Catalytic hydrotreating of shale oil and shale oil coker distillates
by Alan F McKee
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 Alan F McKee (1956)
Abstract:
An investigation was conducted to determine the effect of several process variables on the
hydrotreating of crude gas-combustion shale oil and shale oil coker distillate. A bench-scale,
continuous-flow, fixed-bed, catalytic process unit was utilized.
The effect of temperature and space velocity on three charge stocks was evaluated under the following
conditions: temperature — 775°F to 875°F; space velocity — 0.25 to 1.0 grams of oil per gram of
catalyst per hour; pressure — 1000 psi; gas flow rate — 7500 SCF/bbl; catalyst — 100 grams of l/l6-in.
Harshaw cobalt molybdate pellets. It was found that the nitrogen content of the effluent oil decreased
with increases in temperature and with decreases in space velocity regardless of the charge stock used.
The efficacy of recycling effluent oil for further treating was evaluated by treating a hydrogenated
nominal 650°F E.P. coker distillate under the following conditions: temperature — 825°F; space
velocity — 1.0 to 0.25 g/g/hr; pressure — 1000 psi; gas flow rate — 7500 SCF/bbl; catalyst — 100
grams of l/l6-in, Harshaw cobalt molybdate pellets. It was found that recycling of effluent to effect
nitrogen removal became less efficient than a single equivalent contact time treatment as the space
velocity of the recycle treatment approaches 1.0 g/g/hr.
An attempt was made to evaluate the hydrotreating characteristics of crude gas-combustion shale oil. It
was found that, under the conditions used, coking preceded hydrogenation, and therefore, the material
being hydrotreated was actually a crude form of coker distillate having indeterminate characteristics.
Changes in preheater design might remedy this situation and enable the treating of true crude shale oil.
Seven new catalysts were evaluated as hydrodenitrogenation catalysts at both mild and severe
conditions by processing a nominal 750°F E.P. shale oil coker distillate at two sets of conditions. The
first, or mild, treatment involved the following conditions: temperature — 825°F; space velocity— 1.0
g/g/hr; pressure — 1000 psi; gas flow rate — 2500 SCF/bbl. In the second, or more severe, set of
conditions, the temperature was raised to 950°F and the gas flow rate to 4000 SCF/bbl. It was found
that an HF-activated cobalt molybdate supplied by Esso Research and Engineering Company was the
most efficient denitrogenation catalyst.
An investigation was made of data from various denitrogenation studies to determine the order of the
hydrodenitrogenation reaction.
The results indicate that the controlling reaction involved is of the first order. CATALYTIC HYDROTREATING OF SHALE OIL
AND SHALE OIL COKER DISTILLATES
by
,,
ALAN F . McKEE
A THESIS
S ubm itted t o th e G raduate F a c u lty
in
p a r t i a l f u l f i l l m e n t o f th e re q u ire m e n ts
f o r th e d e g re e o f
M aster o f S c ie n ce i n Chem ical E n g in ee rin g
at
Montana S ta te C o lleg e
Approved:
Chairman
lin in g Committee
Dean, Graduapee D iv is io n
Bozeman, Montana
,August, 1956
X 31*
-2 , i/
TABLE OF CONTENTS
ABSTRACT................................................................................................................................... 3
I
I n tr o d u c tio n .............................................................................................................. 4
II
E q u i p m e n t ...................................................................................................................9
A. Flow S h e e t s ...........................................
9
B. S p e c i f i c a t i o n s ...............................................................................................11
III
T e s ts , P ro c e d u re s, and M a t e r i a l s ................................................................ 14
A. T e s t s ................................................................................................................ 14
B. P r o c e d u r e s ........................................................................................................14
C. M a t e r i a l s .......................................................................................................16
IV
Sample C a lc u la tio n s
V
E x p e rim en ta l D esign ........................................................................................... 17
A. E f f e c t o f O p eratin g V a ria b le s ......................................................... 17
B. E f f e c t o f Chem ical T reatm en ts ......................................................... 21
VI
D iscu ssio n o f R e s u l t s ...................................................................................... 22
A. Tem perature and Space V e lo c ity ......................................................... 22
B. R ecy clin g of E f f l u e n t ..................................................................................22
C. P ro c e s sin g of Crude S hale O i l ...........................................................23
D. C a t a l y s t s ........................................................................................................24
E. N itro g en P r o f i l e o f H y d ro tre a te d M a te r ia l...................................... 25
F . R eactio n O r d e r ...............................................................................................25
G. Batch R e a c tio n s ...............................................................................................26
V II
S u m m a r y .....................................................................................................................27
V III
A cknow ledgm ent........................................................................................................28
IX
B i b l i o g r a p h y ............................................................................................................ 29
X
A p p e n d ix .....................................................................................................................30
........................................................................................ 17
11922?
-3 -
ABSTRACT
An i n v e s t i g a t i o n was conducted t o d eterm in e th e e f f e c t o f s e v e r a l
p ro c e s s v a r ia b le s on th e h y d r o tr e a tin g o f cru d e g as-co m b u stio n s h a le o i l
and s h a le o i l co k er d i s t i l l a t e . A b e n c h - s c a le , c o n tin u o u s -flo w , f ix e d bed,: c a t a l y t i c p ro c e s s u n i t was u t i l i z e d .
The e f f e c t o f te m p e ra tu re and sp ace v e lo c i ty on th r e e charge sto ck s
was e v a lu a te d u n d er th e fo llo w in g c o n d itio n s : te m p e ra tu re — 775°F to
S75°F; space v e l o c i t y — 0 .2 5 t o 1 .0 grams o f o i l p e r gram o f c a ta ly s t
p e r h o u r; p r e s s u r e — 1000 p s i'; gas flo w r a t e — 7500 SC F/bbl; c a ta ly s t
— 100 grams of l / l 6 - i n . Harshaw c o b a lt m olybdate p e l l e t s . I t was found
t h a t th e n itr o g e n c o n te n t o f th e e f f l u e n t o i l d e c re a se d w ith in c r e a s e s in
te m p e ra tu re and w ith d e c re a s e s i n space v e lo c i ty r e g a r d le s s o f th e charge
s to c k u se d .
The e f f ic a c y o f re c y c lin g e f f lu e n t o i l f o r f u r t h e r t r e a t i n g was
e v a lu a te d by t r e a t i n g a hyd ro g en ated nom inal 650°F E .P . co k er d i s t i l l a t e
u n d er th e fo llo w in g c o n d itio n s : te m p e ra tu re — 8250F 5 space v e lo c i ty —
1 .0 t o 0 .2 5 g / g / h r ; p re s s u re — 1000 p s i;- gas flo w r a t e — 7500 SC F/bbl;
c a t a l y s t — 100 grams o f l / l 6 - i n , Harshaw c o b a lt m olybdate p e l l e t s . I t
was found t h a t re c y c lin g o f e f f lu e n t t o e f f e c t n itr o g e n rem oval became
l e s s e f f i c i e n t th a n a s in g le e q u iv a le n t c o n ta c t tim e tre a tm e n t a s th e
space v e l o c i t y o f th e r e c y c le tre a tm e n t ap p ro ach es 1 .0 g / g / h r .
An a tte m p t was made t o e v a lu a te th e h y d r o tr e a tin g c h a r a c t e r i s t i c s of
crude gas-co m b u stio n sh a le o i l ^ I t was found t h a t , under th e c o n d itio n s .
u s e d , coking p reced ed h y d ro g e n a tio n , and t h e r e f o r e , th e m a t e r i a l b ein g
h y d ro tr e a te d was a c t u a l l y a crude form o f co k er d i s t i l l a t e h aving i n ­
d e te rm in a te c h a r a c t e r i s t i c s . Changes i n p r e h e a te r d e sig n m ight remedy
t h i s s i t u a t i o n and e n a b le th e t r e a t i n g o f t r u e crude s h a le o i l .
Seven new c a t a l y s t s were e v a lu a te d a s h y d ro d e n itro g e n a tio n c a t a l y s t s
a t b o th m ild and se v e re c o n d itio n s by p ro c e s s in g a nom inal 750°F E .P .
s h a le o i l c o k er d i s t i l l a t e a t two s e t s o f c o n d itio n s . The f i r s t , o r m ild ,
tre a tm e n t in v o lv e d th e fo llo w in g c o n d itio n s : te m p e ra tu re — 825°F; space
v e l o c i t y '— 1 .0 g / g / h r ; p re s s u re — 1000 p s i ; gas flo w r a t e — 2500,
SC F/bbl. I n th e second, o r more s e v e re , s e t o f c o n d itio n s , th e tem per­
a tu r e was r a is e d t o 950°F and th e gas flo w r a t e to 4000 SC F/bbl. I t was
found t h a t an H F -a c tiv a te d c o b a lt m olybdate s u p p lie d by Esso R esearch and
E n g in e e rin g Company was th e most e f f i c i e n t d e n itro g e n a tio n c a t a l y s t .
An in v e s t i g a t i o n was made o f d a ta from v a rio u s d e n itro g e n a tio n
s tu d ie s to d eterm in e th e o rd e r of th e h y d ro d e n itro g e n a tio n r e a c t i o n .
The r e s u l t s i n d i c a t e . t h a t th e c o n tr o llin g r e a c tio n in v o lv e d i s o f th e
f i r s t o rd e r.
-4 -
I
INTRODUCTION
"The U nited S ta te s i s ru n n in g s h o rt o f p e tro le u m ,11 These words have
echoed th ro u g h th e c o u n try f o r tw e n ty y e a rs o r m ore, and have caused con­
c e r n , n o t o n ly i n th e p e tro le u m in d u s tr y , b u t w ithiti. th e g e n e r a l po p u lace
a s w e ll.
These co n cern s have been c o u n te re d by th e f a c t t h a t new
p e tro le u m r e s e r v e s have been d is c o v e re d a s r a p id ly a s th e o ld ones have
I
been u sed u p , and a t th e p re s e n t tim e th e known p etro leu m r e s e r v e s i n t h i s
c o u n try should s u f f i c e f o r tw e n ty o r tw e n ty -fiv e y e a rs a t p re s e n t r a t e s of
consum ption.
N e v e rth e le s s , th e tim e i s a p p ro ach in g when th e r a t e of
consum ption w i l l exceed t h a t o f d is c o v e ry , and we w i l l th e n be fa c e d w ith
th e p ro s p e c t of tu r n in g t o f o r e ig n so u rc e s o f p etro leu m o r o f d e v elo p in g
o th e r so u rc es o f hydrocarbon f u e l s .
Our p r e s e n t r a t e o f d is c o v e ry i s
b e in g m a in ta in e d o n ly by d r i l l i n g t o g r e a t d e p th s , and by d r i l l i n g in
d i f f i c u l t l y a c c e s s ib le a re a s such a s th e tid e w a te r a r e a s , and th e tim e
w i l l come when d r i l l s can go no d e e p e r, and r i g s can be lo c a te d no f u r t h e r
from la n d .
We a r e , a t p r e s e n t, n e t im p o rte rs o f p e tro le u m , and in th e
f u tu r e we s h a l l come t o im p o rt more and more crude p e tro le u m t o s a t i s f y
' o u r demands.
R e f in e r s , th e r e f o r e , a r e se a rc h in g f o r new m a te r ia ls from
which t o produce l i q u i d hydrocarbon m a t e r i a l s .
I t i s t r u e t h a t th e com­
m e r c ia l iz a tio n of atom ic power w i l l r e l i e v e some o f th e demand f o r f u e l ,
b u t th e in c re a s e d u se o f p etro leu m f o r o th e r p u rp o se s, e . g , , petrochem ­
i c a l s , n e g a te s th e p o s s i b i l i t y t h a t o u r p etro leu m demands w i l l d e crea se
i n th e f u t u r e .
The C ongress of th e U n ited S ta te s h a s re c o g n ize d th e im p o rtan ce of
-5 -
d ev elo p in g new so u rc e s of hydrocarbon m a t e r i a l s , and i n 1944 e n ac te d in to
law th e S y n th e tic L iq u id F u e ls A ct, which p ro v id e s f o r r e s e a r c h in to an d
developm ent o f new so u rc es o f l i q u i d h y d ro carb o n s, such a s c o a l, o i l
s h a le , and a g r i c u l t u r a l p ro d u c ts .
The Bureau of M ines, u n d e r th e
a u s p ic e s o f t h i s a c t , h as accom plished a la r g e amount o f in v e s t ig a ti o n
d e a lin g - w ith th e m ining o f s h a le , and th e re c o v e ry and p ro c e s s in g of" th e
o rg a n ic m a te r ia l p re s e n t t o y i e l d l i q u i d f u e l s .
The r e s e rv e s o f hydrocarbon m a te r ia l c o n ta in e d i n o i l s h a le a re
trem endous, and th e a c t u a l p ro d u c tio n o f l i q u i d f u e l s from sh a le a n te ­
d a te s th e p ro d u c tio n from o rd in a ry p etro leu m by ab o u t tw e n ty y e a r s .
How­
e v e r, th e s h a le o i l in d u s tr y could n o t su rv iv e th e c o m p e titio n fo llo w in g
th e d is c o v e ry o f p e tro le u m , and o n ly a sm all number o f s h a le re c o v e ry
o p e r a tio n s i n f o r e ig n c o u n tr ie s were i n e x is te n c e a t th e b e g in n in g of
W orld War I I .
(I).
The l a r g e s t known r e s e r v e o f o i l s h a le i n th e U n ited S ta te s l i e s
u n d e r th e Green R iv e r p la te a u i n C o lo rad o , Wyoming and U tah, and c o n ta in s
an e s tim a te d 500 b i l l i o n b a r r e l s o f cru d e s h a le o i l , an amount g r e a te r
th a n th e known and proven p e tro le u m re s e r v e s of th e c o u n try .
The b u lk of
t h i s d e p o s it i s lo c a te d ' u n d er th e P ic a n ce Creek b a s in , i n n o rth e rn
C o lo rad o .
T h is s e c tio n o f th e d e p o s it c o v ers an a re a o f 1000 square
m ile s , a v e ra g e s 500 f e e t i n th ic k n e s s , and c o n ta in s r e s e r v e s e stim a te d a t
350 b i l l i o n b a r r e l s of m a te ria l,.
The lo w er 80 to 100 f e e t o f t h i s d e p o s it
i s known a s th e Mahogany Ledge, and th e s h a le i n t h i s fo rm a tio n a ss a y s 30
g a llo n s o f hydrocarbon m a t e r i a l p e r to n , more th a n tw ic e t h a t o f th e r e s t
-6 -
o f th e d e p o s i t .
The r e s e r v e s i n th e Mahogany Ledge a lo n e a re e stim a te d
a t 100 b i l l i o n b a r r e l s .
The p ro d u c tio n o f l i q u i d f u e l from o i l s h a le in v o lv e s some problem s
u nique i n th e -petroleum in d u s tr y .
S in ce th e Mahogany Ledge l i e s deep
u n d er th e e a r t h 's s u r f a c e , th e s h a le m ust be mined u s in g h a rd ro c k te c h ­
n iq u e s .
A lso , th e hydrocarbons p re s e n t i n th e ro ck a r e found i n th e form
o f a s e m iso lid m a t e r i a l known a s k e ro g e n , and a t p re s e n t th e o n ly s a t i s ­
f a c t o r y method o f e x tr a c ti n g t h i s m a te r ia l in v o lv e s r e t o r t i n g o f th e
s h a le .
The Bureau o f Mines and o th e r in d ep en d en t o rg a n iz a tio n s have i n ­
v e s ti g a te d problem s in v o lv e d i n th e m ining o f s h a le , re c o v e ry o f th e o i l ,
and developm ent of econom ical r e f in in g te c h n iq u e s a p p lic a b le to th e o i l .
M ining.
The B ureau, u s in g a new m ining te c h n iq u e known a s th e room -and-
p i l l a r m ethod, h as been a b le to mine th e s h a le and d e l i v e r i t t o p ro c e s s ­
in g p la n ts f o r a d i r e c t c o s t of 32 c e n ts p e r to n o f s h a le
(1 3 ).
In t h i s
method o f m in in g , rooms 60 f e e t sq u are and 70 f e e t h ig h a r e c u t ou t of
th e s h a le , le a v in g 25 p e rc e n t o f th e o r i g i n a l m a te r ia l a s su p p o rt f o r th e
ro o f.
The broken s h a le i s th e n h a u le d ou t o f th e mine and s e n t to
c ru s h in g and re c o v e ry f a c i l i t i e s .
R ecovery.
The hydrocarbon m a te r ia l i s re c o v e re d from th e ro ck by h e a tin g
in a r e to r t.
The B u re a u 's f i r s t r e t o r t , known a s th e NTU r e t o r t , was a
b a tc h - ty p e o p e r a tio n .
P re s e n t r e t o r t s , a s developed by th e Bureau and by
th e Union O il Company, a re c o n tin u o u s .
In th e s e r e t o r t s th e s h a le i s
p a sse d downward c o u n te r c u r re n t to a r i s i n g stream of h o t com bustion g a se s
form ed by b u rn in g re c y c le d o f f - g a s e s and carbonaceous m a te r ia l c o n ta in e d
-7 -
i n th e sp en t s h a le .
The o rg a n ic m a te r ia l i s d riv e n o f f by th e h e a t th u s
s u p p lie d , and th e r a t e of com bustion i s so r e g u la te d t h a t th e v a p o rs a re
condensed w ith in th e r e t o r t , th e re b y n e g a tin g th e . need f o r condensing
w a te r.
P ro p e rtie s .
The cru d e s h a le o i l re c o v e re d from th e r e t o r t s i s a heavy,
b la c k m a te r ia l having a g r a v i t y o f 21° API and a p o u r p o in t o f ab o u t 9 0°F .
I t i s d i s s i m i l a r t o norm al p etro leu m i n t h a t i t c o n ta in s many o l e f i n s and
a h ig h p e rc e n ta g e o f non-hydrocarbon" m a te r ia l.
The p a r a f f i n s and o l e f i n s
a re o f a s t r a i g h t - c h a i n n a tu r e , and th e r e f o r e th e g a s o lin e produced from
th e crude s h a le o i l h a s a low o c ta n e r a t i n g .
The cru d e c o n ta in s t a r a c id s
such a s p h e n o l, th e e r e s o l s , and x y le n o ls , and t a r b a s e s i n th e form of
s u b s t i t u t e d p y r id i n e s and q u in o lin e s .
s u b s t i t u t e d th io p h e n e s .
S u lf u r i s p re s e n t i n th e form o f
N itro g e n compounds com prise a p p ro x im a te ly 43
p e rc e n t by w eight o f th e c ru d e .
U n tre a te d crude s h a le o i l and th e d i s t i l l a t e s produced th e re fro m a re
ra th e r u n s a tis fa c to ry f u e ls .
As m en tio n ed , th e y have h ig h s u l f u r .and
n itr o g e n c o n te n ts and a h ig h p e rc e n ta g e o f u n s a tu r a te d m a t e r i a l .
They
a r e o d o r if e r o u s , c o r r o s iv e , and u n s ta b le i n re g a rd t o c o lo r i n c o n ta c t
w ith a i r .
The s u l f u r compounds p re s e n t cau se c o rro s io n , add t o th e gum-
form ing te n d e n c y o f th e m a t e r i a l , and produce an obnoxious ex h au st upon
com bustion.
The u n s a tu r a te d m a te r ia ls a r e e a s i l y o x id iz e d t o form gums,
and t h i s o x id a tio n i s a c c e le r a te d by th e n itr o g e n compounds p re s e n t
(9 ).
A lso , s u lf u r and n itr o g e n a re d e tr im e n ta l t o v a rio u s c a t a l y s t s now u sed
i n r e f i n i n g p ro c e s s e s , 'and i t i s now g e n e r a lly a c c e p te d t h a t c a t a l y t i c
p ro c c e s s e s a re n e c e s s a ry t o produce e co n o m ica lly h ig h - q u a lity f u e l s .
—d”
e s p e c i a l l y g a s o lin e .
F o r th e s e re a s o n s , i t becomes obvious t h a t some
tr e a tm e n t o r tre a tm e n ts m ust be evolved to produce a m a te r ia l v a lu a b le t o
r e f i n e r s a s raw f u e l m a t e r i a l .
R e f in in g .
Many known p e tro le u m r e f in in g p ro c e s s e s have been in v e s tig a te d
f o r a p p l i c a b i l i t y in th e p ro d u c tio n of f u e l s from s h a le o i l .
Among th e s e
a r e v is - b r e a k in g , d i s t i l l a t i o n , th e rm a l c ra c k in g , c a t a l y t i c c ra c k in g ,
v a rio u s chem ical tr e a tm e n ts , s o lv e n t e x t r a c t i o n , and h y d r o tr e a tin g .
A lso ,
s in c e th e crude s h a le o i l h as a r a t h e r h ig h carbon-hydrogen r a t i o a s
/
compared t o norm al p e tro le u m , th e p o s s i b i l i t y of s u b je c tin g th e crude t o
a d e lay e d re c y c le coking t o low er t h i s r a t i o , fo llo w e d by d i s t i l l a t i o n of
th e v ap o rs th u s produced p r i o r t o r e f i n i n g , h as been in v e s t ig a te d .
S ince n itr o g e n compounds' com prise 43 p e rc e n t o f th e crude m a te r ia l,
and s in c e a com parable s i t u a t i o n p ro b a b ly e x i s t s f o r s u l f u r , i t becomes
obvious t h a t o n ly s u l f u r and n itr o g e n , and n o t t h e i r compounds, may be
removed from th e crude i f i t i s t o be u t i l i z e d i n f u e l p ro d u c tio n .
‘
,
F u r th e r , s in c e th e u n s a t u r a t e s p re s e n t cau se gum fo rm a tio n , i t would be
d e s ir a b le t o s t a b i l i z e th e m a te r ia l b e fo re p ro c e s s in g t o produce f u e l s .
I t would seem, from th e re a so n s s t a t e d above, t h a t h y d ro tre a tm e n t
would accom plish most of th e d e s ir e d r e s u l t s .
The Bureau o f Mines has
in v e s t ig a te d c a t a l y t i c h y d ro tre a tm e n t o f n ap h th as and g as o i l s produced
from NTU c ru d e s , and h as succeeded i n p ro d u cin g a g a s o lin e c o n ta in in g
ab o u t 0 ,1 p e rc e n t n itr o g e n .
T his g a s o lin e was s t a b l e , b u t had a v e ry low
o c ta n e r a t i n g .
S in ce th e p ro d u c tio n o f f u e l s from s h a le o i l i s o f i n t e r e s t t o manyla r g e o i l com panies, th e Esso R esearch and E n g in eerin g Company has spon-
-9 -
so re d a p r o je c t a t Montana S ta te C o lleg e t o develop an econom ical h y d ro t r e a t i n g p ro c e s s which w i l l produce a s ta b l e m a te r ia l h av in g a low
n itr o g e n and s u lf u r c o n te n t, s u ita b le f o r r e f in in g by c o n v e n tio n a l methods
t o produce l i q u i d f u e l s such a s g a s o lin e and d i e s e l s .
King (2 ) re p o rte d
:
an in v e s t i g a t i o n o f th e a c tio n of f o u r c a t a l y s t s on c o k er d i s t i l l a t e , and
H olecek (3) r e p o rte d on th e e f f e c t o f v a ry in g re c y c le gas com position
upon h y d ro tre a tm e n t o f coker d i s t i l l a t e .
T h is p a p e r i s in te n d e d t o r e p o r t
f u r t h e r i n v e s t i g a t i o n s of th e e f f e c t o f p ro c e s s v a r i a b l e s , in c lu d in g
|
te m p e ra tu re and space v e l o c i t y , a s tu d y o f seven new c a t a l y s t s , and an
i n v e s t i g a t i o n o f s e v e r a l b a tc h -ty p e tr e a tm e n ts o f s h a le o i l coker
d is tilla te .
II
A.
Flow S h e e t.
EQUIPMENT
j
I n th e c o n tin u a tio n o f in v e s t ig a ti o n o f h y d ro -
Il
g e n a tio n p r o c e s s e s , a c o n tin u o u s -flo w , fix e d - b e d , c a t a l y t i c p ro c e s s u n i t ,
a s p r e v io u s ly b u i l t and i n s t a l l e d , ( 3 ) , was u t i l i z e d .
I n a d d itio n ,
a n o th e r r e a c t o r , d i f f e r i n g i n c o n f ig u r a tio n from th e f i r s t i n t h a t i t had
a lo n g , narrow c a t a l y s t b e d , was b u i l t and u t i l i z e d in c o n ju n c tio n w ith
th e rem ain d er of th e o r i g i n a l u n i t .
The c a t a l y s t bed o f th e o r i g i n a l
r e a c t o r had a r a t i o o f le n g th to d ia m e te r o f l e s s th a n u n i t y , w h ile i n
th e second r e a c t o r t h i s r a t i o was in c re a s e d t o a p p ro x im a te ly 7 :1 .
A b lo c k flo w diagram o f th e p ro c e s s u n i t i s shown i n F ig , I , and a
d e t a i l e d flo w sh e e t o f th e o r i g i n a l u n i t i s shown in F ig . 2 .
I n th e
o r i g i n a l u n i t , o i l from th e o i l fe e d r e s e r v o i r was pumped to th e to p of
th e r e a c t o r , whence i t flow ed downward o v er a p r e - h e a t s e c tio n c o n ta in in g
I
■I
^
-1 0 -
alun&um b a l l s and th e n c e th ro u g h a c a t a l y s t b ed .
I t th e n flow ed th ro u g h
a condenser t o a c a p a c ity ta n k and s ig h t g la s s and f i n a l l y to a r e c e iv e r
a t a tm o sp h eric p r e s s u r e .
The t r e a t i n g g as flow ed from a fe e d ta n k th ro u g h
a n e e d le v a lv e a n d 'r o ta m e te r to th e to p o f th e r e a c t o r , th e n c e down
th ro u g h th e r e a c to r and out th ro u g h th e p re s s u re c o n tr o l v a lv e t o a
s to ra g e ta n k .
I f re c y c le o f th e fe e d gas was n o t d e s ir e d , i t was v e n ted
t o th e atm osphere from t h e p re s s u re c o n tr o l v a lv e .
I f re c y c le was d e s ire d ,
th e g a s was allow ed to flo w from th e s to ra g e ta n k t o a com pression ta n k ,
from w hich i t was d is p la c e d w ith o i l and fo rc e d i n t o th e fe e d ta n k .
Upon
i n s t a l l a t i o n o f th e new r e a c t o r , th e s ig h t g la s s was e lim in a te d from th e
u n i t and th e condenser was sh o rte n e d in an e f f o r t to red u ce holdup of
p ro c e ss e d o i l w ith in th e u n i t .
D uring th e c o u rse o f th e e x p e rim e n ta tio n , i t became d e s ir a b le t o u se
J
crude s h a le o i l a s th e charge s to c k to th e u n i t , r a t h e r th a n coker
d is tilla te .
S ince cru d e s h a le o i l h a s a h ig h pour p o i n t , (+ 90°F),. and
c o n ta in s some s o l i d s , a h e a te d s to ra g e r e s e r v o i r was i n s t a l l e d in th e
u n i t i n c o n ju n c tio n w ith a f i l t e r .
The crude was p la c e d in th e r e s e r v o i r ,
and from th e r e was pumped th ro u g h h e a te d p ip in g t o th e f i l t e r , from whence
i t flow ed t o th e fe e d r e s e r v o i r p re v io u s ly d e s c rib e d .
S e v e ra l b a tc h - ty p e tre a tm e n ts o f s h a le o i l co k er d i s t i l l a t e
c a r r ie d o u t a s p a r t o f t h i s p r o j e c t .
were
I n th e stu d y o f th e s e tr e a tm e n ts ,
a bomb a p p a ra tu s b u i l t by th e P a rr In s tru m e n t Company was u t i l i z e d in
o rd e r t h a t th e r e a c tio n s m ight be c a r r ie d o u t a t e le v a te d te m p e ra tu re s
and p r e s s u r e s .
T his bomb was o f th e ro c k in g ty p e , and p o s se ss e d p ro v i­
s io n s f o r p r e s s u r iz in g w ith p ro c e s s g as b e fo re o r d u rin g th e co u rse of
-li­
th e tr e a tm e n t.
B.
S p e c ific a tio n s .
O r ig in a l R e a c to r:
The r e a c to r was made from an 1 8 - in . le n g th of
2 ^ - i n . , sch ed 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 .
m achined from 18-8 s t a i n l e s s s t e e l .
r e a c t o r was 3000 p s ig .
re a c to r.
End b lo c k s were
Maximum o p e ra tin g p r e s s u r e f o r th e
Three n i chrome h e a tin g c o i l s w ere wound on th e
The to p and bottom c o i l s were 3 3 - f t lo n g and th e m iddle c o i l
was 2 8 - f t lo n g .
These ceram ic-b ead s tru n g c o i l s were f i r s t wrapped over
a la y e r o f a s b e s to s t a p e , th e n co v ered w ith a second la y e r o f a s b e s to s
ta p e , and f i n a l l y i n s u l a t e d w ith ab o u t one in c h of 8$ p e rc e n t m agnesia.
A, 1 - i n . , sch ed u le 80, 18-8 s t a i n l e s s s t e e l p ip e was u sed a s a therm ow ell
i n th e r e a c t o r .
New R e a c to r:
■
The r e a c t o r was made from a, 3 0 - i n . le n g th o f nom inal
1 - i n ^ GD, sea m le ss, Type 18-8 s t a i n l e s s s t e e l p ip e .
w ith two Vogt 60 0 0 -lb fla n g e d u n io n s.
C lo su re was o b ta in e d
The r e a c to r was wrapped w ith th r e e
3 3 - f t lo n g n i chrome h e a tin g c o i l s in th e manner p r e v io u s ly d e s c rib e d , and
f i n a l i n s u l a t i o n was accom plished by e n c lo s in g th e r e a c t o r and h e a te rs
i n a s e c tio n of form ed m agnesia p ip e i n s u l a t i o n .
A 3 / l 6 - i n . le n g th of
s t a i n l e s s s t e e l tu b in g was u t i l i z e d a s a th erm o w ell by p la c in g an Ermeto
tu b in g union a t th e to p of th e r e a c t o r .
O il Feed R e s e rv o ir:
The o i l fe e d r e s e r v o i r was made from a 2 - i n , , '
sch ed u le 4 0, b la c k - ir o n p ip e 2 1 -in . lo n g .
n i chrome h e a tin g c o i l and la g g ed w ith
I t was wound w ith a 1 0 - f t
i n . o f 85 p e rc e n t m agnesia,
A
50-c c b u r e t t e was a tta c h e d th ro u g h a s id e arm t o in d i c a t e o i l l e v e l i n
th e r e s e r v o i r .
-1 2 O il S to ra g e R e s e rv o ir :
g a llo n o i l can .
The s t o r a g e r e s e r v o i r w as m ade fro m a 5 -
I t was wound w ith a 3 3 - f t lo n g n i chrome h e a tin g c o i l and
la g g ed w ith ^ - i n . of 85 p e rc e n t m ag n esia.
When crude s h a le o i l was u sed
a s c h arg e s to c k , i t was s to r e d in t h i s r e s e r v o i r and k e p t a t flo w in g
te m p e ra tu re by means o f th e h e a te r .
The o i l was t r a n s f e r r e d from th e
r e s e r v o i r by means o f a sm a ll g e a r pump t o a f i l t e r and th e n c e t o th e
fe e d r e s e r v o i r .
Sediment Bowl:
Crude F i l t e r :
C ondenser:
A s ta n d a rd a u to m o b ile -ty p e sedim ent bow l.
A s ta n d a rd a u to m o b ile -ty p e o i l f i l t e r .
A 1 6 - in . le n g th o f -g -in ., sch ed u le 80, b la c k - ir o n p ip e
surrounded by a 2 - i n . , sch ed u le 4 0 , b la c k - ir o n p ip e a c tin g a s a w a ter
ja c k e t.
S ig h t G la ss e s:
E ig h t-in c h Jerg u so n s ig h t g la s s e s w ith i - i n .
s ta n d a rd p ip e t a p s ;
C a p a c ity Tank:
A 2 - i n . , sch ed u le 160, b la c k - ir o n p ip e , 9& i n . lo n g .
i
P re s s u re C o n tro l V a lv e : An a i r - t o - c l o s e , g - i n . , M ason-N ielan
diaphragm v a lv e .
P re s s u re C o n tr o lle r :
A r e v e r s e - a c tin g F ish e r-W iz ard p re s s u re
c o n t r o l l e r w ith 9, 5 0 0 0 -p si Bourdon tu b e .
Rotam eters.:
Brooks arm ored ro ta m e te rs w ith 3 /3 2 - i n . b a l l s .
A u to tra n s fo rm e rs :
R ecom pression Pump:
Tw o-hundred-tw enty v . P o w e rs ta ts ,
A Pesco #051012-020 g e a r pump r a te d a t 4«5
g a l/m in a t 2800 rpm and 1200 p s i .
a tio n i s 1200 p s i .
P re s s u re l i m i t f o r c o n tin u o u s o p er­
-1 3 -
Gas C y lin d e rs :
H a rris b u rg S te e l C o rp o ra tio n
C y lin d e rs , two
1320-c u i n . , and one 2640-cu i n . c a p a c ity .
Com pression O il R e s e rv o ir:
High P re s s u re P ip in g :
Schedule 80 b l a c k - i r o n .
High P re s s u re P ipe F i t t i n g s :
Low P re s s u re P ip in g :
High P re s s u re T ubing:
Low P re s s u re Tubing:
High P re s s u re V alv es:
M etering V alves:
Gas M eter:
G ages:
Two 5 - g a l o i l can s.
Henry Vogt 3000 p s i f o r g e d . s t e e l .
Schedule 40 b la c k - i r o n .
Type 304 SS, l / 8 - i n . OD, 0 .0 2 0 - in , w a ll.
C opper, % -in . OD.
Hoke SS b lu n t- s p in d le n e e d le v a lv e s .
Hoke b ra s s -b o d y , 2 0 -tu rn ^ to -p p e n n e e d le v a lv e s
P r e c is io n S c i e n t i f i c 20-cu f t Wet T est M eter.
M a rsh a ll 2000 p s i .
T herm ocouples:
Three ir o n - c o n s ta n ta n .
T em perature I n d i c a t o r :
A Leeds and N o rth ru p 1 8 -p o in t in d ic a tin g
p o te n tio m e te r.
R upture D isk:
S c ru b b e rs:
A B lack , S i v a l l s , and Bryson 2250 p s i d is k .
O n e - lite r E rlenm eyer f l a s k s .
—14—
III
A.
TESTS, PROCEDURES, AND MATERIALS
T e s ts
N itro g e n a n a ly s e s :
A ll n e c e s s a ry n itr o g e n a n a ly s e s were perform ed
by a m o d ified K je ld a h l method a s d e s c rib e d i n A n a ly tic a l C hem istry
(4)■
O il sam ples were washed tw ic e w ith an e q u a l volume o f d i s t i l l e d w ater
and d r ie d w ith OaClg b e fo re b e in g a n a ly z e d .
B.
P ro ce d u re s
R e a c to r assem bly:
The r e a c t o r was p la c e d i n an in v e r te d p o s itio n
and j^ -in . alundum b a l l s were i n s e r t e d u n t i l th e y a t t a i n e d a p re ­
d e term in e d l e v e l .
At t h i s p o in t th e d e s ir e d charge o f c a t a l y s t was i n ­
s e r te d , and th e r e a c t o r was th e n c o m p le te ly f i l l e d w ith more alundum
b a lls .
A c i r c l e t of s t a i n l e s s s t e e l sc re e n was th e n wedged i n t p th e
u n io n a t th e bottom of th e r e a c to r to keep th e charge i n p la c e when th e
r e a c t o r was r ig h t e d , th e r e a c t o r was p la c e d i n p o s itio n w ith in th e u n i t ,
and a l l n e c e s s a ry c o n n e c tio n s were made.
U sing th e o r i g i n a l r e a c t o r ,
th erm o co u p les were th e n in s e r t e d to re a d te m p e ra tu re s i n th e c e n te rs of
th e f i r s t and second p re h e a t s e c tio n s and th e c a t a l y s t bed .
•
I n th e new
r e a c t o r , therm ocouples w ere p erm an en tly p la c e d t o in d i c a t e th e tem per­
a tu r e a t th e m iddle of th e p re h e a t s e c tio n and th e s u rfa c e of th e c a t a l y s t
b ed .
A, t h i r d therm ocouple was w elded t o th e o u ts id e o f th e r e a c to r i n
such manner a s to in d i c a t e th e te m p e ra tu re a t th e bottom o f th e c a t a l y s t
bed.
S ta r t - u p :
W ith th e r e a c t o r i n p la c e , th e u n i t was f i r s t ev acu ated
back t o th e fe e d ro ta m e te r and th e n p r e s s u r iz e d w ith hydrogen and t e s t e d
f o r le a k s .
The h e a tin g c o i l s were th e n e n e rg iz e d , and th e r e a c to r was
-1 5 -
h e a t ed t o o p e ra tin g te m p e ra tu re o v er an approxim ate tw o -h o u r p e rio d .
Gas flo w was begun when i n t e r n a l te m p e ra tu re s reach ed ab o u t 400°C, and
o i l flo w was begun when th e te m p e ra tu re s re a ch e d 440°C.
O p e ra tio n :
A ll i n t e r n a l te m p e ra tu re s were m a in ta in e d a t 440°C by-
means o f th e a u to tra n s fo rm e rs su p p ly in g power t o th e v a rio u s h e a te r
c o ils .
Space v e l o c i t y was m a in ta in e d by m easuring th e v o lu m e tric o i l
flo w r a t e and a d ju s tin g th e o i l fe e d pump' s tro k e a c c o rd in g ly .
Samples
w ere drawn a s d e s ir e d from th e r e c e iv e r a t th e bottom of t h e c a p a c ity
ta n k , weighed and b o t t l e d .
At t h i s tim e , when u s in g c o k er d i s t i l l a t e
fe e d s to c k , th e fe e d r e s e r v o i r was f i l l e d and th e charge b o t t l e w eighed,
th e amount o f o i l charged d u rin g a sample p e rio d b ein g d eterm in ed by
d if f e r e n c e s in w e ig h t.o f th e charge b o t t l e .
When crude s h a le o i l was
u sed a s f e e d , th e r e s e r v o i r was f i l l e d , a f t e r sam pling, by pumping th e
m a te r ia l from th e s to ra g e r e s e r v o i r t o th e fe e d r e s e r v o i r , th e amount
charged b e in g d eterm in ed by th e d if f e r e n c e i n r e s e r v o i r l e v e l s b e fo re
and a f t e r f i l l i n g .
Gas fe e d was m a in ta in e d a t a p re d e term in ed r a t e by
means of th e fe e d r o ta m e te r.
Gas was g e n e r a lly f e d from b o th th e fe e d
c y lin d e r and from a com m ercial c y lin d e r co n n ected i n s e r i e s w ith i t .
Pure hydrogen was p sed a s p ro c e s s gas w ith o u t r e c y c lin g .
The recom pres­
s io n system was u sed t o e f f e c t more com plete e x h a u stio n o f com m ercial
hydrogen c y lin d e r s , s in c e o p e ra tin g c o n d itio n s made t h e i r d i r e c t use
im p o ssib le below 1 0 0 0 -p s i.
In p r a c t i c e , com m ercial c y lin d e r s were used
d i r e c t l y u n t i l t h e i r i n t e r n a l p r e s s u r e f e l l t.o a p p ro x im a te ly 1 1 0 0 -p s i.
They were th e n connected t o th e recom pression, system and e x h au ste d to
a p p ro x im a te ly 500- p s i ,
-1 6 S h u t-d o w n :
When sh u t-d o w n w as d e s i r e d , t h e o i l f lo w t o t h e r e a c t o r
was s to p p e d , th e h e a te r s were tu rn e d o f f , and gas flo w was c o n tin u e d f o r
an hour o r m ore,^ th e n sh u t o f f .
G.
<
M a te ria ls
The charge s to c k s u sed i n t h i s re s e a rc h were a nom inal 650°F E .P .
and a nom inal 750°F E .P . co k er d i s t i l l a t e produced by r e c y c le delayed
coking o f gas-co m b u stio n crude s h a le o i l , and f u l l - r a n g e gas-com bustion
cru d e s h a le o i l .
These s to c k s were su p p lie d by th e U. S. Bureau o f Mines
d e m o n stra tio n p la n t a t R i f l e , C olorado.
L a b o ra to ry s p e c if ic a tio n s f o r
th e s e s to c k s a r e giv en i n T able I .
Hydrogen' gas was su p p lie d by th e Whitmore Oxygen Company of
S a lt Lake C ity , U tah.
C a ta ly s ts were s u p p lie d by th e Harshaw Chem ical Company, th e P e te r
Spence Company, and th e Esso R esearch and E n g in ee rin g Company.
S p e c if ic a tio n s of th e v a rio u s c a t a l y s t s u sed a re g iv en i n T able I I I .
The alundum b a l l s u sed f o r p re h e a t and c a t a l y s t su p p o rt were % -in.
sp h e re s and l / S - i n . rod s e c tio n s su p p lie d by th e N orton Company.
-1 7 -
IV
Y ie ld ;
SAMPLE CALCULATIONS
(ESO SA-B)
Grams o i l charged
Grams o i l p ro d u c t
Grams lo s s
Y ie ld :
Space v e lo c i ty :
848.0
810.3
3 7 .7
8 1 0 .3 /8 4 8 .0 = 95-6$
(ESO 84-B)
Grams o i l charged
Charge p e r io d , h o u rs
Grams c a t a l y s t
Space v e lo c i ty :
V
A.
848.0
8 .0
100.0
8 4 8 .0 /1 0 0 .0 x 8 .0 = 1 .0 6 1 g / g / h r .
EXPERIMENTAL DESIGN
E f f e c t o f v a rio u s o p e ra tin g v a r i a b l e s on n itr o g e n , c o n te n t of
e fflu e n t o i l ;
L in e o u t:
F o llow ing u n i t s t a r t u p o r changes in o p e ra tin g c o n d itio n s
d u rin g o p e r a tio n s , a c e r t a i n amount o f tim e was n e c e s s a ry t o a llo w th e
u n i t t o e s t a b l i s h uniform r a t e s o f n itr o g e n re m o v al.
F or th e p u rp o ses o f
t h i s p a p e r, t h i s tim e la g w i l l be r e f e r r e d t o a s 1lin e o u t tim e 1.
P rev io u s
d a ta h as in d ic a te d t h a t t h i s tim e la g should be a p p ro x im a te ly 24 h o u rs
fo llo w in g s t a r t u p and 12 h o u rs fo llo w in g changes i n o p e ra tin g c o n d itio n s
d u rin g o p e r a tio n s .
T em perature:
To e v a lu a te th e e f f e c t o f r e a c tio n te m p e ra tu re on
n itr o g e n c o n te n t of th e e f f lu e n t o i l , ru n s ESO 55-65 were ex ecu ted i n th e
fo llo w in g m anner:
The r e a c t o r was ch arg ed and lin e d o u t a t a te m p e ra tu re
o f 775°F and a space v e l o c i t y of 1 .0 .
F ollow ing l i n e o u t , a sample was
ta k e n , and th e space v e l o c i t y was a l t e r e d to 0 .5 .
F o llo w in g lin e o u t a t
-1 8 -
t h i s space v e l o c i t y , a n o th e r sample was ta k e n , and space v e l o c i t y was
a g a in a l t e r e d , t h i s tim e to 0 .2 5 .
sample ta k e n .
L in eo u t tim e was a g a in a llo w ed , and a
F ollow ing t h i s sequence o f o p e ra tio n s a t 775°F, o p e ra tin g
c o n d itio n s were changed t o 825°F and a space v e l o c i t y o f 1 .0 .
The u n it
was allo w ed t o l i n e o u t and sam ples were ta k e n a s n o te d aboye a t space
v e l o c i t i e s o f 1 .0 , 0 .5 0 , and 0.2 5 •
The r e a c t o r te m p e ra tu re was r a is e d to
875°F and a n o th e r s e r i e s o f th r e e sam ples were ta k e n a t th e d e s ir e d space
v e lo c itie s .
The c a t a l y s t u sed d u rin g th e s e ru n s was 100-gram s of Harshaw
0 2 0 1 - T - l / l 6 - i n . c o b a lt m o lybdate, th e ch arg e sto c k was 750°F E .P . coker
d i s t i l l a t e , and th e gas r a t e was 7500 SC F/bbl.
Space v e l o c i t y :
The e f f e c t o f space v e l o c i t y on n itr o g e n rem oval
e f f i c i e n c y was e v a lu a te d in term s o f a l l th r e e s ta n d a rd charge sto c k s by
e x e c u tin g ru n s ESO 50-52, 58-60, and 7 2 -7 3 .
u sed in ru n s 58-60 has been d e s c rib e d .
The method o f e v a lu a tio n
Runs ESO 50-52 were made u sin g
650°F E .P . coker d i s t i l l a t e a s charge s to c k , and th e r e a c to r was o p e ra te d
a t s u b s t a n t i a l l y c o n s ta n t space v e l o c i t y f o r th e d u ra tio n o f each ru n .
Space v e l o c i t i e s o f 1 .0 and 0 .2 5 were in v e s t i g a t e d .
Runs ESO 72-73 were
e x ec u te d u s in g a p p ro x im a te ly th e same scheme o f o p e ra tio n , th e charge
s to c k b e in g crude s h a le o i l .
D uring a l l o f th e s e ru n s , th e c a t a l y s t used
was 100 grams o f Harshaw 0 2 0 1 - T - l/l6 - in . c o b a lt m o lybdate, th e tem per­
a tu r e was 825°F, and th e g as r a t e was 7500 SCF/bbl.
To e v a lu a te th e e f f ic ie n c y o f re p ro c e s s in g e f f lu e n t o i l t o e f f e c t
f u r t h e r n itr o g e n rem oval, ru n s ESO 66-68 were made u n d er th e same co n d i­
t i o n s a s th o s e p r e v a ilin g f o r ru n s ESO 52-52.
charge s to c k s .
The o n ly d if f e r e n c e was in
Runs 66-68 were made u s in g h y d ro g en ated 650°F E .P . co k er
-1 9 -
d i s t i l l a t e from th e p ro c e s s u n i t .
T h is m a te r ia l had o r i g i n a l l y been p ro ­
c essed a t a space v e l o c i t y of a p p ro x im a te ly 1.0'.
P ro c e s sin g o f c ru d e :
D uring th e c o u rse o f t h i s e x p e rim e n ta tio n , i t
became d e s ir a b le t o e v a lu a te th e p ro c e s s in g c h a r a c t e r i s t i c s o f gas-com­
b u s tio n crude s h a le o i l .
Runs ESO 72-78 were ex ecu ted f o r t h i s p u rp o se .
A ttem pts were made t o i n v e s t i g a t e th e e f f e c t s of te m p e ra tu re and space
v e l o c i t y upon e f f i c i e n c y o f n itr o g e n rem oval, and two long ru n s were
ex ecu ted i n an e f f o r t to a s c e r t a i n th e e f f e c t o f ru n n in g tim e upon
c a ta ly s t a c tiv ity .
I n ’th e m ain, th e s e ru n s were d is a p p o in tin g because o f
d i f f i c u l t i e s in v o lv e d i n m a in ta in in g o p e ra tin g v a r ia b le s a t s p e c if ie d
l e v e l s d u rin g th e c o u rse of a ru n .
D u p lic a tio n of r e s u l t s :
D uring th e c o u rse of t h i s r e s e a r c h , th e
q u e s tio n a ro s e a s t o w h eth er o r n o t a d eq u a te d u p lic a tio n o f r e s u l t s b e bween i d e n t i c a l ru n s was b e in g a t t a i n e d .
F ig u re 10 shows th e r e s u l t s
o b ta in e d i n two i d e n t i c a l r u n s , ESO 49 and 50, and a n o th e r ru n , ESO 41,
which d i f f e r e d from th e s e o n ly i n th e s iz e of c a t a l y s t p e l l e t s u se d .
S in ce v i s u a l exam ination o f d a ta su g g e ste d t h a t c o r r e l a t i o n between
i d e n t i c a l ru n s was o n ly f a i r , i t was d e c id e d t o b u ild a new r e a c to r i n an
a tte m p t t o o b ta in b e t t e r d u p lic a tio n o f r e s u l t s ,
The o r i g i n a l r e a c to r
in v o lv e d u se o f a c a t a l y s t bed a p p ro x im a te ly l | - i n . t h i c k and 2 |- i n . in
d ia m e te r, n e g le c tin g th e space occupied by th e th e rm o w e ll, th u s g iv in g th e
c a t a l y s t bed a r a t i o o f le n g th t o d ia m e te r o f l e s s th a n u n i t y .
Since
th e r e i s an in v e r s e r e l a t i o n s h i p betw een th e m agnitude o f t h i s r a t i o and
th e amount o f c h an n e lin g which may o c cu r th ro u g h th e b e d , and sin c e chan­
n e lin g can r a d i c a l l y a l t e r th e e f f e c t o f t h i s ty p e o f c a t a l y t i c p ro c e s s ,
-2 0 -
a new r e a c t o r was b u i l t h aving a c a t a l y s t ,bed a p p ro x im a te ly seven in c h e s
lo n g and one in c h i n d ia m e te r i n an a tte m p t t o m inim ize th e e f f e c t of
c h a n n e lin g th ro u g h th e c a t a l y s t b ed .
A lso , th e th erm o w ell o f th e new
r e a c t o r was ex tended o n ly th ro u g h th e u p p er s u rfa c e of th e c a t a l y s t bed
i n th e hope t h a t c h a n n e lin g would be f u r t h e r m inim ized,
F ollow ing i n ­
s t a l l a t i o n o f th e new r e a c t o r , ru n s ESO 86 and 8? were ex ecu ted u n d er
i d e n t i c a l c o n d itio n s to d e term in e w h eth er o r n o t th e new r e a c t o r en ab led
;)
.
.
b e t t e r d u p lic a tio n of r e s u l t s th a n d id th e o ld one. V is u a l exam ination
o f d a ta from th e s e ru n s su g g e ste d t h a t d u p lic a tio n was s a t i s f a c t o r y .
It
was a ls o found by exam ining d a ta from ru n s ESO 85 and 86 t h a t th e most
e f f i c i e n t n itr o g e n rem oval was accom plished when th e te m p e ra tu re o f th e
c a t a l y s t bed was b ro u g h t t o 825°F b e fo re th e o i l was s t a r t e d th ro u g h th e
u n it.
I n run ESO 85, o i l was s t a r t e d th ro u g h a t ab o u t 795°F» w h ile i n
-
run ESO 86 i t was s t a r t e d th ro u g h a t 825°E .
C a t a ly s ts :
Follow ing i n s t a l l a t i o n and t e s t i n g of th e l o n g - c a t a l y s t -
bed r e a c t o r , e ig h t c a t a l y s t s were t e s t e d f o r e f f ic ie n c y a s compared to
th e Harshaw c o b a lt m olybdate c a t a l y s t which had been u t i l i z e d up t o t h a t
p o in t.
T h is was done i n an a tte m p t to i s o l a t e a c a t a l y s t which would
e f f e c t r e l a t i v e l y com plete d e n itro g e n a tio n a t re a so n a b le space v e l o c i t i e s .
The s p e c i f i c a t i o n s o f th e c a t a l y s t s t e s t e d a re giv en i n T ab le I I I .
A
c o b a lt m olybdate c a t a l y s t produced by th e P e te r Spence Company was
s e le c te d a s a s ta n d a rd o f com parison on th e b a s is o f p re v io u s ex p erim en t­
a t i o n ( 3 ) , and a l l o th e r c a t a l y s t s were compared to i t f o r e f f ic ie n c y of
n itr o g e n rem oval u n d er two s e t s "of o p e ra tin g c o n d itio n s .
t i o n s a r e summarized i n /T able I I I .
These co n d i­
To e v a lu a te th e s e c a t a l y s t s , ru n s
-2 1 ESO 8 9 -9 7 w e re e x e c u te d i n t h e f o l l o w i n g m a n n e r:
The r e a c t o r w as c h a rg e d
w ith th e d e s ir e d c a t a l y s t and s t a r t e d up u n d er th e f i r s t s e t o f co n d i­
tio n s .
Samples were ta k e n a t i n t e r v a l s o f 2 , 4 , 6, 8, 12, 20, and 28
h o u rs.
The u n i t was th e n changed t o th e second s e t o f o p e ra tin g co n d i­
t i o n s and sam ples were ta k e n a t l i k e i n t e r v a l s .
The charge s to c k d u rin g
a l l ru n s was 750°F E .P . co k er d i s t i l l a t e .
B.
E f f e c t of v a rio u s chem ical tr e a tm e n ts on n itr o g e n c o n te n t of
s h a le o i l c o k er d i s t i l l a t e .
C a u s tic :
To e v a lu a te th e e f f e c t o f h o t c a u s tic b a th tre a tm e n t on
c o k er d i s t i l l a t e , ru n s ESO 80-81 were ex ecu ted i n th e fo llo w in g m anner:
The P a r r bomb r e a c tio n a p p a ra tu s was ch arg ed w ith 100 grams o f o i l and
100 grams of anhydrous c a u s t i c .
The a p p a ra tu s was th e n h e a te d to 8250F,
and o p e ra te d f o r p e rio d s o f 2-g- and 9 h o u rs, r e s p e c tiv e ly . I n an a tte m p t
t o e f f e c t d e n itr o g e n a tio n .
The a p p a ra tu s was th e n c o o le d , th e charge
removed and d e c a n te d , and p ro p e r a n a ly s e s p erfo rm ed .
T e tra lin :
To e v a lu a te th e e f f e c t o f t e t r a l i n tre a tm e n t on coker
d i s t i l l a t e , ru n ESO 98 was ex ecu ted in th e fo llo w in g m anner:
The P a rr
bomb r e a c tio n a p p a ra tu s was charged w ith 100 cc of 750°F E .P . coker
d i s t i l l a t e and 100 cc o f t e t r a l i n , o r te tra h y d ro n a p h th a le n e .
The a p p a r­
a tu s was th e n s e a le d , p r e s s u r iz e d w ith hydrogen gas t o 500 p s i , and
-
o p e ra te d f o r a p e rio d of f o u r h o u rs a t a te m p e ra tu re o f 870°F i n an
a tte m p t t o e f f e c t d e n itr o g e n a tio n .
charge removed and a n a ly z e d .
o p e ra tio n was 1500 p s i .
The a p p a ra tu s was th e n co o led and th e
The maximum p re s s u re a t t a i n e d d u rin g th e
-
VI
A.
22 -
DISCUSSION OF RESULTS
T em perature and Space V e lo c ity
N itro g e n a n a ly s e s f o r ru n s ESO 55-65 in d ic a te t h a t th e e f f ic ie n c y of
n itr o g e n rem oval in c r e a s e s w ith te m p e ra tu re a t a l l o f th e sp ace v e lo c ­
i t i e s u n d er c o n s id e r a tio n .
F ig . 3•
These r e s u l t s a re in d ic a te d g r a p h ic a lly in
F ig . 5j b ased on d a ta o b ta in e d from ru n s ESO 50-52, 55-65, and
72- 73, i n d i c a t e s t h a t t h i s s i t u a t i o n i s t r u e f o r b o th crude s h a le o i l and
s h a le o i l c o k er d i s t i l l a t e s .
S in ce o n ly a sm all amount o f d a ta
were
a v a i l a b l e , th e r e l a t i o n s h i p betw een te m p e ra tu re and n itr o g e n c o n te n t of
th e e f f lu e n t o i l was assumed to be l i n e a r o v er th e range c o n s id e re d , and,
where n e c e s s a ry , th e r e g r e s s io n l i n e s were o b ta in e d by th e method of
l e a s t s q u a re s .
V a r ia tio n s from th e l i n e s a re assumed to be due to
f l u c t u a t i o n s i n o p e ra tin g c o n d itio n s , e . g . , space v e l o c i t y .
I t may be
n o te d t h a t y ie ld s v a ry in v e r s e ly w ith o p e ra tin g te m p e ra tu re s and d i r e c t l y
w ith space v e l o c i t y , (F ig . 4 and T able I l) - .
Hence, a t an o p e ra tin g temp­
e r a tu r e o f .875°F and a space v e l o c i t y o f 0 .2 5 , y ie ld s may be o n ly about
65 p e rc e n t o f c h a rg e , w h ile a t low er o p e ra tin g te m p e ra tu re s and a space
v e l o c i t y o f 1 .0 y i e l d s te n d t o approach 100 p e rc e n t o f c h a rg e .
Changes
i n space v e l o c i t y seem t o e x e r t o n ly a sm all e f f e c t when 650°F E .P . coker
d i s t i l l a t e i s p ro c e s s e d , w h ile a l a r g e r e f f e c t i s e x e rte d when 75O0F E .P .
co k er d i s t i l l a t e o r crude s h a le o i l a r e p ro c e ss e d .
B.
R ecy clin g of e f f lu e n t
Runs ESO 50-52 and 66-68 were made u n d er i d e n t i c a l o p e ra tin g c o n d i­
t i o n s i n an e f f o r t t o d e term in e th e e f f e c t o f re c y c lin g e f f l u e n t o i l to
-2 3 -
th e p ro c e s s u n i t to e f f e c t fu rth e r; n itr o g e n rem o v al,
The charge sto ck
u sed i n ru n s ESG 50-52 was a nom inal 650°F E .P . co k er d i s t i l l a t e , w h ile
t h a t used i n ru n s ESO 66-68 was nom inal 650°F E .P . co k er d i s t i l l a t e which
had been h y drogenated once a t a space v e lo c i ty o f 1 ,0 .
I f m a te r ia ls were
t o be p ro c e sse d tw ic e , b o th tim e s a t space v e l o c i t i e s o f 1 .0 , arid i f th e
e f f e c t s o f r e p ro c e s s in g and s in g le - p a s s in g were e q u iv a le n t, th e e f f lu e n t
m a te r ia l from th e second p a s s should have a n itr o g e n c o n te n t e q u iv a le n t
to th a t- o f m a te r ia l which had been p ro c e ss e d once a t a space v e lo c i ty of
0 .5 , a l l o th e r o p e ra tin g c o n d itio n s b e in g th e same.
ru n s in d ic a te t h a t t h i s i s n o t t r u e .
The r e s u l t s of th e s e
As shown in F ig . 6, a s in g le t r e a t ­
ment a t a space v e l o c i t y o f 0 .5 w i l l le a v e l e s s n itr o g e n i n th e e f f lu e n t
(0 .1 9 p e rc e n t) th a n w i l l two tre a tm e n ts a t a space v e lo c i ty o f 1 .0 (0 .2 2
p e r c e n t) .
However, one tre a tm e n t a t a space v e l o c i t y o f 0 .3 3 w i l l le a v e
more n itr o g e n i n th e e f f lu e n t (0 .1 6 p e rc e n t) th a n w i l l two tre a tm e n ts a t
space v e l o c i t i e s o f 1 .0 and 0 . 50, r e s p e c t i v e l y , (0 .0 6 p e r c e n t) , and i n
b o th schemes o f p ro c e s s in g th e o i l h a s e q u iv a le n t re s id e n c e tim e s in
c o n ta c t w ith th e c a t a l y s t .
S in ce t h i s i s c o n tr a r y to re a s o n in g , f u r t h e r
s tu d y o f t h i s problem would be most d e s i r a b l e .
C.
P ro c e s sin g o f crude sh a le o i l
Two lo n g ru n s (ES0 ?2 and 74) were made to d eterm in e th e o p e ra tin g
c h a r a c t e r i s t i c s o f gas-co m b u stio n crude s h a le o i l .
Both ru n s were made
a t th e same te m p e ra tu re (825°F) b u t a t d i f f e r e n t space v e l o c i t i e s .
It
was found t h a t , in b o th c a s e s , th e r e a c t o r became s o l i d l y plugged w ith
coke a f t e r a p p ro x im a te ly 15,000 grams of m a te r ia l had been p ro c e ss e d , and
i n b o th c a s e s coking o c c u rre d i n th e p re h e a t s e c tio n o f th e r e a c to r and
—2Z|.—
n o t in th e c a t a l y s t bed.
S in ce coking o f th e crude s h a le o i l o ccu rred
p r i o r t o i t s p a ssa g e th ro u g h th e c a t a l y s t b ed , th e m a te r ia l a c t u a l l y
p a sse d o v e r th e c a t a l y s t w as, i n e f f e c t , a cru d e form o f co k er d i s t i l l a t e
w ith i n d e f i n i t e c h a r a c t e r i s t i c s .
I t w ould, th e r e f o r e , seem d e s ir a b le
e i t h e r to coke th e crude sh a le o i l u n d er c o n tr o lle d c o n d itio n s p r i o r to
h y d r o tr e a tin g o r t o d e v is e some method whereby th e crude c o u ld be h e ate d
t o r e a c tio n te m p e ra tu re w ith o u t r e s u l t a n t c o k in g .
The f i r s t h as been
accom plished by th e Bureau o f Mines in th e p ro d u c tio n o f co k er d i s t i l ­
la te s .
The l a s t m ight p o s s ib ly be accom plished by changes i n p re h e a te r
d e s ig n .
D.
C a ta ly s ts
The s tu d y o f seven new c a t a l y s t s o f f e r e d a s d e n itro g e n a tio n c a t a l y s t s
produced o n ly one w hich was a more e f f i c i e n t n itr o g e n rem over th a n was
th e s ta n d a rd Spence c o b a lt m olybdate c a t a l y s t .
T h is one was an HF-
a c ti v a te d c o b a lt m olybdate, and a t th e second s e t o f o p e ra tin g c o n d itio n s
(te m p e ra tu re - 950°F, g as r a t e - 4000 SC F/bbl) i t produced an e f f lu e n t
c o n ta in in g ab o u t 0 .2 0 p e rc e n t n itr o g e n , w hereas th e s ta n d a rd c a t a l y s t
produced an e f f lu e n t h aving a n itr o g e n c o n te n t of about 0 .5 4 p e r c e n t.
The perform ances o f a l l c a t a l y s t s s tu d ie d a re ta b u la te d i n F ig . 7.
The d e f i n i t i o n of c a t a l y s t a c t i v i t y i s som ething o f a problem .
For
th e p u rp o se s o f t h i s p a p e r, i t s h a l l be d e fin e d a s th e r a t i o o f th e
n itr o g e n c o n ta in e d i n th e e f f lu e n t o i l from th e s ta n d a rd c a t a l y s t to th e
n itr o g e n c o n te n t o f th e e f f l u e n t o i l from th e c a t a l y s t u n d er c o n s id e r­
a tio n .
Thus, th e a c t i v i t y o f th e s ta n d a rd c a t a l y s t i s 100 p e r c e n t, w h ile
th e a c t i v i t y o f th e HF- a c t i v a t e d c o b a lt m olybdate i s 27Q p e rc e n t a t th e
-2 5 -
second s e t o f o p e ra tin g c o n d itio n s .
Approxim ate a c t i v i t i e s f p r a l l
c a t a l y s t s s tu d ie d a r e l i s t e d , in.'Tables I I I ,
E„
N itro g e n p r o f i l e o f h y d ro tr e a te d m a te r ia l
A sample o f hy d ro g en ated 65Q °F,E.P, c o k er d i s t i l l a t e was f r a c t i o n ­
a te d t o produce c u ts q f 3 0 , 3 0 , 20, and 20 volume p e rc e n t o f th e m a te r ia l.
N itro g e n a n a ly s e s were th e n perform ed qn each of th e c u ts t o d eterm in e
w h eth er th e lo w ^ h o ilin g o r .h ig h - b o ilin g m a te r ia ls p re s e n t c o n ta in e d th e
re s id u a l n itro g e n .
F ig , 8 p r e s e n ts - th e r e s u l t s o f t h i s i n v e s t i g a t i o n .
I t may be n o te d t h a t th e lo w -b o ilin g m a te r ia ls c o n ta in alm o st no n itr o g e n ,
(0 .0 2 p e r c e n t) , w h ile th e h ig h ^ b o ile r s c o n ta in a h ig h p e rc e n ta g e of
n itr o g e n (0 .3 3 p e r c e n t ) ,
Thus, i t m ight be p o s s ib le t o produce a low-
n itr o g e n g a s o lin e from s h a l e , q i l co k er d i s t i l l a t e w ith o u t n e a r ly com plete
d e n itro g e n a tio n o f a l l th e m a te r ia l,
F.
R e a c tio n o rd e r .
A f i r s t - o r d e r r e a c tio n i s one in ' which th e r a t e o f r e a c tio n i s found
t o b e d i r e c t l y p r o p o r tio n a l b ° th e c o n c e n tra tio n o f th e r e a c tin g su b stan ce.
Thus, th e s i t u a t i o n i s d e s c rib e d m a th e m a tic a lly a s f o llo w s s
-
dA
dt
=
kA
w here:
A = c o n c e n tra tio n q f r e a c ta n t a t tim e t
k = r e a c tio n p r o p o r t i o n a l i t y c o n sta n t
t = tim e
-
-2 6 -
The in te g r a te d form o f t h i s ' e q u a tio n i s :
A
9
—
In
=
A
In
0
"A ^
=
kt
.
w here:
Aq = c o n c e n tra tio n of Mg a t tim e .t = o
x- = A0 - .A = amount o f Mg (p e rc e n t) removed
up t o tim e t .
I t t h e r e f o r e becomes obvious t h a t ^ fo p a f i ^ s t - o r d e r r e a c tio n , a s t r a i g h t
l i n e i s produced when th e lo g a rith m o f th e c o n c e n tra tio n i s p lo tte d
a g a in s t tim e .
D ata from ru n s BSO 55-65 were e v a lu a te d i n an a tte m p t
d is c o v e r th e o rd e r o f th e d e n itro g e n a tio n r e a c tio n in v o lv e d i n t h i s
re se a rc h .
A graph was made i n which tim e was p l o t t e d v e rs u s th e lo g a rith m
o f c o n c e n tr a tio n , a s e x p re ss e d by th e r e l a t i o n s h i p
In
Time was d e fin e d a s th e r e c i p r o c a l o f space v e l o c i t y .
/'Q
Ap - x
= k t.
F ig . 9
shows th e r e s u l t s , o f t h i s e v a lu a tio n a t each o f th r e e o p e ra tin g tem per­
a t u r e s , and th e p e p l o t s in d ic a te t h a t th e o v e r a ll d e n itro g e n a tio n r e a c tio n
i s o f th e f i r s t o rd e r o v er th e te m p e ra tu re ran g e c o n sid e re d i n t h i s
e x p e rim e n ta tio n .
I t i s p ro b a b le t h a t more th a n one r e a c tio n i s in v o lv e d
i n th e d e n itro g e n a tio n of s h a le o i l , b u t th e one which d e te rm in e s th e r a t e
o f r e a c t i o n , t h a t i s , fh e slo w est one, i s p ro b a b ly o f th e f i r s t o rd e r.
G.
B atch r e a c tio n s
The c a u s tic and t e t r a l n n tr e a tm e n ts o f s h a le o i l c o k er d i s t i l l a t e a t
e le v a te d te m p e ra tu re s and p r e s s u r e s produced l i t t l e d e n itr o g e n a tio n .
The
r e s u l t s of th e s e tr e a tm e n ts a r e in d ic a te d ,in T able IV , and show t h a t fh e
n itr o g e n c o n te n t o f th e c o k er d i s t i l l a t e ■■was o n ly reduced from 1 .9 0 p e r - ­
c e n t b e fo re tre a tm e n t t o 1 .6 0 p e rc e n t a f t e r tre a tm e n t i n b o th c a s e s .
-2 7 -
HI
SUMMARY
The minimum r e a c tio n te m p e ra tu re u sed i n t h i s r e s e a r c h t o a tte m p t
th e d e n itro g e n a tio n o f s h a le o i l and s h a le o i l co k er d i s t i l l a t e s was
775°F , and any in c r e a s e s above t h a t f i g u r e te n d to d e c re a se th e n itr o g e n
c o n te n t o f th e e f f l u e n t o i l , r e g a r d le s s o f th e charge s to c k u se d .
In ­
c re a s e s in te m p e ra tu re w i l l a ls o te n d t o d e c re a se y i e l d s .
The n itr o g e n c o n te n t o f th e e f f l u e n t o i l te n d s to d e c re a se w ith
d e c re a s e s i n space v e l o c i t y , r e g a r d le s s o f th e charge sto c k u se d .
N itro g e n may be alm ost t o t a l l y removed a t v e ry low space v e l o c i t i e s , b u t
th e y ie ld te n d s t o d e c re a se a s th e space v e l o c i t y i s lo w ered .
P ro c e s sin g o f crude s h a le o i l u n d er th e p re h e a t c o n d itio n s s e t f o r t h
i n t h i s p a p e r i s n o t recommended, s in c e coking o c c u rs i n th e r e a c to r
p re h e a t s e c tio n .
The r e s u l t was t h a t a crude form o f c o k er d i s t i l l a t e
1
w ith in d e te rm in a te p r o p e r tie s was a c t u a l l y p assed o v er th e c a t a l y s t b ed .
Of th e group of c a t a l y s t s s tu d ie d , t h e H F -a c tiv a te d c o b a lt m olybdate
a p p e a rs t o be th e m ost e f f i c i e n t f o r h y d ro d e n itro g e n a tio n o f sh a le o i l
c o k er d i s t i l l a t e s .
T h iS' c a t a l y s t i s n o t a v a il a b le co m m ercially .
The
Spence c o b a lt m olybdate was th e n e x t- b e s t c a t a l y s t .
A lthough s e v e r a l r e a c tio n s a re p ro b a b ly in v o lv e d in th e c a t a l y t i c
h y d ro d e n itro g e n a tio n o f s h a le o i l , th e c o n tr o llin g r e a c tio n a p p e a rs t o be
f ir s t- o r d e r in n a tu re .
T reatm ent o f s h a le o i l co k er d i s t i l l a t e w ith c a u s tic o r t e t r a l i n a t
e le v a te d te m p e ra tu re s and p re s s u r e s i n an a tte m p t t o e f f e c t d e n itro ^
g e n a tio n was n o t e f f e c t i v e .
-2 8 -
V III
ACKNOWLEDGMENT
The a u th o r w ish es to th a n k th e Esso R esearch and E n g in ee rin g
Company f o r sp o n so rin g t h i s re s e a rc h p r o j e c t ; P r o fe s s o rs Lloyd B erg,
L . G. M ay field , and H. A. S aner f o r t h e i r su g g e s tio n s and c r i t i c i s m s ;
and Dale Benson f o r h i s a b le a s s i s t a n c e .
L
-2 9 -
BIBLIOGRAPHY
(1)
B erg, C lyde, "Advancements i n F u e ls P ro d u ctio n from S h ale O il."
Union O il Company o f C a l if o r n ia , 1954«
(2)
K ing, G. A ., M.S. T h e s is , Montana S ta te C o lle g e , 1955.
(3 )
H olecek, R. J . , M.S. T h e s is , Montana S ta te C o lle g e , 1955.
(4 )
Lake, G. R ., e t a l , " E ff e c ts o f D ig e stio n Tem perature on
K je ld a h l A n a ly se s ." A n a ly tic a l C h em istry , 23, p . 1634-38
(November, 1951)•
(5 )
M ay field , L. G ., P e rs o n a l ,communication.
(6)
W e ik a rt, J . H ., P e rs o n a l com m unication.
(7 )
MacLaren, D ,, P e rs o n a l cpm m unipation.
(8)
U. S. Bureau o f Mines O il-S h a le Mine and E n g in e e rin g Experim ent
S ta tio n : R ep o rt- on Coking Gas-Combustion Crude S hale O il f o r
Maximum P ro d u c tio n o f Gas O i l . R i f l e , C olorado (F e b ru a ry , 1954)
( 9)
U. S. Bureau "of M ines:
R eport o f I n v e s tig a t io n s 4457
(1 0 )
U. S . Bureau o f M ines:
R eport of I n v e s tig a t io n s 5^44
(1 1 )
U. S. Bureau of M ines:
R eport o f I n v e s tig a t io n s 4771
(1 2 )
E x cav atin g E n g in e e r, 4 3 , No. 11, p . 20 (November, 1 9 4 9 ).
(
-3 0 -
X
APPENDIX
T able I
Charge S tock P r o p e r t i e s ......................................................... . , . 31
T able I I
O p e ratin g C o n d itio n s and P ro d u ct Data
on S h ale O il T r e a tin g . . . . ......................................................... 32
r
T able I I I
C a ta ly s t A c t i v i t y ...................................................................
A3
T able IV
R e s u lts o f B atch T reatm en ts of S hale O i l ..........................
44
F ig u re I
Block F low sheet of H y d ro tre a tin g U n i t .........................................45
F ig u re 2
D e ta ile d F lo w sh e e t....................................................................................45a
F ig u re 3
N itro g e n Removal a s a F u n ctio n of
T em perature and Space V e lo c ity ......................................................... 46
F ig u re 4
Y ie ld a s a F u n c tio n of Space V e lo c ity
and Charge S t o c k ................................................................................... 47
F ig u re $
N itro g e n Removal a s a F u n c tio n of
Space V e lo c ity and Charge S t o c k .....................................................48
F ig u re 6
N itro g e n Removal a s a F u n c tio n of
Space V e lo c ity and E f f lu e n t R e c y c l e ............................................ 49
F ig u re 7
N itro g e n Removal a s a F u n c tio n of
5
On-Stream Hours and C a t a l y s t s ........................................* . . .
F ig u re 8
N itro g e n P r o f i l e a s a F u n c tio n of
P e rc e n t o f M a te ria l D i s t i l l e d ............................................ . . .
50
51
F ig u re 9
R ea c tio n Time a s a F u n c tio n o f th e Logarithm
o f th e C o n c e n tra tio n o f N itro g e n i n th e E f f l u e n t ..................52
F ig u re 10
N itro g e n Removal a s a F u n ctio n o f Time
f o r Runs Made Under I d e n t i c a l C o n d itio n s
53
TABLE I
CHARGE STOCK PROPERTIES ( £ )
P ro p e rty
Crude
S hale
O il
G ra v ity
V is c o s ity , SHU. at" 130 F .
Carbon R e sid u e , Ramsbottom
S u lf u r
N itro g e n
ASTM D i s t i l l a t i o n , D-15S
IBP "
$$ a t
10
20
30
40
50
60
70
80
90
95
' E .P .
R ecovery
0API a t 60°F.
sec.
W t. p e rc e n t
W t. p e rc e n t
W t. p e rc e n t
0F.'
2 1 .0
90. +
1 .3
0 .7 7
2 .0 7
370
517
577
699
V ol. p e rc e n t
Charge Stock
750UF . E .P .
Coker
D is tilla te
2 $ .6
46
0 .9 8
0 .6 1
1 .9 0
257
362
425
484
529
571
612
647
682
716
742
754
754
-97
650°F. E .P .
Coker
D is tilla te
3 5 .4
31
0 .6 2
O.63
1.6 5
161
253
297
354
396
432
464
- 492
522
554
591
616
672
98
V
TABLE LI
Sample
No.
Time—Hours
from S ta rtu p
T em perature
C a ta ly s t
P rh t.
0C.
0C.
Space
V e lo c ity
g /g /h r.
Al-A
B
■C
D
E
F
G
12-16
16-20
20-24
24-28
28-32
32-36
36-40
440
438
441
441
449
443
441
440
438
444
440
434
437
441
1.025
1.054
1.030
1.015
' 1.038
1.079
'1 .0 5 1
A6 -A
B
H
I
J
E
L
5- 9
9-13
13-17
17-21
21-25
25-29
29-33
33-37
37-41
41-45
45-49
49-53
447
441
439
439
444
442
443
441
436
438
439
435
438
440
437
440
439
438
441
438
443
441
440
439
0.260
0.270
0.232
0.217
0.175
0.245
0.242
0.245
0.-237
0 .227
0.217
47—A
B
C
D
0- 4
4- 6
6- 8
8-10
431
443
444
437
460
454
441
426
c :
D
E-
F
G
ON SHALE OIL TREATING
Gas Flow ^
R ate SC F/bbl.
7500
7500
Charge
Stock
650
Coker
D is tilla te
650
Coker
D is tilla te
Y ield
P e rc e n t
P e rc e n t Ng
i n E f f lu e n t
96;7
95.5
96 .1
96 .8
9 6 .8
9 3 .1
96.7
0 .7 2 7
0 .7 9 6
0 .7 4 1
0.803
0 .839
0 .7 1 8
0 .6 8 6
8 2 .0
9 1 .G
8 2 .0
8 6 .0
9 4.0
8 4 .0
8 1 .0
8 6 .0
8 7 .0
8 6 .0
8 0 .0
0.180
0.154
0 .1 5 2
0.110
0.112
0.102
0 .0 9 4
0.100
0 .1 1 1
0 .090
0 .100
0 .0 9 6
---
0 .3 3 8
0 .2 1 0
0.280
0.363
—
■.........
1.072
1.362
1.424
7500
650
Coker
D is tilla te
—
97 .0
8 1 .0
7 1 .0
-EC-
OPERATING CONDITIONS AND PRODUCT DATA
TABLE L I ( c o n t i n u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
Time—Hours
from S ta rtu p
Tem perature
C a ta ly s t
P rh t.
°c.
0C. •
Space
V e lo c ity
g /g /h r .
AS-A
B
C
D
E
F
G
H
I
J
K
L
2- 6
6-10
10-14
14-18
18-22
22-26
26-30
30-34
34-38
34-4242-46
46-50
430
420
417 '
410
410
420
413
415
414
424
422
421
476
446
440
438
443
441
444
435
439
448
442
441
0.995
1 .0 0 0
0 .968
0 .9 8 6
1.002
0 .9 7 4
0 .9 8 6
0.985
1.005
1 .0 2 8
0 .9 1 8
—---
49-A
B
C
D
E
F
G
H
I
J
4- S
8-12
12-16
16-20
20-24
24-28
28-32
32-36
36-40
40-44
442
441
439
441
438
439
445
442
440
437
441
439
440
441
440
438
443
439
439
439
0 .9 9 0
0 .9 8 0
0 .9 8 6
—
0 .991
0 .9 2 0
0.887
0 .899
0.849
1 .000
50-A
B
C
D
2- 6
6-10
10-14
14-18
446
444
443
441
442
440
441
437
0 .960
0.980
0.960
0 .9 4 8
Gas Flow
R ate SCF/ b b l .
7500
Charge
Stock
650
Coker
D is tilla te
-
7500
650
Coker
D is tilla te
Y ield
P e rc e n t
P e rc e n t Np
i n E f flu e n t
8 9 .6
8 8 .8
92 .6
9 3 .2
94.3
89 .7
94 .2
94.3
9 3 .1
9 1 .8
96 .6
—
0 .538
0.757
0.811
0 .859
0 .842
0.828
0.811
0.818
0.882
0.785
0.869
0.895
7 8 .2
77.3
7 8 .1
7 8 .4
8 4 .8
8 3 .0
85 .5
8 3 .9
8 5 .7
0.187
0.206
0.206
0.194
0.215
0.224
0 .2 3 4
0.238
0.257
0.227
93.2
91 .6
9 3 .4
9 4 .0
0.257
0.233
0.249
0.240
TABLE I I
(c o n tin u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
Tem perature
Time—H o u rs_ P r h t .
C a ta ly s t
from S ta rtu p
°C .
0C.
Space
V e lo c ity
g /g /h r.
50-E
F
G
H
I
J
K
L
18-22
22-26
26-30
30-34
34-38
38-42
42—46
. 46-50
437
440
442
447
443
440
436
437
442
440
440
439
441
441
440
439
1.028
0.995
1.041
0.976
0 .9 7 0
51-A
B
C
D
E
,F
G
H
I
J
K
L
M
N
0
P
Q
E
3 -H
11-19
19-27
27-35 '
35-43
43-51
51-59
59-6?
67-75
75-83
83-91
91-99
99-108
108-115
115-123
123-131
131-139
139-147
452
453
438
448
441
437
440
440
440
440
441
438
440
440
438
442
441
438
442
439
441
441
440
441
440
441
441
440
441
440
441
440
442
442
440
441
0 .292
0.263
0.275
0 .2 5 1
0.232
0.161
0 .2 3 6
0 .3 1 0
0 .3 1 4
0.277
0.312
0.319
0.300
0 .3 5 9
0.298
0 .3 1 9
0 .3 2 1
0.322
Gas Flow
R ate SC F/bbl.
7500
Charge
Stock
650
Coker
D is tilla te
— — —
1 .029
1.006
7500
-
650
Coker
D is tilla te
Y ie ld
P e rc e n t
P e rc e n t Np
in E fflu e n t
8 8 .6
9 4 .2
8 8 .1
9 2 .0
95 .2
9 4 .4
94 .2
8 6 .9
0.234
-0.279
0.269
0.292
0.299
0.330
0.313
0 .326
6 5 .7
8 1 .9
7 0 .4
8 0 .6
8 3 .3
8 2 .4
8 8.3
7 3 .6
8 9 .8
8 5 .1
8 3 .2
8 1 .8
8 5 .1
8 5 .3
8 9 .1
7 7 .6
0.516
0 .151
0 .136
0.182
0.097
0.069
0.120
0,219
0.221
0.165
0.153
O.148
0,163
0.154
0.188
0.173
—
7 9 .0
0.151
TABLE I I
(c o n tin u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
55
56
57
58
59
60
61
62
63
64
65
66
67
68
•
72-A
B
C
D
,
E
F
G
H
I
J
K
L
Time—Hours
from S ta rtu p
3-1
31-46
46-63
63-83
83-96
96-115
115-130
130-143
143-164
164-174
174-190
222-254
254-254
278-278
36
44
70
79
92
100
108
116
124
132
140
148
T em perature
P rh t.
C a ta ly s t
0C.
°c.
Space
V e lo c ity
2/% /h r.
409
408
413
441
432
441
465
467
460
470
440
442
444
444
412
413
413
438
440
440
466
467
470
470
440
442
440
439
1.148
0 .496
0.271
0 .9 5 6
0.700
0.241
1.060
0.509
0 .2 4 4
0 .2 0 1
0 .2 8 4
0.982
0 .4 3 8
0 .316
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
0.513
0 .6 1 6
0 .129
0 .237
0 .0 8 4
0.591
0.195
0 .1 9 8
0.349
0.240
, 0.120
0.090
Gas Flow
R ate SC F/bbl.
Charge
Stock
Y ield
P e rc e n t
—
—
—
7500
750
Coker
D is tilla te
7500
650
Coker
D is tilla te
Hydrogena te d
90 .0
8 3 .9
7 8 .6
7 5 .9
64.3
65.18 8 .9
90.2
88.5
92.5
7 8 .8
7 3 .1
9 0 .0
90 .0
78.5
—
—--69.5
8 3 .0
7 9 .4
69.6
—
P e rc e n t Ng
i n E f flu e n t
1.129
0.786
0.535
0.674
0.690
0.279
0.960
0.657
0 .4 4 6
0 .2 5 2
0.412
0.222
0.041
0.041
0.874
0.816
O.663
0.563
0.510
0 .868
0.727
0.680
0.850
1.031
0.689
0.465
TABLE I I
(c o n tin u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
72-M
N
O
P
Q
R
S
T
U
V
V
X
Y
Z
AA
BB
CC
DD
EE
FE
GG
74-A
B
C
D
E
F
G
Time—Hours
from S ta rtu p
T em perature
C a ta ly s t
P rh t.
0C.
0C.
Space
V e lo c ity
g /g /h r .
164
172
180
188
196
204
220
236
2$2
268
284
300
316
332
348
364
380
396
412
492
$03
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440 *
440
440
440
440
440
440
440
440
440
440 .
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440"
0.105
0 .0 9 6
0.105
0.126
0 .0 9 1
0.087
0 .1 0 8
0.119
0.096
0 .1 7 0
0.086
—— —
0 .0 9 1
246
254
260
26?
273
279
282
440
440
440
440
440
440
440
440
440
440
440
440
440
440
0 .211
0.173
0.186
0.203
0 .2 0 6
0 .232
0 .1 8 9
Gas Flow
R ate SC F/bbl.
Charge
Stock
Y ield
P e rc e n t
7500
Crude
Shale
O il
6 6.7
65.6
6 4 .0
63.3
—
——
66.3
64.4
68.5
67.8
'
———
67.6
68.8
—
0 .2 3 1
0.103
0.06?
0.079
0 .1 3 0
0 .114
0.337
———
—
7500
Crude
S h ale
O il
———
——
— ----
8 0.0
80 .0
8 0 .0
8 0.0
80.0
80.0
80.0
P e rc e n t ]
i n E fflm
0.465
0.455
0.470
0.470
0.470
0.477
0.467
0.467
0 .5 3 4
0 .5 1 9
———
0.401
0.713
0 .8 3 0
0 .8 5 9
0.425
0.425
0.737
0.191
0.437
—■MUM
0.650
0.698
— ——
TABLE L I ( c o n t i n u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
74-H
I
J
K
L
'
M
N
0
P
Q
R
S
T
U
V
¥
X
YZ
Time—Hours
from S ta rtu p
288
294
300
312
326
326
342
352
358
375
383
391
349
407
415
423
431
439
447
85-A ‘
B
C
D
E
17
25
34
42
49
86-A
B
C
D
E
F
2
4
6
8
12
20
.
Tem perature
P rh t.
C a ta ly s t
0C.
0C.
Space
V e lo c ity
g /g /h r.
0.242
0.249
0.314
0 .1 8 4
0.205
0.205
0.202
0.215
0 .1 9 8
0 .102
0 .130
0.213
0 .1 8 6
- 0 .174
0 .1 7 1
0 .2 1 8
0 .1 9 1
0 .156
a . 179
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440.
440
440
440
440
440
440
440
440
440
440
440
440
440
440
440 '
440
440
1.017
1.017
1.017
1.017
1.017
440
440
440
440
440
440
440
440440
440
440
440
1.045
1.045
1.045
1.045
1.045
1.045
Gas Flow
R ate S C F /bbl.
2500
7500
7500'
Charge Y ield
Stock P e rc e n t
Crude
S hale
O il
750
Coker
D is tilla te
750
Coker
D is tilla te
P e rc e n t N2
i n E f flu e n t
8 5 .0
8 5 .0
8 4 .0
8 4 .0
84.0
8 2 .0
8 2 .0
8 2 .0
8 2 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
8 7 .0
0 .8 0 0
0 .9 5 8
™—
0 .6 5 1
0 .6 5 1
———
——
—
———
——
———
———
———
„ ——
—
---—
———
———
—
—
87.5
87.5
87 .5
87 .5
87.5
0.802
0.945
0 .9 6 0
0.980
—
9 5 .0
95 .0
95 .0
95 .0
9 5 .0
9 5 .0
0.749
0.807
0.678
0.807
0.707
0 .826
.
TABLE I I
(c o n tin u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
Time—Hours
from S ta rtu p
Tem perature
Space
P rh t.
C a ta ly s t V e lo c ity
°c.
0C.
g /g /h r.
Gas Flow
R ate SC F/bbl,
86-G
H
I
J
28
36
44
52
440
440
440
440
440
440
440
440
1.045
1.045
1.045
1.045
87-A
B
C
D
E
F
G
2
46
8
12
19
24
440
440
440
440
440
4-40
440
440
440
440
440
440
440
440
0 .987
0 .987
0 .9 8 ?
0 .987
0 .9 8 7
Q.987
0.987
88-A
■B
C
D
E
F
G
2
4
6
8
12
20
28
440
440
-440
440
440
440
440
440
440
440
440
440
440
440
1.010
1.010
1.010
1 .0 1 0
1 .0 1 0
1.010
1 .0 1 0
2500
8 9-1-A
B
C
D
E
F
G
2
4
6
8
12
20
24
440
440
440
440
440
440
440
440
440
440
440
440
440
44O
1.030
1.030
1.030
1.030
1.030
1.030
1.030
2500
2500
2500
2500
2500
2500
2500
7500
Charge
Stock
750
"Coker
D is tilla te
-
Y ield
P e rc e n t
P e rc e n t Ng
i n E f flu e n t
95 .0
9 5 .0
95.0
95.0
0 .8 7 0
0 .9 2 2
0 .9 2 8
0 .9 4 1
96 .7
96 .7
96.7
96 .7
96.7
96 .7
96.7
0 .5 9 8
0 .6 1 7
0 .6 1 8
0 .6 8 9
0.702
0.713
0 .8 1 9
™
0 .7 9 8
0.843
0.785
0 .8 0 9
0.863
0 .8 7 1
0.885
98 .4
9 8 .4
9 8 .4
9 8.4
98 .4
9 8 .4
9 8 .4
1.008
0 .8 5 6
0.762
0.742
0 .7 4 8
0 .7 9 1
0.825
1
—
—
750
Coker
D is tilla te
— — —
— — ——
750
Coker
D is tilla te
—
—----------
TABLE L I ( c o n t i n u e d )
OPERATING CONDITIONS AND PRODUCT- DATA ON SHALE OIL TREATING
Sample
No.
Time—Hours
from S ta r tu p
Tem perature
C a ta ly s t
P rh t.
°C.
0C.
29
31
33
35
39
47
510
510
510
510
510
510
91-I-A
B
C
D
E
F
G
II-A
B
C
D
E
F
2
4
6
8
12
20
26
32
34
36
38
42
50
440
440
440
440
440
440
440
510
510
510
510
$10
$10
92-I-A
B
C
D
E
F
G
2
4
6
8
12
20
28
440
440
440
440
440
440
440
'
'
Gas Flow
R ate SC F/bbl.
$10
$10
$10
$10
$10
$10
1.017
1.017
1.017
1.017
1.017
1.017
4000
4000
4000
4000
4000
4000
81 .3
81.3
81.3
8 1 .3
8 1 .3
81 .3
440
440
440
440
440
440
440
$10
$10
$10
$10
$10
$10
1 .0 4 0
1 .0 4 0
1 .040
1.040
1 .040
1 .0 4 0
1 .040
1 .0$0
1.0$0
1 .0 $ 0
1.0$0
1.0$0
1.0$0
2$00
2$00
2$00
2$00
2$00
2$00
2$00
4000
4000
4000
4000
4000
4000
9 6.7
96 .7
9 6 .7
96 .7
9 6 .7
96 .7
96 .7
9 0 .0
9 0 .0
90.0.
90 .0
9 0 .0
90.0
440
440
440
440
440
440
440
0.960
0 .9 6 0
0 .9 6 0
0 .9 6 0
0 .9 6 0
0 .9 6 0
0.960
2$00
2$00 .
2$00
2$00
2$00
2$00
2$00
'
Charge
Stock
Y ield
P e rc e n t
750
Coker
D is tilla te
750
Coker
D is tilla te
750
Coker D i s t .
9 6 .1
9 6 .1
9 6 .1 ,9 6 .1
9 6 .1
9 6 .1
9 6 .1
P e rc e n t Np
i n E f flu e n t
<
0.32$
0 .$01
0.6$6
0.523
0 .5 3 6
—
1.100
, 1.019
1.020
1.118
1.080
1.170
—
1.074
0 .8 6 4
1.123
0.698
0.673
0.670
0.551
0.578
0.500
0 .5 3 6
0.578
0.583
0.670
-39"
8 9 -H -A
B
C
D
E
F
Space
V e lo c ity
g /g /h r.
TABLE Xl ( c o n t i n u e d )
Sample
No.
Time—Hours
from S ta rtu p
9 2 -II-A
B
C
D
E
F
G
93-I-A
B
C
D
E
F
G
II-A
B
94-1-A
B
C
D
E
F. II-A
B
C
D
E
■
Tem perature
C a ta ly s t
P rh t.
°C.
0C.
Space
V e lo c ity
g /g /h r.
Gas Flow
Charge
R ate SC F/bbl. - Stock
33
35
37
39
43
51
59
• 510
510
510
510
510
510
510
510
510
510
510
510
510
510
0.975
0.975
. 0.975
0.975
0.975
0.975
0.975
2
4
6
"8
12
20
25
33
35
-440
440
440
440
440
440
440
510
510
440
440
440
440
440
440
440
510
510
1.000
1.000
1 .000
1 .0 0 0
1.000
1.000
1.000
1.020
1.020
2500
2500
2500
2500
2500
2500
2500
4000
4000
2
4
6
8
12
20
24
26
28
30
34
440
440
440
440
440
440
510
510
510
510
510
440
440
440
440
440
440
510
510
510
510
510
1.010
1 . 010
1.010
1 .010
1.010
1.010
0.980
0 .980
0 .9 8 0
0 .9 8 0
0.980
2500
2500
2500
2500
2500
2500
4000
4000
4000
4000
4000
‘
4000
4000.
4000
4000
4000
4000
4000
Y ield
P e rc e n t
P e rc e n t No
in E f flu e n t
8 0 .0
8 0 .0
8 0 .0
8 0 .0
8 0 .0
8 0 .0
8 0 .0
0 .1 0 4
0.147
0.203
0 .181
0 .2 0 6
0.210
0 .198
95 .0
9 5 .0
9 5 .0
9 5 .0
95 .0
9 5 .0
9 5 .0
8 5 .0
8 5 .0
0 .576
0.863
0.994
1.038
1.238
1.413
1.528
1 .5 3 8
1.747
9 2 .0
9 2 .0
9 2 .0
9 2 .0
9 2 .0
650
9 2 .0
Coker
8 7 .0
D i s t i l l a t e 8 7 .0
8 7 .0
8 7 .0
8 7 .0
1.629
750
Coker
D is tilla te
750
Coker
D is tilla te
—
—
1.723
— —
1.645
1.128
——
—
1.297
———
1.441
-O iI-
OPERATING CONDITIONS 'AND PRODUCT DATA ON SHALE OIL TREATING
TABLE I I
(c o n tin u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Time—Hours
from S ta rtu p
95-1-4
B
C
D
E
F
G
II-A
B
C
D
E
F
2
4
6
8
12
20
28
39
41
43
45
49
57
96-1-A
B
C
D
E
F
II-A
B
C
D
E
F
2
4
6
8
12
20
27
29
31
33
37
45
‘
' 440
440
440
440
440
440
440
510
510
510
510
510
510
440
440
440
440
440
440
510
510
510
510.
510
510
Space
V e lo c ity
g /g /h r.
Gas Flow
R ate SCF/bbl
440
440
440
440
440
440
440
510
510
510
510
510
510
0.990
0.990
0.990
0.990
0 .9 9 0
0 .9 9 0
0.990
1.010
1.010
1.010
1.010
1.010
1.010
2500
2500
2500
2500
2500
2500
2500
4000
4000
4000
4000
4000
4000
440
440
440
440
440
440
510
510
510
510
510
510
1.000
1 .0 0 0
1.000
, 1 .000
1 .000
1 .000
1 .0 0 0
1.000
1.000
1.000
1.000
1.000
2500
2500
2500
2500
2500
2500
. 4000
4000
4000
4000
4000
4000
Charge
Stock
650
Coker
D is tilla te
650
Coker
D is tilla te
Y ie ld
Perceni
P e rc e n t No
i n E f flu e n t
99 .0
9 9 .0
9 9 .0
9 9 .0
9 9 .0
9 9 .0
9 9 .0
8 5 .0
8 5 .0
8 5 .0
8 5 .0
8 5 .0
8 5 .0
1.136
96 .0
9 6 .0
9 6 .0
9 6 .0
9 6 .0
9 6 .0
8 5 .0
8 5 .0
8 5 .0
8 5 .0
8 5 .0
8 5 .0
1.155
1.212
1.350
1.380
1.474
1.058
1.039
1.419
1.011
1 .071 '
1 .376
1.510
1.090
1.322
1.420
1.483
-TtT-
Sample
No.
Tem perature
C a ta ly s t
P rh t. 0C.
0C.
TABLE I I
(c o n tin u e d )
OPERATING CONDITIONS AND PRODUCT DATA ON SHALE OIL TREATING
Sample
No.
97-1-A
B
C
D
E
F
II-A
B
C
D
E
F
Time—Hours
from S ta rtu p
2
k
.
6
8
12
20
23
25
27
29
33'
41
T em perature
P rh t.
C a ta ly s t
0C.
°C .
440
440
440
440
440
440
510
510
510
510
510
510
440
440
440
440
440
440
510
510
510
510
510
'510
Space
V e lo c ity
g /g /h r.
0 .990
0 .9 9 0
0.990
0 .990
0 .990
0 .990
1.000
1 .0 0 0
1 .0 0 0
1.000
1.000
1.000
Gas Flow
R ate SC F/bbl.
'
■
2500
2500
2500
2500
2500
2500
. 4000
4000
4000
4000
4000
4000
Charge
Stock
\
650
Coker
D is tilla te
Y ield
P e rc e n t
P e rc e n t Ng
in E fflu e n t
95 .0
9 5 .0
9 5 .0
95 .0
95 .0
8 6 .0
8 6 .0
8 6 .0
8 6 .0
8 6 .0
8 6 .0
8 6 .0
1.120
1.108
■1
.1.196
1.230
0.547
0.579
i1
0.652
0.752
.I,..
-4 3 -
TABLE I I I
CATALTSTi ACTIVITY
C a ta ly s t
Run No.
ESO 89
Spence c o b a lt molyb­
d a te , 5/ 32- i n . p e l l e t s
A c tiv ity a t
#1 Op. C o n d itio n
#
A c tiv ity a t
#2 Op. C o n d itio n
#
■ 100
100
71
82
270
ESO 91
L a rg e -p o re c o b a lt
m olybdate
ESO 92
H F -a c tiv a te d c o b a lt
m olybdate
130
ESO 93
Molybdenum s u lf id e
59
ESO 95
P la tin u m (Type 1000)
59
51
ESO 96
MoOo d e p o s ite d on DA-I
c ra c k in g c a t a l y s t .
1 3 .5 # - 8 6 .5 # .
50
37
ESO 97
O ro n ite hydroform ing
c a ta ly s t
66 '
75
O p e ratin g V a ria b le
T em perature
Space v e l o c i t y
Gas r e c y c le
Charge s to c k
°F .
g /g /h r.
SC F/bbl.
c o k er '
d is tilla te
C o n d itio n #1
825
1 .0
2500
750
E .P .
C o n d itio n # 2
950
1 .0
4000 '
750
E.P
-4 4 TABLE IV
RESULTS OF BATCH TREATMENTS OF SHALE OIL
Treatm ent
P ro p e rty
Ng i n e f f l u e n t , %
Charge s to c k , c o k er d i s t i l l a t e
Ng i n charge s to c k , %
T em perature, °C .
C a u s tic
1 ,6 6
750
1 .9 0
450
T e tra lin
1 .8 0
E .P .
750
' 1 .9 0
450
;
■45-
O IL
SUPPLY
PREHEAT
FEED GAS SUPPLY
CATALYST
MAKEUP
GAS SUPPLY
CONDENSER
GAS
COMPRESSION
GAS STORAGE
SIGHT
GLASS
RECEIVER
VENT
F ig u re I .
Block Flow sheet o f H y d ro tre a tin g U n it.
VE1NT
PANEL
VENT
TT R U P T U R E
TO
BOARD
DI SK
PRESSURE
GAGES
VACUUM
AIR
SUPPLY
VENT
MA K E U P
PRESSURE
CONTROLLER
LT__i
C O MP R E S S I O N
OIL R E S E R V O I R
WET TEST
METER
VUIO
COMPRESSION
OIL PUMP
MO
SCRUBBER
RECEIVER
LEGEND
-------------------
l/6f SS
TUBI NG
---------------------R U B B E R
TUBING
--------------- 1/4" c o p p e r TUBING
PIPE
FIG. 2. DETAILEDFLOWSHEET
GAS
SPACE
VELOCITY
-9 V-
SPACE
I- 0 . 5 -
SPACE
TEMPERATURE,
F ig u re 3 .
DEGREES
FAHRENHEIT
N itro g e n Removal a s a F u n c tio n of Tem perature and Space V e lo c ity .
C harge, 750°F E .P . co k er d i s t i l l a t e .
IOOn
-o
0.00
0.25
0.50
SPACE
F ig u re 4 .
0.75
1.00
VELOCITY
Y ield a s a F u n c tio n o f Space V e lo c ity and Charge S to c k .
T em p eratu re, 825°F.
1.0
Iz 0.8 Ui
3
_l
U.
u.
Ul
E 0.6Z
Ui
O
o
OC
f
tZ 0.4 -
lZ
Ui
O
(C
o! 0.2 -
o .o 4 —
o.oo
I
I
I
0.25
0.50
0.75
SPACE
F ig u re 5I
1.00
VELOCITY
N itro g en Renoval a s a F u n c tio n o f Space V e lo c ity and Charge S to ck .
T em perature, 825°F.
-6 V-
0 .3 -
Figxire 6.
N itro g en Removal a s a F u n ctio n o f Space V e lo c ity and E f flu e n t R ecycle.
T em perature, 825°F.
ESO 89
Spence CoMo
5 /3 2 - in . p e l l e t s
ESO 91
L arg e-p o re CoMo
ESO 92
H F -a c tiv a te d CoMo
ESO 93
P t (Type 1000)
PERCENT
-5 0 -
NI TROGEN
IN E F F L U E N T
ESO 95
ESO 96
MoO- on DA-I
c ra c k in g c a t .
ESO 97
O ro n ite hydroform ing
HOURS
F ig u re 7.
ON
S TREAM
N itro g e n Removal a s a F u n ctio n o f On-Stream Hours and C a ta ly s ts
0.40
0.35
----i
0.30
0.25
0.20
0.06
40
PERCENT DISTILLED
F ig u re 8 .
N itro g en P r o f i l e a s a F u n ctio n o f P e rc e n t o f M a te ria l D i s t i l l e d .
S to ck , hyd rogenated 650°F E .P . co k er d i s t i l l a t e .
5 -|
ViT
ro
I
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LN
F ig u re 9 .
0.5
CONCENTRATION
R ea c tio n fim e a s a F u n c tio n o f th e Logarithm of th e
C o n c e n tra tio n of N itro g e n in th e E f f l u e n t .
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1.0
I- 0.8 z
Ui
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I
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H
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Z
50
Ui
O
ESO 4 9
CK
Ui
0-2
-
N ote: ESO 49 and 50 - l / 1 6 - i n . CoMo p e l l e t s
ESO 41
- l / 8 - i n . CoMo p e l l e t s
0.0
JQ
2 0
30
HOURS
F ig u re 10.
ON
40
50
STREAM
N itro g en Removal a s a F u n ctio n o f Time f o r Runs
Made Under I d e n t i c a l C o n d itio n s .
60
3
762 1001 4777 4
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McKee, A. F .
C a ta ly tic h y d ro tre a tin g of
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