Catalytic hydrotreating of shale-oil coker distillate
by Russell J Holecek
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 Russell J Holecek (1955)
Abstract:
An investigation was conducted to determine what effect the concentration of hydrogen in the treating
gas would have when hydrotreating a Colorado shale-oil. coker distillate using a bench-scale,
continuous-flow, fixed-bed, catalytic process unite A nominal 650°F E.P. .coker distillate from
gas-combustion crude shale oil was treated with hydrogen-methane mixtures varying from 100 percent
to 30 percent hydrogen under, the following conditions: space velocity - 1.0 grams of oil per gram of
catalyst per hour, temperature - 440°C, pressure - 1000 psig, gas flow rate - 7500 SCF/bbl, catalyst 100 grams of "l/8-in. Harshaw cobalt molybdate pellets. When.changing recycle gas (hydrotreating
gas) from one composition to another, twelve hours -Iineout time were found necessary to reach
equilibrium conditions. Catalyst activity did not change appreciably during on-stream times of 200
hours or less." It did, however, decline slightly as the hydrogen content of the recycle'gas decreased.
In the range 30-100 mol percent hydrogen, sulfur removal from the charge stock varied linearly in
direct proportion to the hydrogen"content, of the recycle gas. The regression equation for this
relationship is Y ' . ¦ S = 0.305 H + k where S is the percent sulfur removed from the charge stock, H is
the mol percent hydrogen in the recycle gas, and k is ah" intercept dependent upon physical
characteristics of the reaction system. In the same range of gas concentration, nitrogen removal from
the charge stock obeys the same type relation and follows the equation: N = 0.523 H + k' where N is
the percent nitrogen removed from the charge stock, H is the mol percent hydrogen in the recycle gas,
and k' is an intercept dependent upon the physical characteristics of the reaction system.
No correlation was found between product boiling range and recycle gas hydrogen content.
At 1000 psig and 440°C with a space velocity of 1.0 gm/gm hr, a gas flow rate of 7300 SCF/bbl, cobalt
molybdate catalyst, and pure-hydrogen recycle gas, sulfur in the coker distillate charge stock was
reduced from 0.63.percent to 0.049 percent and nitrogen was reduced from 1.65 percent to 0.410
percent. Color stability of the oil was improved, but the sample still discolored on standing. CATALITIC HIDROTEEATINC OF SHALE-OIL
COKER DISTILLATE
by
RUSSELL J» HOLECEK
A THESIS
Subm itted to 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 deg ree of
M aster of S cience i n Chem ical E n g in ee rin g
at
Montana S ta te C o lleg e
Approved:
Bozemanl9 Montana
O ctober5 1955
TABLE OF CONTENTS
page
ABSTRACT...........................................................................................................................................
I
I n tr o d u c tio n ....................................................................................................................... I;
II
E q u ip m e n t...................................................................................................................... ......
III
17
A.
Flow S h e e ts ......................................................................................................... ......
B.
S p e c if ic a t io n s .
..............................................................................................
9
T e s ts , P ro c e d u re s, and M a te r ia ls . . ................................................................ 12
A.
T e s t s ...................................................................................................................... .....
B.
P ro c e d u re s ............... ..............................................................................................12
C.
M a te ria ls ..............................
Sample C a lc u la tio n s
15
.........................................................................................
V
E xperim ent D esign .
VI
D isc u ssio n of R e s u lts ............................... . . . . . . . .
.1 5
.............................................................................................. 18
....................... 19
A.
L in eo u t Time........................................................................................................
19
B.
C a ta ly s t O r ie n ta tio n .......................................................................................... 20
C.
C a ta ly s t A c t i v i t y ...............................................................................................20
D.
S u lfu r and N itro g en R e m o v a l..................................................
E.
B o ilin g Range of P ro d u c t.................................................................................... 23
21
V II
Summary ..............................................................................................................................23
V III
Acknowledgment.....................................................................
2k
IX
B ib lio g ra p h y ........................................................
25
X
Appendix................................... .................................................................. . . . . 2 6
-3 -
ABSTRACT
An i n v e s t ig a ti o n was conducted to d eterm in e w hat e f f e c t th e concen­
t r a t i o n of hydrogen in th e t r e a t i n g gas would have when h y d r o tr e a tin g a
C olorado s h a l e - o i l c o k er d i s t i l l a t e u s in g a b e n c h - s c a le , c o n tin u o u s -flo w ,
f ix e d - b e d , c a t a l y t i c p ro c e s s u n ite
A nom inal 65>0°F E6P . .coker d i s t i l l a t e from g as-co m b u stio n crude s h a le
o i l was t r e a t e d w ith hydrogen-m ethane m ix tu re s v a ry in g from 100 p e rc e n t
to ^O p e r c e n t hydrogen under, th e fo llo w in g c o n d itio n s : sp ace v e l o c i t y IeO grams o f o i l p e r gram o f c a t a l y s t p e r h o u r, te m p e ra tu re r IjljD0C,p re s s u re - 1000 p s ig , gas flo w r a t e - 7^00 SG F/bbl, c a t a l y s t - 100 grams
o f " l / 8- i n . Harshaw c o b a lt m olybdate p e l l e t s * "When.changing re c y c le gas
( h y d r o tr e a tin g g as) from one co m p o sitio n to a n o th e r , tw elv e h o u rs - I in e o u t
tim e w ere found n e c e s s a ry to re a c h e q u ilib riu m c o n d itio n s . C a ta ly s t
a c t i v i t y d id n o t change a p p re c ia b ly d u rin g o n -s tre a m -tim e s o f 200 h o u rs
o r l e s s , " I t d id , how ever, d e c lin e s l i g h t l y a s th e hydrogen c o n te n t of th e
r e c y c le gas d e c re a se d ,
I n . th e ran g e 50-100 mol p e rc e n t h y d ro g en , s u l f u r rem oval from th%
ch arg e s to c k v a r ie d l i n e a r l y in d i r e c t p r o p o r tio n to th e hydrogen," content,
o f th e re c y c le g a s . The r e g r e s s io n e q u a tio n f o r t h i s r e l a t i o n s h i p i s : "
S = 0 .305 H + k ■
w here S i s th e p e rc e n t s u l f u r removed from th e ch arg e s to c k , H i s th e mol
p e r c e n t hydrogen in th e re c y c le g a s , and k i s a n " in te r c e p t d ependent upon
p h y s ic a l c h a r a c t e r i s t i c s of th e r e a c tio n system . In th e same ran g e of
gas c o n c e n tr a tio n , n itr o g e n rem oval from th e charge s to c k obeys th e same
ty p e r e l a t i o n and fo llo w s th e e q u a tio n :
N = 0.523 H + k '
w here N i s th e p e rc e n t n itr o g e n removed from th e charge s to c k , H i s th e
mol p e rc e n t hydrogen in th e re c y c le g a s , and k* i s an i n t e r c e p t dependent
upon th e p h y s ic a l c h a r a c t e r i s t i c s o f th e r e a c tio n system ,
No c o r r e l a t i o n was found betw een p ro d u c t b o ilin g ra n g e and r e c y c le
gas hydrogen c o n te n t,
At 1000 p s ig and UUQ0C w ith a space v e l o c i t y of 1 .0 gm/gm h r , a. gas
flo w r a t e o f 7500 SG F/bbl, c o b a lt m olybdate c a t a l y s t , and pu re-h y d ro g en
re c y c le g a s , s u l f u r in th e c o k er d i s t i l l a t e charge s to c k was reduced from
0, 6 3 .p e r c e n t to 0. 0U9 p e r c e n t and n itr o g e n was red u ced from 1 ,6 5 p e rc e n t
to O.UlO p e r c e n t. C o lo r s t a b i l i t y o f th e o i l was im proved, b u t th e sample
s t i l l d is c o lo r e d on s ta n d in g .
I
INTRODUCTION
" In 15>ii8 th e U nited S ta te s became a n e t im p o rte r o f o i l ." 1
These
w o rd s, sounded by an o f f i c i a l o f th e U n ited S ta te s Bureau o f M ines, a re
a w arning f o r a l l to h e a r t h a t a tim e w i l l come when th e n a t i o n 's p e t r o l ­
eum r e s e r v e s w i l l be e x h a u ste d .
T hat tim e i s n o t th e p r e s e n t -
our
n a t i o n 's known r e s e r v e s a re g r e a te r th a n e v e r b e fo re and have been in ­
c re a s e d e v e ry y e a r f o r s e v e r a l decades a t a r a t e g r e a t e r th a n th e n a t i o n 's
consum ption r a t e .
In s p i t e of se v e n ty y e a rs w arn in g s t h a t o u r p etro leu m
r e s o u rc e s w ill, soon be e x h a u ste d , th e tim e must come when th e n a t i o n 's
p e tro le u m consum ption w i l l exceed t h a t a v a il a b le .
Then we w i l l be fa c e d
w ith th e p ro s p e c t of im p o rtin g o i l o r d e v elo p in g o th e r so u rc e s bf hydro­
carbon f u e l s .
A lthough atom ic power c o m m e rc ia liz a tio n w i l l u n d o u b ted ly
r e l i e v e some o f th e demand f o r hydro carb o n f u e l s , th e in c re a s e d a p p li­
c a tio n o f p e tro le u m to u s e s o th e r th a n f u e l s , e . g . , p e tro c h e m ic a ls ,
n e g a te s any p o s s i b i l i t y o f a le s s e n in g i n th e demand f o r p e tro le u m .
The C ongress of th e U n ited S t a t e s , c o n tem p latin g th e im portance o f a
lo n g -te rm ■su p p ly o f l i q u i d f u e l s , p a sse d th e S y n th e tic L iq u id F u e ls Act
o f 19i|U w hich a u th o riz e d r e s e a r c h and developm ent work on new so u rces of
o i l - c o a l, o i l s h a le , and a g r i c u l t u r a l and f o r e s t r y p r o d u c ts .
The developm ent of l i q u i d f u e l s from o i l s h a le would seem to have
g r e a t p o t e n t i a l , f o r b e n e a th th e Green R iv e r p la te a u o f C o lo rad o , U tah,
Wyoming and Idaho l i e s an o i l ' sh a le bed c o n ta in in g an e s tim a te d £00
b i l l i o n b a r r e l s o f o i l - more th a n our n a t i o n 's t o t a l p ro v en p etro leu m
re serv e s.
The p r i n c i p a l p a r t of t h i s b e d , th e P ican ce C reek B asin of
1R eferen ce 8 , p . I .
-
5
-
n o rth w e s te rn C olorado, e x te n d s over 1000 sq u are m ile s , i s £00 f e e t t h ic k ,
and h as an e s tim a te d r e s e r v e of 3^0 b i l l i o n b a r r e l s .
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 led g e and a ss a y s 30 g a llo n s
o f o i l p e r to n , o r a b o u t tw ic e t h a t o f th e r e s t of th e d e p o s it .
The e s t i ­
mated re s e r v e o f th e Mahogany le d g e ' i s 100 b i l l i o n b a r r e l s .
A lthough o i l p ro d u c tio n from o i l s h a le a n te d a te s th e p ro d u c tio n o f ■
o i l from w e lls by a b o u t tw en ty y e a r s , th e s h a le o i l in d u s tr y was u n ab le to
s u rv iv e c o m p e titio n from c o n v e n tio n a l p e tro le u m .
Those few p la n ts t h a t
s u rv iv e d p r i o r to World War H w ere lo c a te d in S c o tla n d , E s to n ia , and
M anchuria ( I ) ,
W ith th e p assag e o f th e S y n th e tic L iq p id F u e ls Act of 1.9kk, th e
U n ite d S ta te s Bureau o f M ines, to g e th e r w ith c o o p e ra tiv e r e s e a r c h g ro u p s,
s e t o u t t o develop an econom ical method f o r m ining and r e t o r t i n g C olorado
s h a le , to in v e s t ig a te th e p r o p e r tie s o f s h a le o i l , and to d ev elo p s u ita b le
and econom ical r e f in in g te c h n i q u e s 'f o r s h a le o i l .
M ining
At R i f l e , C olorado, a ro o m -a n d -p illa r method o f m ining u s in g
la r g e m echanized equipm ent h a s been d ev elo p ed -an d can now produce o i l s h a le
f o r 32 c e n ts /to n d i r e c t c o s t ( 2 ) ,
In t h i s m ethod, rooms 7 0 - f t h ig h and
60- f t sq u are a re q u a rrie d i n th e s h a le bed le a v in g tw e n ty -fiv e p e rc e n t o f
th e o r i g i n a l s h a le a s s u p p o rtin g p i l l a r s , ' Broken s h a le i s h a u le d .to th e
mine e n tra n c e where i t may be conveyed to c ru sh in g and r e t o r t i n g f a c i l i t i e s .
R e to r tin g
R ecent r e t o r t d e sig n s have p ro g re s se d from th e B u reau 's
ECU r e t o r t , a b a tc h - ty p e u n i t , to c o n tin u o u s gas com bustion system s of th e
Bureau and Union O il Company, . S ta n d a rd O il Development Company (now E sso
R esearch and E n g in ee rin g C o,) worked on a f l u i d i z e d r e t o r t d e s ig n .
The gas
-
6-
com bustion r e t o r t , seems to be q u ite s u c c e s s f u l and b o th Union O il Company
and th e Bureau have com m ercial desig n s*
P r o p e r tie s
In general",- crude s h a le o i l i s a b la c k , waxy l i q u id
h av in g a g r a v i t y o f a b o u t 21° A P I'a n d , because o f i t s h ig h wax c o n te n t, a
p o u r p o in t o f 90°Fo
"S h ale o i l i s composed o f h y d ro carb o n ?, as w e ll as
l e s s e r amounts o f s u l f u r , n itr o g e n , and oxygen compounds.
I t d i f f e r s from
p e tro le u m in t h a t a la r g e p ro p o r tio n o f th e h y d ro carb o n s a re o l e f i n i c and '
t h a t th e nonhydrocarbon c o n s titu e n ts ' a re p r e s e n t in l a r g e r am ounts.
P a r a f f i n s and o l e f i n s in s h a le o i l naphtha w ere found to be p re p o n d e ra n tly
o f th e s t r a i g h t c h a in ty p e , th u s a c c o u n tin g f o r th e low o c tan e r a t i n g o f '
s h a le o i l g a s o lin e .
b o ilin g p o i n t .
A ro m a tic ity o f s h a le o i l in c r e a s e s w ith in c re a s e in
-"Tar a c id s p r e s e n t in s h a le o i l w ere shown t o c o n ta in
p h e n o l, th e c r e s o l s , and some x y le n o ls "while th e t a r b a se s p r e s e n t c o n ta in
,s u b s tit u te d p y rid e n e s and q u in o lin e s .
Most o f th e s u lf u r in s h a le o i l i s
p r e s e n t in th e form o f s u b s tit u te d th io p h e n e s ." 2
In a d d itio n , th e Bureau
o f Mines h a s found t h a t th e NTU cru d e h a s an approxim ate m o le c u la r w eig h t
o f 320 and t h a t n itr o g e n compounds com prise k3 p e r c e n t o f NTU gas o i l
(623 - IlOO0F . ) .
U n tre a te d s h a le o i l and i t s d i s t i l l a t e s do n o t make s a t i s f a c t o r y
l i q u i d f u e l s becau se of t h e i r h ig h s u l f u r c o n te n t, h ig h n itr o g e n c o n te n t,
u n s a tu r a ti o n , low o c tan e ( f o r g a s o li n e ) , c o lo r i n s t a b i l i t y , and h ig h gum
c o n te n t.
S u lf u r i s o b je c tio n a b le becau se i t s compounds have o b je c tio n a b le
o d o rs , a re c o rro s iv e o r p o t e n t i a l l y c o r r o s iv e , have p o o r c o lo r s t a b i l i t y ,
^R eferen ce 8 , p . h7
^R eferen ce 8 , p . h 8
■
-7 -
and g iv e o f f a c r i d fumes when b u rn ed ,
U n sa tu ra te d compounds, w h ile im- .
p ro v in g o ctan e r a t i n g o f g a s o lin e , a re v e ry prone to o x id a tio n and a re
p o te n t gum fo rm e rs .
N itro g e n i s u n d e s ir a b le in t h a t i t i s a t l e a s t
p a r t i a l l y r e s p o n s ib le f o r gum fo rm a tio n ( 8 ) ,
S ince c o lo r d e g re d a tio n
accom panies gum fo rm a tio n i t i s u n d e s ir a b le n o t so much f o r i t s e l f a s f o r
th e gum t h a t o c cu rs w ith i t .
V ery d a rk c o lo rs a re b a d , how ever, because
th e y c an n o t be masked and th e buying p u b lic w ants a p ro d u c t t h a t resem bles
t h a t to w hich th e y a re accustom ed.
R e fin in g
In t h e i r in v e s t ig a ti o n o f s u ita b le r e f i n i n g p ro c e ss e s f o r
s h a le o i l , th e Bureau o f Mines t r i e d m ost p e tro le u m r e f i n i n g p ro c e s s e s ,
in c lu d in g v is - b r e a k in g , c o 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 , r e c y c le
c h ec k in g , c a t a l y t i c c ra c k in g , chem ical t r e a t i n g , s o lv e n t e x tra c tio n ^ ' and
h y d r o tr e a tin g , - S ince p r e lim in a ry s tu d ie s re v e a le d t h a t "n itro g e n compounds
accounted, f o r k3 p e r c e n t o f NTU gas o i l and s in c e a s im ila r 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 compounds, i t becomes n e c e s s a ry to remove o n ly
th e n itr o g e n and s u l f u r , and n o t t h e i r compounds, i f re a s o n a b le f u e l y i e l d s
a re to be o b ta in e d .
In a d d itio n , s in c e n itr o g e n i n h i b i t s th e a c t i v i t y o f
c ra c k in g c a t a l y s t s and s in c e c ra c k in g p ro c e s s e s appeah n e c e s s a ry to in ­
c re a s e g a s o lin e y i e l d s , n itr o g e n would have to be removed p r i o r to a
c a t a l y t i c c ra c k in g o p e r a tio n .
F u r th e r , s in c e o x id a tio n o f u n s a tu r a te s r i n
th e o i l p ro b a b ly a c c o u n ts f o r some o f th e c o lo r d e g re d a tio n , s a tu r a ti o n
o f th e s e compounds would be d e s ir a b le .
H y d ro tre a tin g o r h y d ro g e n a tio n i s a p ro c e s s w hich m eets m ost of th e
re q u ire m e n ts s e t f o r t h „in th e p re c e d in g p a ra g ra p h f o r a s u c c e s s f u l r e f i n ­
in g p r o c e s s .
In view of t h i s , th e Bureau o f l i n e s d ir e c te d many of t h e i r
«—8—
e f f o r t s tow ard in v e s t ig a ti n g t h i s p ro c e s s and i t s a p p lic a tio n .
Most o f
t h e i r work was done on n a p h th as and gas o i l s from NTU and e n tra in e d s o lid s
re to rtin g (9 ).
The NTU crude c o n ta in e d v e r y l i t t l e g a s o lin e and about
5>0 p e r c e n t .n o n d i s t i l l a b l e residuum .
made i n th e ran g e 5OO-I^OO p s ig .
3000 p s ig .
I n i t i a l h y d r o tr e a tin g s tu d ie s were
L a te r s tu d ie s were made from 1000 to
At th e lo w er p r e s s u r e s n itr o g e n was red u ced from around 1 .6
p e rc e n t to O0US-O03!? p e r c e n t and h ig h p r e s s u r e ru n s w ere s u c c e s s fu l in
re d u c in g n itr o g e n to l e s s th a n 0 .1 p e r c e n t in th e g a s o lin e f r a c t i o n .
A lthough th e l a t t e r g a s o lin e was qjuite s t a b l e , i t s o c tan e r a t i n g was about
U6.'
Inasmuch as s h a le o i l i s o f i n t e r e s t to a l l m ajor o i l com panies a s .a
f u tu r e so u rc e o f hydrocarbon f u e l s , th e Esso R esearch and E n g in eerin g
Company ag reed to sp o n so r a re s e a rc h p r o j e c t a t Montana S ta te C o lleg e to
d ev elq p an econom ical p ro c e s s f o r making g a s o lin e o r d i e s e l f u e l , o r b o th ,
from ^jhale o i l .
The p la n f o r th e i n i t i a l p a r t of th e r e s e a r c h h as been
to in v e s t ig a te lo w -p re s su re h y d r o tr e a tin g of s h a l e - o i l c o k er d i s t i l l a t e
u s in g hydrogen d i lu te d w ith methane as a t r e a t i n g g a s.
c o n s id e r a tio n w ere 300 p s ig and 1000 p s ig .
-
P ressu res^ u n d e b
King (3 ) r e p o r te d o n "th e p e r ­
form ance o f f o u r c a t a l y s t s u se d f o r h y d r o tr e a tin g co k er d i s t i l l a t e charge
s to c k s u s in g a 63 p e r c e n t hydrogen - 33 p e r c e n t methane m ix tu re as re c y c le
g as.
T h is p a p e r d is c u s s e s an in v e s t ig a ti o n o f th e e f f e c t o f r e c y c le gas
co m p o sitio n on h y d r o tr e a tin g s h a l e - o i l c o k er d i s t i l l a t e a t 1000 p s ig and
UUO0C w ith a c o b a lt m olybdate c a t a l y s t .
7'.
II
A0
Elotr S h e e t,
.-EQUIPMENT
In a n t i c i p a t i o n o f re s e a rc h in v e s tig a tio n s , in v o lv ­
in g h y d ro g e n a tio n and o th e r p ro c e s s e s a t v a rio u s p r e s s u r e s and te m p e ra tu re 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 w ith a gas re c y c le
p ro v is io n was d esig n ed and b u i l t .
A b lo c k flo w diagram o f th e p ro c e ss
u n i t i s shown in F ig , I and a d e t a i l e d flo w s h e e t o f th e u n i t i s shown in
F ig . 2 .
'In t h i s 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 i s pumped to th e
to p o f th e r e a c to r whence i t flo w s downward th ro u g h a p r e h e a t s e c tio n con­
ta in in g alundurti b a l l s and th e n ce over a c a t a l y s t bed.
I t th e n flow s
th ro u g h a condenser to 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
I
r e c e iv e r a t atm o sp h eric p r e s s u r e .
The h y d r o tr e a tin g gas flo w s from a fe e d
c y lin d e r th ro u g h a n e e d le v a lv e and ro ta m e te r t o th e to p o f th e r e a c t o r
and th e n ce down th ro u g h th e p re h e a t and c a t a l y s t s e c tio n s t o th e co n d en ser
and o u t th ro u g h th e diaphragm p r e s s u r e - c o n tr o l v a lv e to a s to ra g e ta n k .
I f th e h y d r o tr e a tin g gas i s re c y c le d i t flo w s from th e s to ra g e ta n k to a
com pression ta n k and i s th e n d is p la c e d w ith o i l to f o r c e i t in to th e fe e d
ta n k ,
B.
S p e c if ic a tio n s
R e a c to r:
The r e a c t o r was made from an 1 8 - in . le n g th o f 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 .
18-8 s t a i n l e s s s t e e l .
p s i.
End b lo c k s w ere machined from
Maximum o p e ra tin g p r e s s u r e f o r th e r e a c t o r i s 3000
See F ig u re s 3 and b f o r d e t a i l s on r e a c t o r c o n s tr u c tio n .
T h re e .
nichrdm e h e a tin g c o i l s w ere wound on th e r e a c t o r * , The to p and bottom c o i l s
w ere 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-bead
s tru n g c o i l s w ere f i r s t wrapped over a l a y e r o f a s b e s to s t a p e , th e n
-1 0 -
COTered w ith a second l a y e r o f a s b e s to s ta p e and f i n a l l y in s u la te d w ith
a b o u t one in c h o f 8g p e r c e n t m agnesia,
A ^ - 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 in th e r e a c t o r ,
V1
O il fe e d r e s e r v o i r :
The o i l fe e d r e s e r v o i r was made from a 2 - i n , ,
sch e d u le IiO;, b la c k —ir o n p ip e 21—in , lo n g .
nichrom e h e a tin g c o i l and la g g ed w ith
I t was wound w ith a 10—f t
i n , of 85. p e rc e n t m agnesia,
A
5 0 -ec b u r e t t e was a tta c h e d th ro u g h a s id e arm to in d ic a te o i l l e v e l in
th e r e s e r v o i r * .
Sedim ent bowl:
A s ta n d a rd a u to m o b ile -ty p e sedim ent bow l.
O il fe e d pump: ■ A H ills-M cCanna h ig h -p r e s s u re p ro p o r tio n in g pump w ith
a
in* p i s to n .
C ondenser:
A l 6- i n . le n g th o f I - i n , , sch e d u le 80, b la c k - ir o n p ip e
su rrounded b y a 2—in * , sch e d u le 1| 0 , b la c k —ir o n p ip e a c tin g a s a w a te r
ja c k e t*
S ig h t g la s s e s :
E ig h t-in c h Jerg u so n s i g h t g la s s e s w ith ! - i n , s ta n d a rd
p ip e taps*
C a p a c ity ta n k :
A 2—in * , sch e d u le
......... P r e s s u r e c o n tr o l v a lv e t
l6o, b la c k —ir o n
p ip e , 9 !—in , long*
An a i r - t o - c l o s e , ! - i n . , M ason-N ielan d ia ­
phragm v a lv e .
P ressu re c o n tro lle r:
A r e v e r s e - a c tin g F is h e r W izard p re s s u re con­
t r o l l e r w ith a 5000 p s i Bourdon tube*
R o tam eters:
Brooks armored ro ta m e te rs w ith 3 /3 2 -in . b a lls *
Autotransformers:
Two 220 v . P o w e rs ta ts f o r ' th e 3 3 - f t r e a c t o r c o i l s
and one HO v . P o w e rs ta t f o r th e 2 8 - f t r e a c t o r c o i l .
O il pump f o r th e g as reco m p ressio n system :
*
A Pesco #051012-020 g e a r
-1 1 -
pmnp r a te d a t be!? g a l/m ln a t 2800 rpm and 1200 p sio
P ressu re lim it fo r
c o n tin u o u s o p e ra tio n i s 1200 p si«
Gas c y lin d e r s :
H a rris b u rg S te e l Gorpe c y lin d e r s , two 1320-cu i n .,,
and one 26^ 0- c u i n . c a p a c ity .
Com pression o i l r e s e r v o i r :
High p r e s s u r e pip in g ;-
Schedule 80 b la c k - ir o n .
High p r e s s u r e p ip e f i t t i n g s :
Low p r e s s u r e p ip in g :
High p r e s s u r e tu b in g :
Low p r e s s u r e tu b in g :
High p r e s s u r e v a lv e s :
M etering v a lv e s :
Gas m e te r:
Gages:
Two 5 - g a l o i l c an s.
Henry Vogt 3000 p s i fo rg e d s t e e l .
Schedule W b la c k - and g a lv a n iz e d -iro n .
Type 30lt SS, l / 8- i n . OB, 0 .0 2 0 - in . w a ll.
Copper, l / l |.- in . OB.
Hoke SS b lu n t- s p in d ie n e ed le v a lv e s .
Hoke b ra s s -b o d y , 20 tu rn - to -o 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 e s t M eter.
M a rsh a ll 2000 p s i .
Therm ocouples:
Three ir o n - c o n s ta n ta n .
Tem perature in d ic a to r :
A Leeds and N orthrup 1 8 -p o in t in d ic a tin g
p o te n tio m e te r.
R upture d is k :
Scrubberstr
A B lack, S i v a l l s , and Bryson I4.200 p s i d is k .
One l i t e r E rlenm eyer f l a s k s .
/
-1 2 -
III
A*
TESTS, PROCEDURES, AND MATERIALS
T e s ts
S u lf u r a n a ly s e s :
These a n a ly s e s w ere perform ed a cc o rd in g to ASTM
D90-50T w ith th e a i r su p p ly m o d ified so t h a t a i r was drawn from atm osphere
o u ts id e th e la b o ra to ry *
O il sam ples w ere washed once w ith an e q u a l volume
o f 7o5> p e r c e n t NaOH, th r e e tim e s w ith an e q u a l volume of d i s t i l l e d w a te r ,
and th e n d r ie d ! - h o u r w ith GaCl2 p r i o r to b u rn in g .
N itro g e n a n a ly s e s :
N itro g e n s were d eterm in ed by a m o d ified K je ld a h l
method d e s c rib e d i n A n a ly tic a l C hem istry (U ),
O il sam ples w ere washed
once w ith an e q u a l volume o f d i s t i l l e d w a te r and d rie d w ith CaCl2 b e fo re
b e in g a n a ly z e d .
P ro d u c t d i s t i l l a t i o n :
API g r a v ity :
Perform ed' a c c o rd in g to ASTM D86-£[|.,
S p e c if ic g r a v ity was determ in ed w ith a W estphal b a lan c e
and th e n c o n v e rte d to 0API by form ula,Gas a n a ly s e s :
Be
D eterm ined by lo w -te m p e ra tu re r e c t i f i c a t i o n .
P ro c e d u re s
R e a c to r assem bly:
W ith th e r e a c t o r su p p o rte d in an in v e rte d
p o s i t i o n , 1/V - in . alundum b a l l s were p o ured in to th e r e a c t o r u n t i l i t was
a b o u t tw o - th ir d s f u l l .
Next 100 grams o f c a t a l y s t were p o ured i n and th e n
th e rem ain in g space was f i l l e d w ith alundum b a l l s .
T h is scheme p la c e d th e
c a t a l y s t bed in th e m iddle of th e lo w e st r e a c t o r h e a tin g c o i l .
The r e -
a c t o r was ta p p ed w ith a hammer d u rin g th e f i l l i n g o p e ra tio n to m inim ize
I
v o id sp ac e . A s t a i n l e s s s t e e l sc re e n was p la c e d in th e u n io n a t th e
bottom o f th e r e a c t o r to keep th e b a l l s from f a l l i n g o u t when th e r e a c to r
was r ig h t e d . . The r e a c t o r was' th e n s e t i n p la c e and th e n e c e s s a ry l i n e s
-1 3 -
•were co n n ected to it*
Thermocouple^ were in s e r te d in th e therm ow ell to
re a d te m p e ra tu re s in th e m iddle o f th e f i r s t p re h e a t s e c tio n , th e second
p re h e a t s e c tio n , and th e c a t a l y s t se c tio n *
S ta rt-u p ?
W ith th e r e a c t o r in p la c e th e r e a c t o r , c o n d en se r, and
s i g h t - g l a s s s e c tio n s o f th e u n i t were ev ac u a ted and th e n p r e s s u r iz e d w ith
hydrogen*
The r e a c t o r was th e n h e a te d -to o p e ra tin g te m p e ra tu re over a
tw o-hour p e r io d .
When th e c a t a l y s t te m p e ra tu re reach ed UOO0G5 gas flo w
was s t a r t e d th ro u g h th e system and o i l flo w was s t a r t e d when th e c a t a l y s t
te m p e ra tu re re a c h e d UUO0G*
O peration?
T em peratures were c o n tr o lle d by a d ju s tin g power in p u t t o
th e r e a c t o r h e a tin g c o i l s w i t h ■a u to tra n sfo rm e rs *
The f i r s t p re h e a t s e c tio n
was h e ld a t 32d - 3U0°G; th e second p r e h e a t s e c tio n was h e ld a t UBS0Cj and
th e c a t a l y s t s e c tio n was h e ld a t UU0°C.
Space v e l o c i t y was c o n tr o lle d by
m easuring th e v o lu m e tric o i l fe e d r a t e and th e n a d ju s tin g th e s tro k e of
th e fe e d pump u n t i l th e d e s ir e d r a t e was a t t a i n e d .
At th e b e g in n in g and
end of a sample p e rio d th e o i l l e v e l in th e s i g h t - g l a s s above th e p ro d u c t
r e c e iv e r was d ra in e d down to a l i n e and th e o i l fe e d r e s e r v o i r was f i l l e d
to th e z e ro on th e b u r e t t e .
The charge b o t t l e was w eighed
a f t e r each
a d d itio n and th e w e ig h t of o i l added was o b ta in e d by th e d if f e r e n c e .
o i l sample ta k en from th e r e c e iv e r was w eighed and b o t t l e d .
The
When p re s s u re
in th e gas fe e d c y lin d e r became to o low. to f o r c e gas th ro u g h th e r e a c t o r ,
gas in th e s to ra g e c y lin d e r was recom pressed to th e fe e d c y lin d e r .
S ince
th e r e a c tio n u n d e r s tu d y consumed hydrogen and l i b e r a t e d m eth an e, enough
re c y c le gas was purged to remove a l l methane l i b e r a t e d and enough hydrogen
was added to make up f o r t h a t consumed p lu s t h a t l o s t b y purging*
These
•
i
p u rg e s and a d d itio n s were made b e fo re each re co m p ressio n o f th e re c y c le
gas*
Purged gas was drawn o f f th e s to ra g e c y lin d e r , scru b b ed , and m etered
b e fo re v e n tin g *
Hydrogen was added to th e com pression c y lin d e r v ia th e
makeup ro tam eter*
Shut—down?
To s h u t th e u n i t down, th e o i l fe e d pump was tu rn e d o f f ,
th e r e a c t o r h e a te r s w ere tu rn e d o f f , and gas flo w was c o n tin u e d f o r an
a d d itio n a l h o u r, th e n s h u t o f f .
Gas sam pling::
A fte r p u rg in g th e l i n e th ro u g h which th e sample was
to be draw n, th e sample was c o lle c te d o v e r w a te r in 8- l i t e r g la s s b o t t l e s .
Gas makeup:
S ince v a rio u s r e c y c le gas m ix tu re s w ere t o be used in
t h i s r e s e a r c h , i t was d e cid e d to make them up a s needed from s to c k hydro­
gen and m ethane,
When making up a new c y lin d e r of a p a r t i c u l a r gas m ix tu re ,
th e c y lin d e r was f i r s t ev ac u a ted and th e n f i l l e d by m e te rin g v ia a r o ta ­
m e te r s u f f i c i e n t q u a n t i t i e s of hydrogen and methane to make a m ix tu re o f
th e d e s ir e d c o m p o sitio n .
When a gas m ix tu re was to be made up to a
p r e s s u r e g r e a t e r th a n t h a t d e liv e r a b le by th e diaphragm r e g u la to r used pn
th e hydrogen and methane ta n k s , th e gas was f i r s t m etered t o th e compres­
s io n c y lin d e r and th e n pumped to . th e fe e d c y lin d e r .
M ixing o f the. g ases
was accom plished by a llo w in g them to expand in to th e com pression c y lin d e r
and th e n pumping them back to th e fe e d c y lin d e r .
When th e fe e d c y lin d e r
a lre a d y c o n ta in e d a gas o f g iv en co m p o sitio n and a d i f f e r e n t com p o sitio n
was d e s ir e d , th e s ta n d a rd c u b ic f e e t o f each gas p r e s e n t wpre computed
assum ing i d e a l gas b e h a v io r.
Then th e amount of hydrogen o r methane
n e c e s s a ry t o a d ju s t th e co m p o sitio n t o th e d e s ir e d v a lu e was m etered in to
th e com pression c y lin d e r and pumped t o th e fe e d c y lin d e r .
I f -the gas was
-1 5 -
b e in g made up in th e s to ra g e c y lin d e r , a s im ila r p ro ced u re was fo llo w e d .
Ge
M a te ria ls
The s h a le o i l used in t h i s re s e a rc h was a nom inal 65o°F EeP0 coker
d i s t i l l a t e produced by re c y c le delay ed coking o f gas com bustion crude
s h a le o i l .
T his coker d i s t i l l a t e was s u p p lie d by th e TI, S . Bureau of
Mines d e m o n stra tio n p la n t a t R i f l e , C o lo rad o .
L a b o ra to ry in s p e c tio n d a ta
f o r t h i s charge s to c k a re g iv en in T able I .
Hydrogen used f o r making up gas m ix tu re s was s u p p lie d b y th e lh itm o re
Oxygen Company o f S a l t Lake C ity , Utah*
M ethane, com m ercial g ra d e , was
su p p lie d by th e M atheson Company.
P e l l e t i z e d c o b a lt m olybdate c a t a l y s t made by th e Harshaw Chemical ■
Company, d e s ig n a tio n Co-Mo 0 2 0 1 -T -1 /8 ", was used f o r t h i s s tu d y .
One-
e ig h th in ch p e l l e t s were used*
The alundum b a l l s used f o r p re h e a t and c a t a l y s t s u p p o rt were J - i n .
sp h e re s s u p p lie d by th e N orton A brasive Company.
IV
Y ie ld :
SAMPLE CALCULATIONS
(ESO lpLTA)
Grams o i l charged
Grams o i l p ro d u c t
L oss, grams
Y ie ld :
Space v e l o c i t y :
ItlO.O
396.7
13*3
396.7/klO .O = 96. 7#
(ESO 1|1TA)
Grams " o il charged " ij.10.0.
Charge " p e rio d , h o u rs
~'k*0
Grams c a t a l y s t
1 0 0 .0
Space v e l o c i t y :
1
UlO.O/lOQ. OxiieO = 1.025
'
- 16-
R ecycle gas p r e p a r a tio n : (ESO lji|.)
U n it S ta tu s
A c y lin d e r ( s to ra g e )
B c y lin d e r (com pression)
G c y lin d e r (fe e d )
750 p s ig W H2
750 p s ig k0% H2
1080 p s ig 50% H2
D e sire d S ta tu s
A
B
C
c y lin d e r
c y lin d e r
c y lin d e r
1^00 p s ig 30% H2
ItOO p s ig 30% H2
llj.00 p s ig 1:0% H2
3f C c y lin d e r i s v e n ted to 800 p s ig , i t s c o n te n ts a re si
261:0 In^ x I f t ^ x 8 l5 p s ia x ii.5>20R = 78*5 SCF
1728 in3 l i t . 7 p s ia
^3 0 %
. Hydrogen i n C c y lin d e r i s :
0*5 mol f r a c t i o n H2 x 7 8 .5 SGF = 39*2 SCF Hg
Volume of gas to be made is :.
39*2 SGF Ho__________ z 98 SGF ■
O.ltO mol f r a c t i o n H2
Volume o f CH^ to add i s :
98 SCF - 78*5 SCF = 19*5 SGF
S in ce B c y lin d e r a ls o c o n ta in s h-0% Hg, i t s c o n te n ts a re
pumped to C c y lin d e r*
Then th e c o n te n ts of A c y lin d e r a re :
1320 in3 x
I f t 3 x 765 p s ia x lt92®R
1728 in3 .
lit* 7 p s ia
33 0 %
z
Hydrogen in A c y lin d e r i s :
O.ItO mol f r a c t i o n Hg x 36*9 SGF = l it *8 SGF
Volume of gas to be made in A c y lin d e r i s :
l i u 8 SGF Ho'
' =‘ " z U8*2 SCF
0 * 30.m o l ,f r a c t i o n .H2
Volume o f CHjt
added to A c y lin d e r i p :
U8.2 SCF - 36*9 SCF = 8 .6 SCF
36*9 SCF
A c y lin d e r and B c y lin d e r a re th e n e q u a liz e d .
Purge and A d d itio n :
(ESO ItG)
W ith one p a s s th ro u g h th e r e a c t o r , p u re H2 re c y c le gas was
d i lu te d w ith s u f f i c i e n t CH^, e t a l t o have th e a n a ly s is :
CH),, e t a l
91. 6#
8,1;# '
100. 0%
R ecycle gas flo w r a t e - 7^00 SC F/bbl, o r 5 ,^ 2 SCF/hr
E stim a te d hydrogen consum ption - 800 SCF/bbl o r 0 ,589 SCF/hr
Ih e n u s in g p u re hydrogen, hydrogen e f f l u e n t from r e a c t o r i s
5 .5 2 SCF/hr - 0.589 SCF/hr = it.9 3 SCF/hr
When u s in g p u re hydrogen, volume of e f f l u e n t gas i s
It. 93 SCF/hr Ho_______ =
0.916 mol f r a c t i o n H2 '
5 .3 8 SCF/hr
Volume o f GH^, e t a l produced i s
5 .3 8 SCF/hr - it.93 SCF/hr H2 r
0.1t5 SCF/hr
Flow r a t e s f o r 80% Hg - 20% GHli m ix tu re
5 .5 2 SCF/hr x 0 .8 0 mol f r a c t i o n H2 = It.it2 SCF/hr H2
5 .5 2 SCF/hr x 0 .2 0 mol f r a c t i o n GHli = 1 .1 0 SCF/hr GHji
E f f lu e n t flo w r a t e s when u s in g th e above re c y c le m ix tu re
lt.lt2 SCF/hr - 0.589 SCF/hr H2 = 3,8.3 SCF/hr H2
1 .1 0 SCF/hr CHji * 0,it5 SCF/hr GHji = 1 .5 5 SGF/hr CHji
C om position o f e f f l u e n t gas i s
1 .5 5 SCF/hr CH),
______ = 0 ,29 mol f r a c t i o n CHi,
3 .8 3 SCF/hr .H2 + .1 .5 5 SCF/hr CHji
,^
Gas to be purged from A c y lin d e r i s th e n
0 .4 5 SCF/hr CH),.
= 1 .5 5 SCF/hr
0 .2 9 mol . f r a c t i o n -GHji
Hydrogen to be added i s
0.589 SCF/hr + (1 .5 5 SCF/hr - 0 ,it5 SCF/hr CHji ) - 1 ,689 SCF/h
-
7
18-
EXPERIMENT DESIGN
To o b ta in d a ta re g a rd in g th e e f f e c t o f re c y c le gas hydrogen c o n te n t
on h y d r o tr e a tin g s h a le c o k er d i s t i l l a t e th e fo llo w in g sequence o f ru n s was
e x e c u te d .
S t a r t i n g w ith f r e s h c a t a l y s t each tim e , ru n s ESO 3 2 , 3 3 , 3k,
3$, and i*0 w ere made w ith nom inal r e c y c le gas co m p o sitio n s o f 100, 80, 60,
liO, and 80 p e r c e n t h ydrogen, r e s p e c tiv e ly .
F o r d u p lic a tio n p u rp o s e s, ru n s
ESO 36R5 37, 3 8, and 39 w ere made w ith nom inal r e c y c le gas co m p o sitio n s o f
60, 80, 100, and I4.O p e rc e n t hydrogen, r e s p e c t i v e l y .
These ru n s w ere made ■
c o n s e c u tiv e ly fo llo w in g ESO 35 w ith o u t s h u ttin g down th e u n i t o r changing
th e c a t a l y s t .
th e s e ru n s w ast
W ith th e e x c e p tio n of ru n ESO 33 th e sequence f o r each of
l i n e o u t w ith p u re hydrogen a s r e c y c le g a s , ru n w ith pure- '
hydrogen and ta k e an e f f l u e n t o i l sample (T) f o r t i e - i n o r c ompa-r.at i y e
p u rp o s e s , l i n e o u t w ith a r e c y c le gas m ix tu re , ru n w ith th e m ix tu re and
ta k e th r e e sam p les. A, B, and G, f o r a n a l y s i s .
ceded by a t i e p e rio d w ith p u re hydrogen.
Run ESO 33 was n o t p re ­
The le n g th o f l i n e o u t p e rio d
and sample p e rio d were changed d u rin g th e co u rse o f th e s tu d y .
in g up w ith f r e s h c a t a l y s t a 2U-hour l i n e o u t p e rio d was u s e d .
When s t a r t ­
When
changing re c y c le gas co m p o sitio n a H -hour l i n e o u t p e rio d was u sed in ru n s
p r i o r t o ESO 36R and 8 -h o u rs was used t h e r e a f t e r .
B efore ESO 36R t i e
,sample p e rio d s w ere H -hours lo n g and r e g u la r sample p e rio d s were 8-h o u rs
lo n g ; t h e r e a f t e r th e r e g u la r sample p e r io d s were s h o rte n e d to H -hours.,
P r e lim in a r y a n a ly s is o f th e d a ta o b ta in e d from th e fo re g o in g ru n s
in d ic a te d t h a t f u r t h e r d u p lic a tio n was n e c e s s a ry and t h a t a more a c c u ra te
knowledge of .re q u ire d l i n e o u t tim e was n eed ed .
Hence ru n s ESO H i, H2, H3,
and HH w ere made w ith nom inal re c y c le gas co m p o sitio n s o f 70, 60, 5 0, and
-IP ItO p e rc e n t hydrogen, r e s p e c tiv e ly .
F re sh c a t a l y s t was p la c e d in th e r e ­
a c to r a t th e s t a r t of th e s e r i e s and th e n u sed th ro u g h o u t th e . rem ain in g
ru n s.
The scheme f o r th e s e ru n s was th e same u sed in th e p re v io u s s e r i e s —
t h a t i s , a t i e - i n ru n w ith hydrogen fo llo w e d by a ru n w ith th e re c y c le
g a s m ix tu re ,
L in e o u t tim e s w ere e s tim a te d from n itr o g e n a n a ly s e s o f ■
U -hour sam ples ta k e n d u rin g th e i n i t i a l t i e ru n and th e fo llo w in g ru n w ith
70 p e r c e n t h y d rogen.
U sing t h i s in fo r m a tio n , each su b seq u en t change in
ga3 c o m p o sitio n was fo llo w e d by a 12-h o u r l i n e o u t p e rio d b e fo re s t a r t i n g
a sam ple.
The fo llo w in g c o n d itio n s w ere u sed f o r a l l o f th e ru n s in th e study;?
space v e l o c i t y - 1 ,0 grams o f o i l p e r gram o f c a t a l y s t p e r h o u r, gas flo w 7500 SC F/bbl, c a t a l y s t te m p e ra tu re - IjitQ0C, p re h e a t te m p e ra tu re - IjJS0C,
p r e s s u r e - 1000 p s ig , c a t a l y s t charge - 100 gram s.
S in ce p r e lim in a r y s tu d ie s in d ic a te d t h a t th e r e a c t i o n u n d e r-stu d y produced methane and consumed hydrog en , a s y s te m a tic p u rg e and a d d itio n
scheme was tised to h o ld re c y c le gas c o m p o sitio n c o n sta n t*
IVhen ru n n in g
w ith p u re hydrogen, th e e f f l u e n t gas from th e r e a c to r was n o t re c y c le d ,
b u t was v e n te d .
VI
A,
DISCUSSION OF RESULTS
L in e o u t t i m e '
- N itro g e n a n a ly s e s f o r sam ples ESO UlTA-tlTG in d ic a te t h a t when s t a r t i n g
i p w ith 100 grams o f f r e s h ' c a t a l y s t u n d e r th e c o n d itio n s s e t f o r t h in
th e p re c e d in g s e c tio n of t h i s p a p er e q u ilib riu m was a t t a i n e d in 12 to 16
h o u rs o f o p e r a tio n .
A lthough su b seq u en t sam p les, i , e , , ESO UlTE, had
h ig h e r n itr o g e n c o n te n ts , th e s e were a t t r i b u t e d to f l u c t u a t i o n in o p e ra tin g
—20—
c o n d itio n s , p a r t i c u l a r l y te m p e ra tu re , and n o t to a d e la y in re a c h in g
e q u ilib riu m * - The second l i n e o u t p e rio d s tu d y , ru n s li.lA-lj.11, re v e a le d t h a t
when r e c y c le gas co m p o sitio n was changed, new e q u ilib riu m was reach ed in
ab o u t 12 h o u rs .
F ollow ing th e change in gas c o m p o sitio n , th e n itro g e n
c o n te n t of th e e f f l u e n t o i l sam ples changed s t e a d i l y f o r a b o u t 12 h o u rs ,
a f t e r w hich i t m erely f l u c t u a t e d w ith te m p e ra tu re v a r i a t i o n s ,
B,
C a ta ly s t o r i e n t a t i o n
The t i e sam ples f o r ru n s ESO 32, 3 k , 3 5 , lj.0, and k l w ere a l l made
u n d e r e s s e n t i a l l y th e same c o n d itio n s , t h a t i s , new c a t a l y s t , same l i n e o u t
p e r io d , same le n g th o f sample p e r io d , same o p e ra tin g c o n d itio n s , and pure
hydrogen re c y c le g a s.
The o n ly d if f e r e n c e betw een th e ru n s was t h a t
d i f f e r e n t p e o p le p la c e d th e c a t a l y s t in th e r e a c t o r ,
Under th e s e circunH
s ta n c e s , one would e x p e c t t h a t th e n itr o g e n c o n te n t of th e t i e sam ples
would be ab o u t th e same f o r a l l th e r u n s ,
Howevbr, ex am in atio n of th e
d a ta in T able I I shows t h a t t h i s d e f i n i t e l y was n o t th e c a s e .
T his d i f ­
fe re n c e in n itr o g e n c o n te n ts su g g e s ts t h a t c a t a l y s t o r i e n t a t i o n w ith in th e
r e a c t o r a f f e c t s th e perform ance o f th e c a t a l y s t .
S ince d i f f e r e n t p eo p le
p la c e d th e c a t a l y s t , and s in c e th e c a t a l y s t bed was q u ite t h i n , about
o n e -in c h , i t seems p o s s ib le t h a t th e v a r i a t i o n s in p lacem en t co u ld a f f e c t
th e c o n ta c tin g e f f i c i e n c y o f th e c a t a l y s t and hence co u ld v e ry i t s p e r­
fo rm ance,
W ithout f u r t h e r i n v e s t ig a ti o n o f c o n ta c tin g e f f i c i e n c y , no
d e f i n i t e c o n c lu s io n can be drawn re g a rd in g c a t a l y s t o r i e n t a t i o n and
c a t a l y s t p erfo rm an ce,
C,
C a ta ly s t a c t i v i t y
In F ig , U two c u rv e s a re shown, b o th r e p r e s e n tin g c a t a l y s t a c t i v i t y
-2 1 -
as a f u n c tio n o f on—stream, time*
A ll th e p o in ts on th e s e c u rv es were
o b ta in e d when u s in g p u re hydrogen a s a re c y c le g a s.
Hence th e y r e p r e s e n t
checks o f c a t a l y s t a c t i v i t y as th e r e c y c le gas co m p o sitio n was v a rie d from
one v a lu e to a n o th e r .
The d if f e r e n c e in th e o r i g i n a l a c t i v i t y of th e
c a t a l y s t f o r th e two c u rv e s i s a p p a r e n tly due to some p h y s ic a l c h a r a c te r ­
i s t i c o f th e r e a c tio n sy stem , p e rh a p s c a t a l y s t o r i e n t a t i o n .
The, u p p er
c u rv e , f o r ru n s ESO UlT - U5T, in d ic a te s t h a t c a t a l y s t a c t i v i t y d e c lin e d
a s th e ru n s e r i e s p ro g re s s e d .
T his d e c lin e m ight be due to d e c re a sin g
hydrogen c o n te n t o f th e r e c y c le gas o r t o a d e c re a se in a c t i v i t y w ith
tim e , o r b o th .
Inasmuch a s th e low er c u rv e , f o r ru n s ESO 3^T and 380,
shows no p a r t i c u l a r d e c re a se in c a t a l y s t a c t i v i t y when th e ru n s w ere made
in o rd e r o f in c r e a s in g r e c y c le gas hydrogen c o n te n t, th e m ajor d e c lin e in
a c t i v i t y m ust n o t be a t t r i b u t e d to a tim e f u n c tio n , b u t r a t h e r to a
hydrogen c o n c e n tra tio n f u n c tio n .
T h is c o n c lu s io n i s f u r t h e r s u p p o rte d by. -
Bureau o f Mines i n v e s t ig a ti o n s on th e l i f e o f c o b a lt m olybdate when u sed
f o r a s h a le o i l h y d ro g e n a tio n c a t a l y s t .
T h e ir i n v e s t i g a t i o n , made w ith
p u re h ydrogen, re v e a le d a c a t a l y s t l i f e i n e x c e ss o f 300 h o u rs ( £ ) .
S ince
th e s tu d ie s u n d er c o n s id e r a tio n h e re w ere 200 h o u rs o r l e s s in le n g th , i t
would seem t h a t d e c lin e in c a t a l y s t a c t i v i t y w ith tim e would be q u ite s m a lli
D. S u lf u r and n itr o g e n rem oval
Upon a p p ly in g l i n e a r r e g r e s s io n . T able V, to th e s u l f u r rem oval d a ta
from th e two ru n s e r i e s , ESO 35-38 and ESO Iil-IiU, th e fo llo w in g e q u a tio n s
f o r s u l f u r rem oval in term s of r e c y c le gas hydrogen c o n te n t w ere o b ta in e d
f o r th e ran g e 50-100 mol p e rc e n t hydrogens:
-2 2 S = 0 .# 7 E * hk»9
(I)
S = 0.223H + 73.7
(2)
w here S i s th e p e rc e n t s u l f u r removed and H i s th e mol p e r c e n t hydrogen
i n th e re c y c le g a s,
A " S tu d e n t's ” t t e s t was a p p lie d to th e h y p o th e sis
HlBl = b2> w here B i s th e t r u e slo p e o f th e r e g r e s s io n l i n e .
The h y p o th e sis
co u ld n o t be r e j e c t e d , so a pooled e s tim a te o f th e r e g r e s s io n l i n e slo p e
was made and found to be 0,305»
S in ce th e d if f e r e n c e i n i n t e r c e p t s of th e
above e q u a tio n s stem s from n o n - r e p r o d u c ib ility o f c a t a l y s t p erfo rm an ce,
th e r e l a t i o n betw een s u l f u r rem oval and re c y c le gas hydrogen c o n te n t f o r
th e i n t e r v a l 50 - 100 mol p e r c e n t hydrogen may be e x p re sse d by th e
)
e q u a tio n
S = 0«,305>H .*• k
where k i s an in te r c e p t*
(3)
F ig u re 6 p r e s e n ts g r a p h ic a lly th e r e l a t i o n
betw een s u l f u r rem oval and re c y c le gas hydrogen co n ten t*
When l i n e a r r e g r e s s io n was a p p lie d t o th e n itr o g e n rem oval d a ta ,
r e s u l t s s im ila r to th o s e f o r s u lf u r rem oval w ere o b tained*
The r e g r e s s io n
e q u a tio n s a re
N = 0*ii73H - 11*3
(It)
N = 0»601H - 2,it6
• (5 )
w here N i s th e p e rc e n t n itr o g e n removed, from th e charge s to c k and H i s
th e mol p e r c e n t hydrogen in th e r e c y c le gas*A " S tu d e n t's " t t e s t was a p p lie d to th e h y p o th e s is HrBj4 = Bg an d , s in c e
th e h y p o th e s is co u ld n o t be r e j e c t e d , a p o o led e stim ate , o f th e re g r e s s io n
l i n e slo p e was made.
U sing t h i s pooled e s tim a te , th e r e l a t i o n betw een
n itr o g e n rem oval and re c y c le gas hydrogen c o n te n t may be e x p re sse d by th e
-2 3 -
e q u a tio n
N = 0.323H * k r
(6 )
where k* i s an i n t e r c e p t .
G ra p h ic a lly tl^ is r e l a t i o n i s .shown' i n ■F ig u r e . 7»
E»
B o ilin g range o f p ro d u c t
No c o r r e l a t i o n was seen betw een hydrogen c o n te n t o f re c y c le gas and
th e b o ilin g range o f th e e f f l u e n t o i l sam ples g iv en in T able 17.
V II
SUMMMI
,;
J
1
Twelve .hours l i n e o u t tim e were found n e c e s s a ry when changing r e c y c le
gas co m p o sitio n from one v a lu e to a n o th e r u n d er th e s e o p e ra tin g c o n d itio n s ?
!1
100 grams c a t a l y s t , 1 .0 gm/gm h r s p a p e iw lo .c it^ O ^ O O f^ S E I ^ ls g S to f'lO w tra te ,
S in ce r e s u l t s from ru n s made w ith new c a t a l y s t and s i m i l a r o p e ra tin g
c o n d itio n s were n o t th e same, c a t a l y s t o r i e n t a t i o n w ith in th e r e a c to r was
'
th o u g h t to a f f e c t c a t a l y s t perform ance and d a ta r e p r o d u c i b i l i t y .
I
C a ta ly s t a c t i v i t y d id n o t change a p p re c ia b ly d u rin g o n -stre a m tim es
o f 200 h o u rs o r le s s *
I t d id , how ever, d e c lin e s l i g h t l y a s th e hydrogen
:
;
c o n te n t of th e re c y c le gas d e c re a se d .
'
■
’
'
ch arg e s to c k v a r ie d l i n e a r l y in d i r e c t p r o p o r tio n to th e hydrogen c o n te n t
o f th e r e c y c le g a s .
\
I
i
In th e ran g e £0-100 mol p e rc e n t h y d ro g en , s u lf u r rem oval from th e
The r e g r e s s io n e q u a tio n f o r t h i s r e l a t i o n s h i p i s
S = 0 .3 0 5 H * k
w here S i s th e p e rc e n t s u lf u r removed from th e charge s to c k , H i s th e mol
I
p e rc e n t hydrogen in th e r e c y c le g a s , and k i s an in t e r c e p t dependent upon
p h y s ic a l c h a r a c t e r i s t i c s o f th e r e a c tio n sy stem .
In th e same range o f gas
:
:!
c o n c e n tr a tio n , n itr o g e n rem oval from th e charge s to c k obeys th e same ty p e
-:l
-2 l± -
r e l a t i o n ' and fo llo w s th e 'equation
N = 0 .523 H + k '
w here N i s th e p e r c e n t n itr o g e n removed from th e charge s to c k , H i s th e
mol p e rc e n t hydrogen in th e re c y c le g a s , and k f i s an i n t e r c e p t dependent
upon th e p h y s ic a l c h a r a c t e r i s t i c s o f th e r e a c tio n system .
No c o r r e l a t i o n was found betw een p ro d u c t b o ilin g ran g e and hydrogen
c o n te n t o f th e r e c y c le g a s .
At- 1000 p s ig and IiUO0G w ith a space v e lo c i ty o f 1*0 gm/gm h r , a gas
flo w r a t e o f 7500 S C F /bbl, and c o b a lt m obalt m olybdate c a t a l y s t , s u lf u r in
th e c o k er d i s t i l l a t e charge s to c k was red u ced from 0*63 p e r c e n t to 0*0U9
p e r c e n t and n itr o g e n was red u ced from 1*65 p e r c e n t to 0*Ul0 p e r c e n t.
;■
C o lo r
s t a b i l i t y o f th e o i l was im proved, b u t th e sample s t i l l d is c o lo r e d on
s ta n d in g ,
V III
ACKNOWLEDGMENT
The a u th o r w ish es t o th an k th e E sso R esearch and E n g in e e rin g Company
f o r sp o n so rin g t h i s r e s e a r c h project; P r o f e s s o r s Lloyd B erg, L. G. M a y fie ld ,
,!
and H6 A, S aner f o r t h e i r s u g g e s tio n s and c r i t i c i s m s ; Glenn King and Dale
Benson f o r t h e i r a b le a s s is ta n c e ; and D re B ernard O stle f o r h i s h e lp w ith
th e s t a t i s t i c a l p a r t of t h i s p a p e r,
I
!
—25—
UC BIBLIOGRAPHY
(1)
B erg, C lyde, "Advancements i n F u e ls P ro d u c tio n from S h ale O il6"
Union O il Company o f C a l if o r n ia , 195U
(2)
E x c a v atin g E n g in e e r, k 3, No6 11# p 6 20 (November, 19h9)
(.3)
K ing, G6 A6, M6S6 T h e s is , Montana S ta te C o lle g e , 1955
(4)
L ake, G6 R6 e t a l , " E f f e c ts o f D ig e stio n Tem perature on K je ld a h l
A n a ly s e s .” A n a ly tic a l C h em istry , 23, p 6 1635-38 (November, 1951)
(5)
M a y fie ld , L6 G6, P e rs o n a l com m unication
(6 )
O s tle , B ernard, S t a t i s t i c s i n R esearch . Amesr Iowa S ta te C ollege
P r e s s , 1955 789
(7 )
U6 S6 Bureau of Mines O il-S h a le Mine and E n g in eerin g Experim ent
■ S ta tio n : R ep o rt on. Coking .G as-Combustion Crude S h ale O il f o r
Maximum P ro d u c tio n .of Gas O il. R i f l e , C olorado (F e b ru a ry , 1955)
(8)
U6 S6 Bureau o f M ines:
R eport o f I n v e s tig a tio n s
5557
(9 )
U6 S6 Bureau o f l i n e s :
R ep o rt o f I h v e s tig a tio h s 5055
- 26-
X APPENDIX
page
T able I
Charge S tock P r o p e r tie s . ........................................................
T able I I
O p e ratin g C o n d itio n s and P ro d u c t D ata.
T able I I I
C o r r e la tio n D ata ..................................
T ab le 17
ASTM D i s t i l l a t i o n s o f E f f lu e n t O il . . . . . . . . . . . .
T able 7
R e g re ssio n A n aly ses. . . . . . . . . . . . . . . . . . . . .
F ig u re I
Block F lo w sh eet of H y d ro tre a tin g U n it. . . . . . . . . . . . 3 5
F ig u re 2
D e ta ile d F low sheet o f H y d ro tre a tin g U n it . . . . . . . . . .
36
F ig u re 3
D e ta il o f Top o f R e a c to r ....................... . . . . . . . . . . . .
37
F ig u re k
D e ta il o f Bottom o f R e a c to r. ............................... . . . . . . . .
38
F ig u re £
C a ta ly s t A c tiv ity as a F u n c tio n o f On-Stream Time* . . . . .
39
F ig u re 6
R e la tio n Between S u lf u r Removal and R ecycle Gas
Hydrogen C on ten t ...............................................
lj.0
R e la tio n Between N itro g e n Removal' and R ecycle Gas
Hydrogen C ontent . . . . . . . . . . . . . . . . . . . . . .
I^l
F ig u re 7
27
^ . 28
31
.3 2
33
-2 7 -
TABLE I
CHARGE STOCK PROPERTIES (7)
■Gravity
OAPI @ 60?F
V is c o s ity , SeHe @ 130°F
see.
Carbon re sid u e ., Ramsbottom
.w te p e rc e n t
H
M
S u lf u r ,
Il
Il
N itro g en
ASTM d i s t i l l a t i o n , D-U j S (c o r r e c te d t o 760 mm Hg)
op
I eBePe
TI
at
Il
10
Il
20
30
"
Il
• bo
TI
50
It
60
11
70
It
80
It
90
It
9Z :
It
End P o in t
R ecovery
v o le p e rc e n t
3 2 .b
31
0 .62
0 .6 3
1*69
161
293
297
3Zk
'396
b32
b6k
U92
322
ZZk
Z91
616
672
98
TABLE I I
OPERATING CONDITIONS.AND PRODUCT DATA
Sample
No,
32 A
B
C
33 A
B
C
3h T
'
4
B
C
35 T
4
B
C
" ."Sample "" T em perature 0C""
B iie r v a l Hf P p eh eai C a ta ly s t
Erpm S ia ritip
& L :3 2 '
32 - UO
Uo ^ U8
2U - 32
32 ,- Uo
Uo - U8
2U - 28
32 - Uo
Uo.- U8
U8-56
-
B
C
UU5
U38
0 .9 7 2
U39
0.99Q
100,0
1 0 0 .0
1 0 0 .0
U39
U38
UU3
UUl
UU2
.0 .9 9 8
1 .0 0 6
0 .9 9 2
7 6 .8
-8 1 .8
8 2 .2
UU5
U38 .
U36
UUo
. UU3
'
1 .0 0 0
1.112
1 0 0 .0
UU3
■U35
UUi
0 .9 8 9
0 .9 6 1
0 .9 8 7
6 0 .2
5 5 .0
U39
i,o 5 5
. 0 .99U
1 0 0 .0
U39
-
UU3
UU2
UUo
U3U
U35
UUi
UUU
U3U
U37
UUU
UUo
120 - 12U
UU6
132 - 136
U36
U36
136 - 1 U0
1U0 - iUU ■ U37
U35
UUo
UUo
32 - UO
Uo - U8
U8 - 56
36 TR ' . .8 8 - 92.
ioo - ioU
W
BR
IGU - 108
108 - 112
CR
37 T "
4
UU.2
UU5
U37
UUi
U37
UUl
UUo
2U-28
Space Mol % H0-""
V e lo c ity in R ecycle
.
■Gas' . .
UU3
1.000
1.008
. 1 .0 2 0
1.031
1 .0 0 0
Q .980
1,028
0 .9 8 7
1.0 U 0
1 .0 2 5
60.2
U1 .2
U6 .3
U 7.2
100.0
6 6 .U
6 7 .2
6U.9
1 0 0 .0
83 .U
8 2 .1
8U.6
'
-
P ro d u ct D ata
0API
WbA % S
Y ield
Mt.
%
N
\
91.5 )
9 2 .1 I
9 3 .9
9 3 .7 j
9 5 .6 )
9U .2
86.3
0.803
I
8 8 /3 >
8 8 .2 )
8 7 .2
8 7 .8
J
9 3 .2
9U .3
9 0 .6 j.
8 9 .5
" 9 2 .7
9U .0 )
8 9 .8
9 2 .8
I
a
0 .6 3 5
0 .6 7 0
0 .08 U
0.807
0 ,8 0 7
_
0.828
0 .8 1 9
0 .8 1 3
O.68U
0.807
0.086
0.090
0.095,
r.
8 8 .0 )
9 0 .5
8 7 .7
0 .0 8 9
0 .08U
"
0 .7 7 1
0 .7 9 2
0.OU9
0 ,0 7 5
0 .06U
0 .U10
0.727
0.739
0 .0 5 3
0 .6 8 7
0.163
1.072
0 .2 9 6
1 .3 8 6
6.266
1.U72
0 .2 7 7
1 .U89
6 .0 9 6
0.207
0,136
0.151
0.91U
1 .3 0 5
1 .2 5 7
1 .3 0 6
6 .1 U7
0 .1 U6
1 .2 8 5
o .i5 3
0.105
1 .10U
• 1 .1U2
1.117
38 A
B
C
39 A
B
C
Uo T.
A
B
C
Ul TA
TB
TC
'"Sample
I d te r v a l Hr
From S ta r tu p
1^2 E i56
' 1U6 - 160
160 - l6'U
T em perature ciC
Space"
P rp h d at
C a ta ly s t ■V elocity
U37
UU2 ■
UUi
U35
U38
UUo
2U - 28
38 - U6
U6 - 3U
5U - 62
UUU
.UU2
UU3
U39
UUl
UUo
UUi
U37
UUo
UUo
U38
UUU
UUP
..U3U
U37
UUi
- 16
- 20
20 - 2U
2U - 28
U38
TE
TG
32 - 36
36 - Uo
UUi
UUi /
UU9 1
.UU3
UUi
Ul A"
Uo-UU
UU - U8
U8 - 52
52 - 56
56 - 60
60 - 6U
6U - 68
68 - 72
75 - 76
UUi
UU2
..UUU
UUi
UU5
■UUU
U36
UU2
•$D
TE
B
C
D
E
F
Q
H
I
UU2 ■ 0 .9 6 5
0 .9 7 3
UUi
1.
012
U37
172 - 176
176 - 180
180 - 18U
12
16
28-32
U39
I b l i 'H 2
. -In H e b y c le
Gas
U35
..UUU
UUi .
UU6
UU6
UUo
UU6
0 .9 8 7
0,9U 2
0 .9 5 0
3 8 .5
3 9 .5
U 0.8
UU950
100,0
81.0
81.1
0 .9 7 8
0 .9 5 9
0 .9 7 3
,1.025
i.o5U
.1 ,0 3 0
.1.015
1.038 .
1+079
l.o5i
•—
0 .9 8 0
0 .9 8 5
1.018
. U39
'UU2 ■ 0 ,9 9 6
U38
U35
U38
100.0
100.0.100,0
0 .9 9 6
8 1 .8
100,0
1 0 0 .0
1 0 0 .0
100.0
100.0
100.0
1 0 0 .0
—
—
—
**
.i,oi5
1 .0 3 0
7 0 .2
P ro d u c t Data
OfiPT
Y ie ld
f
Sample
No,
-‘
9 5 .7
.9 3 .5
8 9 .7
Wt. % N
-
.
.
CO
TABLE I I (c o n tin u e d )
OPERATHG CONDITIONS AND PRODUCT DATA
)'
) 0 .8 1 3
).
91.U ) '
91.9 ).0.826
8 8 .8 )
-
9 3 .6
9 6 .1
)
95i5 ) 0 .8 1 5
? h .S I
.
9 6 .7 '
9 5 .5
9 6 .1
9 6 .8
9 6 .8
.
0.112
1.015
0 .07U
1 .0 0 9 .
1 .0 3 2
0.18U
0.155
1.357
1.362
1.U30
0.12U
0.170
0.087
0 .0 7 5
0 .0 7 6
0 .0 6 2
-
0.902
0.9UU
0.971
0 .9 7 7
0.727
0 .7 9 6
-
0.7U1
0.803
93,1
—
96+7
0.0272
0.718
0.686
«
9 3 .7
93.1
9 6 .7
-9U.6
9 6 .3
9 6 .3
9 3 .3
—
—
—
—
—
—
0.0518
0 .8 3 9
0 .7 6 9
0.907
I.060
1.03U
1 .0 8 3
1 .0 3 0
1.065
1 .0 2 8
0 .9 9 7
!
i
..........
TABl E IT (c o n tin u e d )
OPEKATIN a ,COMDTTIONS AMD PRQDUCT DATA
U2 T
A
' 8U - 88 .
IOli - 112:
Wtl
il32
WlO
U36
1.013
0.992
1 0 0 .0
6 2 .3
98 .2
9 6 .2
12li - 132
lW l - 132
Wl2
Ii38
UU2
U39
0.983
1 .018
100.0
3 7 .6
9 7 .1
93 .9
Wl T
A
. l61i - 172
18U - 192
ItUo
U33
U37
W tl
0.960
0.961
100.0
3 0 .2
99 .9
9 3 .3
U5.T
192 - 20k
WtO
WtO
0 .9 6 1
1 00.0
9U.U
Space ’
V e lo c ity
Mbl %"E2
i n R ecycle
-•
Y ield
P ro d u ct Data
0APl
:
:
.U3 T '
A
-
-
-
CO ■
T em p eratu re"0C"
"Sample
I n t e r v i l Hr P re h e a t
C a ta ly s t
Erom S ta rtu p
i
Sample
Mo.
wt % :
0.0318
0,0973
0.722
1.100
0.0230
0.0801
0 .7 1
1. 1U
0.0U67
0.09UU
0 .8 0
i.l3
0 .7 6
-3 1 TABLE I I I
CORRELATION DATA
Sample
No,
Sample I n te r v a l
H r, From S ta rtu p
C
2U - 28
U8 - 56
108 - 112
1U0 - lUU •
160 - 16 U
180 - 18U
Ul TC
Ul T
U2 T
U2 A
U3 T '
U3 A
UU T
UU A
U5 T
Uo .
72 - 76
8U - 88
10 U - 112
12U - 132
IUU - 152
16 U - 172
18U - 192
192 - 20U
'35 T
35 c.
36 CR
37 C
38 C
39
36 -
I o l % Hp
Sample Data
P e rc e n t S
in
Wt % S Wt % N Removed
R ecycle Gas
<\
100,0
U7,2
0 .1 6 3
0 .2 7 7
o.i5i
6 U .9
.8U06
100,0
Uo,8
0.105
1.117
0 .12 U 1.032
0 .170 , 1.U30
1 0 0 .0
7 0 .2
1 00.0
6 2 .5
100.0
5 7 .6 .
100.0
5 0 .2
1 00.0
1.072
1 .U89
1 .3 0 6
.
0.0272
0.0518
0.686
-
7U .2
5 6 .0
3 5 .0
1 0 .1
. 76.1
20.8
32.3
37.U
8 3 .3
8 0 .3
73.0
1 3 .3
9 5 .7
9 6 .3
8 7 .3
5 8 .U
3 9 .6
5 6 .2
3 3 .3
5 7 .0
3 0 .9
0 .8 0
9 2 .6
i.i5
85.1
—
5 1 .5
0 .9 9 7
0.0318 0.722
0 .0 9 7 3 1.100
0.0230 0.710
0.0 8 0 1 IolU
0.0U 67
0.09UU
P e rc e n t N
Removed
0.7 6
■9 1 .7
9U .9
8U.6
'
3 0 .3
5 3 .9
.
-3 2 -
TABLE IF
ASTM DISTILLATIONS OF EFFLUENT OIL
Composite 32A,B,C
Sample Nos.
Mol % H2 in
R ecycle Gas
B arom etric
P re s s u re
IBP
10 cc
20 cc
30 cc
ItO cc
50 cc
60 cc
70 cc
80 cc
90 cc
End P o in t
R ecovery
3^A,B,C
3 ^ B5C 36AEt5BR5CR 37A5B5C 39A5B5C ItOA5B5C
100.0
6 0 .2
4 6 .8
66*2
8 3 .4
3 9 .6
81.3
632.6
6 32.6
6 4 2 .1
6 42.1
6 4 2 .1
6 4 2 .1
6 42.1
I i tIt 0F
' 138°f
220
1380F
218
278
331
376
4 i4
446
492
234
280
624
1320F
228
293
340
380
4 l6
422
496
232
280
606
1480F
236
284
334
376
412
448
498
234
284
618
142°F
220
302
348
388
431 '
467
26o
232
276
638
9 7 .4 cc
92*7 cc
i
2 o° f
228
280
327
362
ItOO
khz
h79
22k
271
312
320
391
k3h
k71
2 i2
2o8
26^
630
262
63U
97*2 cc
9 7 .2 cc
276
328
374
4l 6
■ 426
490
.231.
282
646
9 7 .4 cc
97 .2
CO
9 7 .1 cc
-3 3 -
TABLE V
REGRESSION ANALYSES (6)
R e g re ssio n e q u a tio n :
e s tim a te d b y :
Y = A * BX
Y = a + bX
where
b = nX xY - Z X Z y
n£X^ - (JLX)^
and
a =%Y - bj>X
n
E q u a tio n s r e p r e s e n tin g s u l f u r rem oval d a ta :
S = 0.327 H + kh»9
S = 0.233 H + 73 .7
E q u a tio n s r e p r e s e n tin g n itr o g e n rem oval d a ta :
N = 0.14.73 H - 1 1 .3
N = 0 .6 0 1 H - 2*14.6
T e s t of h y p o th e s is Hs B^.= Bg
t ca bI - bg w ith (n^
s b|L“ bg
R e je c t a t 9$% l e v e l
ng - U) d e g re e s of
freedom
and
sE =
" bI Z ^ i Y i ) * f ( £ y p - b g ^ z g y g )
. -
■n -j_
*f*
------------
TABEL V (c o n tin u e d )
REGRESSION ANALYSES (6 )
"bSulfu r = OoTW-I- w ith 6 d e g re e s o f freedom
^ n itr o g e n = 2*1 0 8 w ith 6 d e g re e s of freedom
.N either t e s t i s s i g n i f i c a n t a t th e
p e rc e n t Ie v e le
P ooled e s tim a te o f r e g r e s s io n l i n e slo p e?
bg:-a Oo29^76
= 0*^3617
Note: W hile t h i s p o o lin g p ro c e d u re may n o t be e x a c t, i t i s
s u f f i c i e n t l y a c c u ra te to be u sed w ith th e d a ta p re s e n te d h e re in *
^ S ig n if ic a n t a t 90% l e v e l
-3 5 -
OIL S U P P L Y
PR EHEA T
F E E D GAS SUPPLY
CATALYST
MAKEUP
GAS S U P P L Y
CONDENSER
GAS
C O M P R E S S IO N
GA S
STORAGE
SIGHT
GLASS
RECEIVER
t.
F ig u re I*
Block F low sheet o f H y d ro tre a tin g U n it
VENT
PANEL .,BOARD
VENT
DISK
PRESSURE
GAGES
FEED
PUMP
VACUUM
AIR
SU PPLY
OIL
VENT
MAKEUP
GAS
a
4 -CxM—t--PRESSURE
CONTROLLER
COMPRESSION
WET
RESERVOIR
CYLINDER
OIL
TEST
METER
or Z
COM PRESSION
OIL
RECEIVER
PUMP
F E E D
FEED
OIL
FROM
TO
RUPTURE
BOWL,
RESERVOIR,
SEDlM EJiI
—
(Z) o
SC R U B B E R
LEGEND:
-------------------------
1/8"
SS
-------------------------R U B B E R
------------------------ i/ 4 -
TUBING
TUBING
COPPER
FIG. 2 .
TUBING
PIPE
I
DETAILED
FLOW SHEET
OF
HYDROTREATING
UNIT
-3 7 -
SS 3 / 4 '- 1/8" BUSHING
3/4" FORGED STEEL CROSS
3 /4
WELDED
NIPPLE
END BLOCK, SCREWED
INTO REACTOR
WELDED
REACTOR WALL
I___________
L
THERMOWELL, WELDED INTO
BUSHING
NOT TO SCALE
F ig u re 3 .
D e ta il o f Top o f R e a c to r
-3 8 -
THlS JOINT WELDED WHEN
CLOSURE WOULD NOT SEAL
REACTOR WALL
END BLOCK, SCREWED
INTO REACTOR
WELDED
I NIPPLE
NOT TO SCALE
F ig u re U.
D e ta il o f Bottom o f R ea c to r
O
I-
IOO
HOURS ON STREAM
Notes
P o in ts shown r e p r e s e n t t i e - r u n sam ples (made -with 100,i Hg) tak en b e fo re
ru n s w ith re c y c le gas m ix tu re s . Upper l i n e i s f o r th e run s e r i e s ESO U l-W .
Bottom l i n e i s f o r th e ru n s e r i e s ESO 3 5 -3 3 .
F ig u re 5 .
C a ta ly s t A c tiv ity as a F u n c tio n o f On-Stream Time
IOO-I
PERCENT SULFUR REMOVED
90-
IOO
^ 1-Ure 6 .
80
70
60
MOL PERCENT HYDROGEN IN RECYCLE GAS
R e la tio n Bettreen S u lfu r Removal and R ecycle Gas Hydrogen C ontent
-Itr
-30-
80
70
MOL PERCENT HYDROGEN IN RECYCLE GAS
O
F ig u re 7.
R e la tio n Between N itro g en Removal and R ecycle Gas Hydrogen C ontent
MONTANA STATE UNIVERSITY LIBRARIES
IllllllllllllfflliIIlIIIi
762 100 4 3 4 3 5
I lj3 7 8
hi? 14c
- Icop . 2
hole c e
I
Mf
115470
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C a t a l y t i c
j s h a l e - o i l
c<
h y d r o t r e a t i n g
5k e r
d i s t i l l a t e
FE 2 3 m
Ywe • *
MAR 2 5 ’6 3
H f ’E R U B B A R ?
rL' k i ^
z V 7 v i - t -/xTe-t
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1154?0
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