The catalytic hydrodesulfurization of coal tar aromatic distillates
by Robert L Jacobson
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Doctor of Philosophy in Chemical Engineering
Montana State University
© Copyright by Robert L Jacobson (1958)
Abstract:
The primary purpose of this investigation was to determine the operating conditions necessary to
reduce the thiophene content of crude aromatics from approximately' 0.7% to less than 1 ppm in a
catalytic hydrodesulfurization pilot unit. The effect of process variables on the degree of
desulfurization using a pseudo first-order rate equation and the Arrhenius equation was studied.
Light oil produced by Jones and Laughlin Steel Corporation and United States Steel Corporation was
desulfurized using Harshaw CoMo 0301-T catalyst crushed and sized to 10-14 mesh. Pure hydrogen
and 50% H2 - 50% H2 were used as treat gases.
Results of the investigation show that light oil containing less than 1 ppm thiophene can be obtained
under a variety of operating conditions. The degree of desulfurization is affected favorably with: (1)
increased pressure in the range of 100 to 800 psig; (2) increased temperature in the range of 575 to
850°F; (3) increased treat gas rate in the range of 500 to 1000 ft3/bbl; (4) increased hydrogen to oil
ratio in the range of 0.22 to 0.86; and (5) increased contact time.
The degree of desulfurization is also dependent on the boiling range of the light oil; higher boiling
material requires more severe process conditions. THE CATALYTIC HYDRODESULFURIZATION
OF COAL TAR AROMATIC DISTILLATES
byR obert L„ Jaco b so n
A THESIS
S u bm itted t o th e G rad u ate F a c u lty
in
p a r t i a l f u l f i l l m e n t o f th e re q u ire m e n ts
f o r th e d eg ree o f
D octor o f P h ilo so p h y i n C hem ical E n g in ee rin g
at
M ontana S ta te C o lleg e
Approved:
Head, M ajor D epartm en
Bozeman, Montana
J a n u a ry , 1958
RESTRICTED STACK
_p
J
?>nZ
'
i s Vc TABLE OF CONTENTS
,Page
A b s t r a c t .......................................
3
I n tr o d u c tio n . . . „ ............................................ .... . . ,...........................
4
K in e tic E q u a tio n s Used t o D e sc rib e th e R ea c tio n
7
...........................
Equipm ent5 M ethods, A n a ly sis o f P ro c e sse d L ig h t O il. . . . . .
Equipment
...............................
11
11
M ethods.' .........................................................................................................
12
A n a ly s is o f P ro c e sse d L ig h t O il
13
. . . . . . . . . . . . .
D isc u ssio n and R e s u lts ............................................................................... . .
15
I n i t i a l I n v e s tig a t io n Concerned w ith th e
F e a s i b i l i t y o f H y d ro fin in g Crude L ig h t O il
ifl a H y d ro d e su lfu riS a tio n P i l o t U n it . . . . . . . . . . .
15
C onclusion .............................................................
20
The Study o f P ro c e ss V a ria b le s Through
the'"Use o f R ate E q u a tio n s ■. .
Vv . . . . . . . . .
21
C onclusion . . . . . . . . . . . . . . . . . .
Acknowledgment . . . . . . . . . . . .
........................... 28
............................... . . . . .
30
L i t e r a t u r e C ite d
Appendix . . . . . . . . . . . . . . . . . . . .
30 a
............................... 31
ABSTRACT
The p rim a ry purp o se o f t h i s in v e s t i g a t i o n was t o d e term in e th e
o p e ra tin g c o n d itio n s n e c e s s a ry to red u ce th e th io p h e n e c o n te n t o f crude
a ro m a tic s from a p p ro x im a te ly ' CL7$ to l e s s th a n I ppm i n a c a t a l y t i c
h y d r o d e s u lf u r iz a tio n p i l o t u n i t . The e f f e c t o f p ro c e s s v a r ia b le s on th e
d eg ree o f d e s u lf u r iz a ti o n u s in g a pseudo f i r s t - o r d e r r a t e e q u a tio n and
th e A rrh e n iu s e q u a tio n was s tu d ie d .
L ig h t o i l produced by Jo n es and L au g h lin S te e l C o rp o ra tio n and
Ultiited S ta te s S t e e l C o rp o ra tio n was d e s u lf u r iz e d u s in g Harshaw CoMo
0301-T c a t a l y s t cru sh ed and s iz e d t o 10-14 m esh. Pure hydrogen and
50% Hg - 50% Hg were u sed a s t r e a t g a s e s .
R e s u lts o f th e i n v e s t i g a t i o n show t h a t l i g h t o i l c o n ta in in g l e s s
th a n I ppm th io p h e n e can be o b ta in e d u n d e r a v a r i e t y o f o p e ra tin g con­
d i t i o n s . The d eg ree of d e s u lf u r iz a ti o n i s a f f e c t e d fa v o r a b ly w ith :
( l ) in c r e a s e d p r e s s u r e i n th e ran g e o f 100 t o 800 p s ig ; ( 2 ) in c re a s e d
te m p e ra tu re i n t h e ran g e o f 575 t o 850°F; (3 ) in c re a s e d t r e a t gas r a t e
i n th e ran g e of 500 t o 1000 f t- ^ /b b l; ( 4 ) in c re a s e d hydrogen t o o i l
r a t i o i n th e range o f 0 .2 2 t o 0 . 8 6 ; and ( 5 ) in c re a s e d c o n ta c t tim e .
The d e g re e o f d e s u lf u r iz a ti o n i s a ls o dependent on th e b o ilin g range o f
th e l i g h t o i l ; h ig h e r b o ilin g m a te r ia l r e q u ir e s more se v e re p ro c e ss
c o n d itio n s .
-4 -
INTRODUCTIQN
R ecent developm ents i n th e p e tro le u m in d u s tr y have b ro u g h t about
th e p ro d u c tio n o f e x tre m ely p u re a ro m a tic s .
As a r e s u l t , th e p ro d u c e rs
o f c o a l c h em ica ls have found th e m selv e s i n a poor c o m p e titiv e p o s itio n
b ecau se t h e i r a ro m a tic s have a r e l a t i v e l y h ig h s u lf u r c o n te n t (th io p h en e
d e riv a tiv e s ).
The Jo n es and L au g h lin S te e l C o rp o ra tio n , see k in g t o b e t t e r
t h e i r c o m p e titiv e p o s i t i o n , c o n s u lte d Esso R esearch and E n g in e e rin g t o
d e term in e i f th e y co u ld f in d a p ro c e s s f o r t r e a t i n g crude a ro m a tic s .
Esso,
p roposed th e p o s s i b i l i t y o f t r e a t i n g c o a l t a r l i g h t o i l (c ru d e a ro m a tic s)
i n a c a t a l y t i c h y d r o d e s u lf u r iz a tio n u n i t a f t e r th e y had com pleted a 24h o u r ru n .
They were u n a b le t o c o n tin u e th e i n v e s t ig a ti o n and i t was
tu rn e d o v er t o chem ical e n g in e e rin g g ra d u a te s tu d e n ts a t Montana S ta te
C o lle g e u n d er th e d ir e c tio n o f D r. Lloyd Berg f o r f u r t h e r developm ent.
The Jo n es and L au g h lin cru d e a ro m a tic l i g h t o i l s (b en zen e, to lu e n e ,
and Dtylene) from th e b y -p ro d u c t coke ovens c o n ta in a p p ro x im a te ly 0 .7 2
p e rc e n t (7200 ppm) th io p h e n e d e r i v a t i v e s .
I n o rd e r t o m eet custom er
s p e c i f i c a t i o n s th e a ro m a tic s m ust c o n ta in l e s s th a n one ppm s u l f u r and
have an a c c e p ta b le a c id c o lo r and c o rro s io n t e s t .
-X-
The d e s u lf u r iz a ti o n p ro c e s s c o n s t i t u t e s h y d ro g e n a tio n o f th e crude
l i g h t o i l i n th e p re se n c e o f a s u ita b le c a t a l y s t a t e le v a te d te m p e ra tu re
and p r e s s u r e .
A s u b s t a n t i a l sav in g s i n in v e stm e n t and o p e ra tin g c o s ts
c o u ld be e f f e c t e d by h y d ro fin in g th e cru d e l i g h t o i l s c o l l e c t i v e l y r a t h e r
th a n h y d ro fin in g b e n zen e, to lu e n e and x y le n e s e p a r a te ly ; t h e r e f o r e , work
"D efined u n d er "A n aly sis o f P ro ce sse d L ig h t O il"
-5 -
was done o n ly on p r o c e s s in g crude l i g h t o i l s c o l l e c t i v e l y .
A m ix tu re o f
50% Hg - 50% Mg was u sed a s t r e a t g as f o r much o f th e work b ecau se hydrogen
was t o be o b ta in e d from th e c ra c k in g o f ammonia.
The c a t a l y s t u sed f o r
th e h y d r o d e s u lf u r iz a tio n com prises " a c tiv e c e n te r s ” o f c o b a lt and moly­
bdenum ox id e im p reg n ated i n an aluminum o x id e b ase c a r r i e r o f h ig h s u r­
fa c e a re a .
T his c a t a l y s t , u sed t o c o n v e rt th io p h e n e t o hydrogen s u lf id e
and h y d ro c a rb o n s, i s n o t a c ti v e enough t o h y d ro g en ate th e benzene r in g .
The p r i n c i p a l o p e ra tin g v a r ia b le s s tu d ie d in c o n n e c tio n w ith c a ta ­
l y t i c h y d r o d e s u lf u r iz a tio n a f t e r th e c a t a l y s t has been d eterm in ed a re
p r e s s u r e , c o n ta c t tim e , te m p e ra tu re , c o m p o sitio n o f h y d ro g e n -ric h t r e a t
gas and r a t i o o f h y d ro g e n -ric h t r e a t g as t o cru d e o i l .
A program was s e t up to d eterm in e th e t e c h n i c a l a s p e c ts o f u s in g a
c a t a l y t i c h y d r o d e s u lf u r iz a tio n p ro c e ss f o r h y d ro fin in g cru d e a ro m a tic s .
The i n i t i a l o b je c tiv e s t o be accom p lish ed i n th e in v e s t i g a t i o n were
d e s u lf u r iz a ti o n o f cru d e l i g h t o i l a t m o d e ra tely s e v e re c o n d itio n s :
(A)
To d eterm in e w h eth er a s a t i s f a c t o r y p ro d u c t co u ld be produced
from th e s ta n d p o in t o f s u l f u r c o n te n t, c o rro s io n t e s t and a c id c o lo r t e s t .
(B)
To o b ta in in fo rm a tio n c o n cern in g o p e r a tio n a l d i f f i c u l t i e s
w hich a r i s e and t o e lim in a te such d i f f i c u l t i e s .
A f te r th e above m entioned o b je c tiv e s had been acco m p lish ed , i t was
e v id e n t t h a t a com m ercial p la n t co u ld be s u c c e s s f u l.
T h e re fo re , a de­
t a i l e d ch em ical k i n e t i c s tu d y was u n d e rta k e n t o d e term in e th e e f f e c t o f
o p e ra tin g v a r ia b le s on th e deg ree of d e s u l f u r i z a t i o n „
- 6 -
D uring th e i n i t i a l i n v e s t i g a t i o n , Mr. W illiam H a ll, a r e p r e s e n ta tiv e
from Jo n es and L au g h lin S te e l C o rp o ra tio n , was s e n t t o Montana S ta te C ol­
le g e t o d e fin e th e q u a l i t y s p e c i f i c a t i o n s o f p ro c e ss e d l i g h t o i l and t o
o b serv e work b e in g done.
Based on th e recommendation o f Mr. H a ll and
r e p r e s e n ta tiv e s o f Esso R esearch and E n g in e e rin g a com m ercial l i g h t o i l
h y d ro fin in g p la n t c o s tin g a p p ro x im a te ly th r e e m illio n d o l l a r s was b u i l t
by Badger M an u factu rin g Company f o r th e Jo n es and L au g h lin S te e l C orpora­
t i o n a t A liq u ip p a , P e n n s y lv a n ia .
Much o f th e d a ta o b ta in e d i n t h i s i n ­
v e s t i g a t i o n was u se d by Badger i n d e sig n in g th e com m ercial p l a n t .
The
com m ercial p la n t was p u t o n -stre a m ab o u t J u ly o f 1957* w ith a c a p a c ity
o f 1000 b a r r e l s o f l i g h t o i l p e r day.
-7 -
KINETIG equations used to describe the reaction
The p r i n c i p a l o v e r a l l r e a c tio n i n th e p ro c e s s o f rem oving s u lf u r
from l i g h t o i l i s ;
0Z1hA S + AH2 --------$
H2S + Cz H10
The fo llo w in g i s a summary o f th e m athem atics u sed t o .d e s c r i b e th e
re a c tio n .
1.
Assume t h a t th e r a t e o f r e a c tio n i s dependent oh th e c o n c e n tra ­
t i o n o f th io p h e n e j th e c o n c e n tra tio n o f hydrogen, and th e c o n c e n tra tio n
o f a c ti v e c e n te r s on th e c a t a l y s t (o r some o th e r m easure o f c a t a l y s t
a c t i v i t y ) , and t h a t th e p h y s ic a l s te p s o f d if f u s io n in v o lv e d , i n th e c a ta ­
l y t i c r e a c tio n do n o t c o n tr o l th e r a t e o f r e a c t i o n .
Then th e d e c re a se i n
c o n c e n tra tio n o f th io p h e n e i s g iv e n by th e fo llo w in g e q u a tio n ;
-A(Cth) " kC V t 0H/
0I
(A)
dt
Where (C^j1) i s th e c o n c e n tra tio n o f th io p h e n e a t any tim e ( t ) ,
(Cu ) i s th e c o n c e n tra tio n o f hydrogen a t any tim e ( t ) , and
“2
C1 i s th e number o f a c ti v e c e n te r s which can e n te r i n t o th e
r e a c t i o n , o r some o th e r m easure o f c a t a l y s t a c t i v i t y .
b i s th e o rd e r o f th e r e a c tio n w ith r e s p e c t t o th e c o n c e n tra tio n
o f hydrogen.
2.
L et x e q u a l th e amount o f th io p h e n e re a c te d a t any tim e ( t ) .
The d e c re a se i n th io p h e n e w i l l be e q u a l t o th e amount o f th io p h e n e r e ­
a c te d (x) a t any tim e ( t ) .
dx
dt
= k C1 (A-X) (B -y)^
Then e q u a tio n ( l ) can be w r itt e n ;
(2)
-S Where dbc i s th e r a t e a t which th io p h e n e r e a c t s , o r decom poses,
dt
k i s th e r e a c tio n r a t e c o n s ta n t, dependent on te m p e ra tu re and th e
p a rtic u la r c a ta ly s t,
A i s th e i n i t i a l c o n c e n tra tio n o f th io p h e n e ,
B i s th e i n i t i a l c o n c e n tra tio n o f hydrogen,
x i s th e amount o f th io p h e n e r e a c te d a t any tim e ( t ) , and
y i s th e amount o f hydrogen r e a c te d .
3.
S in ce th e amount o f Hg consumed d u rin g th e r e a c tio n i s n e g lig ib le
compared w ith th e i n i t i a l c o n c e n tra tio n o f hydrogen ( 2 ) , th e v a lu e o f y
can be n e g le c te d . ■ I t fo llo w s , th e n , t h a t ;
_dx_ = k C1 (A-X) (B)b
(3)
dt
I n any s e t o f ru n s where th e c o n c e n tra tio n o f hydrogen and c a t a l y s t a c t i ­
v i t y rem ain c o n s ta n t, e q u a tio n (3 ) , when in te g r a te d betw een th e l i m i t s
x=o and x=x, and t= o t o t = t , becomes;
In A-In(A-X) = k (B)*3 C^t
(4)
Where x i s th e amount o f th io p h e n e r e a c te d i n tim e ( t ) .
W ith a flo w -ty p e r e a c t o r where a l l r e a c t a n t s a r e i n th e v ap o r phase
i t i s custom ary t o m easure ( t ) , which i s a m easure o f a p p a re n t c o n ta c t
tim e , a s r e c i p r o c a l v ap o r r a t e (w eight o f c a t a l y s t / f e e d r a t e ) .
The
a p p a re n t c o n ta c t tim e v a r i e s w ith th e flo w o f r e a c ta n ts o v e r th e c a t a l y s t
and can be c o r r e c te d f o r v a r i a t i o n s i n te m p e ra tu re , p r e s s u r e , t r e a t gas
r a t e and space v e l o c i t y (gm o i l p e r h r p e r gm o f c a t a l y s t ) w ith th e
e x p re s s io n :
-9 -
1
= (lb oil/lOO gm. c a t„/hr . 359 . z + ift^-gas/lOO gm ca tl/h r)
V6R.
Av. M6W6 of o i l
x
A92(P..+ 13)
(T + 460) (14.7)
Where T i s the operating temperature (0F )j
P i s the operating pressure (p s ig ),
z i s the com pressibility factor for lig h t o i l , and
I
i s reciprocal vapor rate and i s given in cu f t of reactants
V6R6
(at operating conditions) per 100 grams of catalyst per hour.
Reciprocal vapor rate can then be used in the place of (t) the
apparent contact time and equation (-4) can be rewritten as:
In
A
A—
x
= K1 I
V6R6
Where K^ equals k(B)^
(5)
in which the reaction rate constant (k) i s
the only variable with respect to temperature a fter the correction for
contact time i s made.
The term (B)*3 i s a function of to ta l pressure
and ra tio of hydrogen-rich trea t gas to charge o i l which must be kept
constant fo r a particular value of ..K^6
4.
The Arrhenius equation i s of the form;
In k = InA - EaRT
Where k i s the reaction rate constant,
A i s the frequency factor which i s constant,
Ea i s the activation energy, and
T i s the absolute temperature,
R i s the gas constant„
= (6)
Ii
11
-
I ?> I
10-
Sub s t i t u t i n g f o r th e r e a c tio n r a t e c o n s ta n t i n te rm s o f
i n t o e q u a tio n
( 6 ) i t becomes:
In
K1
" W r C1
= InA - Ea
ET
(?)
Which can be w r itt e n :
In K1 = InA + b InB + In C1 - Ea
1 RT
Where
(B)
and T a r e th e o n ly v a r ia b le s when th e p re s s u re te rm i s c o n sta n t
and the ca talyst i s established to be 100 percent active throughout a
g iv e n ru n .
Io g 10
E q u atio n (5) can be r e w r itte n :
A ...
A-X '
=
Km
t V
V.R.
(9)
and equation (8) can be rewritten:
Io g 1Z1 Km =
-E a .
2.3; RT
+ lo g C
(10)
Equations.(9) and (10) were used in the k in etic study and values of K^
were determined at various desulfurization conditions.
■I
r s .
Ui
- i i -
EQUIEMEMTj METHODS, AMD ANALYSIS OF PROCESSED LIGHT OIL
'
Equipment
Two r e a c t o r s d e sig n e d f o r u se a t p r e s s u r e s up to 800 p s ig were used
f o r th e i n v e s t i g a t i o n .
The e s s e n t i a l d if f e r e n c e i n th e r e a c to r s was th e
d ia m e te r and le n g th o f c a t a l y s t b ed .
a c to r s was e s s e n t i a l l y th e same.
A u x ilia r y equipm ent f o r b o th r e ­
A sch em atic diagram o f th e p ro c e s s i s
shown i n F ig u re I .
R e a c to r No. I c o n s is te d of an 1 8 -in c h le n g th o f 2 - 3 /8 - in c h I . D . ,
sch ed u le 80, s t a i n l e s s s t e e l p ip e .
The th e rm o w e ll, e x te n d in g down th ro u g h
t h e r e a c t o r from th e to p , was c o n s tr u c te d o f l / 4- in c h , sch e d u le 80, s t a i n ­
l e s s s t e e l p ip e .
Heat was su p p lie d t o th e r e a c t o r w ith 3 3 -f o o t le n g th s
o f beaded Michrome c o i l s co n n ected t o 1 1 0 -v o lt a u to tra n sfo rm e rs .. , The
r e a c t o r was in s u l a t e d w ith l - l / 2 - i n c h la y e r o f m agnesia mud.
P reh e a t
m edia and c a t a l y s t su p p o rt c o n s is te d o f l / 8- in c h alundum (aluminum o x id e )
p e lle ts .
A c a t a l y s t bed o f 100 grams was a p p ro x im a te ly 1 -1 /4 in c h e s i n
le n g t h .
R e a c to r No. 2 was c o n s tr u c te d from 1 -in c h , sch e d u le 80, s t a i n l e s s
s t e e l p ip e a p p ro x im a te ly 28 in c h e s lo n g .
The th erm o w ell, c o n s tru c te d o f
l / 4 - i n c h s t a i n l e s s s t e e l tu b in g , ex ten d ed th ro u g h th e c a t a l y s t b ed .
F iv e
th erm o co u p les spaced a p p ro x im a te ly th r e e in c h e s a p a r t were ,lo c a te d w ith in
th e th e rm o w e ll.
The p re h e a t s e c tio n and c a t a l y s t su p p o rt c o n s is te d o f
l / 8- in c h alundum. p e l l e t s .
The h e a tin g , e lem en ts com prised f o u r .3 3 -fo o t
le n g th s o f beaded Nichrome c o i l s su p p lie d w ith c u rre n t from f o u r 110- v o l t
a u to tr a n s f o r m e r s .
The c o i l s were wound o n to th e r e a c t o r o v e r a la y e r o f
I
a s b e s to s ta p e and in s u l a t e d w ith a 2 -in c h la y e r o f m agnesia mud.
A c a ta ­
l y s t bed o f 100 grams was a p p ro x im a te ly e lev e n in c h e s i n le n g th .
A u x ilia r y equipm ent c o n s is te d o f a p r e - v a p o r iz e r , O a lib ra te d r o t o m e te r, wet t e s t m e te r, w a te r c o o led c o n d e n se r, No. 2 gas c y lin d e r s and
h ig h - p r e s s u r e r e g u l a t o r s , Jerg u so n p ro d u c t r e c e iv e r , and a l k a l i and
w a te r p ro d u c t s c ru b b e rs .
The a l k a l i p ro d u c t s c ru b b e r c o n ta in e d 30 p e r­
c e n t aqueous NaOH s o lu tio n .
Methods
C o n tro l and measurem ent o f p ro c e s s o p e ra tin g v a r ia b le s were con­
d u c te d a s d e s c rib e d i n th e fo llo w in g p a ra g ra p h s „
(1 )
P ressu re:
The r e a c t o r p re s s u re was c o n tr o lle d w ith a l/2 - in c h
M ason-N eilan sm a ll volume a i r - t o - e l o s e r e g u la to r v a lv e , and a F is h e r Wizard'. p r o p o r tio n a l c o n t r o l l e r .
A h ig h p r e s s u r e gage down stream from
th e r e a c t o r was u sed to m easure p r e s s u r e .
M easurem ents were re c o rd ed
a t l / 2-h o u r i n t e r v a l s .
(2)
T em p eratu re:
T em perature was c o n tr o lle d by a d ju s t in g th e i n ­
p u t t o th e Nichrome h e a tin g elem en ts w ith a u to tr a n s f o r m e r s .
C o n stan t
v o lta g e was s u p p lie d to th e a u to tra n s f o rm e rs w ith a 2000 w a tt c o n sta n t
v o lta g e tr a n s f o r m e r .
T em peratures were m easured At 3 0-m inute i n t e r v a l s
w ith iro h ^ c o n s ta n ta n th erm o co u p les u sed i n c o n ju n c tio n w ith a Leeds and
N o rth ro p in d ic a tin g p o te n tio m e te r .
(3 )
T r e a t-g a s r a t e :
T r e a t-g a s r a t e was c o n tr o lle d by a d ju s tin g
th e n e e d le v a lv e lo c a te d downstream from th e fe e d ta n k , h ig h p re s s u re
r e g u l a t o r and c a l i b r a t e d ro to m e te r.
C o n sta n t p re s s u re was m a in ta in e d
-1 3 -
i n th e ro ta m e te r w ith th e h ig h p r e s s u r e r e g u la to r co nnected t o th e fe e d
ta n k .
M easurem ents and a d ju stm e n ts were made a t l/2 - h o u r i n t e r v a l s .
(U)
Space v e l o c i t y :
Space v e l o c i t y was a l t e r e d by pump a d ju stm e n ts
and d eterm in ed a t th e end of each run from c a lc u la tio n s in v o lv in g th e
W eight o f o i l c h arg ed , th e c a t a l y s t c h a rg e , and th e o n -stre a m tim e .
A n a ly sis o f P ro c e sse d L ig h t O il
Methods for determining the thiophene content, corrosiveness and
acid-wash color of the processed lig h t o i l are summarized in the follow ­
ing paragraphs.
The d etailed step by step determinations for acid-wash
color and corrosiveness are given in Tables XX and XXE, resp ectively (3 ).
(l)
Thiophene D e te rm in a tio n :
A n a ly sis f o r th io p h e n e i n benzene
i s a s ta n d a rd t e s t proposed by duPont ( l ) .
The b a s is o f th e t e s t i s th e
r e a c tio n o f i s a t i n and th io p h e n e i n a s o lu tio n o f f e r r i c s u l f a t e in
s u lfu ric a c id .
A compound c a ll e d in d o p h en in i s form ed which h as a
c h a r a c t e r i s t i c deep b lu e -g rd e n c o lo r .
m easure o f th io p h e n e c o n c e n tr a tio n .
The i n t e n s i t y o f th e c o lo r i s a
A s ta n d a rd c a l i b r a t i o n curve w ith
tra n s m is s io n v e rs u s th io p h e n e ( p a r t s p e r m illio n th io p h e n e on w eight
b a s is ) i s d eterm in ed w ith th e a id o f a s p e c tro p h o to m e te r.
d i s t i l l a t i o n i s c a r r ie d o u t on th e p ro c e s s e d l i g h t O i l i
A sim ple
The f i r s t f i v e
p e rc e n t o f l i g h t o i l d i s t i l l e d o v e r and th e m a te r ia l b o ilin g above 90°C
a r e d is c a rd e d and th io p h e n e d e te rm in a tio n s a r e made on th e rem aining o i l
(benzene c u t ) .
The end p o in t o f t h i s f r a c t i o n i s so low t h a t e s s e n t i a l l y
no a l k y l th io p h e n e s co u ld be p r e s e n t.
Thiophene c o n te n t o f th e benzene
c u t i s r e p o r te d i n ppm on a w eight b a s i s .
—1/j—
(2 )
A cid c o lo r t e s t s
to lu e n e , and x y le n e c u t s .
The a c id c o lo r t e s t s were made on th e benzene,These sim ple d i s t i l l a t i o n c u ts a r e : b en zen e-
I 0B0P . t o 90°C; to lu en e-9 0 °G t o IlO 0C; xylene-110°C to E .P .
Seven m i l l i ­
l i t e r s o f re a g e n t g ra d e s u l f u r i c a c id and 28 m i l l i l i t e r s o f sample a re
p la c e d i n a s p e c ia l t e s t b o t t l e and th e c o n te n ts a g i t a t e d a t a s p e c if ie d
r a t e f o r 15 seco n d s.
The la y e r s a r e allo w ed t o s e t t l e and th e c o lo r o f
th e a c id la y e r i s m atched w ith th e c o lo r o f a s ta n d a r d i
a re numbered from 0 t o 14«
The s ta n d a rd s
The number o f th e s ta n d a rd w hich b e s t m atches
th e sample i s r e p o r te d a s th e acid -w ash c o lo r number o f th e sam ple.
(3)
C o p p e r -s trip c o rro s io n t e s t :
A pproxim ately 50 m l o f p ro c e sse d
l i g h t o i l a r e p la c e d i n a 200 m l f l a s k co n n ected t o a v e r t i c a l co n d en ser.
A c le a n p o lis h e d copper s t r i p i s p la c e d i n th e f l a s k and th e o i l i s r e ­
flu x e d f o r o n e -h a lf h o u r.
The o i l i s s a id t o be c o rro s iv e i f th e copper
s t r i p u n dergoes a n o tic e a b le d a rk e n in g .
-1 5 -
DISCUSSION AND RESULTS
I n i t i a l I n v e s tig a t io n Concerned W ith The F e a s i b i l i t y Of H y d ro fin in g
Crude Light. O il I n A H y d ro d e s u lfu riz a tio n P i l o t P l a n t .
The purp o se o f th e i n i t i a l i n v e s t i g a t i o n was t o d e term in e w hether
cru d e l i g h t o i l co u ld be h y d ro fin e d e f f e c t i v e l y i n a c a t a l y t i c hydro­
d e s u lfu riz a tio n u n it.
A t o t a l o f n in e ru n s were made, th r e e u s in g l i g h t
o i l produced by Jo n es and L au g h lin (j& L -l, - 2 , -3 ) and s i x ru n s u sin g
l i g h t o i l produced by U n ite d S ta te s S te e l C o rp o ra tio n ( U .S .S .- l , - 2 , - 3 ,
-4 ,
- 6) .
The ASTM D i s t i l l a t i o n d a ta f o r Runs J& L -l, - 2 , and -3 and
Runs U .S .S .- i , - 2 , - 3 , -k> - 5 , and -6 a r e g iv en i n T ab les I and V,
re s p e c tiv e ly .
R e a c to r No, I d e s c rib e d u n d e r th e h ead in g "Equipment"
was u sed th ro u g h o u t th e r u n s .
R e s u lts f o r each o f th e n in e ru n s a re
d e s c rib e d i n t a b l e form i n th e a p p en d ix .
A b r i e f resume o f each run
i s given i n th e fo llo w in g p a ra g ra p h s .
Run J& L -l:
The c o n d itio n s chosen f o r th e run to acco m p lish th e
d e s ir e d deg ree o f p ro c e s s in g were 600 t o 650°F, 400 p s ig , 2 gm o f o i l p e r
h our p e r gm o f c a t a l y s t , and 1000 f t ^ / b b l f o r te m p e ra tu re , p r e s s u r e , space
v e l o c i t y , and t r e a t gas r a t e , r e s p e c tiv e ly .
Pure hydrogen t r e a t gas was
u sed f o r th e f i r s t 245 h o u rs o n -stre a m tim e and a m ix tu re o f 50 p e rc e n t
hydrogen and 50 p e rc e n t n itr o g e n was u sed to com plete th e ru n .
F re s h ly
d i s t i l l e d crude l i g h t o i l s to r e d u n d er an atm osphere o f n itr o g e n was
u sed a s f e e d .
The thiophene content in the benzene-nut from the product o i l was
reduced from approximately 7200 ppm (0 . 72%) to 0.43 ppm a fte r 27 hours
IL
-
11
16 -
o n -stre a m t i m e .a t a space v e l o c i t y o f 2gm/hr/gm.
The a c id c o lo r t e s t s
were s a t i s f a c t o r y a t t h i s tim e and th e c o rro s io n t e s t s became s a t i s f a c t o r y
a f t e r $0 h o u rs on stre a m .
Two d is tu rb a n c e s o c c u rre d d u rin g th e ru n ; th e f i r s t a f t e r 63 h o u rs
and th e second a f t e r 151 h o u rs on stre a m .
Both d is tu r b a n c e s , caused by
m e c h a n ic a l f a i l u r e , r e s u l t e d i n p o o r p ro d u c t (T ab le I I ) .
A f te r 240 h o u rs on stre a m , th e fe e d o i l was changed from l i g h t o i l
p r o te c te d from a i r t o a l i g h t o i l t h a t had been s to re d f o r s e v e r a l months
i n a drum w ith no p re v e n tio n from c o n ta c t w ith a i r d u rin g s to r a g e .
l i g h t o i l te n d s t o darken on s ta n d in g .
S to re d
Carbon form ed w ith in th e r e a c to r
r e s u l t i n g i n e x c e s s iv e p r e s s u r e drop a c r o s s th e r e a c t o r a f t e r 260 h o u rs
on stre a m .
Eun J&L-2:
T h is run was a c o n tin u a tio n Run J& L-l a f t e r carbon f o r ­
m ation on th e p r e - h e a t m edia and c a t a l y s t w ith in th e r e a c tio n had been
b u rn ed o f f w ith a i r .
The f i r s t p a r t o f th e ru n was made u s in g pure
hydrogen t r e a t gas and th e l a t t e r p a r t u s in g 50% Hg - 50%
t r e a t gas.
The l a t t e r p a r t o f th e run (T able I I I ) showed t h a t th e th io p h e n e in l i g h t
o i l co u ld be reduced from 7200 ppm t o l e s s th a n I ppm a t o p e ra tin g co n d i­
t i o n s o f 650°F, 400 p s ig , 2 gm/hr/gm and 1000 f t ^ / b b l 50% Hg - 50% Ng f o r
te m p e ra tu re , p r e s s u r e , space v e l o c i t y and t r e a t g a s , r e s p e c tiv e ly .
Thus,
a t th e s e c o n d itio n s , s p e c i f i c a t i o n p ro d u c t can be produced when a t r e a t
g a s c o n ta in in g 50% hydrogen and 50% n itr o g e n i s u se d .
Run J&L-3;
A r e c u r r e n t o p e ra tin g d i f f i c u l t y was e n co u n te re d when
ch arg e o i l which had been s to r e d w ith no p r o te c tio n from a i r was u sed .
-1 7 -
A b u ild - u p o f coke form ed where th e o i l was v a p o riz e d , c a u sin g e x c e s siv e
p r e s s u r e drop th ro u g h th e r e a c t o r .
I n th e J&L-3 ru n , a p r e - v a p o r iz e r
(F ig u re l ) was connected i n t o th e o i l l i n e le a d in g from th e fe e d pump t o
th e r e a c t o r .
The p r e - v a p o r iz e r was m a in ta in e d a t a te m p e ra tu re o f 600°F
th ro u g h o u t th e ru n .
Ho n o tic e a b le p r e s s u r e drop was e n co u n te re d d u rin g .
th e 72-h o u r ru n , and p ro d u c t c o n ta in in g a p p ro x im a te ly 0 .1 ppm th io p h e n e
was produced c o n tin u o u s ly (T able IV ) .
Most o f th e carbon laydown, r e ­
s u l t i n g when th e l i g h t o i l i s v a p o riz e d , o c c u rre d i n th e p r e - v a p o r iz e r
r a t h e r th a n i n th e r e a c t o r .
Carbon m ust be c lea n e d from t h e p re ­
v a p o r iz e r p e r i o d i c a l l y .
Bun U . S . S . - l :
O p e ra tin g c o n d itio n s f o r th e ru n were a p p ro x im a te ly
2 gm/hr/gm and 580°F;• p u re hydrogen was u sed a s t r e a t g a s .
v a p o r iz e r was u s e d .
No p re ­
The charge o i l had a c o n s id e ra b ly h ig h d i s t i l l a t i o n
end p o in t and c o n ta in e d a p p ro x im a te ly 15 p e rc e n t more x y le n e th a n d id
th e o i l u se d d u rin g th e JScL r u n s .
A com parison o f th e r e s u l t s from ASTM
d i s t i l l a t i o n s f o r th e ru n s can be made from T ab les I and V i n th e a p p en d ix .
The charge o i l which had n o t been p r o te c te d from a i r d u rin g s to ra g e con­
t a i n e d a s m a ll amount o f po ly m erized m a te r ia l.
B e s u lts o f th e a c id c o lo r t e s t s on th e p ro d u c t o i l (T ab le VI) were
v e ry p o o r — i n th e ran g e o f 12 t o 14 f o r th e benzene c u t.
These r e s u l t s
in d ic a te d t h a t a l i g h t o i l h av in g a h ig h e r b o ilin g ran g e (c o n ta in in g more
x y le n e ) r e q u ir e d a h ig h e r degree o f p ro c e s s in g .
Bun U .S .S .- 2 :
T h is run was a c o n tin u a tio n o f Bun U .S . S . - l ,
O p erat­
in g c o n d itio n s were th e same ex cep t t h a t th e te m p e ra tu re was in c re a s e d
C
11'
-1 8 from a p p ro x im a te ly 580°F t o 6$0°F.
R e s u lts o f t h i s ru n (T ab le H I ) were ,
b e t t e r th a n th o s e o f th e p re c e d in g r u n , b u t n o t a s good a s th e r e s u l t s
from JSeL r u n s , a lth o u g h o p e ra tin g c o n d itio n s f o r th e ru n s were ab o u t th e
same.
T h is run i n d ic a te d , a s d id th e p re v io u s ru n , t h a t th e h ig h e r
b o ilin g l i g h t o i l i s more d i f f i c u l t t o p ro c e ss th a n i s th e lo w er b o ilin g
lig h t o il.
Run U oSoS,-3:
Run U ,S ,S ,-3 was conducted f o r 570 h o u rs a t space
v e l o c i t i e s ra n g in g from 0 ,7 t o 2 .5 gm /hr/gm ; o th e r c o n d itio n s were 650°F
and 400 p s i g .
The charge o i l was th e same a s t h a t u sed i n Run U .S .S .-2 .
The p r e - v a p o r iz e r , u sed th ro u g h o u t t h e ru n , was c le a n e d tw ic e b ecau se o f
e x c e s s iv e p re s s u re drop caused by carbon fo rm a tio n ,
As th e p re s s u re drop
th ro u g h th e p r e - v a p o r iz e r in c r e a s e d ,th e spaed v e l o c i t y d e c re a se d and th e
t r e a t gas r a t e in c r e a s e d , c a u sin g v a r i a t i o n s i n o p e ra tin g v a r i a b l e s .
The r e s u l t s o f T able H I I in d i c a t e t h a t th e l i g h t o i l from th e U n ited
S ta te s S t e e l C o rp o ra tio n can be
s u c c e s s f u lly d e s u lf u r iz e d a t a space
v e l o c i t y o f 1 .5 gm/hr/gm f o r a t l e a s t 400 h o u rs u s in g p u re hydrogen t r e a t
g as.
R e s u lts a ls o show t h a t p ro d u c t h av in g a s a t i s f a c t o r y a c id c o lo r t e s t
and c o n ta in in g a p p ro x im a te ly 8 ppm th io p h e n e can be produced a t a space
v e l o c i t y o f I gm/hr/gm u s in g mixed g a s .
A com parison o f r e s u l t s from th e b e g in n in g o f th e ru n w ith r e s u l t s
n e a r th e end of th e ru n show t h a t th e c a t a l y s t had d e g e n e ra te d somewhat
(c h e m ica l d e a c tiv a tio n o f th e c a t a l y s t was r e f e r r e d to a s c a t a l y s t de­
g e n e r a tio n th ro u g h o u t t h i s i n v e s t i g a t i o n ) .
Thiophene c o n te n t o f th e
p ro d u c t had in c r e a s e d from a p p ro x im a te ly 2 ppm t o 9 ppm o v e r a p e rio d o f
LI fi
-1 9 -
400 h o u rs » D uring J& L-l r u n , c a t a l y s t a c t i v i t y rem ained f a i r l y c o n s ta n t
f o r 245 h o u rs on s tre a m .
Thus, a ch arg e o i l which h as n o t been p r o te c te d
from a i r c a u se s more c a t a l y s t d e g e n e ra tio n a s a r e s u l t o f carbon fo rm a tio n
on th e c a t a l y s t .
Run U .S .S .- 4 :
D uring t h e ru n , two te m p e ra tu re s were u sed — 600°F
and 650°F; and t h r e e t r e a t g a s m ix tu re s were employed — 50# H2 - 50#
N2 , 100# Hg, and 50# H2 - 50# CH^„
A p r e s s u r e o f 400 p s ig was u se d .
The r e s u l t s giv en i n T ab le IZ show t h a t b e t t e r d e s u lf u r iz a ti o n i s
acco m p lish ed a t 650°F th a n a t 600°F when u sin g 50# Hg - 50# Ng t r e a t g a s .
At 650°F and 600°F, a p ro d u c t c o n ta in in g 0 ,2 5 and 4 .5 ppm th io p h e n e ,
r e s p e c t i v e l y , i s o b ta in e d a t space v e l o c i t i e s o f a p p ro x im a te ly I gm/hr/gm.
The r e s u l t s from t h i s ru n a ls o show, a s d id th e r e s u l t s o f Run. U .S .S .-3 ,
t h a t a p ro d u c t (Sample 3 5 , T able IX) c o n ta in in g l e s s th a n I ppm th io p h e n e
co u ld be produced a t 650°F, 400 p s ig , 1 .0 gm/hr/gm and 1000 f t ^ / b b l p u re
hydrogen t r e a t g a s .
A com parison o f th e r e s u l t s from Samples 39 th ro u g h
46 w ith th e r e s u l t s from Samples 50 th ro u g h 62 (T able IX) shows t h a t
a p p ro x im a te ly th e same d e g re e o f p ro c e s s in g i s o b ta in e d when u s in g e i t h e r
n itr o g e n o r m ethane a s a d ilu e n t i n th e t r e a t gas a t th e g iv e n o p e ra tin g
c o n d itio n s .
Run U .S .S o -5 , - 6 ?
From th e r e s u l t s d is c u s s e d i n th e p re c e d in g tU S .S .
R uns, o p e ra tin g c o n d itio n s were d e term in e d a t which U .S .S . l i g h t o i l
c o u ld be p ro c e ss e d e f f e c t i v e l y .
f i c a t i o n l i g h t , o i l was p ro d u ced .
However, o n ly a sm all q u a n tity o f s p e c i­
I n th e fo llo w in g two r u n s , s p e c i f i c a t i o n
l i g h t o i l was produced c o n tin u o u s ly f o r 155 and 138 h o u rs , r e s p e c tiv e ly .
r
-2 0 -
Both ru n s w ere conducted a t a p p ro x im a te ly 650°F , 400 p s ig , and 1000 f t V
b b l p u re h ydrogen.
The charge o i l u sed i n Run U .S .S .- 5 had a s l i g h t l y lo w er b o ilin g
ran g e th a n t h a t u sed i n Run U .S ,S ,T6 .
A com parison o f th e r e s u l t s shown
i n T a b le s X and XX i n d i c a t e s t h a t w ith th e lo w er b o ilin g l i g h t o i l , a
p ro d u c t c o n ta in in g an a v erag e o f 0 . 1$ ppm th io p h e n e co u ld be produced a t
a space v e l o c i t y of 1 .3 3 gm /hr/gm , w h ile w ith th e h ig h e r b o ilin g l i g h t
o i l , (Run U .S .S 0- 6 ) , a p ro d u c t c o n ta in in g an av erag e o f 0 ,3 1 ppm th io p h e n e
co u ld be o b ta in e d a t 1 .0 gm /hr/gm .
b o th ru n s were s a t i s f a c t o r y .
A cid c o lo r and c o rro s io n t e s t s f o r
No n o tic e a b le c a t a l y s t d e g e n e ra tio n o c c u rre d
d u rin g th e ru n s ; how ever, b o th ru n s were i n t e r r u p t e d f o r s h o r t p e rio d s
a s a r e s u l t o f carbon fo rm a tio n w ith in th e p r e - v a p o r iz e r .
C o n c lu sio n :
R e s u lts o f th e fo re g o in g ru n s show t h a t l i g h t o i l hav­
in g a b o ilin g range o f a p p ro x im a te ly l 60- 280°F can be e f f e c t i v e l y p ro ­
c e sse d i n a h y d r o d e s u lf u r iz a tio n u n i t a t 600°F, 400 psig> 1000 f t ' 5/ b b l
p u re hydrogen and 2 gm/hr/gm f o r te m p e ra tu re , p r e s s u r e , t r e a t gas r a t e ,
and space v e l o c i t y , r e s p e c t i v e l y .
L ig h t o i l h aving a h ig h e r b o ilin g
ran g e m ust be h y d ro fin e d a t more s e v e re c o n d itio n s .
A . t r e a t gas c o n ta in ­
in g e i t h e r 50% Hg - 50% Ng o r 50% Hg - $0^ CH^ can be u sed e f f e c t i v e l y
i n th e p ro c e s s b u t more s e v e re c o n d itio n s a r e re q u ire d th a n when pure
hydrogen t r e a t gas i s u s e d .
More s e v e re c o n d itio n s can be o b ta in e d by
in c r e a s in g such v a r ia b le s a s te m p e ra tu re o r c o n ta c t tim e
space v e l o c i t y ) .
(d e c re a se d
Charge o i l which has been s to r e d f o r s e v e r a l months
w ith o u t p r o te c tio n from a i r c au ses c o n s id e ra b ly more carb o n laydown
-2 1 -
vd.thin th e equipm ent th a n does l i g h t o i l which has been f r e s h l y d i s t i l l e d
o r p r o te c te d from a i r d u rin g s to r a g e .
The Study Of P ro c e s s V a ria b le s Through The Use Of. R ate E q u a tio n s .
A t o t a l o f f o u r te e n ru n s d e s ig n a te d U .S .S .-1 0 th ro u g h U .S .S .-2 4 was
made t o i n v e s t i g a t e th e k i n e t i c s o f th e r e a c tio n f o r rem oving s u lf u r from
l i g h t o i l w ith hydrogen.
Runs U .S .S .-1 0 th ro u g h U .S .S .-1 9 and Runs
U .S .S .-2 1 and -2 2 were conducted w ith l i g h t o i l which had been p re v io u s ly
s to r e d f o r s e v e r a l m onths, w h ile Runs U .S .S .-2 0 , -2 3 , and -2 4 were con­
d u c ted u s in g f r e s h l y d i s t i l l e d l i g h t o i l .
The ASTM d i s t i l l a t i o n d a ta f o r
th e v a r io u s charge s to c k s a r e given i n T ab le X II.
R e a c to r No. I was u sed
d u rin g Runs U .S .S .-IO th ro u g h U .S .S .-1 6 and R e a c to r No. 2 was used th ro u g h ­
o u t th e rem ain in g r u n s .
S h o rt ru n s were conducted when s to r e d l i g h t o i l was u sed a s fe e d ,
t o in s u r e c o n s ta n t c a t a l y s t a c t i v i t y .
When f r e s h l y d i s t i l l e d l i g h t o i l
fe e d was u s e d , a run l a s t i n g 386 h o u rs (Run U .S .S .-2 3 ) was conducted w ith
no a p p a re n t c a t a l y s t d e g e n e ra tio n and w ith o u t n o tic e a b le p r e s s u r e drop
a c r o s s th e p r e - v a p o r iz e r o r r e a c t o r .
L ess th a n 0 .0 1 w eig h t p e rc e n t of
th e charge o i l was tra n s fo rm e d t o carbon i n th e p r e - v a p o r iz e r when
f r e s h l y d i s t i l l e d charge o i l was u se d .
The r e s u l t s o f th e k i n e t i c stu d y were a n aly z e d th ro u g h th e u se of
th e p s e u d o - f ir s t o rd e r e q u a tio n , namely;,
lo g A
A-Z
= Km___1_ .
(9)
V.R.
Where A i s th e i n i t i a l c o n c e n tra tio n o f th io p h e n e (7200 ppm on w t. b a s i s ) .
-2 2 -
A-X i s c o n c e n tra tio n o f th io p h e n e rem ain in g a f t e r d e s u lf u r iz a ti o n
(ppm ).
Kt i s th e o v e r a ll r a t e c o n s ta n t (ft^ /lO O gm c a t / h r a t o p e ra tin g
c o n d itio n s and i s r e s t r i c t e d to a g iv en te m p e ra tu re , t o t a l p r e s s u r e ,
p a r t i a l p re s s u re o f hydrogen and p a r t i a l p r e s s u r e o f d ilu e n t g a s .
V.R. i s giv en a s t o t a l cu f t o f t r e a t g as and o i l p e r 100 grams of
c a t a l y s t p e r h o u r a t c o n d itio n s o f th e r e a c t i o n .
V alues o f Kt .were d e te r
m ined a t v a rio u s c o n d itio n s and compared q u a n t i t a t i v e l y .
I n F ig u re s 2 and 3 , th e r e s u l t s shown i n T a b le s XIV and XV from
Run - I ? and Run -2 2 , r e s p e c tiv e ly , a r e p l o t t e d w ith lo g A/A-X v e rs u s
r e c ip r o c a l v ap o r r a t e .
The f i g u r e s in d i c a t e t h a t th e k i n e t i c s o f th e
r e a c tio n can be d e s c rib e d , w ith in e x p e rim e n ta l a c c u ra c y , f a i r l y w e ll by
t h e p s e u d o - f i r s t - o r d e r r a t e e q u a tio n .
The r a t e e q u a tio n f o r th e s e two
ru n s i s v a l i d f o r c o n c e n tra tio n s o f th io p h e n e a s low a s 0 .5 ppm.
R e s u lts
f o r Runs -1 9 and ^20 shown i n T able XV and p l o t t e d i n F ig u re 4 (lo g A/A-X
v e rs u s r e c ip r o c a l v a p o r r a t e ) a ls o i n d i c a t e t h a t th e r a t e e q u a tio n i s
v a l i d f o r c o n c e n tra tio n s o f th io p h e n e i n th e ran g e o f 0 .2 5 ppm.
E f f e c t Of T em perature On Kt ;
The q u a n t i t a t i v e e f f e c t o f te m p e ra tu re
on th e v a lu e o f Kt h a s been s tu d ie d th ro u g h t h e u se of th e A rrh e n iu s
e q u a tio n , nam ely:
lo g
K =
1U 1
"Where:
-E a
+ In C
2.3 RT
Ea i s a c t i v a t i o n energy (K c a l/ m o l) .
R i s th e g as c o n s ta n t (K c a l/m o l °K) .
T i s r e a c tio n te m p e ra tu re ( 0K ).
(10)
-2 3 -
V alues o f
were d e term in e d a t v a rio u s te m p e ra tu re s from e q u a tio n (9)
a t c o n s ta n t t o t a l p re s s u re o f hydrogen and p a r t i a l p r e s s u r e o f d ilu e n t
gas.
V a r ia tio n s in a p p a re n t c o n ta c t tim e , caused by changes i n tem pera­
t u r e , a r e com pensated f o r th ro u g h th e u se o f e q u a tio n ( 9 ) .
T h e re fo re ,
th e d if f e r e n c e s i n th e v a lu e s o f K d eterm in ed a t v a rio u s te m p e ra tu re s
shotild be a r e s u l t e s s e n t i a l l y due t o th e e f f e c t o f te m p e ra tu re on
R e s u lts o f th r e e ru n s were u sed t o s tu d y th e e f f e c t o f te m p e ra tu re
on Krp„ Runs d e s ig n a te d U ,S0S .-10 and -1 1 (T able K i l l ) were r e p l i c a t e
ru n s w ith d i f f e r e n t te m p e ra tu re sequences ($ te m p e ra tu re s f o r each ru n )
p ic k e d a t random.
T em peratures ra n g in g from 650 t o 850°F were employed.
O th er o p e ra tin g v a r ia b le s were 400 p s ig and 1000 f t ^ / b b l $0% Hg - 50$ Ng
tr e a t g as.
Run d e s ig n a te d U .S .S .-2 4 (T ab le KVII) was c a r r ie d o u t a t
te m p e ra tu re s ra n g in g from 525 t o 725 ° F , 200 p s ig and 1000 f t ^ / b b l t r e a t
g as.
Two te m p e ra tu re sequences were in v e s t ig a te d d u rin g th e ru n ; one
sequence was made u sin g p u re hydrogen and th e o th e r u s in g 50$ Hg - 50$ Ng
tr e a t g as.
The ta b u la te d r e s u l t s o f Runs U .S .S .-1 0 and -1 1 a r e g iv en i n T able
K i l l and a p l o t o f th e s e r e s u l t s i s shown i n F ig u re 5«
The term
2 + lo g
Km i s p l o t t e d v e rs u s r e c ip r o c a l a b s o lu te te m p e ra tu re ( 0K ). A
10 i
s t r a i g h t l i n e w ith a slo p e b q u al t o -E a /2 .3 RT i s o b ta in e d . C a lc u la tio n
o f Ea , th e en erg y o f a c t i v a t i o n , r e s u l t s i n a v a lu e o f a p p ro x im a te ly 10 JC
c a l/m o l.
T a b u la te d r e s u l t s o f Run U .S .S .-2 4 a r e g iv en in T ab le KVII and p l o t ­
t e d i n F ig u re 6 .
These r e s u l t s a r e a ls o d e s c rib e d q u ite a d e q u a te ly w ith
th e u se o f t h 6 A rrh e n iu s e q u a tio n .
Nhen I + I o g ^ K^ i s p l o t t e d v e rs u s
- lZhrr e c ip r o c a l te m p e ra tu re , a s t r a i g h t l i n e r e s u l t s when e i t h e r p u re hydrogen
o r 50$ Hg - 50$ Wg t r e a t g as i s u sed f o r d e s u l f u r i z a t i o n .
However, i t i s
a p p a re n t t h a t th e v a lu e o f Ea (13 K c a l/m o l) when u s in g p u re hydrogen i s
s i g n i f i c a n t l y d i f f e r e n t from th e v a lu e o f Ea (8 K c a l/m o l) when u sin g
$0$ Hg - 50% W2 t r e a t g a s .
The r e s u l t s p l o t t e d i n F ig u re 6 a ls o in d ic a te
t h a t th e v a lu e s o f Kjt may be n e a r ly e q u a l a t te m p e ra tu re s i n th e range
o f 500°F„
E f f e c t Of P re s s u re On Kj :
I n o rd e r t o d eterm in e th e e f f e c t o f t o t a l
p r e s s u r e and r a t i o o f p a r t i a l p r e s s u r e hydrogen t o p a r t i a l p re s s u re o i l
on th e r a t e o f d e s u l f u r i z a t i o n , th e r a t e c o n s ta n t (Kj,) was c a lc u la te d
from th e v a rio u s p l o t s o f lo g A/A-X v e rs u s r e c ip r o c a l v a p o r r a t e .
In
c a s e s where o n ly one s e t o f c o n d itio n s was u s e d , th e v a lu e o f Kp was c a l ­
c u la te d d i r e c t l y from th e d a ta w ith th e u se o f e q u a tio n ( 9 ) .
R e s u lts from Runs D ,S .S .-1 5 i tJ .S .S e -lS , -1 9 , and -2 1 , and U .S .S ,-2 3
g iv e n i n T a b le s XTF, XV", and XVI, r e s p e c t i v e l y , were u sed t o show th e
e f f e c t o f t o t a l p r e s s u r e on th e v a lu e o f Kj,.
V alues o f Kjl were o b ta in e d
a t c o n s ta n t c o n d itio n s , e x ce p t f o r p r e s s u r e and space v e l o c i t y d u rin g
each ru n .
v a lu e s o f
A resume o f th e s e r e s u l t s i s shown i n T able XVIII and th e
v e rs u s t o t a l p r e s s u r e a r e p l o t t e d i n F ig u re 7«
The r e s u l t s shown i n F ig u re 7 i n d i c a t e t h a t th e v a lu e o f Kj, i s , in
g e n e r a l, a f f e c t e d a d v e r s e ly w ith in c r e a s e i n p r e s s u r e ,. w h eth er pure
hydrogen o r mixed gas i s u sed a s t r e a t g a s .
T h is a d v e rse e f f e c t has been
a t t r i b u t e d t o p r e f e r e n t i a l a d s o rp tio n of o i l on th e c a t a l y s t s u rfa c e a t
h ig h e r p r e s s u r e s , th u s e lim in a tin g " i s l t e s " o r " a c tiv e c e n te r s " cap ab le
o f a d so rb in g hydrogen0
I i Ii I
-2 5 TABLE XVIII
R e s u lts P lo t te d i n F ig u re 7
Run No.
U .S .S .-1 5
U .S .S .-1 8
U .S .S .-1 9
0 .S .S .- 1 9
U o S .S .-2 i
U .S .S .-2 3
T re a t Gas
50# H ,-50# N2
50# Hp-50# Np
50# Hg-50# Np .
Pure Hg
P ure Hg
Pure Hg
Ky ( a t fo llo w in g p r e s s u r e s , p s ig )
100
200
400
800
—
—
-
1 .3 4
0 .8 1
0 .6 1
—
—
1 .3 2
1 .1 0
0 .6 3
0 .5 9
0 .4 2
0 .8 1
0 .8 9
1 .2 9
0 .4 9
0 .3 9
0 .3 9
0.8 3
0 .5 5
The e f f e c t o f t o t a l p r e s s u r e on th e d eg ree o f d e s u lf u r iz a ti o n can be
seen from F ig u re 8 (T ab le XV), where lo g A/A-X i s p l o t t e d v e rs u s r e c ip r o ­
c a l v ap o r r a t e o
The d eg ree o f d e s u lf u r iz a ti o n was d eterm in ed a t 200, 400,
and 800 p s ig u s in g b o th p u re hydrogen and 50# H2 - 50#
slo p e o f ta n g e n ts drawn t o th e cu rv es i s e q u a l t o Ky.
t r e a t g as.
The
Again i t i s a p p ar­
e n t t h a t a s th e t o t a l p re s s u re i s in c r e a s e d , th e v a lu e of Ky i s d e c re a se d .
However, i t should be n o te d t h a t th e d eg ree o f d e s u lf u r iz a ti o n i s much
g re a te r a t g re a te r p re ssu re s.
The v a lu e o f Ky d eterm in ed a t d i f f e r e n t '
p r e s s u r e s and c o n s ta n t w eig h t r a t i o o f fe e d t o c a t a l y s t does n tit r e l a t e
th e t r u e e f f e c t of p r e s s u r e on th e d eg ree o f d e s u l f u r i z a t i o n .
An in c r e a s e
i n p r e s s u r e w i l l in c r e a s e th e a p p a re n t c o n ta c t tim e ( r e c i p r o c a l vapor
r a t e ) and t h i s f a c t o r h as a much g r e a t e r e f f e c t on th e d eg ree o f d e s u lf u r i­
z a tio n th a n does th e d e c re a se i n Ky caused by in c re a s e d p r e s s u r e .
The e f f e c t on Ky caused by ad d in g d ilu e n t gas such a s n itr o g e n to
th e t r e a t g as can be d eterm in ed from com parisons Of r e s u l t s shown i n
F ig u r e s 9, 10, and 11 (T ab le s XIV, XV, XVI, r e s p e c t i v e l y ) , where lo g A/A-X
i s p l o t t e d v e rs u s r e c i p r o c a l v ap o r r a t e .
These com parisons in d i c a t e t h a t
t h e v a lu e o f -K j, when u s in g 1000 f t ^ / b b l 50# Hg - 50# Hg Us t r e a t g a s , i s
y
—26—
a p p ro x im a te ly 60-70 p e rc e n t of t h a t when u sin g 1000 f t 3 / b b l o f p u re
hydrogen t r e a t gas i n th e ran g e o f 200 t o 400 p s ig and 62$ t o 650°F.
At
t r e a t gas r a t e s o f 1000 f t 3/ b b l p u re hydrogen and 1000 f t ^ / b b l $ (# H2 $0% N2 , th e r a t i o s of th e p a r t i a l p r e s s u r e s
p ro x im a te ly 0 ,8 6 and 0 ,4 3 , r e s p e c t i v e l y .
hydrogen to o i l i s d e c re a s e d , th e v a lu e o f
o f hydrogen t o o i l a re ap­
T h e re fo re i when th e r a t i o o f
d ecreases.
The e f f e c t o f d e c re a s in g th e r a t i o o f p a r t i a l p r e s s u r e hydrogen to
o i l i s a ls o shown i n F ig u re 1 2 .
V alu es o f K_ c a lc u la te d a t $00 f t ^ / b b l
$0^ H2 - $0% N2 a r e c o n s id e ra b ly lo w er th a n v a lu e s o f
a t r e a t gas r a t e of 1000 f t ^ / b b l o f $0% H2 - $0% N2 .
c a lc u la te d a t
The r a t i o s of
p a r t i a l p r e s s u r e hydrogen t o o i l a t t r e a t gas r a t e s o f $00 and 1000 ft*V
b b l a r e a p p ro x im a te ly 0 .2 2 and 0 , 43, r e s p e c tiv e ly .
From th e p re c e d in g d is c u s s io n i t a p p e a rs t h a t th e v a lu e o f
depends
more on th e r a t i o of th e p a r t i a l p r e s s u r e s o f hydrogen t o o i l th a n on
.hydrogen p a r t i a l p r e s s u r e s a lo n e .
T h is c o n c lu sio n i s s u p p o rte d when
c o n s id e rin g th e e f f e c t o f t o t a l p re s s u re on th e v a lu e o f K^.
As th e t o t a l
p r e s s u r e i s in c r e a s e d , t h e p a r t i a l p r e s s u r e s o f hydrogen and o i l a re i n ­
c re a s e d , w h ile th e v a lu e o f
i s d e c re a se d somewhat.
E f f e c t Of High. B o ile rs . On Krp ?
As in d ic a te d p r e v io u s ly , th e deg ree
o f d e s u lf u r iz a ti o n depends on th e b o ilin g ran g e o f th e ch arg e s to c k .
Two
ch arg e s to c k s , h av in g a b o ilin g ran g e o f 1$8-243°F and 1$8-282,$°F were
d e s u lf u r iz e d a t 400 p s ig , 6$0°F and 1000 f t ^ / b b l o f p u re hydrogen t r e a t
g a s to d eterm in e th e q u a n t i t a t i v e e f f e c t o f h ig h b o ilin g m a te r ia l on K^.
The low er b o ilin g l i g h t o i l f e e d , d e s ig n a te d "u n d ercu t f e e d " , i s a zero
t o 90 p e rc e n t sim ple d i s t i l l a t i o n f r a c t i o n o f th e r e g u la r f e e d .
I l 'I t
-2 7 The r e s u l t s p l o t t e d i n F ig u re 4 (T ab le XV) show t h a t th e u n d e rc u t
f e e d , (K^j, = 1„13) can be d e s u lf u r iz e d more r e a d i l y th a n th e r e g u la r fe e d
(Kfj, = 0 .8 0 ) .
The th io p h e n e c o n te n t i n th e benzene c u t from b o th fe e d s
was a p p ro x im a te ly th e same; th e r e f o r e , th e f a c t t h a t th e l i g h t e r f r a c t i o n
c o u ld be d e s u lf u r iz e d more r e a d i l y may be a t t r i b u t e d to th e ab sen ce o f th e
h ig h e r b o ilin g m a te r ia l .which i s p r e s e n t i n th e r e g u la r f e e d .
A com parison i n th e e ase o f d e s u lf u r iz a ti o n o f ch arg e s to c k s having
d i f f e r e n t b o ilin g ra n g e s can a ls o be made u t i l i z i n g r e s u l t s from Runs
U iS.So—22 and U .S .S .-2 3 .
At s im ila r c o n d itio n s ( 625°F , 400 p s ig , and
1000 f t ^ / b b l p u re hydrogen t r e a t g a s ) , v a lu e s o f Km e q u a l t o 0 .6 5 and 1.0 3
w ere o b ta in e d f o r Runs -2 2 and -2 3 , r e s p e c t i v e l y .
The charge s to c k s u sed
i n Runs U .S .S .-2 2 and -2 3 had b o ilin g ra n g e s o f 161-282,.5°F and. 1 5 8 -2 5 1 .5 °^
re s p e c tiv e ly .
The v a lu e o f
i n th e c a se o f th e h ig h e r b o ilin g fe e d was
a p p ro x im a te ly 60% o f t h a t f o r th e lo w er b o ilin g f e e d .
The h ig h e r b o ilin g
m a te r ia l made a g r e a t d e a l o f d if f e r e n c e i n th e v a lu e o f K^.
C o n ta c tin g E f f ic ie n c y Of The C a ta ly s t I n R e a c to r N o . - I and No. 2 :
D iffu s io n o f r e a c ta n ts from th e main gas stream t o th e s u rfa c e o f th e
c a t a l y s t and d if f u s io n o f p ro d u c ts from th e c a t a l y s t s u rfa c e t o th e main
g a s stream a r e dependent on th e v e l o c i t y o f th e main gas stre am th ro u g h
th e c a t a l y s t b e d .
d iffu s io n .
I n g e n e r a l, h ig h e r v e l o c i t i e s w i l l prom ote b e t t e r f ilm
I t i s d e s ir a b le t o o b ta in enough v e l o c i t y so t h a t d if f u s io n
does n o t l i m i t th e r e a c t i o n .
A h ig h e r v e l o c i t y can be o b ta in e d , w h ile
m a in ta in in g a c o n s ta n t c o n ta c t tim e , by in c r e a s in g th e le n g th o f t h e . c a t a ­
l y s t b ed .
The v e l o c i t y o f th e gas stre am a t c o n sta n t o p e ra tin g c o n d itio n s
Ill I
-
28 -
i s d i r e c t l y p r o p o r tio n a l t o th e le n g th o f th e c a t a l y s t b e d .
R e s u lts from Samples 9, 11, and 16 i n Runs U ,S .S .- 15, -1 6 , and - I ? ,
r e s p e c t i v e l y , a re g iv en i n T able XEX and p l o t t e d i n F ig u re 13,
O p eratin g
c o n d itio n s were s im ila r and th e l i g h t o i l fe e d s were th e same f o r th e
th r e e sam ples.
TABLE XCX
R e s u lts P lo t te d In . F ig u re 13
R e a c to r
Number'
Run
U .S ,S .
Sample
Number
C a ta ly s t
Charge (gm)
V.R. f t 3/ l 0 0
g m .c a t/h r .
I
I
2
15
16
17
9
11
16
100
250
100
0 .2 5 9
0 .2 6 8
0,263
lo g
A
A-X
2 .4 0 4
3 .3 3 8
4 .0 3 2
K
,
C a t. Bed
Depth ( in )
0 .6 2 4
0.895
1 ,0 6
1.25
3 .3
11.
The r a t e c o n s ta n t v e rs u s c a t a l y s t bed d e p th : ( v e lo c ity ) i s p l o t t e d i n
F ig u re 1 3 .
The p l o t i n d i c a t e s t h a t d if f u s io n h as a v e ry d e f i n i t e e f f e c t
on th e r a t e c o n s ta n t where c a t a l y s t bed d e p th s o f o n ly I o r 2 in c h e s a r e
employed^ and t h a t th e e f f e c t becomes l e s s pronounced so t h a t l i t t l e bene­
f i t co u ld be o b ta in e d by u s in g a bed d ep th g r e a t e r th a n 10 o r 11 in c h e s
f o r t h i s p a r t i c u l a r r e a c tio n and c a t a l y s t s iz e ( 10-14 m esh ).
C o n clu sio n ; •
The r e s u l t s of th e k i n e t i c stu d y i n d i c a t e t h a t ;
(1 )
The v a lu e o f th e r a t e c o n s ta n t (K^) d e c re a s e s w ith
in c r e a s e d p r e s s u r e i n th e ran g e o f 100 to 800 p s i g ,
(2 )
The d eg ree o f - d e s u lf u r i z a tio n in c r e a s e s (lo g A/A-X in c r e a s e s )
w ith in c r e a s e d p re s s u re b ecau se c o n ta c t tim e a ls o in c r e a s e s ,
(3)
The v a lu e o f
u s in g 1000 f t ^ / b b l o f $0%
- 50%
is
I t Jl
- 29a p p ro x lm a te ly 60-70 p e rc e n t o f t h a t u s in g 1000 f t ^ / b b l
o f pu re hydrogen t r e a t gas i n th e ran g e o f 625 t o 650°F
and 200 t o 400 p s ig .
(4)
The v a lu e o f K^, d e c re a s e s a s th e r a t i o o f t r e a t g as t o o i l
d ecreases,
(5)
The v a lu e of
te m p e ra tu re .
in c r e a s e s s u b s t a n t i a l l y w ith in c r e a s e d
The energy o f a c t i v a t i o n f o r th e r e a c tio n
i s i n th e neighborhood o f 10 K c a l/m o l.
( 6)
The v a lu e o f Krp i s dependent on th e b o ilin g ran g e o f th e
f e e d ; w ith h ig h e r b o ilin g m a te r ia l r e q u ir in g more sev e re
p ro c e s s ,c o n d itio n s ,
(7)
F ilm d if f u s io n h a s a lim i t i n g e f f e c t when c a t a l y s t bed
d e p th s o f l e s s th a n 10 in c h e s a r e u se d ,
(S)
The v a lu e o f
o b ta in e d a t s im ila r c o n d itio n s u s in g
R e a c to r No, I w ith a 100-gram c a t a l y s t charge was
a p p ro x im a te ly 50 p e rc e n t o f t h e v a lu e o f
o b ta in e d
u s in g R e a c to r No. 2 w ith a 100-gram c a t a l y s t c h a rg e .
-3 0 -
ACKNOtiILEDGMEWT
The a u th o r acknow ledges w ith th a n k s th e c o u rte s y o f th e Esso
X
R esearch and E n g in e e rin g Company who sp onsored th e work i n t h i s
i n v e s t i g a t i o n and f u r n is h e d many m a te r ia ls u sed th ro u g h o u t th e work.
The a u th o r a ls o w ish es t o acknow ledge D r. Lloyd B erg, d i r e c t o r o f th e
r e s e a r c h ; Mr. John W e ik a rt, c o n s u lta n t and c o o rd in a to r from E sso ; and
M r. R. G. Waterman, Mr. R, A. Mahugh, and M r. M. K. O p p rech t, fe llo w
r e s e a r c h w o rk e rs.
-3 0 a LITEEATUEE CONSULTED
(1 )
Esso L a b o r a to r ie s , P ro c e ss R esearch D iv is io n , "D eterm in atio n o f
Thiophene in B enzene"; L in d en , New J e r s e y .
(2)
Hoeg, H ., C a t a ly ti c H y d ro -D e su lp h u riz atio n o f F u e l O il;
K o n in k lijk e , S h e ll-L a b o rato riu m ., Amsterdam.
(3)
Jo n es and L au g h lin S te e l C o rp o ra tio n , " S p e c if ic a tio n s f o r C oal
C hem icals"; P it ts b u r g h , P e n n s y lv a n ia .
-3 1 append ix
T able I
A .S.T.M , D i s t i l l a t i o n o f L ig h t O il Feed
• Used In. Runs J& L -l, - 2 , and - 3 .........................................
Page
.33
T ab le I I
T a b u la te d D ata f o r Run J& L-l
............................... .... .
T able I I I
T a b u la te d D ata f o r Run J&L-2
............................... . » 36
34
......................................... 37
T able IV
T a b u la te d D ata f o r Run J&L-3
T ab le V
A.S.T.M . D i s t i l l a t i o n o f L ig h t O il Feed
Used i n Runs U .S .S .- l Through U .S .S .- 6
T ab le VI
T a b u la te d D ata f o r Run U .S .S .- l
T able V II
. . . . .
•. . . . ; .
38
...
39
T a b u la te d D ata
f o r Run U ,S .S .-2 . ...............................
39
T ab le V IlI
T a b u la te d D ata
f o r Run U .S .S .-3 . . . . . . . . .
40
T ab le IX
T a b u la te d D ata
f o r Run U .S .S .-4 .................................... 42
T ab le X
T a b u la te d D ata
f o r 'RunU . S . S . - 5 ......................................... 43
T able XE
T a b u la te d D ata
f o r RunU .S .S . - 6 ......................................... 44
T ab le XEI
A.S.T.M . D i s t i l l a t i o n o f L ig h t O il Feed
Used i n Runs U .S .S .-1 0 Through U i S . S . - 2 4 ....................... 45
T ab le XEII
R e s u lts From Runs U .S .S .-1 0 and -1 1 . .............................
T ab le XEV
R e s u lts From Runs U iS .S .-1 2 , -1 3 , -1 5 , -1 6 ,
and - I ? ........................................................................................ 47
T ab le XV •
R e s u lts From Runs U .S .S .-1 8 , -1 9 , -2 0 ,
—21, and —22
. . . . . . . . . . . . . . . . . .
46
49
T ab le XVI
R e s u lts From Runs U .S .S .-2 3
51
T ab le XVII
R e s u lts From Run U .S .S .-2 4 ................................................ • 52
T ab le XX
S p e c if ic a tio n s For Goal C hem icals
T ab le XXI
C o p p e r-S trip C o rro sio n T e s t. .......................
. . . . . . . .
. . . . .
53
57
-32APPENDIX ( c o n t i n u e d )
F ig .
F ig .
Fig*
F ig .
F ig .
F ig .
I
2
3
4
5
6
Schem atic Diagram o f D e s u lf u r iz a tio n U nit
F o r P ro c e s s in g L ig h t O i l .......................... .........................
58
D e s u lf u r iz a tio n v s . R e c ip ro c a l Vapor
R ate (Run U .S .S .- l? ) . . . ................................................
59
D e s u lf u r iz a tio n v s . R e c ip ro c a l Vapor
R ate (Rug U .S .S .-2 2 ) .................................................* . .
60
D e s u lf u r iz a tio n v s . R e c ip ro c a l Vapor
R ate (Runs U .S .S .-1 9 and -2 0 . . ...................................
61
D e term in atio n o f th e E f f e c t o f T em perature (Ea )
on Ep (Runs U .S .S .-1 0 and -1 1 ) . . . * ......................
62
D e term in atio n of th e E f f e c t o f Tem perature (Ea ) . .
on Er (Run U .S .S .- 2 4 ) . . .....................................................
63
F ig .
7
E f f e c t o f T o ta l P r e s s u r e on K p ................................... ....
64
F ig .
8
E f f e c t o f P r e s s u r e on Kr, and th e Degree o f
D e s u lf u r iz a tio n a t C o n stan t R a tio o f Feed
t o C a t a l y s t . ...............................................................................
65
9
E f f e c t o f D ilu e n t Gas on Kt (Run U .S iS .- l6 )
. . .
66
F ig . IO
E f f e c t of D ilu e n t Gas on Kt (Run U .S .S .-1 9 )
. . ,
67
F ig . 11
E f f e c t o f D ilu e n t Gas on Kp (Run U .S .S .-2 3 )
. . .
68
F ig . 12
E f f e c t o f T re a t Gas R ate on K p ......................
69
F ig . 13
E f f e c t o f C a ta ly s t Bed Depth on Kj ...............................
70
F ig .
-3 3 table
I
A.S.T.M . DISTILLATION OF LIGHT OIL #EED
USSD IN BUNS J& L -l, - 2 , and -3
(C o rre c te d t o 7,60 mm)
EUNS...J&L-1 and - 2
Volume %
D is t0
I .BoPc
5
10
20
30
-40
50
60
70
80
90
95
E0Po
RUN J&L-3
Temp, °F
Volume %
D is te
Temp0
161.5
162.5
163.
164.
165.
167.
168.5
171.
175.5
188.
217.5
245.
268.
I 0B0P .
5 .
10
20
30
40
50
60
70
80
90
95
E0P0
160
163.5
164.
165.
1 6 6 .5
167.5
170.
173.
178.5
189.
2 2 1 .5
251.
2 7 8 .5
TABIS I i
.
C a ta ly s t R e fe re n c e :
Grams o f C a ta ly s t:
O il C harged: ASTM D i s t .
Range:
Com posite Y ie ld : ¥fc.^:
T o ta l C a t.
Hours TemPb0F
6
617
h
612
11
9
608
12
10
601
11
13
16
583
14
23
25
574
630
25
27
576
30
28
36-38
34-36
651
622
39
37
6.13
47
45
48
610
46
608
48
50
610
47-50
49-52
622
53-56
51-54
622
55-62
57-64
622
55-61
57-63
66
669
64
65-72
63-70
653
73-80
642
71-78
81-88
79-86
649
89-96
649
87-94
648
95-102 97-104
1 0 3 -1 1 0 , 105-112 649
Sample
Number
TABULATED DATA FOB RUN J & L - l
Harshaw CoMo 0301-T 3 /1 6 " p i l l s cru sh ed t o 8-20 mesh.
250
l 6l . 5- 268°F
97%
R e a c to r
P ress.
400 400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
Space V e l.
gm/hr/gm
1 .9
2 .0
2 .0
2 .0 3
2 .05
2.0 5
2 .0 8
1 .9 7
1 .9 7
—
———
1 .9 7
1 .9 7
■ 1 .9 7
1 .9 2
1.9 5
2 .0 6
2 .0 6
2 .0 7
2 .0 9
2 .0 8
2 .0 6
2 .0 8
T re a t Gas
F t3 Zbbl
1050
1000
1000
990
980
980
960
1020
1020
—
1020
1020
1020
1040
1020
970
970
970
960
960
970
960
Thiophene
Ppm
———
—
—
1 .0
. . 3 .4
0 .4 3
——
0.3 3
0 .6
---—
—--—
0.7 5
0.95
6 .5
4.35
12 .0
6 .5
0 .7 6
0.15
0 .3 2
0.3 3
0 .1 7
Acid C olor
Ben.
T o l.
4+
7+
4
II
0+
0+
3+
0
0+
——
—
——
0
0+
0+
I0+
0
0
0
0
0+
C o p p e r-S trip
C o rro . T est
■
———
———
— nn
2I
0+
0+
4
0
0+
—
——
—
—
0
0+
0+
——
0+
0+
0+
0+
0.
0
0+
C
C
—
C
———
C
C
C
•O.K.
———
"
———
———
——
O.K.
O.K.
O.K.
O.K.
O.K.
TABLE I I ( c o n t i n u e d )
TABULATED DATA FOR RUN J & L - l ■
Sample
Number
T o ta l
Hours
111-118
119-126
127-134
135-144
I 43- I 49
151-158
159-166
150
167-174
175-182
183-190
191-198
199-206
207-214
215-222
223-230
231-238
239-243
105-112
113-120
121-128
137-146
145-151
153-160
161-168
152
169-176
177-184
185-192
193-200
201-208
209-216
217-224
225-232
233^240
241-245
*T race
C a t.
Temtu0F
E e a c to r
P ress.
655
655
651
648
648
649
649
644
648
653
651
644
655
648
646
651
651
651
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
Space V e l.
gm/hr/gm.
1.8 3
2 .2
2 .0 6
1 .9 6
1 .9 6
2 .1 4
2 .0 9
■.....
1 .9 7
1 .9 6
1 .8 6
1.8 3
1 .8 6
1.83
2 .0
2 .2
2 .0 4
2 .1 5
T re a t Gas
F t3 /b b l
Thiophene
Ppm
1090
910
970
1020
1020
930
960
0 .1 0
0:18
0.1 3
0 .1 8
0 .3 7
0 .9 2
0 .2 1
7 .3
T#
0 .1 0
0.2 3
0 .5 4
0 .5 4
T
'0 .6 7
T
T
0 .2 6
1020
1020
1080
1090
1080
1090'
1000
910
980
930
A cid C o lo r
Ben. T o l,
0
0
0
0
0
0
0
0
0
0
0
0
0 .
0
0
0+
0
0+
0
0+
0+
0
0
0
0+
0
0+
0+
0+
0
0+
0+
Copper—S t r i p
C o rro . T est
O.K.
O.K.O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
TABLE I I I
TABULATED DATA .FOR RUN J& L -2
C a ta ly s t R eferen c e;
Grams o f C a ta ly s t;
O il C harged: ASTM D is t .
Com posite Y ie ld : Wfc.^:
.H arshaw .CoHo .0301-T..1/16". p i l l s .crushed t o 8-20 mesh.
250
l 6l . 6- 268°F
97$
\
Sample
Number
T o ta l
Hours
5-8*
9-12*
18-21
33-37
39-43
38-45
46-53
249-256
257-260
267-270
287-291
293-297
292-298
300-307
C a t. Q
Temp. F
R ea c to r
P ress.
649
648
657
655
400
400
400
400
400
-400
400
— — —
653
653
Space V e l.
gm/hr/gm.
T re a t Gas
F tjY h b l
Thiophene
Ppm-
1 .9 7
2 .0 2
IOlO
990
'0 . 1 8
0 .2 6
0 .6 ?
0 .1 8
— — — —
—
2 .0
2 .0
1000
1000
— —
T
0 .5 8
Acid C olor
Ren. T o l.
0
0
0+
— —
0+
0+
0+
0
0+
0+
0+
0+
0+
0+
C o p p e r-S trip
C o rro . T est
O.K.
O.K.
O.K.
C
C
C
C
TABLE IV
TABULATED DATA FOR RUH J&L-3
C a ta ly s t R eferen c e:
Grains o f C a ta ly s t:
O il C harged: ASTM D i s t . Range:
Com posite Y ie ld : Wt.%:
Sample
Humher .
T o t a lHours
Cat,*
Temp10F
4 -7
8-12
13-16
42-54
56-64
66-72
64O
644
650
Harshaw CoMo 0301-T 3 /1 6 " p i l l s c ru sh ed to 12-16 mesh.
200
1 6 0 -2 8 7 .5°F
96#
R e a c to r - Space V e l.
P ress. m /h r /m
400
400
400
2.15
2 .0 6
2 .0 2
T re a t Gas
F tV b b l
Thiophene
Ppm
930
970
990
0 .1
0 .1
0 .1
A cid -C olor
Ben. T o l.
0+
0+
0+
0+
0+
0+
C o p p e r-S trip
G o rro . T e st
O.K.
O.Ki
O.K.
TABLE V
A .5.T.M . DISTILLATION OF LIGHT OIL FEED
USED. IN. EUNS U . S . S . - l THROUGH U .S .'S .-6
(C o rre c te d t o 760 nun)
BUN U .S.S , - I
RUNS U .S .S . - 2 AND -3
Volume % Temp.
op
D ie t.
Volume %
D is t.
I .B .P .
5
10
20
30
40
50
60
70
80
90
95
E .P .
158
178
178
188
195
204
217.5
236
257
278
303
3 29.5
330.5
I .B .P .
5
10
20
30
40
50
60
70
' 80
90
95
EtfP o
Temp.
0F
-
163
166.5
168
171
173 •
175.5
179
186
199
220
259
294.5
302.5
RUNS U .S.S.--4 AND -5
RUN U .S.S .- 6
Volume %
Di s t .
Temp.
0F
Volume $
D is t.
Temp.
0F
I .B .P .
5
10
20
30
40
50
60
70
80
90
95
. E .P .
160.5
165
166
165.5
169.5
172
174.5
178.5
184.5
196
229
259
273.5
I .B .P .
5
10
20
30
40
50
60
70
80
90
95
E .P .
162.5
167
168.5
170.5
173
176.5
179
187.5
197.5
220
259
289
2 99.5
TABIE TO
TABULATED DATA FOR E lE U . S . S . - l
C a ta ly s t R e fe re n c e :
-.
Harshaw CoMo 0301-T 3 /1 6 " - p il ls cru sh ed t o 12-16 mesh.
Grams C a ta ly s t:
100
O il C harged: ASTM D i s t . Range: 158-331°F
Com posite Y ie ld : W t.#:
9#
Sample
Number
5
7
T o ta l
Hours
C a t.
Temp00F
R ea c to r
P ress,
41
49
581
583
400
400
Space V e l0 T re a t Gas
m /h r /m
F fV b b l
- 2 .0 6
1 .9 8
Thiophene
- Ppm
- 970
1010
12
12
TABLE TOI
TABULATED DATA FOR RUN U-S .S .-2
C a ta ly s t R eferen c e:
Grams C a ta ly s t:
O il C harged: ASTM D i s t 0 Range:
Com posite Y ie ld : Wt«,$:
Sample
Number
. 3
10
15
T o ta l
Hours
96
124
144
.
Acid C olor
Ben0 T o l.
C o p p e r-S trip
C o rro . T e st
14
14
———
'
Harshaw CoMo 0301-T 3 /1 6 " p i l l s cru sh ed to 12-16 mesh
100
163-302e5°F
97^
Cat .■
Temp. F
R ea c to r
P ress.
624
639
649
400
400
400
Space V e l.
m /h r/a n
2 .0 6
2 ,0 8
T re a t Gas ■Thiophene
F t3Zbbl
Ppm
970
960
..
^—
—■1
-----
Acid C olor C o p p e r-S trip
Ben0 T o l0 C o rro . T est
8+
3+
2
8+
3+ '
3 ;;
«m—
I
xO
I
TABLE V l I I
TABULATED DATA FOR RUN U . S . S . - 3
C a ta ly s t R e fe re n c e :
Grams C a t a l y s t :
O il C harged: ASTM D i s t . Range;
Harshaw GoMo 0301-T 3 /l6 " . .p i l l s cru sh ed t o 12-16 mesh
100
1 6 3 -3 0 2 .5°F
Sample
Number
T o ta l
Hours
C a t. Temp. F
R e a c to r
"P ress.
2
6
12
IS
12-18
- -22
19-23
24-27
30
33
36
33-37
42
4 8.
54
45-54
60
■63
64
68
73
64-69
77
87
66
82
106
130
106-130
146
_134-150
154-166
178
190
202
190-206
226
250
276
238-276
300
320
328
360
400
328-368
416
462
646
648
648
646
648
648
647
648
642
648
655
650
650
651
648
648
650
642
642
65O
648
648
644
6.51
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
Space Vel
gm/hr/em
2 .4 8
2 .3 2
1 .8 8
1 .5 8
1 .7 2
2 .2 1
2.1 3
2 .1 6
2 .2 8
1 .6 7
1 .2 1
1 .3 7
2 .4 2
O.67
1 .7 6
1 .3 7
1 .4 3
1 .1 6
1 .1 3
0 .9 5
1.0 5
1 .0 1
1 .4
2 .0
T rg a t Gas
F t3 Zbbl
Thiophene
Pm
753
860
1030
1260
1160
910
940
930
880
1200
1650
1460
830
3000 '
1140
1460
1400
1720
1716
2010 .
1820
1980
1430
1000
2.4 5
2 .1
1 .0
2.25
1 .4
- 2 .2 2
2 .5 1
1.0 5
2 .9 5
0 .8 8
0 .4 2
0 .3 2
1 .8
0 .2 6
0 .6 7
0 .6 1
0 .4 7
0 .3 2
0 .6 8
3 .3 5
0 .6 2
0.3 5
2 .9 8
9 .0
Acid C olor
Ben. T o r.
0+
I0+
I
I
I
2
2 '
2
I
1+
I
I
0+
0+
0+
0+
0+
0+
0+
0+
0+
I
0+
2
2
2
3+
3+
3
4
3t
4 v
3
4
3
3
3
I
1+
IU
2
2
1+
.2
2
3
3+
C o p p e r-S trip
C o rro . T est
C o rro .
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
i
?
TABLE V I I I
( c o n tin u e d )
TABULATED DATA FOR RUM U . S . S . - 3
Sample
Mumber
93
105
107
108
109
T o ta l
C a t. 0
Hours . Temp..- F
■
486
530
554
562
570
646
644
646
648
646
* 50 % H2 - 50% N2
R e a c to r
P ress.
400
400
400
400
400
Space V e ll
,gm/hr/gm
2 .0
2 .0 4
1 .0 4
1 .0
0 .9 4
T re a t Gas
F tjV b b l
Thiophene
. Epm
1000
,9 8 0
670*
670*
670*
9 .0
3 .8
8 .7
B.O
6 .7
A cid C olor
Ben. T o l.
0+
0+
0+
0+
1+
2+
2+
0+
0+
1+
C o p p e r-S trip
C o rro . T est
O.K.
O.K.
O.K.
O.K.
O.K.
TABLE I X
TABULATED DATA FOR HIM U 0S 0S 0-A
C a ta ly s t R e fe re n c e ;
Grams o f C a t a l y s t ;
O il Charged; ASTM D ist« Range;
Com posite Y ie ld ; Wt0^ ;
Sample
Number
2
10
16
22
28
35
39
37-46 '
46 . '
50-52
55
62
.
T o ta l
H ours
52
84
108
132
156
188
204
196-232
232
248-256
274
288
G a t„
Temp00F
586
605
610
601
600
646
649
648
648
649
655
652
*50$ H2 - 50$ N2 ■
"100$ Hp
#50$ H2 - 50$ CH4
Harshaw CoMo 0301-T 3 /1 6 " p i l l s cru sh ed t o 12-16 mesh
200
16005-273«5
95$
R e a c to r
P ress,
400
400
400
.400
400
400
40G
400
. 400
400
400
.
400
Space V e l0 T re a t Gas
F t3 Zbbl
gm/hr/gm.
1 J-3
0 .9 9
1 .0 1
1 .0 4
1 .1 4
1 .0
0 .9 8
0 .9 8
1 .0 2
0 .9 8
1 .3 9
1 .3 1
. 1770*
2020*
1980*
1920*
1660*
1000"
2040*
2040*
I 960*
2040#
1440#
1470#
Thiophene
ppm
7 .8
7 .8
7 .8
4 .5
7.75
0 .15
0 .2 5
7 .65
2 .7
9 .0
2 .7
1 .5 2
Acid C olor
Ben. T o l.
I
2
I
0+
0
——
0+
I
1+
3
2
0+
0+
0+
0+
— —
I
I
C o p p e r-S trip
G o rro . T est
O.K.
O.K.
Oi K.
O.K.
■ O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
O.K.
TABLE X .
. TABULATED DATA FOR RUN U .S .S .-5
C a ta ly s t R e fe re n c e :
...Grams C a ta ly s t?
.
O il C harged: ASTM D i s t 0 Range:
■Composite Y ie ld : Wb.$:
.
Sample
' T o ta l
Number— Hours
5-8.
9-12
13-18
19-22
23-26
27-30
31-36
37-40
41-44
45-4%
29-38
41-50
53-68
71-80
83-92
. 95-104
107-122
.125-134 .
137-146
149-155
C a t,.
Temp00F
650
650 .
649,
649
649
649
651
650 ■
651
652
Harshaw CoMo 0301-T 3 /l6 " . p i l l s cru sh ed t o 12-16 mesh
200
160,5-273»5
95$
R e a c to r Space V e l. ’ T re a t Gas
P r e s s , -gm/hr/gm.
F t3 Z bbl '
400
400
400
400
400
400
400
400
. 400
400
1 .3 6
.1*34
1 .3 3
1 .3 7
1 .3 2
1.45
1 .3 8
1 ,4 0
1 .3 9
1 .3 3
..
.
.
980
1000
1000
1000
Thiophene
; PPHL
_
io o o
920
965
950
960
1000
.
.
A cid C o lo r
Ben, T o l„
0*25
■0+
0+
0 ,2 3
0 ,2
0+
0 .2
0+
0 .1
Of
0 ,1
. 0+
0 ,1 . - 0+
0 ,1
■ 0+
0+
0 .1 4
0+
0.15
0+
0+
0+
0+
0+
0+
0+
0+
0+
I
C o p p er-S trip
C o rro . T e st .
OoK0
OoK,
0.K .
O.K.
O.K.
O.K,
O.K.
OoK0
O.K.
O.K.
TABLE JL
i
.
' TABULATED DATA FOR R U N U .S .S.-6
-C a ta ly st R e fe re n c e ;
Harshaw CoMo 0301-T 3 /1 6 " p i l l s cru sh ed t o 12-16 mesh
Grams C a t a ly s t;
200
O il Charged; ASTM D i s t , R ange; 162„5 - 299. 5°F
Com posite Y ie ld ; Wfc.^;
92%
-Sample
Numbar
T o ta l
Hours'
C at.
-Temp60F
R e a c to r
P ress.
1 -4
5 -8
11-14
15-18
19 -2 2 •
23-26
30-42
46-58
78-90
94-106
110-122
126-138
648
650
650
651
650
651
400
400
400
400
400
400
Space V e l. ■Treat Gas Thiophene
m /h r /m
ppm
F t jV b b r *
1 .0 2
0 .9 7
1 .0 3
0 .9 7
0 .9 7
0 .9 5
980
1030
970
• 1030
1030
1050
0 .3 8
0 .3 8
0 .3
0 .3
0.25
0.2 5
Acid C olor
Ben. T o l.
0+
0+
0+
0+
0+
0+
I
I
I
I
I
I
'
C o p p er-S trip
C o rro . T est
O.K.
O.-K.
O.K.
O.K.
O.K.
O.K.
I
TABLE H I
A.SoToM. DISTILLATION OF LIGHT OIL'FEED
USED IN RUNS U .S .S .-IO THROUGH U .S .S .-2 4
(C o rre c te d t o ?60 mm)
RUNS U0S 0S0—10 -Bnd —11
,Volume %
D ie t,
I 0B1P 0
5
10
20
30
• 40
50
60
70
80
90
95
E 0P 0
Temp,
°F .
163
165
166,5
168
170
. 173
175.5
182
183.5
213
251
■ 271.5
283.5
RUNS U0SoS0i-12 through U0S05 0-2 2 *
Volume %
D is t0
I .BoP.
5
10
20
30
40
50
60
70
80
90
95
■ E .P ,
■^Excluding Runs.U,S„S.-14-and U .S „S ,-2 0
Temp,
0F .
l6 l
165
166
167.5
I69
173
175.5
181
189
205.5
242.5
269.5
282,5
RUN U,S.,5 ,-2 3
Volume % Temp.
D ie t,
0F .
I 0B0R 0
5.
10
20
30
40
50
60
70
80
90
. 95
E 0P 0
158
162.5
164
165
166.5
169.5
172
175.5
181
192.5
219
243
251.5
RUN U0S0S0-2 4 ■
Volume %
D is t,
Temp,
0F 0
I 0B0P 0
5
10
20
30
40
50
60
70
80
90
95
E 0P 0
158
161,5
162.5
164
I 65
166,5
168.5
171.5
175.5
184.5
209.5
237.5
259.
TABLE U I I
RESULTS FROM RUNS U .S .S .-IO AND - H
C a ta ly s t R eferen ces
O il C harged: ASTM D i s t . Range:
T r e a t Gas R ates
R e a c to r P r e s s u r e :
T o ta l
Hours
Sample
Number
Harshaw CoMo 0301-T 3 /1 6 " p i l l s cru sh ed to 10-14 mesh, 100 gm,
163-283»5°F
1000 f t 3 / b b l 50% H2 - 50% N2
400 p s ig
1/T °K
x io 3
Vapor
R ate
644
700
801
752
846
1 .6 3 0
1.553
1.425
1.483
1.380
0 .2 4 6
0 .2 5 8
0 .2 9 6
0 .2 4 8
0 .3 0 2
648
' 801
752
849
698
1 .6 3 0
1.425
1.485
1.377
1.557
: 0 .2 4 4
0.293
0 .2 7 0
0 .306
0 .256
■Temp.
0F
(A-X) ppm
Thiophene
10510 E r
v
S H o g io kT
U ,S ,S ,-1 0
4
8
12
16
20
35 .
51
67
83
97 -
140.
1 5 .6
0 .5 4
6.5- _
0 .0 1
1.711
2.664
4 .1 2 4
3 .0 4 6
5.858
0.421
0.685
1.203
0.756
1.62
1.,624
1 .836
2.080
1 .878
2 .210
225.
0 .9 1
8 .0
0 .4 8
2 6 .7
1.505
3 .8 9 8
2 .9 5 4
4 .1 7 6
2 .4 3 2
0.367
1.1 4
0.796
' 1.28
. 0.622
1.564
2.057
1.901
2.107
1 .7 9 4
U .S .S i--11
3
6
10
15
18
.
.
24
36
52
68
80
TABLE ZEV
RESULTS FROM RIMS U .S .8 .- 1 2 / -1 3 , -1 5 , -1 6 , and - I ?
C a ta ly s t R eferen ces
O il C harged: ASTM D is t . Ranges
T re a t Gas Rate's
Sample
Number
T o ta l
Hours
U .S .S .-1 2 .
4
7
Vapor
R ate
Harshaw CoMo 0301-T 3 /l6 " p i l l s crushed t o 10-14 mesh
1 6 1 -2 8 2 .5°F
1000 f t ^ / b b l 50% Hg - 50% Ng
T re a t Gas
F t^ /b b l
0 .2 7
0 .124
960
1030
U .S .S .-1 3
9
16
(A-Z) ppm
Thiophene
A /A -x .l0 ~2
Io g nn
A/A-T
Km
^
400
400
702
698
63.
1 .1
1 .1 4
65.5
2 .0 5 7
3 .8 1 6
0.556
0.473
REACTOR NO. L—100 gras CATALYST
32
70
0 .712
0 .1 3 9
1320
935
U .S .S .-1 5
5
9
14
18
22
Temp.
°F
REACTOR NO. I —100 gms CATALYST
-
42
74
R e a c to r
P ress.
400
400
700
702
168.
0 .2 1
-43
343.
1 .6 3 2
4 .5 4
1.162
0 .6 3 2
194.
2.5 3
0.409
3 7 .9
86.6
4 .2 8 9
2 .404
1.612
3 .5 7 9
3 .9 3 8
0.493
O.624
0.825
0.300
0 .450
REACTOR NO. I-—100 gras CATALYST
31
47
67
83
99
0.115
0 .2 5 9
0 .511
0 .0 8 4
0 .1 1 4
1010
1000
1050
495
1020
800
408
200
805
BOO
703
698
' 700
701
704
0 .3 7
28.
176.
1 -9
0.8 3
I
5
1
TABLE U Y
(c o n tin u e d )
RESULTS FROM RUNS U . S . S . - 1 2 ,
T o ta l
Hours
Sample
Number
Vapor
R ate
U .S .'S .- 16
R ea c to r
P ress.
Temp.
0F
(A-X) ppm
Thiophene
A/A-X.10-2
!H
kT
0»60
2 1 .8
4 .5
1.778
3 .3 3 8
2 .6 5 4
0,450
0.895
0.667
108.
1 8 .5
0 .5 5
4.032
3 .2 2 6
1.744
1 .0 6
REACTOR NO. 1—250 gms CATALYST
6
11
15
3 5 .5
48.-0
5 5 .5
0.253
0 .2 6 8
0 .251
U .S.S . - I ?
16
20
27
T re a t Gas
F t3 Zbbl
-1 3 , - 1 5 , - 1 6 , a n d - I ?
87
99
108.5
*P ure H
2
930
940
940*
400
400
400
651
703
647
120.
3 .3
16.
,
REACTOR NO... 2— 100 gms CATALYST '
0.263
0,443
0.657
990
1050
990
400
400
400
702
703
694
0 .6 ?
3 .9
130.
1.45 jL
1.107 T1
T A B IIE JOT
EESULTS FEOM EUHS U .S .S .-1 8 , -1 9 , -2 0 , -2 1 , and -22
C a ta ly s t R eferen c e;
O il 'Charged; ASTM D is t, Range;
T r e a t Gas R a te ;
Sample
Humber
Vapor
R ate
T o ta l
Hours
Harshaw CoMo Q3Q1-T 3 /l6 " p i l l s cru sh ed t o 10-14 mesh
U .S .S .-1 8 , -1 9 , -2 1 , and -2 2 , 1 6 1 -2 8 2 .$°F;
U0S0So-2 0 , 158-251,5°F.
1000 f t 3 / b b l 50% H2 - 50% H2
T re a t Gas
F t3 /b b l
R e a c to r
P ress.
Temp.
Gp
(A-X) ppm
Thiophene
A/A-X.10-2
Kt
A /fii
UoSoS.-1 8
Oo1065
0,1019
0,243
0 ,499
0 ,712
1000*
1000
1020
1000
500
800
800
400
200
805
650
648
650
650
650
28
37
45
53
61
70
0 .247
0,205
0 .4 9 2
0 ,2 0 4
0.483
0.245
980
990
980
1000*
.1010*
1000*
.400
800
400
800
400
400
650
648
648
648
651
648
20
30
0 .2 4 9
0 .4 4 2
970*
980*
400
400
648
646
28
hi
63
79
95
4
9
13
17
21
•
1 .1 2
1 .0 6
28.
440.
72 .5
64.80
67.65
2 .5 7
0 .1 6 4
0 .9 9 4
3 .808 0 .4 1 6
3 .830 .0 .3 9 0
2.410 0 .5 8 6
1.215 0.607
1.997 0.142
0 .7 6 7
8 1 .6
0 .0 5 9
1 0.29
•0.515
16,56
1.885
1.912
0.771
3.012
1.712
3.219
O.466
0 .392
0 .379
0.617
0.82?
0.788
4.46
2 .5 8
1.110
1,128
UoS .S o-19
4
8
12
16
20
23
92.
89.
1 , 230.
7.
140.
4 .4
TJoSeSv—
tSO
2
6
l55E ure H2
0.2 5
19.
290000
3 .8 2
TABLE ZV ( c o n t i n u e d )
RESULTS FROM RUNS U . S . S . - 1 8 , - I ? ,
Sample
Number
T o ta l
Hours
Vapor
R ate
T re a t Gas
F t-V b b l
R e a c to r
P ress.
Temp.
op
- 2 0 , ^ 2 1 , .a n d - 2 2
(A-X) ppm
' Thiophene
A/A-X.10"2
A /?1?
kT
U .S .S c- 21
k
8
12
33
49
65
0 ,2 4 4
0,1015
0 ,5 1 0
1000*
1010*
960*
400
800
200
650
650
651
............1-5
,03
19.
1000*
1000*
970*
1010*
.1070*
400
400
400
400
400
625
622
621
621
650
14.5
80.
460.
930.
.34
.
48.40
2 ,4 0 0 .
382.
3 .6 8 4
5.380
2 .5 8
0.897
O.546
1.315
4 .9 6
0 .9 0
0,156
0.077
211.8
2 .696
1.954
1.193
0 .8 8 ?
4 .3 2 6
0,705
0.562
0 .510
liiz i
U .S.S 0—22
13
18
23.
2?
31
117
128
138
. 147.5
164
*Pure H2
0,232
0,363
0 ,471
0.575
0 .2 5 9
TABLE -XVI
EESULTS FROM BUN- U-S0S0-23
C a ta ly s t R e fe re n c e :
O il C harged: ASTM D i s t « Ranges
.T re a t Gas R a te :
Sample
Number
4
9
13
18
23
27
29
33
37
45
49
57
61
65
69
73
78 .
37
92
T o ta l
. Hours
5 0.
70
86
96
116
130
134
148
I 64
195
2l l
243
273
289
305
321
331
362
386
*P ure H2
Vapor
R ate
3 .9 7
7 .8 2
5 .5 0
2 .0 3
4 .0 0
3 .7 9
3 .8 9
1 .9 9
4 .4 2
4 .3 2
4 .0 2
3 .9 4
4 .0 2
3 .9 7
2 .0 0
4 .0 5
2 .0 1
1.805
4 .0 3
Harshaw GoMo 0301-T 3 /1 6 " p i l l s cru sh ed t o 10-1 /, mesh
158-251.5 F
1000 f t 3 / b b l 50^ B2 - 50% N2
R e a c to r
P ress.
400
400
400
400
400
200
200
100
400
400
400
400
400
200
200
400
400
200
400
Temp.
0F
628
626
628
622
628
626
626
626
631
575
624
631
628
628
629
625
630
723
624
(A-X) ppm
Thiophene
.
0 .23
2 .1 1
■ 0 .1 9
85.
0 .0 7
0.4 3
0 .3 4
1 5 .7
0.0 5
109.
0 .0 6
45.
5 .6
1 6 .0
215.
1 .9 8
3 5 .0
0 .7 7
0 .2 1
lo g
A
A-X
4.512
'3 .5 3
4 .5 8
1 .9 2
5.05
4 .2 2
4 .3 3
2 .6 6
5 .16
1.8 2
5 .8
2 .2 4
3 .1 1
2.63
1 .5 2
3 .5 6
2 .3 1
3 .9 7
4 .5 4
T re a t Gas
F t^ /b b l
957*
984*
1030*
1000*
971*
915*
960*
945*
970*
975*
975*
940
980*
1000
1015
995
978*
975
985*
Vj
TABLE JSTLI
RESULTS FROM RUN U . S . S . - 2 4
C a ta ly s t R e fe re n c e :
O il C harged: ASTM B i s t . Range:
T re a t Gas R a te :
R e a c to r P r e s s u r e :
Sample
Number
T o ta l
Hours
8*
12*
16*
20
24
30
32
56
68
80
92
104
124.5
"""129
-j5P u re Hg
Temp.
Op
626
577
522
673
727
628
576
Harshaw CoMo 0301-T 3 /1 6 " p i l l s c ru sh ed t o 10-14 mesh
158-259°F
1000 f t ^ / b b l 50$ H2 - 50$ N2
200 p s ig
1/T °K
• x ICr
1 .6 6
1.735
1.835
1.590
1 .5 2
1,655
1 .7 4 0
■Vapor
R ate
.0 .4 7 8
0.443
0 .4 4 6
0 .5 2 2
0.535
0.483
0.455
(A-^l) ppm
Thiophene
1A z E x
kT-
1 .8 2
.. . . 1.1 5 . .3 .7 9 6
21.
2 .5 3 4 . 1.131 .238
5 .7 8
415.
2 .0
3 .5 5 6 . 1 .8 6
4 .456
0 .2 5 .
Z.3&
3 .168
1 .53
4 .9
. 2.212
1.002
44.
! + l o S1 0 kT
1 .2 6 0
1.053
0 .762
1.270
!.3 7 5
1.185
1.002
1
Vl
I
-5 3 TABLE XX
SPECIFICATIONS FOR COAL CHEMICALS
Jo n e s & L aughliii S t e e l C o rp o ra tio n , P itts b u r g h , P a .
A cid Wash C o lo r o f A rom atic H ydrocarbons
I.
(a )
A pparatus F o r C olor S tan d ard s' - c l e a r and unblem ished,
c le a n , F rench S q u are, f l i n t g l a s s , f l a t bo tto m , g l a s s s to p p e re d , 1 -o z c a p a c ity b o t t l e s h o ld in g 31 t o 33 ml
when f i l l e d t o th e n e c k . The b o t t l e s s h a l l be numbered
c o n s e c u tiv e ly from 0 t o 1 4 .
J
(b)
T e s t B o ttle s - b o t t l e s e x a c tly l i k e th o s e d e sc rib e d
in . ( a ) , e x ce p t t h a t each b o t t l e s h a l l be marked by
e tc h in g t o show when th e b o t t l e c o n ta in s th e volume
o f 7 and 28 m l, r e s p e c tiv e ly . C o lo red c ra y o n s and
s im ila r m arkings s h a l l n o t be u sed f o r m arking th e
b o ttle s .
(a )
S u lf u r ic a c id , re a g e n t g ra d e (96 + 0*5% HgSO^ by wt*)
(b)
S u lf u r ic a c id , re a g e n t g ra d e (78 + 0*5% by w t.)
R eagents
2.
C lean th e b o t t l e s ( s e c tio n I ) w ith a warm chrom ic a c id
c le a n in g s o lu tio n , r i n s e w ith ta p w a te r fo llo w e d by
d i s t i l l e d w a te r, and d ry a t room te m p e ra tu re o r i n oven
a t 105°C f o r I h r . L ik ew ise c le a n a l l o th e r g la ssw a re
u sed i n t h i s m ethod.
3.
P r e p a ra tio n o f R eferen c e C o lo r S ta n d a rd s
4»
(a )
S to ck s o ln s . The fo llo w in g b a s ic re a g e n t s o ln s . s h a l l
be u sed f o r p re p a rin g th e re fe re n c e c o lo r s ta n d a rd s .
S o lu tio n A. D isso lv e 59.50 g . o f n i c k e l - f r e e (IoClg^M)O
i n d i l u t e HCl (p re p a re d by m ixing 25 m l o f HCl — 31% by
wto — w ith 975 ml HgO) and make up t o e x a c tly I l i t e r
w ith th e d i l u t e HCl.
S o lu tio n B. D isso lv e 4 5 .0 5 4 g . o f F e C l^ . 6HgO i n d i l u t e
HCl (p re p a re d by m ixing 25 A l o f HGl —" p l^ by w t. —
w ith 975 ml o f HgO) make t o I l i t e r w ith th e d i l u t e HCl.
IMl
( \
-5 4 TABLE XX ( c o n t i n u e d )
S o lu tio n G„ Mix 3k volum es S o ln . A w ith
S o ln . B and d i l u t e w ith 90 volumes o f HgO.
volumes
S o lu tio n De Mix 3k volum es S o ln e A w ith 364 volumes
S o ln e B,
■
S o lu tio n E 0 P re p a re a s o ln . o f KgGrO, s a tu r a te d a t 21°C.
S o lu tio n F . P re p a re a s o ln , o f KgCrgOn s a tu r a te d a t
210C and d i l u t e w ith an e q d a l volume o f HgOe
4»
(b)
P re p a re re f e r e n c e c o lo r s ta n d a rd s o ln s . h av in g th e
fo llo w in g co m p o sitio n s and numbered from 0- 1 4 :
Mo.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
(c )
O
I
2
3
4
5
6
7
8
9
10
11
12
13
14
D i s t i l l e d HgO.
I volume o f S o ln . C + I volume HgO^
5g volumes o f S o ln . C + 2 volumes HpO.
S o lu tio n G.
I volume S o ln . D + I volum e.HgO,.
5g volum es S o ln . D + I volume HgO.
S o lu tio n D.
5 volum es S o ln . E + 2 volumes HgO.
S o lu tio n E.
7 volumes o f S o ln . E + J volume S o ln . F.
64 volumes o f S o ln . E + I volume Qf S o ln . F .
5s volum es o f S o ln . E + 2 volum es o f S o ln . F .
1 volume o f S o ln . E + I volume o f S o ln . F .
2 volumes o f S o ln . E + 5 volumes o f S o ln . F .
S o lu tio n F .
H inse th e No. 0 b o t t l e ( s e c tio n I ( a ) ) and i t s g la s s
s to p p e r th r e e tim e s w ith d i s t i l l e d HgO; f i l l w ith
d i s t i l l e d HgO and s to p p e r th e b o t t l e . ■
R in se t h e No. I b o t t l e and s to p p e r th r e e tim e s w ith
th e s o ln . in d ic a te d i n p a ra g ra p h ( b ) j f i l l w ith t h i s
s o ln . and s to p p e r th e b o t t l e .
I n t h i s way5 p re p a re th e s e t o f c o lo r s ta n d a rd s having
th e co m position shown i n P arag rap h ( b ) . When f i l l i n g
each b o t t l e 5 le a v e ^ - i n . o f v ap o r space below th e neck
o f th e b o t t l e . S e a l each b o t t l e t o p re v e n t l o s s by
e v a p o ra tio n o r by c re e p in g o u t o f s o l u t i o n .
-5 5 TABLE XX (cotitinued)
P ro ced u re
5«
(a )
T e s ts a t Room Tem perature Below 85°F.
R in se a t e s t b o t t l e ( s e c . 3 ( b ) ) tw ic e w ith HgSO,
(96 + 0 .5 $ HgSO,) and d r a in ; add th e s u l f u r i c a c id up
t o th e 7-m l m ark. Add th e sample to b rin g th e t o t a l
volume t o th e 28-m l m ark. I n s e r t th e s to p p e r , h o ld a .
f i n g e r o v e r th e s to p p e r and g iv e v ig o ro u s shakes o v er
a s tro k e o f $ t o 10 i n . , shaking a t a r a t e c o rre sp o n d in g
t o 5 c y c le s p e r second f o r 15-20 seco n d s. L e t sta n d
away from th e sun i n su rro u n d in g s below 85°F. " A fte r
n i t r a t i o n g ra d e , i n d u s t r i a l g ra d e , and i n d u s t r i a l 90
benzene, n i t r a t i o n g rad e and i n d u s t r i a l g ra d e to lu e n e ,
n i t r a t i o n g ra d e and 5 - and 10-deg x y le n e , o r more
h ig h ly r e f in e d p ro d u c ts , ( f i r s t group) have sto o d
e x a c tly 15 m in ., o r a f t e r i n d u s t r i a l g rad e x y le n e , o r
r e f in e d s o lv e n t n a p th a (2nd group) have s to o d e x a c tly
5 m in ., w ith o u t f u r t h e r d e la y , o b serv e th e c o lo r s of
th e a c id and th e o i l la y e r s a s fo llo w s : I n v e r t th e
b o t t l e g e n tly once o r tw ic e t o o b ta in a u n ifo rm c o lo r
i n th e a c id la y e r . When t e s t i n g th e f i r s t group o f
h y d ro c a rb o n s, th e o i l la y e r sh o u ld rem ain w h ite , b u t
a mere c lo u d in e s s o r haze s h a l l n o t be i n t e r p r e t e d a s
a change i n c o lo r . When t e s t i n g th e second group o f HG,
th e c o lo r o f th e o i l la y e r s h a l l be d is re g a r d e d .
S e le c t two r e f e r e n c e c o lo r s ta n d a rd s , one o f a shade
l i g h t e r and th e o th e r a shade d a rk e r th a n th e c o lo r o f
th e a c id la y e r i n th e t e s t b o t t l e . P la c e th e t e s t
b o t t l e betw een th e s e two re fe re n c e c o lo r s ta n d a rd s
and h o ld them a g a in s t a w h ite background o r d a y lig h t.
U sing such tr a n s m itte d l i g h t , d eterm in e w hich c o lo r
s ta n d a rd shows a c o lo r t h a t i s a shade l i g h t e r o r a
shade d a rk e r th a n th e c o lo r o f th e a c id l a y e r , and
re c o rd t h i s number fo llo w e d w ith a p lu s s ig n o r a minus
s ig n t o in d i c a t e th e ap p ro x im a tio n .
I n t e r p r e t a t i o n o f R e s u lts
6.
(a )
Samples s h a l l be re p o r te d a s p a s s in g th e t e s t o n ly
when th e o i l la y e r shows no change i n c o lo r ( f o r
r e f in e d b e n ze n e s, to lu e n e s , and x y le n e s ) , and when
th e a c id la y e r i s n o t d a rk e r th a n th e r e f e r e n c e
s ta n d a rd c o lo r s o lu tio n p r e s c r ib e d i n th e s p e c i f i ­
c a ti o n s .
—$
6-
TABlE XX (c o n tin u e d )
6„
(b)
A c lo u d in e s s o r haze i n th e o i l la y e r s h a l l n o t be
i n t e r p r e t e d a s a change i n c o lo r .
(c )
A d if f e r e n c e o f hue s h a l l be d is re g a r d e d 5 i t i s o n ly
n e c e s s a ry t o d eterm in e i f th e c o lo r o f th e a c id la y e r
i s l i g h t e r o r d a rk e r th a n th e c o lo r o f th e re fe re n c e
s ta n d a rd t o w hich th e sample most n e a r ly c o rre sp o n d s.
R e p r o d u c ib ility
F o r t e s t s i n which t h e hue o f th e a c id la y e r i s about
th e same a s th e hue o f th e re f e r e n c e c o lo r s ta n d a rd ,
d u p lic a te d e te rm in a tio n s should n o t d i f f e r from one
a n o th e r by more th a n % f r a c t i o n a l p a r t of a number a s
e x p re sse d by a + o r - sig n fo llo w e d by a number. To
o b ta in such agreem ent i t i s n e c e s s a ry to f o llo w th e
p r e s c r ib e d p ro c e d u re c a r e f u l l y and to m a in ta in about
th e same c o n d itio n s o f te m p e ra tu re and v ig o ro u s
a g i t a t i o n . The e f f e c t o f te m p e ra tu re i s i l l u s t r a t e d
by th e f a c t t h a t a Ho. 2 s ta n d a rd a t IOO0F may be
c a ll e d No. 3 when compared w ith a s e t o f s ta n d a rd s
a t 77°F.
-5 7 table
zn
COPPER-STRIP CORROSION TEST
The c o p p e r - s tr ip c o rro s io n t e s t f o r t h e l i g h t o i l f r a c t i o n was
ru n a s f o llo w s ;
(1 )
50 ml o f th e p ro d u c t o i l was p la c e d i n a 200 ml
E rlenm eyer f l a s k .
(2)
A ,c le a n , p o lis h e d copper s t r i p was suspended i n th e o i l
by a copper w ire from th e to p o f th e f l a s k .
(3)
The f l a s k was connected t o a v e r t i c a l L ie b ig condenser
and t h e o i l was r e f lu x e d ( b o ile d ) f o r 1 /2 h o u r.
(4 )
The l i g h t o i l was s a id t o be c o rro s iv e i f th e copper
s t r i p had a n o tic e a b le d a rk e n in g .
-9 8
VACUUM
BLOW
OFF
LINE
GAS INLET
VENT
BK IRON
SCH 8 0
WATER INLET
PRODUCT
OIL
CAUSTIC
CATAlVST-
WATER
OUT
PYREX
SIGHT
GLASS
Z^-THERMOWELU
PRODUCT
RESERVOIR
F ig u re I - Sc h e m a tic diagram o f D e s u l f u r i z a l io n Unit
f o r P r o c e s s i n g L ig h t O i l .
LOG
7 0 0 eF
1000
RECIPROCAL VAPOR
F ig.
2«
RATE
4 0 0 PSIG
F T 3ZBBL 5O y.H 2- 5 0 % N 2
(F T V IO O GM CAT./HR)
D e s u l f u r i z a t i o n v s . R e c ip r o c a l Vapor n a te
(Run U . S . S . - l ? )
LOG
I 2 .0
6 2 5 °F 4 0 0 PSIG
IOOO F T 3ZBBL PURE H
2 .0
RECIPROCAL
F1S°
3=
3 .0
VAPOR
RATE
4 .0
( F T 3ZIOO CM CAT.ZHR)
D e s u l f u r i z a t i o n v s 0 R e c i p r o c a l Vapor Rate
(Run U . S . S . - 2 2 )
0
O 2.0
X
0
RUN
RUN
6 5 0 eF
U S S -20
U S S - 19
4 0 0 PSIG
1 0 0 0 F T ^ / BB L
2 .0
RECIPROCAL
F ig.
4.
3 .0
VAPOR
RATE
,
4 .0
( F T 3 ZIOO
5 .C
GM C A T ./H R )
D e s u l f u r i z a t i o n v s . R e c i p r o c a l Vapor Rate
(Runs U . S . S . - 1 9 a n d -2 0 )
O
2+ LOG K
2.2
F ig 0
5.
D eterm in atio n
of
th e
E ffect
of
T em p eratu re
( Runs U . S . S . - 1 Q a n d - 1 1 )
(Ea )
on
Km
0.6
0 PURE H2
—
X 5 0 % H —5 0 % N
'6 0
1.65
RE C IPR O C A L
1 .70
TEMPERATURE
1.75
1.80
(— L - X l O 3 )
D e t e r m in a t io n o f t h e E f f e c t o f Temperature ( E )
on
(
h n n
IT
S
c
X
‘
3'
0
1.3 -
X RUN
U S S - 15
U S S - 18
Z RUN
U S S - 19
Y RUN
U S S - 19
-
V RUN
USS-21
W RUN
U S S - 23
RATE CONSTANT (K
1.2
RUN
O
10?
200
300
TOTAL
F ig .
7
E ffect
of
400
P RE S S U R E
T o tal
P ressure
500
600
700
(PSIG)
on
th e
R ate
C o n stan t
(K ?)
800
6.0
I
&
LOG
I
12.0
F ig 0 3.
E f f e c t o f Vapor R ate a t V a rio u s P r e s s u r e s
on t h e D e g r e e o f D e s u l f u r i z a t i o n a t
C o n sta n t R atio o f Feed to C a t a l y s t
LOG
RUN
USS-16
650
° F 4 0 0 PSlG
IOOO F T 3ZBBL
RECIPROCAL
F ig 0 9.
VAPOR
RATE
E ffect
of
( F T 0ZIOO
D ilu en t
Gas
GM
on
CAT.ZHR)
4.0
Z
F ig.
IO0
4"
RATE
O
O
VAPOR
-n
RECIPROCAL
5.0
4.0
3.0
H
2.0
GM
CAT./HR)
E f f e c t o f D ilu e n t Gas on kt
4.0
-
LOG
3 . 0 ■—
2.0
-
1.0
-
RUN USS - 2 3
6 2 5 °F
2 0 0 PSIG
IOOO F T 3ZBBL
RECI PROCAL
F ig .
11.
VAPOR
E ffect
RATE
of
( F T 3ZIOO GM CAT.ZHR)
D ilu en t
Gas
on
0.5 -
I- 0.4 —
0.3 -
0.1
—
500
TREAT
12 o
0
RUN U S S - 15
X
RUN USS —18
1000
GAS RATE (FT/BBL)
Effect of Treat Gas Rate on K.
1500
(Kt)
RATE CONSTANT
CATALYST
BED
(INCREASING
F ig 6 13.
L ffect
of
DEPTH
(INCHES)
LINEAR VELOCITY----- >
)
C a t a l y s t Bed D e p t h o n
MONTANA STATE UNIVERSITY LIBRARIES
IiIIlHH
762 10005661
D378
Jl57c
128942
cop. 2
J a c o b s o n , Tl. L .
The catalytic hydrodesulfuriza
tion of coal tar aromatic
distillates.
im a M K
MAR 9
15#
:
Ti S L ' (4,c.^'iKC0
'c a-
#* * #
i/
//>r> /) 4
I-*-"
1Iltttitiii
7
^
X
C X r^
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7"
S ’7 c
C op, g
128942
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