h a t
d r a s t i c a l l y a t 9 2 5 ° F.
The n i t r o g e n and s u l f u r c o n te n ts o f e a c h sam ple a r e a l s o shown i n
F ig u re 4 .
The low v a lu e i n each ' c a s e o c c u r r e d w ith in th e 875° F . r u n .
T h is c o rre s p o n d s t o th e p o in t w here th e c a t a l y s t a c t i v i t y was th e h ig h ­
e s t.
The b e s t n i t r o g e n and s u l f u r v a l u e s w ere 0 .8 7 and 0 .1 7 2 w eig h t p e r ­
c e n t, re s p e c tiv e ly .
These com pare t o 1 .6 $ w eig h t p e r c e n t n i t r o g e n and
O.63 w e ig h t p e r c e n t s u l f u r i n th e c h a rg e s t o c k .
The i n d i c a t i o n , t h e r e ­
f o r e , w ould seem t o be t h a t t h i s c a t a l y s t was b e t t e r f o r rem oving s u l f u r
th a n n i t r o g e n .
The n i t r o g e n c o n te n t s h o u ld be red u ce d s t i l l f u r t h e r , b u t
th e s u l f u r c o n te n t i s w e ll w ith i n th e 0 . 2 $ w e ig h t p e r c e n t l i m i t which
i s s e t a s a s ta n d a r d f o r p e tro le u m g a s o li n e s on th e m a rk e t.
C.
H arshaw t S Molybdenum Oxide C a t a ly s t Prom oted w ith P a lla d iu m
The s e r i e s o f ru n s from 17 th ro u g h 21 w ere made u s in g th e p a lla d iu m
m o ly b d ate c a t a l y s t .
The s tu d y was made u s in g th e 6$0o F .E .P . co k e r
d i s t i l l a t e a s th e c h a rg e s to c k , a r e a c t o r p r e s s u r e o f 1000 p s i g . , sp ace
v e l o c i t y o f 1 . 0 , a r e c y c le g a s r a t e o f 7$00 c u . f t . / b b l . , and tem p er­
a t u r e s b e g in n in g a t 7 25° F . and g o in g t o 9 2 5 ° F . by 50° F» i n c r e a s e s e v e ry
24 h o u r s .
R e s u lts o f th e s tu d y a r e shown i n T able VI and F ig u r e $.
F ig u re 11 c o n ta in s th e r e c y c le g as c o m p o s itio n d a t e .
The a c t i v i t y o f t h e c a t a l y s t a p p e a r s t o have i n c r e a s e d w ith each i n ­
c r e a s e i n te m p e r a tu r e , b u t a d e c lin e was a g a in n o t i c e a b l e d u r in g th e .925° F .
ru n .
A lth o u g h a makeup g as o f 80 p e r c e n t h y d ro g en was u se d d u r in g t h a t
-2 3 -
p e r i o d , th e r e c y c le g as c o m p o s itio n d ro p p ed t o a b o u t 58 p e r c e n t h y d ro g en .
T h is i n d i c a t e d t h a t t h e h y d ro g en was a g a in b e in g consumed a t a f a s t e r r a t e
th a n i t was b e in g a d d e d .
W ith t h i s c a t a l y s t th e low v a lu e s f o r n it r o g e n c o n t e n t , 0 .4 0 9 w eig h t
p e r c e n t , and s u l f u r c o n t e n t , 0 .0 2 2 w e ig h t p e r c e n t , w ere o b ta in e d a t 925° F .
The e f f e c t t h a t th e d e c l in e i n c a t a l y s t a c t i v i t y had on n i t r o g e n and s u l f u r
was n o t a s n o t i c e a b l e a s ' w ith th e in d iu m c a t a l y s t .
However, a t t h a t h ig h
te m p e r a tu r e , th e p r o d u c t y i e l d had d ro p p ed from 90 t o .70 w e ig h t p e r ­
c e n t o f th e c h a r g e .
At lo w e r te m p e r a t u r e s , 825° F . and 8 7 5 ° F . , s a t i s f a c t ­
o ry s u l f u r e l i m i n a t i o n was acco m p an ied by y i e l d s o f g r e a t e r th a n 90 p e r ­
c e n t.
T h is w ould i n d i c a t e t h a t 975° F . was a s a t i s f a c t o r y te m p e ra tu re a t
w hich t o o p e r a t e .
Both th e n i t r o g e n and th e s u l f u r d e te r m in a tio n s i n d i c a t e t h a t th e
p a lla d iu m c a t a l y s t i s d e f i n i t e l y s u p e r i o r t o th e indium c a t a l y s t .
Even
a t th e lo w e r te m p e r a t u r e s , 725° F . and 775° F . , t h e p a lla d iu m c a t a l y s t
y ie ld e d a p ro d u c t w ith a h ig h e r AFI g r a v i t y and a c o n s id e r a b ly lo w e r s u l ­
fu r c o n te n t.
D.
P e t e r Spence & S o n s, L t d . , C o b a lt M olybdate C a t a ly s t
The s tu d y o f th e Spence c o b a l t m o ly b d ate c a t a l y s t was made i n ru n s
22 th ro u g h 2 6 .
T h is c a t a l y s t was s u p p o rte d on a g r a p h i t e - t y p e b a se i n ­
s t e a d o f alu m in a a s was H arshaw 1s c o b a l t m o ly b d a te .
The d a t a c o l l e c t e d
i s shown i n T able V II and th e r e s u l t s a r e p l o t t e d i n F ig u re 6 .
r e c y c le gas c o m p o sitio n d a t a i s c o n ta in e d i n F ig u re 1 2 .
u s e d was th e 650° F .E .P . c o k e r d i s t i l l a t e .
The
The ch arg e s to c k
The r e a c t o r p r e s s u r e was
--24-
100 p s ig o s th e sp ace v e l o c i t y was 1 . 0 , th e r e c y c le g a s r a t e was 7500
c u . f t . / b b l . , and th e te m p e r a tu r e was s t a r t e d a t 725° F . and r a i s e d t o
925° F . by 50° F . in c r e a s e s e v e ry 24 h o u r s .
The c a t a l y s t p e l l e t d ia m e te r
was 5 /3 2 i n . a s com pared t o l / 8 i n . f o r t h e o t h e r c a t a l y s t s .
The API g r a v i t i e s o f th e sam p les fro m th e s e ru n s w ere on th e a v e ra g e
a b o u t 4 ° API h ig h e r th a n th e g r a v i t i e s on th e sam ples from th e indium
i n v e s t i g a t i o n and w ere somewhat h ig h e r th a n th o s e from th e p a lla d iu m
s tu d y .
•
T h is f a c t was p ro b a b ly due t o th e h ig h e r h y d ro g en c o n te n t o f th e
r e c y c le g a s .
By co m p arin g F ig u r e s 1 0 , 1 1 , and 12 i t was fo u n d t h a t th e
a v e ra g e h y d ro g en c o n t e n t o f th e r e c y c le g a s d u rin g th e Spence c a t a l y s t
s tu d y was 75 p e r c e n t a s com pared t o a b o u t 65 and 70 p e r c e n t f o r th e
indium and p a lla d iu m s t u d i e s , r e s p e c t i v e l y .
The b e s t p r o d u c t from t h i s s tu d y had a' n i t r o g e n c o n te n t o f 0 .3 7 1
w e ig h t p e r c e n t and a s u l f u r c o n te n t o f 0 .0 1 8 w eig h t p e r c e n t .
Both low s
o c c u rre d d u rin g th e 875° F . r u n , a s d id th e b e s t v a lu e s f o r th e indium
and p a lla d iu m c a t a l y s t i n v e s t i g a t i o n s .
Above 875° F. th e p ro d u c t y i e l d
d ro p p ed o ff. t o ..65 .w e ig h t .p e rc e n t, .o f t h e c h a r g e .
At 875° F . th e y i e l d
was a b o u t 83 p e r c e n t , and a lth o u g h t h e y i e l d o f th e in d iu m c a t a l y s t was
b e t t e r , 9 2 .5 p e r c e n t , th e a b i l i t y o f t h e Spence c a t a l y s t t o d e n itr o g e n iz e
and d e s u l f u r i z e seemed t o be b e t t e r .
The p a lla d iu m c a t a l y s t a l s o gave
b e t t e r y i e l d s th a n d id th e Spence c a t a l y s t , b u t was n o t a s e f f i c i e n t f o r
rem oving n i t r o g e n and s u l f u r .
P e rh a p s th e d i f f e r e n c e i n h y d ro g en c o n te n t
o f th e r e c y c le g as c o u ld have had a b e a r in g i n th e p e rfo rm a n c e s o f , t h e
c a ta ly s t.
-2 5 -
E.
H arshaw 1s C o b a lt M o ly b d ate C a t a ly s t
The r e s u l t s o f th e Harshaw c o b a l t m o ly b d ate s tu d y a r e g iv e n in T able
V TII and F ig u re 7„
The r e c y c le c o m p o s itio n s f o r th e s e r u n s , 2? th ro u g h 3 1 ,
a r e shown in F ig u re 1 3 .
The c h a rg e s to c k and th e c o n d itio n s w ere th e same
u s e d i n th e o th e r s t u d i e s j e g . , 6 50° F .E .P . c o k e r d i s t i l l a t e , 1000 p s i g . ,
sp a c e v e l o c i t y o f 1 . 0 , r e c y c le g as r a t e o f 7500 c u . f t . / b b l . , and te m p e ra ­
t u r e s from 725° F . t o 925° F .
As was th e c a s e w ith th e Spence c o b a l t m o ly b d a te , th e r e c y c le gas
c o m p o sitio n was c o n s id e r a b ly h ig h e r f o r t h i s i n v e s t i g a t i o n th a n th e d e­
s i r e d 65 p e rc e n t h y d ro g e n , 35 p e r c e n t m e th a n e .
The B ureau o f Mines
r e p o r te d t h a t r e c y c le g a s r a t e s o f p u re h y d ro g en above 3500 c u . f t . / b b l .
had v e r y l i t t l e
n o t i c e a b l e e f f e c t on i n c r e a s i n g th e q u a l i t y o f th e p ro ­
d u c t , b u t t h a t belo w a b o u t 2000 c u . f t . / b b l . th e p ro d u c t q u a l i t y de­
c re a se d r a p id ly .
I t i s q u i t e p o s s i b l e t h a t a s i m i l a r c o r r e l a t i o n m ight
e x i s t f o r th e h y d ro g en c o n te n t o f th e r e c y c le g a s ; e g . , in c r e a s in g th e
p e r c e n t h y d ro g en i n t h e g a s t o above 65 p e r c e n t may have v e r y few b en e­
f i c i a l e f f e c t s , b u t below t h a t s ta n d a r d t h e p ro d u c t q u a l i t y m ig h t become
in c re a s in g ly p o o r.
Once a g a in th e b e s t n i t r o g e n and s u l f u r rem oval o c c u rre d a t 875° F.
The low v a lu e s w ere 0 .0 5 7 w eig h t p e r c e n t s u l f u r and 0 .6 4 2 w eig h t p e r c e n t
n itr o g e n .
C o n s id e ra b le c a t a l y s t d e a c t i v a t i o n o c c u rre d a t 925° F . , and th e
p ro d u c t y i e l d d ro p p ed t o a s low a s 49 w e ig h t p e r c e n t o f th e c h a rg e .
y i e l d was o n ly 78 w eig h t p e r c e n t a t 875° F .
The
The B ureau o f M ines a t a
te m p e r a tu r e o f 850° F. u s in g c o b a lt m o ly b d ate and a p r e s s u r e o f 1000 p s i g .
o b ta in e d y i e l d s o f ab o u t 92 w e ig h t p e r c e n t .
The re a s o n f o r t h e lo w er
—2 6 -
y i e l d s i s n o t known.
T able IX g iv e s a t a b u l a t e d co m p ariso n b etw een th e 875° F . ru n s f o r
each c a t a l y s t s t u d i e d .
F.
ASTM D i s t i l l a t i o n D ata f o r th e 875° F . Run f o r Each C a ta ly s t
T able IX an d F ig u re 14 p r e s e n t th e d a t a and r e s u l t s o f th e AST1M
d i s t i l l a t i o n s o f th e 875° F . ru n f o r each c a t a l y s t .
T his ru n was chosen
b e c a u se i n each c a s e 875° F , a p p e a re d t o be th e te m p e r a tu r e a t w hich each
c a t a l y s t p e rfo rm e d b e s t .
The d i s t i l l a t i o n s w ere done on a co m p o site
sam ple f o r th e r u n ; e g . , th e t h r e e e i g h t - h o u r sam ples w ere co m p o sited
t o g iv e a u n ifo rm sam ple f o r th e 24 h o u r r u n .
The ASTM d i s t i l l a t i o n
c u rv e f o r th e 650° F .E .E . c o k e r d i s t i l l a t e c h a rg e s to c k i s a l s o in c lu d e d
i n F ig u re 1 4 .
A ll c u rv e s w ere c o r r e c t e d t o 760 mm. o f m e rc u ry .
The p a lla d iu m c a t a l y s t and th e Spence c o b a l t m o ly b d ate gave th e h ig h ­
e s t p e r c e n ta g e s o f m a t e r i a l b o i l i n g i n th e g a s o li n e ra n g e ( c o n s id e r in g th e
g a s o lin e b o i l i n g ra n g e t o be belo w 4 0 0 ° F , ) . ■ They y ie ld e d 62 and 60
volum e p e r c e n t , r e s p e c t i v e l y .
F o r ty - s e v e n volum e p e r c e n t o f th e 875° F.
sam ple from th e in d iu m s tu d y was in t h e g a s o lin e r a n g e , w h ile 52 volume
p e rc e n t o f th e same sam ple from th e H arshaw c o b a l t m o ly b d ate i n v e s t i ­
g a t io n b o i l e d b elow 4 0 0 ° .F .
The re m a in d e r o f th e m a t e r i a l i n each c a se
b o i l e d w ith in th e b o i l i n g ra n g e o f d i e s e l f u e l .
-2 7 -
VT
SUMMARY
A co m p ariso n o f th e 875° F 0 r u n s f o r each c a t a l y s t i s s h o w i n T able
IX .
The d a t a fro m th o s e ru n s was w e ll s u i t e d a s a b a s i s on w hich t o make
a c o m p a riso n .
The c a t a l y s t bed te m p e r a tu r e w hich was su p p o sed t o be
875° F . o r 4 6 8 ° C. v a r i e d no more th a n 5° C. f o r an y c a t a l y s t .
The h y d ro ­
gen c o n te n t o f th e r e c y c le g as was f a i r l y c o n s ta n t f o r a l l f o u r r u n s , n o t
v a ry in g m ore th a n a maximum o f 7 p e r c e n t .
The p r e s s u r e was c o n s ta n t a t
1000 p s i g . , and th e sp a c e v e l o c i t y was e s s e n t i a l l y 1 .0 a t a l l tim e s .
On th e b a s is o f th e d a ta o b ta in e d i n th e i n v e s t i g a t i o n s , th e Spence
c o b a l t m o ly b d a te a p p e a re d t o be th e b e s t .
I t gave b e t t e r n i t r o g e n and
s u l f u r rem oval and y i e l d e d a p ro d u c t w hich c o n ta in e d a b o u t 60 volume p e r ­
c e n t o f m a t e r i a l b o i l i n g i n t h e g a s o lin e r a n g e .
The c h a rg e s to c k c o n ta in ­
ed 3 0 volum e p e r c e n t g a s o lin e b o i l i n g ran g e m a t e r i a l .
The p ro d u c t y i e l d
from th e Spence c a t a l y s t was 8 3 .3 w e ig h t p e r c e n t o f th e c h a rg e which was
b e t t e r th a n th e y i e l d from t h e H arshaw c o b a l t m o ly b d a te , b u t n o t a s good
a s t h a t o b ta in e d from th e indium o r p a lla d iu m prom oted c a t a l y s t s .
The p a lla d iu m c a t a l y s t a t 925° F. gave r e s u l t s w hich w ere alm o st a s
good a s th o s e o b ta in e d from th e Spence c o b a l t m o ly b d ate a t 875° F ., b u t t h e
p ro d u c t y i e l d was p o o r , ab o u t 75 w eig h t p e r c e n t .
T his was t h e o n ly c a t a l y s t
i n v e s t i g a t e d w hich d id n o t show a d e c l in e i n s u l f u r and n i t r o g e n rem oving
p r o p e r t i e s , when th e te m p e r a tu r e was r a i s e d from 875° F . t o 925° F.
It is
p o s s i b l e t h a t t h i s c a t a l y s t c o u ld be u s e d a t h ig h e r te m p e r a tu r e s i f th e
y i e l d c o u ld be en h an c ed .
The o t h e r tw o c a t a l y s t s , H arshaw 1s c o b a l t m o ly b d ate and th e indium
m o ly b d a te , w ere l e s s e f f e c t i v e th a n th e Spence c o b a l t m o ly b d a te and th e
-
p a lla d iu m m o ly b d a te .
28 -
The H arshaw c a t a l y s t had p o o r d e n i t r o g e n i z in g p ro ­
p e r t i e s and g a v e ' low p r o d u c t y i e l d s above 825° F .
A m ore th o ro u g h i n ­
v e s t i g a t i o n s h o u ld be co n d u c te d t o d e te rm in e th e re a s o n s f o r th e d i f ­
f e r e n c e s i n r e s u l t s o b ta in e d i n th e s e s t u d i e s ,and th o s e o b ta in e d by th e
B ureau o f M in es.
v e ry e f f e c t iv e .
They fou n d H arshaw 1s c o b a l t m o ly b d ate c a t a l y s t t o be
The in d iu m c a t a l y s t gave good p ro d u c t y i e l d s , b u t i t
h ad p o o r n i t r o g e n and s u l f u r rem oving p r o p e r t i e s .
The c r i t i c a l h y d ro g en c o n te n t o f th e r e c y c le g a s i s b e lie v e d t o i n ­
c r e a s e w ith i n c r e a s e s i n te m p e r a tu r e .
a b le ' a t 925° F .
The e f f e c t was p a r t i c u l a r l y n o ti c e
T his was p ro b a b ly due t o in c r e a s e d h y d ro g en consum ption
a t th e h ig h e r t e m p e r a t u r e s .
The o n ly c o r r e c t i v e m easure fo u n d to be o f
v a lu e was t o u s e a makeup g as d u r in g t h a t p e r io d o f in c r e a s e d hydrogen
co n su m p tio n w hich had a n 80 p e r c e n t o r b e t t e r h ydrogen c o n t e n t .
A more
th o ro u g h s tu d y o f th e e f f e c t s o f r e c y c le g as c o m p o sitio n s h o u ld be made
i n o r d e r t o d e te rm in e t h e i r b e a r in g on th e s h a le o i l h y d r o g e n a tio n p ro ­
cess.
&
A s tu d y o f p h y s ic a l e f f e c t s s h o u ld be; made t o d e te rm in e th e e x te n t
\
o f t h e i r b e a r in g on t h e p r o c e s s . I t i s known t h a t th e B ureau o f Mines
r e c e iv e d c o n s i s t e n t l y b e t t e r n i t r o g e n and s u l f u r rem o v al u s in g th e same
c o n d itio n s a t w hich th e s e i n v e s t i g a t i o n s w ere m ade.
R e a c to r sh ap e f a c t o r
a p p e a rs t o hav e r e s u l t e d i n t h a t d i f f e r e n c e ; e g . , th e B u re a u ’ s c a t a l y s t
bed was 35 i n . lo n g , and th e r e a c t o r was 1 . 5 i n . i n d ia m e te r .
The
r e a c t o r u s e d i n th e s e s t u d i e s was 2 .5 i n . i n d ia m e te r , an d t h e c a t a l y s t
b ed was 1 .5 i n . t h i c k
-2 9 -
V
ACKNOWLEDGMENT
The a u t h o r ack n o w led g es w ith th a n k s th e c o u r te s y o f th e S ta n d a rd O il
Company o f New J e r s e y , who sp o n so re d th e f e llo w s h ip u n d e r w hich t h i s work
was c a r r i e d o u t.
He a l s o acknow ledges t h e c o u r te s y o f t h e U n ite d S t a t e s B ureau o f M in es,
R i f l e , C o lo ra d o , who s u p p lie d th e s h a le o i l u s e d i n t h i s i n v e s t i g a t i o n .
Thanks a r e e x te n d e d t o p r o f e s s o r s L lo y d Berg and Lew is G.. M a y fie ld ,
who s e rv e d a s a d v i s o r s , and t o R. J . H olecek and D ale B. B enson, r e s e a r c h
f e llo w s a l s o a s s ig n e d t o t h i s p r o j e c t .
-3 0 -
VI
LITERATURE CITED
(1 )
A n a l y t i c a l C h em istry 2 3 : 1 6 3 4 -3 8 , 19 5 1 .
(2 )
A. S. T. M. STANDARDS ON PETROLEUM "AND "LUBRICANTS, A m erican S o c ie ty
f o r T e s tin g M a t e r i a l s , P h i l a d e l p h i a , P a . , p . 7 & 2 2 , 1954.
(3 )
B erg , C ly d e , 11Advancem ents i n F u e ls P ro d u c tio n from S h a le O i l , " 1954.
(4 )
B e rg , L loyd and O th e r s , " C a ta ly ti c P o ly fo rm in g o f S h a le O il I s B e t t e r
Than C a t a l y t i c C ra c k in g ," P e tro le u m E n g in e e rin g 2 6 : 1 1 1 -1 5 , A p r i l , 19 5 4 .
(5 )
Cameron, R. J . , "Therm al P r o c e s s in g and C hem ical T r e a tin g o f C olorado
S h a le O i l , " S ep te m b er, 1954.
(6 )
C r e c e l i u s , R. L . , M. S. T h e s is , M ontana S ta t e C o lle g e , 1949.
(7 )
S i l v e y , F . C ., M. S. T h e s is , M ontana S t a t e C o lle g e , 19 5 3 .
(8 )
U n ite d S t a t e s B ureau
o f M ines B u l l e t i n No. 533.
(9 )
U n ite d S t a t e s B ureau
o f M ines R e p o rt o f
I n v e s t i g a t i o n s 4 7 7 1 , 1950.
(1 0 ) U n ite d S t a t e s B ureau
o f M ines R e p o rt o f
I n v e s t i g a t i o n s 5089, 1953.
(1 1 ) U n ite d S t a t e s B ureau
o f M ines R e p o rt o f
In v e s tig a tio n s
5119, 1954.
-
V II
31
“
APPENDIX
page
T ab le I
P r o p e r t i e s o f th e Charge S to ck s „ . . . .
T ab le I I
I d e n t i f i c a t i o n Code and C o m p o sitio n o f C a t a ly s ts Used „ „ .3 4
T able I I I
O p e ra tio n and P ro d u c t D ata f o r 500 p s ig . Runs t o
D eterm in e Optimum O p e ra tin g C o n d itio n s ............................ .... . . .35
T a b le IV
O p e ra tio n and P ro d u c t D ata f o r 1 0 0 0 'p s i g . Runs t o
D eterm in e Optimum O p e ra tin g C o n d itio n s ..................................... . .36
T a b le V
O p e ra tio n and P ro d u c t D a ta f o r Runs U sing th e Indium
P rom oted C a ta ly s t . . . . . . . . . . . . . . .
...................
T able VI
O p e ra tio n and P ro d u c t D ata f o r Runs U sing th e P a lla d iu m
P rom oted C a t a ly s t . . . . . . . . . . . . . . . . . . . .
. ■....................... .... „ .33
.38
T ab le V II
O p e ra tio n and P ro d u c t D ata f o r Runs U sing S p e n c e 's
C o b alt M olybdate C a t a ly s t ................................................................. . .39
T able V III
O p e ra tio n and P ro d u c t D ata f o r Runs U sing H arshaw 's
C o b alt M olybdate C a t a ly s t ........................................................ .... . . .4 0
T ab le IX
P r o p e r t i e s o f P ro d u c t from 875° F . Run f o r Each C a t a l y s t .
.4 1
F ig u re I
S ch em atic D iagram o f th e U n it ............................................................
.42
F ig u re 2
P ro d u c t D ata f o r 500 p s i g . Runs t o D eterm in e Optimum
O p e ra tin g C o n d itio n s ...................................................................................
.43
P ro d u c t D ata f o r 1000 p s i g . Runs t o D eterm ine Optimum
O p e ra tin g C o n d itio n s . . . . . . . . . . . . . . . . . . .
«44
F ig u re 3
F ig u re 4
P ro d u c t D ata f o r Runs U sing t h e Indium P rom oted C a t a ly s t. .4 5
F ig u re $
P ro d u c t D ata f o r Runs U sing th e P a lla d iu m Prom oted
C a ta ly s t. . . . . . . . . . . . . . . . . . . . . . . . .
F ig u re 6
P ro d u c t D ata f o r Runs U sing Spence 1S - C o b alt M olybdate
C a ta ly s to o * 0 * 0 0 ^ 0 0 * * » @ @ @ * @ * 0 0 * * * * ^
F ig u re 7
. 47
P ro d u c t D ata f o r Runs U sing H a rsh a w 's C o b a lt M olybdate
.4 8
F ig u re 8
R ecy c le Gas C o m p o sitio n f o r 500 p s i g . Runs t o D eterm in e
Optimum O p e ra tin g C o n d itio n s . ............................ ................................ .49
-
32 -
V II APPENDIX
( c o n tin u e d )
'
"
Page
F ig u re 9
R ecy cle G a s ' C o m position f o r 1000 p s i g . Runs t o
D eterm in e Optimum O p e ra tin g C o n d i t i o n s ..........................................50
F ig u re 10
R ecy c le Gas C o m p o sitio n f o r Runs U sing th e Indium
Prom oted C a t a l y s t ....................... .... ........................................................51
F ig u re 11
R ecy c le Gas C o m p o sitio n f o r Runs U sing t h e P a lla d iu m
Prom oted C a t a l y s t . ............................................... ...........................
52
F ig u re 12
R ecy c le Gas C om position f o r Runs U sing S p e n c e 's"
C o b a lt M olybdate C a t a l y s t . . ................................................................. 53
F ig u re 13
R ecy cle Gas C o m p o sitio n f o r Runs U sing H arshaw 's
C o b alt M olybdate C a t a l y s t . . . . . .
............................ .... . . .5 4
F ig u re 14
ASTM D i s t i l l a t i o n C urves f o r t h e 875° F. Run f o r
Each C a t a l y s t . ................... . . . . . .
................... . . . . .
\
P
. 55
,
“33TABLE I
PROPERTIES OF THE CHARGE STOCKS
C h a rg e S to c k
• « e o o e o o o e » o o o e
c o k e r d i s t i l l a t e * . . ,,6 5 0 ° F» E«P»
G rd v ity . . . o . . . . . . . . . . . . * . . . . .
A PI a t 60
F.....
V i s c o s i t y , S .U . a t 1 3 0 ° F . . . . . . . s e c o n d s . . . . . . . .
S u H Ur . . . . . . . O f t O . . . . . . . . . . . 0 . 04 . T^t O
N i t r o g e n eo««« 09 poooooooooeo«oo 6 o
ASTM D i s t i l l a t i o n
eeeepeeeoo
6 5 0 ° F» E . P ,
3 5 .4
25.4
31
43
0.
63
0 .6 3
1.
-65
1.95
( c o r r e c t e d t o 7 6 0 mme o f H g ):
o o o o o d e e o e
161
113
O d O d e e e d d
o d o o o o d o d d
297
385
20
d d d o d d d e d o e o d d d d d #
O O d O O d d d d O
354
475
30
o o o o o o o o o e o o o o o o o o
O d O d d d O e e o
396
525
40
OOdOOOOOOOOdOddOOO
d o e e o d o o d o
432
570
50
O d d O d Od o o e e o o o e o d o
o o o o o d d o o e
464
620
60
o o o o o e o e e e o o e o e e e o
o d o o d o o o o d
492
665
70
O d d O d d O d O d d d O O d O d d
, d o o o o o o d d o
$22
710
80
o d o d d d o d d e o o o o o e o d
d d o o d o o o o d
554
760
90
^ o o o o o o o o o d o o o d o o o d
d d o o o o d o o o
591
805
o o e o d o o d d o d d e e d o o o o
o o o o o d d o d o
672
C ut P o in t
I B P o « o' o o e o e e o e e c d d o o o e
10 ^ ode e e e e e d
EPo
P o
R e c o v e r y 00000000000000 v o l 0 ^ d
o o o o d o o d
98.0
89.0
"
34
"
TABLE I I
IDENTIFICATION CODE AND COMPOSITION OF CATALYSTS USED
C a t d l y s t a n d C o m p o s itio n
I d e n t i f i c a t i o n C ode
M a n u fa c tu re r
C o b a l t M o ly b d a te
. 9 .5 % M0O3
3 . 0 % CoO
5 . 0 % S iO 2
2 e0 % G r a p h i t e
8 0 .5 % A l 2 O3
C o - M o - 0 2 0 1 - T - l/8 "
H a rs h a w C h e m ic a l Co
C o b a l t M o ly b d a te
2 . 5 % CoO
1 4 * 0 % M0O3
G r a p h ite B ase
G ra p h ite -ty p e P e l­
l e t s «, 5/ 3 2 " d ia m .
P e te r Spence & Sons
L td .
M olybdenum O x id e *
1 6 % MoO3
7 9 # A l 2 O3
5 % S iO 2
M o - 0 2 0 3 - T - l /8 "
H a rs h a w C h e m ic a l Co
*
The in d iu m a n d p a lla d iu m c a t a l y s t s w e re p r e p a r e d b y im p r e g n a tin g
H a rs h a w 1s M o - 0 2 0 3 - T - l / 8 " , M olybdenum O x id e c a t a l y s t 6 .
.
“35table h i
OPERATION AND PRODUCT DATA FOR 500 PSIG RUN TO
DETERMINE OPTIMUM OPERATING CONDITIONS
Run No.
T em p eratu re 0C
P re h e a t
C a ta ly s t
Y ie ld
Wt. % o f C harge
0API
I A
3 8 5 .1
3 8 5 .8
I B
3 8 4 .5
3 8 6 .0
I C
3 8 1 .2
3 8 4 .5
2 8 .4
2 A
4 1 7 .3
4 1 3 .1
2 9 .5
2 B
4 1 5 .7
4 1 3 .2
2 C
4 1 2 .5
4 1 2 .9
2 9 .7
3 A
4 3 9 .4
4 4 0 .7
3 1 .4
3 B
4 4 1 .2
4 4 1 .2
3 c
4 4 0 .0
4 4 1 .3
3 1 .3
4 A
4 6 8 .2
4 6 6 .5
4 B
4 6 6 .0
4 6 8 .1
4 C
4 6 0 .2
5 A
P ro d u c t
Wt. % S
Wt. % N
2 8 .1
9 7 .8
9 8 .5
2 8 .2
2 9 .7
1 .7 8 8
0 .4 9 7
1 .8 1 0
1 .8 2 0
0 .4 3 5
1 .7 3 5
0 .4 1 7
1 .6 8 3
3 2 .2
0 .3 9 0
1 .7 7 2
3 0 .9
0 .4 0 2
1 .8 0 0
4 6 6 .5
3 0 .6
0 .5 0 5
1 .8 9 7
4 9 6 .1
4 9 6 .3
2 9 .3
0 .6 0 4
2 .1 8 5
5 B
4 9 3 .5
4 9 4 .5
2 9 .0
0 .8 5 2
2 .2 2 5
5 C
4 9 5 .6
4 9 8 .2
2 9 .0
0 .7 9 6
2 .2 4 5
9 4 .5
9 2 .0
8 6 .8
3 1 .4
C a t a l y s t .............U nion O il Co. C o b a lt M o ly b d ate, 3 /1 6 "
R e a c to r P r e s s u r e . . . . 5 0 0 p s i g .
Space V e lo c i ty ............1 .0 g m s ./g m ./h r .
R ecy c le Gas R a t e . ...7 5 0 0 c u . f t . / b b l . (65 p e r c e n t hydro g en )
C harge S to c k ................ 850° F . E .P . C oker D i s t i l l a t e
-3 6 TABLE IV
OPERATION AND PRODUCT DATA FOR IOOO PSIG RUN TO
DETERMINE OPTIMUM OPERATING CONDITIONS
Run N o .
T e m p e r a t u r e °C
P re h e a t
C a ta ly s t
Y ie ld
M t. % o f C h a rg e
0API
P ro d u c t
W t. % S
W t. % N
3 0 .7
0.202
1.662
6 A
3 8 6.2
3 8 5 .9
6 B
3 8 4 .1
3 8 5 .2
9 5 .1
3 0 .5
0 .2 5 3
1 .5 9 0
6 C
3 8 6 .4
3 8 7 .2
9 8 .7
2 9 .8
0 .3 0 8
1 .6 3 0
7 A
4 1 7 .4
4 1 2 .7
9 9 .9
3 1 .4
0 .1 2 9
1 .7 2 0
7 B
4 1 5 .7
4 0 8 .9
9 7 .0
3 2 .0
0 .1 7 6
1 .5 2 5
7 C
411.6
4 1 4 .1
9 7 .8
3 1 .8
0 .2 0 9
1 .5 1 0
8 A
4 3 5 .7
4 3 7 .9
9 6 .3
3 3 .3
0 .1 8 8
1 .3 7 2
8 B
4 3 9 .8
4 4 0 .4
9 6.2
3 4 .4
0 .1 0 7
1.242
8 C
4 3 7 .1
4 3 9 .8
8 9 .1
3 3 .6
0 .2 1 4
1 .3 4 0
9 A
4 6 5 .2
4 6 8 .5
90.8
3 6 .6
0.152
0 .9 6 4
9 B
4 6 9 .5
4 6 4 .8
3 7 .0
0 .1 2 3
0 .8 5 0
9 C
4 6 7 .4
4 6 5 .6
8 9 .0
3 6 .6
0 .0 8 7
1 .030
10 A
4 9 3 .2
4 9 4 .6
7 7 .3
3 6 .2
0 .1 1 2
1 .1 6 5
10 B
4 9 8 .1
4 9 6 .1
7 2 .9
3 2 .7
0 .1 8 9
1 .6 5 1
10 C
4 9 7 .0
5 0 0 .5
7 6 .2
3 2 .2
0 .2 7 6
1 .6 6 3
C a t a l y s t . . . . . ..............
R e a c to r P r e s s u r e .. .
S p a c e V e l o c i t y ...........
R e c y c l e G as R a t e . . .
C h a r g e S t o c k ................
.U n io n O i l C o . C o b a l t M o l y b d a t e , 3 / 1 6 "
.1000 p s i g .
. 1 .0 g m s ./ g m / h r .
.7500 c u . f t . / b b l . (65 p e r c e n t h y d r o g e n )
.8 5 0 ° F . E . P . C o k e r D i s t i l l a t e
-3 7 ta b le
O P E R A T IO N
AND P R O D U C T DATA F O R R U N S U S IN G
IN D I U M
Run No.
V
T em p eratu re 0C
P re h e a t
C a t a ly s t
PR O M O TE D C A T A L Y S T
Y ie ld
M t. % o f C harge
0API
P ro d u c t
Wt. % S
Wt. % N
12 A
3 8 4 .4
3 8 5 .7
9 8 .5
3 7 .5
0 .4 4 0
1 .3 4 0
12 B
3 8 5 .3
3 8 6 .8
9 8 .6
3 7 .6
0 .4 7 8
1 .3 4 5
12 C
3 8 8 .3
3 8 8 .1
9 9 .5
3 7 .6
0 .4 2 5
1 .3 7 5
13 A
4 1 2 .5
4 1 4 .5
9 9 .0
3 8 .9
0.308
1 .2 5 6
13 B
4 1 3 .2
4 1 5 .5
9 8 .0
3 9 .2
0 .3 1 8
1 .210
13 C
4 1 2 .8
4 1 6 .5
9 7 .4
3 9 .1
0 .3 0 4
1 .252
U A
4 3 9 .4
4 4 1 .0
9 7 .0
4 1 .1
0 .2 8 3
1 .0 7 0
14 B
4 3 4 .9
4 4 1 .5
9 5 .6
4 1 .3
0 .2 9 4
1 .0 0 4
14 C
4 4 0 .9
4 4 0 .9
9 5 .8
4 1 .2
0 .2 2 7
1 .0 2 3
15 A
4 6 5 .2
4 7 5 .8
4 4 .0
0 .2 1 8
0 .8 7 0
15 B
4 6 6 .4
4 6 8.6
4 2 .7
0 .1 9 5
0 .9 4 0
15 c
4 6 6 .8
4 7 2 .8
9 2 .5
4 3 .7
0.172
0 .9 2 7
16 A
4 8 5 .7
4 9 9 .0
68 .0
4 4 .5
0.308
0 .8 7 0
16 B
4 9 4 .0
4 9 6 .5
7 0 .5
3 8 .8
0 .3 4 2
1 .0 2 0
16 C
4 8 8 .4
4 9 7 .0
7 1 .1
3 8 .3
0 .1 8 6
1.162
C a t a l y s t .......................... H arshaw *s Molybdenum O xide P rom oted w ith
Indium
R e a c to r P r e s s u r e . . .. 1 0 0 0 p s i g .
Space V e lo c i ty ........... 1 .0 g m s ./g m ./h r .
R e c y c le Gas R a t e . . . . 7500 c u . f t . / b b l . (65 p e r c e n t hydro g en )
C harge S to c k ................ 650° F . E .P . C oker D i s t i l l a t e
-
38-
TABLE V I
OPERATION AND PRODUCT DATA FOR RUNS USING
PALLADIUM PROMOTED CATALYST
R un N o.
T e m p e r a t u r e °C
P re h e a t
C a ta ly s t
Y ie ld
W t. % o f C h a rg e
0API
P ro d u c t
W t. % S
W t. * N
17 A
3 8 5 .3
3 8 6 .9
9 7 .5
4 0 .5
0 .5 3 5
1 .2 0 3
17 B
3 8 5 .5
3 8 5 .5
96 .2
4 0 .2
0 .2 8 3
1 .1 9 4
17 C
3 8 5 .1
3 8 6 .3
100.0
4 0 .0
0 .2 5 1
1 .1 9 4
18 A
4 1 5 .2
4 1 5 .0
8 6 .6
4 1 .8
0 .132
1 .0 0 0
18 B
4 1 3 .0
4 1 1 .9
18 C
4 H .2
4 1 4 .9
9 7 .0
42 .2
0 .1 3 4
0 .9 6 0
19 A
4 3 7 .8
4 3 9 .6
9 7 .6
4 4 .2
0.072
0 .7 9 5
19 B
4 4 5 .2
4 4 1 .3
9 4 .7
44*0
0 .0 8 6
0 .8 0 2
19 C
4 3 9 .0
4 3 6 .8
9 7 .1
4 4 .0
0 .0 8 4
0 .8 0 7
20 A
4 6 5 .4
4 68.1
8 7 .7
4 7 .8
0 .0 6 1
0 .5 2 7
20 B
4 6 9 .0
4 6 3 .3
7 9 .8
4 7 .2
20 C
464.2
464 .O
9 1 .5
4 7 .0
21 A
4 9 4 .2
4 9 2 .3
8 3 .4
4 8 .8
21 B
4 9 4 .0
4 9 3 .7
7 4 .0
4 9 .2
21 C
4 9 7 .5
4 9 6 .5
7 0 .0
4 7 .0
4 1 .6
0 .9 6 1
0 .5 8 8
0 .0 4 1
0 .6 5 1
0 .4 0 9
0.022
0 .5 2 7
0 .6 0 1
C a t a l y s t . .......................... H a rs h a w 1s M olybdenum O x id e P ro m o te d w i t h
P a lla d iu m
R e a c to r P r e s s u r e . ...1 0 0 0 p s i g .
S p a c e V e l o c i t y ............. 1 . 0 g m s . / g m . / h r .
R e c y c l e G as R a t e . . . . 7 5 0 0 c u . f t . / b b l . (6 5 p e r c e n t h y d r o g e n )
C h a rg e S t o c k .................. 6 5 0 ° F . E * P , C o k e r D i s t i l l a t e
-39ta b le
V II
OPERATION AND PRODUCT DATA FOR RUNS USING
SPENCE'S COBALT MOLYBDATE CATALYST
R un N o .
T e m p e r a t u r e °C
C a ta ly s t
P re h e a t
Y ie ld
W t. % o f C h a rg e
0API
P ro d u ct
W t. # N
W t. % S
1 .092
22 A
3 9 0 .3
3 8 5 .7
9 6 .7
4 1 .9
22 B
3 8 7 .3
3 8 7 .6
9 1 .5
42 .8
22 C
3 8 4 .1
3 8 5 .5
9 7 .7
4 2 .5
1 .0 2 6
23 A
4 0 9 .8
4 1 3 .5
9 7 .3
4 5 .0
0 .7 5 5
23 B
4 1 4 .7
4 0 8 .1
9 9 .7
4 4 .1
23 C
4 1 4 .0
416.8
9 8 .6
4 4 .7
0 .6 8 2
24 A
4 3 7 .4
4 4 2 .8
9 3 .5
4 6 .8
0 .5 2 3
24 B
4 4 0 .5
4 4 0 .7
9 4 .2
4 6 .4
24 C
4 4 0 .8
4 3 9 .1
9 5 .8
4 6 .4
0 .5 6 6
25 A
4 6 5 .8
4 6 9 .2
8 6 .5
4 9 .1
0 .3 7 1
25 B
4 6 7 .9
4 7 0 .2
8 0 .8
4 8 .8
25 C
4 6 3 .9
4 6 4 .1
8 2 .6
4 7 .2
0 .5 1 7
26 A
5 0 4 .9
4 9 6 .3
65 .0
4 8 .2
0 .4 2 7
26 B
4 9 7 .2
4 9 2 .6
68 .8
4 7 .9
26 C
4 9 0 .6
4 9 7 .1
7 1 .5
4 7 .7
0 .0 7 6
0 .0 3 2
0 .0 5 4
0 .0 1 8
0.022
1 .0 3 1
0 .7 7 5
0 .5 6 9
0 .4 1 3
0 .5 6 1
0 .5 1 1
S o n s , L t d . , C o b a l t M o ly b d a te
C a ta ly s t,
R e a c to r P r e s s u r e . ...1 0 0 0 p s i g .
S p a c e V e l o c i t y ..............1 . 0 g m s . / g m . / h r .
R e c y c l e G as R a t e . . . . 7 5 0 0 c u . f t . / b b l . (6 5 p e r c e n t h y d r o g e n )
C h arg e S t o c k . . . . . . . . 6 5 0 ° F , E .P . C o k er D i s t i l l a t e
-4 0 TABLE V I I I
OPERATION AMD PRODUCT DATA FOR RUNS USING
HARSHAW' S COBALT MOLYBDATE CATALYST
Run N o .
T e m p e r a t u r e °C
P re h e a t
C a ta ly s t
Y ie ld
W t. $ o f C h a rg e
0API
P ro d u c t
W t. % S
W t. % N
1 .300
2? A
3 8 1 .9
3 8 7 .3
9 7 .8
4 1 .8
27 B
3 8 9 .5
3 8 5 .5
9 8 .4
4 1 .6
27 C
3 8 7 .3
3 8 5 .6
28 A
406.2
4 16.0
28 B
4 1 4 .7
4 1 0 .5
28 C
4 1 2 .9
4 1 3 .1
9 7 .2
4 3 .4
1 .0 8 0
29 A
4 3 8 .6
4 3 9 .8
9 7 .7
4 6 .6
0 .7 7 2
29 B
4 3 9 .6
4 4 4 .8
8 4 .9
4 6 .6
29 C
4 4 2 .6
4 3 9 .6
9 1 .1
4 6 .2
0 .8 6 3
30 A
4 6 0 .3
4 6 4 .5
8 2 .5
4 6 .8
0 .6 5 9
30 B
4 6 5 .0
4 7 3 .1
7 8 .4
4 8 .0
30 C
4 6 5 .1
4 7 0 .0
7 8 .1
4 6 .9
0 .7 5 6
31 A
4 8 9 .5
5 1 5 .7
4 9 .0
4 2 .5
0 .7 0 0
31 B
5 0 1 .3
4 9 4 .6
6 1 .9
4 3 .3
31 C
S h u t Down
9 8 .5
0 .3 2 7
1 .488
4 1 .4
1 .3 2 5
4 3 .9
1 .070
4 3 .5
0 .1 5 3
0 .0 7 9
0 .0 5 7
0 .0 7 6
1 .0 4 8
0 .7 7 6
O .642
0 .9 1 3
C a t a l y s t ............................ H a rs h a w 1s C o b a l t M o ly b d a te
R e a c to r P r e s s u r e ....1 0 0 0 p s i g .
S p a c e V e l o c i t y ............. 1 . 0 g m s . / g m . / h r .
R e c y c l e G as R a t e . . . . 7 5 0 0 c u . f t . / b b l . (65 p e r c e n t h y d r o g e n )
C h a r g e S t o c k .................. 65 O0 F . E . P . C o k e r D i s t i l l a t e
—4 1 —
TABLE IX
PROPERTIES OF PRODUCT FROM 875° F RUN FOR EACH CATALYST
C a ta ly s t
I n d iu m M0O3
P a l l a d i u m M0 O3
S p e n c e 1s
C o b a l t M0 O3
1 /8 "
1/ 8 "
5 /3 2 "
C a t . D iam .
A v e . T em p, o f
C a t . Bed
4 7 2 .4 ° C.
A v e . Hg c o n t .
o f R e c y c l e G as
68
Y ie ld , w t.
o f C h a rg e
4 6 5 .1 ° c .
H a rs h a w 1s
C o b a l t M0 O3
1/ 8 "
4 6 7 .8 ° C.
4 6 9 .2 ° C.
72 $
75 #
75 %
9 2 .5
8 6 .3
8 3 .3
7 9 .6
V o l . % i n G as­
o l i n e R an g e
47
62
60
52
A v e . 0API a t
20° C.
4 3 .4
4 7 .3
4 8 .3
4 7 .2
%
%
Low S , w t .
%
0.172
0 .0 4 1
0 .0 1 8
0 .0 5 7
Low N, w t .
%
0 .870
0 .5 2 7
0 .3 7 1
0 .6 5 9
IB P
158 ° F .
130° F .
134° F.
153° F .
10 %
270
"
189
"
199
"
228
"
50 "
417
"
346
"
364
"
391
"
90 "
543
"
538
«
548
»
566
»
EP
625
"
623
"
614
"
640
»
ASTM D i s t i l l a t i o n
R e c 'r y
98 v o l . %
98 v o l . %
9 6 .6 v o l . %
97.6 v o l
S p a c e V e l o c i t y ......................... , 1 .0 g m s . / g m . / h r .
R e c y c l e G as R a t e ..................... ,7500 c u . f t . / b b l .
R e a c t o r P r e s s u r e ..................... ,1000 p s i g .
C h a rg e S t o c k .............................. ,6 5 0 ° F . E . P . C o k e r D i s t i l l a t e
F igure I.
S chematic
F low Diagram of t he Unit
*
CS
STREAM
HOURS
F G-2
PRODUCT
DATA
FOR
HYDROGENATION
OF
8 5 0 °F
EP
COKfR
DISTILLATE
AT
500
PSIG
WT
- A <i -
T
3
6
API - 20°C
Xx
7 2 5 °F
7 7 5 6F
8 7 5 °F
O-------
-O-
O
— O.
8
40
FIG . 3 .
CATALYST - COBALT MOLYBDATE
B,
48
PRODUCT
DATA
56
FOR
64
HOURS ON STREAM
H Y D R O G E N A T IO N
OF
8 5 0 cF
ER
88
72
COKER
D IS T IL L A T E
AT
IO O O P S IG
104
4
= -
API-
20°C
WT
-
CATALYST - INDIUM ALUMINA MOLYBDATE
HOURS
FIG. 4
.
PRODUCT
DATA FOR
H Y D R O G E N A T IO N
OF
64
ON STREAM
650°F
EP
COKER
D IS T IL L A T E
AT
IO OO
P S IG
WT
- 20°C
API
CATALYST
PALLADIUM ALUMINA MOLYBDAiE
I
HOURS
FIG. 5 .
PRODUCT
DATA FOR
64
ON STREAM
HYDROGENATION OF 6 5 0 °F
EP COKER D I S T I L L A T E AT IOOO PS
AR I - 2 0 0C
WT % S
WT %
-4 7 '
CATALYST - SPE NCE
COBALT
MOLYBDATE
5/32
64
HOURS
r G
6
d p
,D l CT
DAt A
FOR
H Y D R O G E N A T IO N
ON STREAM
OF
6 5 0 °F
ER
COKER
D IS T IL L A T E
AT
IO O C
P S lG
IM
O aOZ
IdV
o ------ o
CATAljYST - HARSHAW
HOURS
FIG
7
PRODUCT
DATA
FOR
H Y D R O G E N A T IO N
OF
CCj-MO 0201 -T- 1/8
o ------ o
64
ON STREAM
650° F
ER
COKER
D IS T IL L A T E
AT
IO O O
P S IG
P ER CE NT
HYDROGEN
70
CATALYST - COBALT
MO L
CHARGE- 8 5 0 ° F
PRESSURE -
ER
MOLYBDATE
COKER
DISTILLATE
5 0 0 PSIG
40
I_ _ _ _ _ _ _ _ _ _
O
IA
B
C
2A
B
C
RUN
FIG. 8
RECYCLE
3A
B
C
4A
NUMBER
GAS
C O M P O S IT IO N
B
O
CATALYST-COBALT
MOLYBDATE
CHARGE - 8 5 0 ° F
COKER
ER
DISTILLATE
MOL
-OS-
PERCENT
HYDROGEN
PRESSURE - IOOO PSIG
RUN
FIG . 9
RECYCLE
NUMBER
GAS
C O M P O S IT IO N
MOL
PERCENT
HYDROGEN
>*
CATALYST - INDIUM ALUMINA MOLYBDATE
CHARGE -
650°F
ER COKER
DISTILLATE
PRESSURE - IOOO PSIG
RUN
F I G . IO
RECYCLE
NUMBER
GAS
C O M P O S IT IO N
HYDROGEN
PERCENT
MOL
CATALYST -
PALLADIUM ALUMINA MOLYBDATE
CHARGE-GSOe F
EP COKER DISTILLATE
PRESSURE - IOOO PSIG
RUN
F I G . II.
RECYCLE
NUMBER
GAS
C O M P O S IT IO N
O
MOL
P ER C EN T
HYDROGEN
80
CHARGE - 6 5 0 ° F
EP COKER DISTILLATE
PRESSURE - IOOO PSIG
50
L
22 A
B
23A
C
RUN
F I G . 12
24A
B
25 A
NUMBER
RECYCLE
GAS
C O M P O S IT IO N
B
26A
70
MOL
P ER CE NT
HYDROGEN
80
CATALYST - HARSHAW CO-MO 0 2 0 1 - T - 1/8"
CHARGE - 6 5 0 ° F ER COKER DISTILLATE
PRESSURE - IOOO PSIG
50
L
27A
B
C
28A
B
_________
C
RUN
F I G . 13.
29A
B
C
30 A
NUMBER
RECYCLE
GAS
C O M P O S IT IO N
B
C
3IA
B
C
55-
700
600 .
500
U-
ISTILLATION
TEMPERATURE
0
400
300
6 5 0 eF F. R COKER DISTILLATE
RUN NO. 15, INDIUM-ALUMINA MOLYBDATE
200
100
"
"
30; HAR SHAW COBALT
"
"
25; SPENCE
"
2 0 ; RALLADIUM-ALUMINA
(CORRECTED TO 760 MN OF MERCURY)
I
I
30
FIG. 14
I
40
50
60
70
PERCENTAGE DISTILLED
ASTM
100
D I S T I L L A T I ON CURVES
114P97
MONTANA STATE UNIVERSITY LIBRARIES
Rfy 9 -m
p ^ g y c ^ c A ^ i&L
I ar 2 5 ' # INTERTlRRARY TfTAK
/ y ^ fc
M e t , , i I^G
- ^W
- ^ik u\AV
M
^ 5 9 8
/ r s e
^ c
C& jq . £
1148P7
i