Characterization of oils for catalytic hydrodesulfurization
by Richard G Waterman
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Doctor of Philosophy in Chemical Engineering at Montana State College
Montana State University
© Copyright by Richard G Waterman (1958)
Abstract:
Catalytic hydrodesulfurization studies were carried out on four oils in the 400 to 700-F boiling range
utilizing cobalt molybdate catalyst. All studies were made with bench scale equipment.
The effects of contact time, temperature, treat-gas composition, treat-gas rate, hydrogen partial
pressure, and oil partial pressure were studied. Desulfurization was found to increase with an increase
in contact time, but the rate of reaction decreased. The rate of desulfurization increased with
temperature; however, temperatures above 700 F tend toward catalyst deactivation. At constant
pressure an increase in hydrogen partial pressure increases desulfurization, and increasing, the treat-gas
rate from 1000 to 2000 ft3/bbl also increased desulfurization. The increase with gas rate was attributed
to lower oil partial pressure at the higher gas rate. A decrease in desulfurization with an increase in
pressure at constant contact time was noted when the hydrogen concentration of the treat-gas was
greater than approximately 85% when using a gas rate of 2000 ft3/bbl, and approximately 55% when
using a gas rate of 1000 ft3/bbl.
The charge oils and three desulfurized samples were analyzed by a mass spectrometer. It was found
that thiophenes are more reactive than benzothiophenes which are more reactive than
dibenzothiophenes. Di-benzothiophene content was correlated with the ease of desulfurization. CHARACTERIZATION OF OILS FOR
CATALYTIC HYDRODESULFURIZATION
by
R ic h a rd G0 Waterman
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 t h e d e g re e o f
D octor o f P h ilo so p h y i n Chem ical E n g in ee rin g
at
Montana S ta te C o lle g e
Approved?
Head, M ajor Department^
Chairm an, Examining J ^ s d ^ ltte e
cDfean, G radudtpf D iv is io n
Bozeman, M ontana •
Ja n u a ry , 195S
RESTRICTED sta c k
" nr ^
_2_
TABLE OF CONTENTS
A b s t r a c t ......................................................................................................... page
I n tr o d u c tio n . . . .
3
...............................................................................
4
Equipm ent.........................................................................................................
IO
M a t e r i a l s .....................................................................................................
10
M e t h o d s ..........................................................................................................
11
D i s c u s s i o n ............................................................................................ .... .
15
T able XVI - Comparison o f S u lf u r Removal From Aramco
L ig h t Waxy D i s t i l l a t e .....................................................
24
S u m m a r y ..........................................................................................................
26
A cknow ledgm ent.............................................................................................
28
L i t e r a t u r e C i t e d ................................................
29
A p p e n d ix ..........................................................................................................
30
145298
-3 -
Abstract
C a t a ly ti c h y d r o d e s u lf u r iz a tio n s tu d ie s were c a r r ie d o u t on f o u r
o i l s i n th e 400 t o 700-F b o ilin g ran g e u t i l i z i n g c o b a lt m olybdate
c a t a l y s t . A ll s tu d ie s w ere made w ith bench s c a le equipm ent.
The e f f e c t s o f c o n ta c t tim e , te m p e ra tu re , t r e a t - g a s c o m p o sitio n ,
t r e a t - g a s r a t e , hydrogen p a r t i a l p r e s s u r e , and o i l p a r t i a l p re s s u re were
s tu d ie d . D e s u lf u r iz a tio n was found to in c r e a s e w ith an in c r e a s e i n con­
t a c t tim e , b u t th e r a t e o f r e a c tio n d e c re a s e d . The r a t e o f d e s u lf u r iz a ­
t i o n irib re a s e d w ith te m p e ra tu re ; how ever, te m p e ra tu re s above 700 F te n d
toward" c a t a l y s t d e a c t i v a t i o n . At c o n s ta n t p r e s s u r e &n in c r e a s e i n
hydrogen p a r t i a l p r e s s u r e in c r e a s e s d e s u lf u r iz a tio n ^ and in c re a s in g , th e
t r e a t - g a s r a t e from 1000 t o 2000 f t ^ / b b l a ls o in c re a s e d d e s u l f u r i z a t i o n .
The in c r e a s e w ith gas r a t e was a t t r i b u t e d t o lo w er o i l p a r t i a l p re s s u re
a t th e h ig h e r g as r a t e . A d e c re a se i n d e s u lf u r iz a ti o n w ith an in c r e a s e
i n p r e s s u r e a t c o n s ta n t c o n ta c t tim e was n o te d when th e hydrogen con­
c e n tr a ti o n o f th e t r e a t - g a s was g r e a t e r th a n a p p ro x im a te ly
when u s in g
a g as r a t e . o f 2000 f t ^ / b b l , and a p p ro x im a te ly 55% when u s in g a g as r a t e
o f 1000 f t V b b l .
The c h arg e o i l s and t h r e e d e s u lf u r iz e d sam ples were a n a ly z e d by a.
mass s p e c tro m e te r. I t was found th a t.th io p h e n e s a re more r e a c t i v e th a n
b e n zo th io p h en e s w hich a r e more r e a c t i v e th a n d ib e n z o th io p h e n e s . D ib e n zo th io p h en e c o n te n t was c o r r e la te d w ith th e e ase o f d e s u lf u r iz a ti o n .
-4 -
INTRGDUdTION
i
F o r many y e a r s th e p e tro le u m in d u s t r y has been c o n fro n te d w ith
p roblem s a r i s i n g from th e p re s e n c e o f s u l f u r compounds i n p e tro le u m .
The problem s a r e becoming more a p p a re n t f o r s e v e r a l re a s o n s : more h ig h s u l f u r crude o i l s a r e b e in g u sed b ecau se th e more d e s ir a b le lo w -s u lfu r
c ru d e s a r e b e in g d e p le te d ; th e p e tro le u m i n d u s tr y h as become more
c o m p e titiv e w ith th e consumer d e s ir in g h ig h q u a l i t y p ro d u c ts ; an d , many
o f th e more r e c e n t l y developed r e f i n i n g p ro c e s s e s a r e hampered by th e
p re s e n c e o f s u l f u r .
..Among th e problem s caused by th e p re s e n c e o f s u l f u r compounds in
v a r io u s in te r m e d ia te s and p ro d u c ts a r e :
1.
The c o rro s iv e e f f e c t s , en co u n te re d i n r e f i n i n g , s to r a g e , t r a n s ­
p o r ta tio n ^ and i n b u rn in g o r com busting o f th e p ro d u c ts
2.
The o b je c tio n a b le o d o rs o f some compounds such a s m ercap­
ta n s and hydrogen s u lf id e
3.
The re d u c tio n o f o c ta n e number o f g a s o lin e s in d u c ed by
c e r t a i n ty p e s of s u l f u r compounds such a s d i s u l f i d e s , p o ly ­
s u l f i d e s , and m ercaptan s
4.
The lo w e rin g o f le a d s u s c e p t i b i l i t y by n e a r ly a l l ty p e s of
s u l f u r compounds (on a 60 is o - o c ta n e -4 0 n -h e p ta n e b le n d con­
t a i n i n g 3 c c . o f t e t r a e t h y l l e a d p e r g a llo n , th e o c ta n e number
was d e p re ss e d ab o u t 4 o c ta n e numbers w ith th io p h e n e s p re s e n t
t o 14 o c ta n e numbers w ith th io p h e n e m ercap tan s p r e s e n t.
These
compounds were p r e s e n t i n c o n c e n tra tio n s e q u iv a le n t t o 0,1%.
-5 -
s u l f u r i n th e f u e l (? ) )
5.
The a d v e rs e e f f e c t s o f s u lf u r compounds on p ro d u c t s t a b i l i t y
6.
The a c r i d fum es g iv en o f f when burned a s i n th e c ase o f f u e l
o ils .
The consequences o f m ost o f th e s e problem s a r e e a s i l y re c o g n iz e d ,
b u t th e manner i n which th e p re se n c e o f s u l f u r a l t e r s some r e f in in g
p ro c e s s e s i s n o t so a p p a r e n t„
C a t a ly ti c p ro c e s s in g i s becoming more popu­
l a r i n th e p e tro le u m i n d u s tr y and a v a r i e t y o f c a t a l y s t s a r e i n u s e ; how­
e v e r , many o f th e s e c a t a l y s t s a r e p o iso n ed by th e p re se n c e o f s u lf u r
Compo1U nds, t h a t i s , th e s u l f u r compounds cause a d e c re a se i n c a t a l y s t
a c tiv ity .
N ic k e l, c o b a lt , c o p p er, i r o n , and p la tin u m , u sed f o r dehydro­
g e n a tio n , p la tin u m and p alad iu m , u sed f o r g a s o lin e re fo rm in g , a re some
o f th e c a t a l y s t s p o iso n e d by s u l f u r (3 ) .
B efore i t was n e c e s s a ry t o u t i l i z e th e h ig h - s u lf u r c ru d e s , methods
w ere employed, such a s d o c to r tr e a tm e n t, t o c o n v e rt th e o b je c tio n a b le
o dor compounds (m ercap tan s) t o o th e r ty p e s o f compounds such a s d i ­
s u lfid e s .
T h is , d f c o u rs e , I b f t th e s u l f u r i n th e o i l .
I f com plete
s u l f u r rem oval was r e q u ir e d , th e o i l was g e n e r a lly t r e a t e d w ith s u l f u r i c
a c id , w hich a ls o r e s u l t e d i n th e l o s s o f some d e s ir a b le c o n s ti tu e n ts .
C e r ta in c a t a l y s t s i n an atm osphere o f hydrogen (h y d r o d e s u lfu riz a ­
t i o n ) w i l l decompose s u l f u r compounds, th e s u l f u r can be e lim in a te d a s
hydrogen s u l f i d e , and lo s s e s o f th e fe e d s to c k a re n e g l i g i b l e .
The c ru x
o f t h i s ty p e of p ro c e s s in g was an economic so u rc e o f hydrogen.
C a t a ly ti c
re fo rm in g , i n w hich p re d o m in a te ly n a p h th en e s a r e c o n v e rte d t o a r o m a tic s ,•
—6—
p ro v id e d t h i s so u rc e o f h y d ro g en .
A t y p i c a l h y d r o d e s u lf u r iz a tio n r e a c tio n in v o lv in g th io p h e n e i s g iv en
below :
Oi H4S .♦
Z1H2 ----------------C4H10
♦
H2S
Many o f th e p r e s e n t day o i l r e f i n e r i e s r e c e iv e t h e i r crude o i l s from
v a r io u s o i l f i e l d s th ro u g h o u t th e -w o rld .
These c ru d es may d i f f e r o n ly
s l i g h t l y i n co m position and s u l f u r c o n te n t, o r th e y may be g r e a t l y d i f ­
fe re n t.
B ecause o f th e d i f f e r i n g c o m p o sitio n o r o th e r re a s o n s , d i f f e r e n t
o i l s may behave d i f f e r e n t l y u n d er s im ila r o p e ra tin g c o n d itio n s and can
c r e a t e many problem s w ith in a r e f i n e r y .
G e n e ra lly , th e r e a c tio n s o f th e
v a r io u s o i l s t o th e p ro c e s s in g c o n d itio n s a re d eterm in ed b e fo re usage
and th e c ru d e s a r e s y s te m a tic a lly sch e d u le d i n t o th e r e f i n e r y .
T h is i s
n o t alw ays p o s s ib le , how ever; and b ecau se o f th e changing economic
c o n d itio n s o f th e w orld to d a y , a r e f i n e r y may have i t s cru d e o i l su p p ly
c u t o f f w ith o u t n o tic e and have t o r e s o r t t o a n o th e r s o u rc e .
I n o rd e r to d e term in e how a p a r t i c u l a r f r a c t i o n w i l l r e a c t to th e
p ro c e s s v a r i a b l e s , th e f r a c t i o n i s g e n e r a lly s u b je c te d t o th e v a r ia b le s
o f th e p ro c e s s on a p i l o t p la n t s c a le .
and tim e-consum ing o p e r a tio n .
T h is can become a v e ry expensive
I f th e co m p o sitio n of th e o i l i n q u e stio n
c o u ld be d e te rm in e d , f o r in s ta n c e by a mass s p e c tro m e te r, a c o r r e la tio n
(.
m ight be found betw een c o m p o sitio n and p ro c e s s a d a p t a b i l i t y .
Once th e
e f f e c t s o f p ro c e s s v a r ia b le s have been e s ta b lis h e d on a p a r t i c u l a r
p e tro le u m f r a c t i o n o r b o i l i n g ra n g e , a com p o sitio n a n a ly s is may be a l l
t h a t would be needed t o p r e d i c t c o n v e rsio n s a t v a rio u s o p e ra tin g c o n d i-
"7 —
tio ris ,
I n o th e r w ords} th e ch arg e o i l s may be c h a r a c te r iz e d by a p a r t i ­
c u la r ' c o n s ti tu e n t o r c o n s t i t u e n t s .
I n t h i s p a p e r, f o u r d i f f e r e n t o i l s i n th e d i e s e l and b u rn e r o i l
ra n g e ( 400-700 F) were s tu d ie d i n c o n ju n c tio n w ith a c a t a l y t i c hydro­
d e s u lfu riz a tio n p ro c e ss.
The aim o f th e re s e a rc h was to d eterm in e th e
e f f e c t s of th e o p e ra tin g v a r ia b le s on th e d e s u lf u r iz a ti o n r e a c tio n , and
t o d e te rm in e i f th e ty p e s o f s u l f u r compounds p re s e n t i n th e o i l could
be lin k e d t o th e e ase of d e s u l f u r i z a t i o n .
The c a t a l y t i c d e s u lf u r iz a ti o n r e a c tio n has been shown to be a p seu d o f i r s t - o r d e r 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 th e s u lf u r ­
b e a r in g compound (5 , 6 , 8 ) ,
The r e a c tio n i s term ed p s e u d o - f ir s t- o r d e r
b ecau se th e c o n c e n tra tio n o f th e hydrogen i s k e p t h ig h enough a t a l l
tim e s t o be c o n sid e re d c o n s ta n t (a p p ro x im a te ly 70 m oles o f H2 p e r mole
o f s u l f u r compound)„ I n view o f t h i s ev id en ce a f i r s t - o r d e r r e a c tio n was
assumed f o r th e d e s u lf u r iz a ti o n r e a c tio n s tu d ie d i n t h i s r e s e a r c h .
The r a t e e q u a tio n u sed was
dCa
dt
=
—kCa
(l)
i n which Ca = th e c o n c e n tra tio n o f th e s u lf u r - b e a r in g compound,
t = c o n ta c t tim e ,
k = r a t e c o n s ta n t,
The a c t u a l c o n ta c t tim e w i l l be p r o p o r tio n a l t o th e a p p a re n t c o n ta c t
tim e and can be e x p re sse d i n te rm s o f space v e l o c i t y , i . e , , grams o f o i l
p e r h o u r p e r gram o f c a t a l y s t ( g / h r / g ) ,
h a s th e u n i t s o f tim e ( h r ) .
The r e c ip r o c a l o f space v e lo c i ty
However, a b e t t e r approach t o th e a p p a re n t
c o n ta c t tim e i s t o u se a f u n c tio n o f th e t o t a l v ap o r r a t e , which i s a
com bination o f t r e a t - g a s and o i l v a p o r p a s s in g o v er th e c a t a l y s t i n a
g iv e n tim e .
and p r e s s u r e .
T h is a llo w s f o r v a r i a t i o n i n c o n ta c t tim e due to te m p e ra tu re
S in ce 100 grams o f c a t a l y s t were u sed i n a l l th e ru n s , th e
v a p o r r a t e was e x p re ss e d a s f t^ y a p o r .
( h r ) (IOOg)
was u sed f o r a p p a re n t c o n ta c t tim e .
The r e c ip r o c a l o f th e v ap o r r a t e
E q u a tio n ( I ) can a l s o be w r itt e n a s
dx
dt
=
k(A -x)
(2)
i n w hich A = i n i t i a l c o n c e n tra tio n o f s u l f u r ,
x = amount o f s u l f u r r e a c te d a t any tim e , t , .
(A-x) = th e amount o f s u l f u r re m a in in g .
( I t can be d eterm in ed
by a sim ple a n a l y s i s . )
I n th e d e s u lf u r iz a ti o n r e a c t i o n , th e r e a c tio n r a t e c o n s ta n t i s
a f f e c t e d by a l l th e p ro c e s s v a r ia b le s and sh o u ld t h e r e f o r e be r e s t r i c t e d
t o th e o p e ra tin g c o n d itio n s i n each in s ta n c e .
To be s p e c i f i c , th e n , th e
r e a c tio n r a t e c o n s ta n t, k , i n E q u a tio n (2 ) sh o u ld be r e s t r i c t e d by th e
s u b s c r ip ts a s in d ic a te d i n E q u a tio n (3 ) .
=
^T.pHg.pOil.Hg'DiC.Ca
^
The s u b s c r ip ts i n d i c a t e , r e s p e c tiv e ly , te m p e ra tu re , hydrogen p a r t i a l p r e s ­
s u r e , o i l p a r t i a l p r e s s u r e , hydrogen c o n c e n tr a tio n , th e ty p e o f d ilu e n t
o r d il u e n t s (g a s e s o th e r th a n hydrogen) i n th e t r e a t - g a s , th e ty p e of
c a t a l y s t em ployed, and th e c a t a l y s t a c t i v i t y , a l l o f which a f f e c t th e
-9 -
v e l o c i t y o f th e d e s u l f u r i z a t i o n r e a c t i o n .
The e f f e c t s o f c a t a l y s t p a r t i c l e
s iz e and c a t a l y s t bed d e p th have been l e f t o u t, assum ing t h a t th e y a re
b o th o f such dim ensions
so a s t o have no e f f e c t on th e r e a c t i o n .
c a s e s , d e c re a s in g c a t a l y s t
p a r tic le s iz e
d e p th w i l l in c r e a s e d e s u l f u r i z a t i o n .
and in c r e a s in g
In some
c a t a l y s t bed
I t i s d e s ir a b le t o o p e ra te where
b o th o f th e s e f a c t o r s w i l l g iv e maximum d e s u lf u r iz a ti o n p ro v id e d th e
p r e s s u r e drop a c r o s s th e c a t a l y s t bed does n o t become tro u b leso m e .
R earrangem ent and i n t e g r a t i o n o f E q u atio n ( 2.) betw een l i m i t s
( t = 0 t o t = t , and x = 0 t o x) g iv e s .
In A =
A-x
or
kt
2 .3 Io g i n A
10A^r
(4)
=
kt
(5)
I f th e r e a c tio n i s f i r s t - o r d e r , a p l o t o f l og A v s . t s h o u ld .g iv e a
A-x
s t r a i g h t l i n e w ith s lo p e k and p a s s in g th ro u g h th e o r i g i n .1
2 .3
S e v e ra l r a t h e r le n g th y te rm s a r e u sed f r e q u e n tly th ro u g h o u t th e
p a p e r and f o r convenience th e fo llo w in g a b b r e v ia tio n s w i l l be u se d ;
Term . ■
A b b re v ia tio n ...
AramcQ--Light-.Waxy. D i s t i l l a t e
Aramco
C a r te r R a ilro a d D ie s e l O il
RRD
C a r te r Medium C ycle O il
MCO
Husky No. 350 B urner O il
Husky
B enzothiophene
BT
D ibenz o th iophene
DBT
-1 0 -
EQUIPMENT
A ll e x p erim en ts were c a r r ie d o u t i n a Ir-inch s t a i n l e s s s t e e l r e a c to r
36 in c h e s lo n g .
The c a t a l y s t was su p p o rte d by l / 8- in c h alundum p e l l e t s
and th e p r e - h e a t s e c tio n above th e c a t a l y s t was a ls o f i l l e d w ith th e p e l­
le ts .
The r e a c t o r was e l e c t r i c a l l y h e a te d by 4 n i chrome h e a tin g c o i l s .
C u rre n t was su p p lie d t o th e c o i l s by f o u r 1 2 0 -v o lt a u to tr a n s f o r m e r s .
F iv e
ir o n - c o n s ta n ta n th erm o co u p les i n a c o a x ia l l / 4- in c h s t a i n l e s s s t e e l therm o­
w e ll were u sed t o m easure th e r e a c t o r te m p e ra tu re .
The r e a c t o r p re s s u re
was c o n tr o lle d by a M ason-N eilan sm all volume a i r - t o - c l o s e back p re s s u re
v a lv e i n c o n ju n c tio n w ith a F ish e r-W iz a rd p r o p o r tio n a l c o n t r o l l e r .
A schem atic diagram o f th e c o n v e n tio n a l h ig h p re s s u re flo w system
i s g iv en i n F ig u re I .
The o i l was pumped t o th e to p of th e r e a c t o r by a
p r o p o r tio n in g p lu n g e r pump.
The hydrogen was ta k e n from a com m ercial
hydrogen c y lin d e r and m e te red t o th e r e a c t o r th ro u g h a ro ta m e te r.
MATERIALS
The c a t a l y s t employed was d e s ig n a te d Harshaw C0M0-03O1T (Harshaw
Chem ical Company).
T h is i s a m ix tu re o f c o b a lt and molybdenum o x id es
su p p o rte d on a lu m in a .
The c a t a l y s t was c ru sh ed and s iz e d t o 10 /1 4 mesh
and c a lc in e d f o r 12 t o 20 h o u rs a t 1100 t o 1200°F i n an atm osphere o f
n itro g e n .
The f o u r o i l s u sed were nam ely:
I.
Aramco L ig h t Waxy D i s t i l l a t e from th e A rabian-A m erican O il
Company, A rab ia
-1 1 -
2.
C a r te r R a ilro a d D ie s e l O il and
3.
C a r te r Medium C ycle O il from th e C a r te r O il Company, B i l l i n g s ,
Montana
4»
Husky No. 350 B urner O il from th e Husky O il Company, Cody,
Wyoming.
I n a d d itio n t o th e s e f o u r o i l s , a b le n d o f 50.w t„# C a r te r R a ilro a d D ie s e l
O il and 50 w t.$ C a r te r Medium C ycle O il was u s e d .
The in s p e c tio n d a ta
o f th e charge o i l s a r e g iv e n i n T ab le I .
Hydrogen Was o b ta in e d i n No. I-A c y lin d e r s from th e Whitmore Oxygen
Company, S a l t Lake C ity , U tah.
Mixed g a se s w ith co m p o sitio n s o f 60%
h y d ro g en -40^ m ethane and 30% hydro g en -70# m ethane by volume were o b ta in e d
i n No. I-A c y lin d e r s from th e M atheson Company, J o l i e t , I l l i n o i s .
METHODS
One hundred grams of c a t a l y s t were u sed i n th e r e a c t o r th ro u g h o u t
th e e x p e rim e n ta l work w ith th e e x c e p tio n o f Run Husky-5 (T ab le I I I ) , i n
w hich 50 grams were u s e d .
The 100-gram c a t a l y s t ch arg e o ccu p ied approx­
im a te ly 10 in c h e s o f th e r e a c t o r le n g th .
The s t a r t - u p p ro c e d u re c o n s is te d o f c h a rg in g th e r e a c t o r w ith c& ta l y s t , h e a tin g u n d er hydrogen flo w a t th e o p e ra tin g p r e s s u r e t o th e de­
s i r e d o p e ra tin g te m p e ra tu re , and th e n s t a r t i n g th e o i l flo w .
Approx­
im a te ly 50 t o 70 h o u rs w ere n e c e s s a r i l y a llo w ed a f t e r th e o i l was s t a r t e d
f o r th e c a t a l y s t t o become f u l l y a c t i v a t e d (T ab le V I, A ram co-5).
hydrogen was s in g le - p a s s e d th ro u g h th e r e a c t o r and v e n te d .
The
-1 2 -
The p ro d u c t o i l was re c e iv e d i n a 1000-m l f l a s k , c a u s tic washed t o
remove hydrogen s u l f i d e , w a te r washed, and a n aly z e d f o r s u l f u r c o n te n t.
The s u l f u r was d e term in e d by com bustion o f th e o i l i n a lamp (ASTM method
D 90-41T), a b s o r b tio n o f th e o x id e s i n hydrogen p e ro x id e , and t i t r a t i o n o f
th e s u l f u r i c a c id form ed w ith sodium h y d ro x id e .
Where h ig h ly a ro m a tic
ch arg e o i l s were u sed (Runs C a r te r - 2 , and -3 ) th e lamp method was u n s a t i s ­
f a c t o r y , and th e s u l f u r was d eterm in ed by th e C a r te r O il Company by com-*
b u s tin g th e sample i n a q u a r tz " b o a t" .
In. g en eral,,, f o u r sam ples were ta k e n f o r each s e t o f r e a c t o r co n d i­
t i o n s and th e t h i r d and f o u r th sam ples were a n aly z e d f o r s u l f u r c o n te n t.
One and two s u l f u r d e te rm in a tio n s were made on th e t h i r d and f o u r th
sam ples, r e s p e c t i v e l y .
T h is p ro c e d u re was u sed to d eterm in e i f th e system
was l i n e d o u t.
A bench mark was r e f e r r e d t o th ro u g h o u t th e ru n s t o check on c a t a l y s t
a c tiv ity .
The c o n d itio n s o f th e bench mark w ere: sp ace v e l o c i t y , 2 g / h r / g j
p r e s s u r e , 200 p s i g | te m p e ra tu re 6$0 F ; t r e a t - g a s r a t e , 1000 f t ^ / b b l of
h y d ro g en .
The ru n s were d e sig n e d t o keep th e e f f e c t s o f c a t a l y s t de­
a c tiv a tio n n e g lig ib le .
The m ass sp e c tro m e te r a n a ly s e s o f t h e charge o i l s and th e Aramco
sam ples (T a b le s XEII and XEV) were made by th e Esso R esearch and E n g in eer­
in g Company, L inden, New J e r s e y .
. The ch arg e o i l f o r a l l th e Aramco ru n s was Aramco L ig h t Waxy D i s t i l ­
l a t e , and th e ch arg e o i l f o r a l l th e Husky ru n s was Husky No. 350 B urner
O il.
The ch arg e o i l f o r Run C a r te r - 1 was C a r te r R a ilro a d D ie s e l F u e l,
-1 3 -
f o r Run C a r te r - 2 was G a rte r Medium C ycle Q il5 f o r Run C a r te r -3 was a 50
w t»$ b le n d o f th e R a ilro a d D ie s e l and Medium C ycle O il.
From th e o p e ra tin g c o n d itio n s o f th e e x p e rim e n ta l work (200-400 p s ig ,
600-700 F ) and th e b o ilin g ran g e o f th e ch arg e o i l s (400-700 F ) , i t i s
a p p a re n t t h a t a l l th e o i l ' w i l l n o t be v a p o riz e d i n th e r e a c t o r .
The
m ethod u sed t o c a lc u la te th e p e rc e n ta g e o f th e o i l v a p o riz e d was ta k e n
from th e ..Es souJBlue .Book (4 ) .
T h is in v o lv e s some e m p iric a l c o r r e l a t i o n s
t h a t have been dev elo p ed f o r p r e d ic tin g e q u ilib riu m v a p o r iz a tio n c u rv es
from d i s t i l l a t i o n d a ta .
To quote from t h e E sso .B lue■Book, th e . method i s
o u tlin e d h s fo llo w s :
"I.
D eterm ine th e F la s h R eferen ce l i n e (FRL) and th e F la s h
V a p o riz a tio n Curve (FVC) from th e ASTM d i s t i l l a t i o n o f
th e fe e d s to c k u s e d .
2.
C a lc u la te th e number o f m oles o f hydrocarbon and gas
e n te r in g th e r e a c t o r .
3.
By th e method o f t r i a l and e r r o r , assum ing a g iv en p e r­
c e n ta g e of th e o i l v a p o riz e d , c a lc u la te i t s p a r t i a l ',
p r e s s u r e u n d er th e p r e v a ilin g r e a c t o r p r e s s u r e .
4.
S h i f t th e f l a s h cu rv e p a r a l l e l t o i t s e l f from atm o sp h eric
p r e s s u r e t o th e c a lc u la te d p a r t i a l p re s s u re o f th e hydro­
carbon i n t h e m ix tu re a s d eterm in ed u n d er ( 3 ) . The amount
by which th e f l a s h cu rv e should be s h i f t e d i s m ost con­
v e n ie n t ly d e term in e d from th e 40% FRL p o in t and th e p a r t i a l
p r e s s u r e o f th e o i l by means o f C h art 4-53 o f th e .B lu e Book.
5.
Compare th e te m p e ra tu re a t th e assumed p e r c e n t v a p o riz e d
on th e s h i f t e d curve w ith th e a c t u a l r e a c to r te m p e ra tu re .
I f t h i s te m p e ra tu re i s h ig h e r th a n th e r e a c to r te m p e ra tu re ,
th e n l e s s o i l i s v a p o riz e d th a n had been assum ed; con­
v e r s e l y , i f th e te m p e ra tu re on th e s h i f t e d curve i s lo w er
th a n th e r e a c t o r te m p e ra tu re , more o i l was v a p o riz e d .
A c c o rd in g ly , r e p e a t s te p s ( 3 ) , ( 4 ) , and (5 ) w ith a n o th e r
assumed p e rc e n ta g e o f o i l v a p o riz e d u n t i l th e c o rre sp o n d in g
te m p e ra tu re on th e s h i f t e d f l a s h cu rv e c o in c id e s w ith th e
• r e a c t o r te m p e ra tu re .■5*11•
—1 4 F ig u re s 2 and 3 a r e p l o t s o f p e rc e n t v a p o riz e d v s . te m p e ra tu re f o r
th e f i v e charge o i l s .
These f i g u r e s show t h a t th e p e rc e n t v a p o riz e d i n ­
c r e a s e s a s te m p e ra tu re and g as r a t e in c r e a s e , b u t d e c re a s e s a s p re s s u re
in c re a s e s .
'.-S
I
-1 5 -
DISCUSSION.
I n th e s tu d y o f a c a t a l y t i c r e a c t i o n , i t i s d e s ir a b le t o know i f
t h e r e a c tio n i s a f f e c t e d by d i f f u s i o n .
The r e a c tio n may be lim ite d by
th e d if f u s io n o f th e r e a c ta n ts from th e main gas stream t o th e c a t a l y s t
s u rfa c e and th e d if f u s io n o f th e p ro d u c ts from th e c a t a l y s t t o th e main
g a s s tre a m .
The e f f e c t s of t h i s ty p e o f d if f u s io n may be k e p t t o a m in i­
mum by u s in g h ig h v e l o c i t i e s th ro u g h th e c a t a l y s t bed and th u s lo w erin g
th e f ilm r e s i s t a n c e on th e c a t a l y s t s u r f a c e .
The e f f e c t s o f d if f u s io n
a c r o s s th e s u rfa c e f i l m can be t e s t e d by making two s e r i e s o f ru n s w ith
& d i f f e r e n t w e ig h t o f c a t a l y s t i n each s e r i e s , p r e f e r a b ly th e c a t a l y s t
c h arg e d i f f e r i n g by a f a c t o r o f two ( 2 ) .
The same o p e ra tin g c o n d itio n s
a r e u sed i n each s e r i e s and by v a ry in g th e sp ace v e l o c i t y a s e t o f p a i r s
o f p o in ts a r e o b ta in e d ; th e p o in ts i n each p a i r a r e a t th e same space
v e lo c ity but a t d iff e r e n t lin e a r v e lo c itie s .
I f d if f u s io n i s l i m i t i n g ,
a p l o t o f th e d a ta from t h e . two s 'e rie s w i l l g iv e two s e p a ra te c u rv e s ;
b u t , i f d if f u s io n i s n o t l i m i t i n g , th e p o in ts from b o th s e r i e s should
f a l l on th e same c u rv e .
T h is method was u se d w ith 100 grams and 50 grams
o f c a t a l y s t and Husky o i l f o r charge o i l .
The r e s u l t s o f th e ru n s
(H usky-1, T ab le I I and H usky-5, T able I I I ) a r e p l o t t e d i n F ig u re 4 , which
shows t h a t w ith in e x p e rim e n ta l a c c u ra c y t h e c o n v e rsio n s were th e same
f o r b o th ru n s and t h a t f i l m d if f u s io n i s n o t a lim it in g f a c t o r i n t h i s
s tu d y .
The r e a c tio n may a ls o be lim it e d by d if f u s io n from th e c a t a l y s t
s u rfa c e t o th e a c ti v e s i t e s i n th e p o re s o f th e c a t a l y s t .
As th e c a t a l y s t
s i z e i s d e c re a s e d , th e r e s i s t a n c e t o i n t e r n a l d if f u s io n i s d e c re a se d u n t i l
-1 6 -
an optimum s iz e i s re a ch e d where a f u r t h e r d e c re a se i n c a t a l y s t s iz e w i l l
no lo n g e r in c r e a s e th e r e a c tio n r a t e .
I t was b e lie v e d t h a t th e c a ta ly s t
s iz e u sed i n t h i s r e s e a r c h ( 10/14 mesh) was w ith in t h i s optimum s i z e .
C a ta ly s t a c t i v i t y i s a v a r ia b le i n c a t a l y t i c r e a c tio n s and i t be­
comes n e c e s s a ry to ta k e i n t o a cc o u n t u n le s s i t i s c o n s ta n t.
F ig u re 5
shows t h a t th e c o b a lt m olybdate c a t a l y s t d e a c tiv a te s v e ry r a p id ly w ith
Aramco charge o i l a t 850 F , 2 g / h r / g , 200 p s ig , and 1000 f t 5/ b b l of
hydrogen; th e s e c o n d itio n s , e x ce p t te m p e ra tu re , a re r e p r e s e n ta tiv e o f
th o s e u sed in . th e e x p e rim e n ta l r u n s .
D e a c tiv a tio n was n o t e d .a t 750 F,
a l s o , (T able V ), b u t was n e g l i g i b l e a t 700 F and lo w e r.
The e x p e rim e n ta l
ru n s were c a r r i e d o u t a t 600 650, and 700 F .
Assuming t h a t th e d e s u lf u r iz a ti o n r e a c tio n i s p s e u d o - f ir s t- o r d e r ,
th e d a ta f o r th e f i v e charge o i l s were p l o t t e d a c c o rd in g t o f i r s t - o r d e r
k i n e t i c s (F ig u re s 6 , 7 , 8 , 9, 10, 11) .
These f ig u r e s show a t once th e
p l o t o f lo g
A v s . c o n ta c t tim e i s n o t a s t r a i g h t l i n e b u t i s d e f i n i t e l y
A-x
curved and i n d i c a t e s t h a t th e d e s u lf u r iz a ti o n o f th e s e o i l s does n o t be­
have a s a p s e u d o - f i r s t - o r d e r r e a c tio n .
These f i g u r e s a ls o show t h a t th e
r a t e o f d e s u lf u r iz a ti o n i s dependent on c o n ta c t tim e , te m p e ra tu re , p r e s ­
s u r e , t r e a t - g a s r a t e , and t r e a t - g a s c o m p o sitio n .
A lthough th e e f f e c t s ,
o f p r e s s u r e , g as r a t e , and g as com p o sitio n were s tu d ie d o n ly on th e Arameo
o i l , i t i s e x p ec te d t h a t th e s e v a r ia b le s w i l l a f f e c t a l l f o u r o i l s , q u a li­
t a t i v e l y , th e same.
F ig u re s 6 , 7 , 8 y 9, 10, and 11 show t h a t a s c o n ta c t tim e in c r e a s e s ,
t h e c o n v ersio n in c r e a s e s b u t th e r a t e o f d e s u lf u r iz a ti o n d e c r e a s e s .
T h is
-1 7 ci
i s p ro b a b ly due to th e s e v e r a l s u l f u r compounds i n th e o i l , each d e s u lfu ­
riz in g a t a d iffe re n t r a te .
I n i t i a l l y th e more e a s i l y d e s u lf u r iz e d com­
pounds a re r e a c tin g v e ry r e a d i l y le a v in g th e l e s s r e a c tiv e s u l f u r com­
pounds r e p r e s e n tin g a g r e a t e r p e rc e n ta g e o f th e re m a in in g s u l f u r . . There
i s no in d i c a t i o n t h a t th e l e s s r e a c tiv e compounds r e a c t o n ly a f t e r th e
more r e a c tiv e compounds have been e x h a u ste d , b u t r a t h e r , t h a t th e y a re
a l l r e a c tin g s im u lta n e o u s ly .
^ h is w ould, of c o u rs e , e x p la in why th e
o v e r a l l d e s u lf u r iz a ti o n r e a c tio n s o f th e s e o i l s do n o t a d h ere to f i r s t o rd e r k i n e t i c s .
An in c r e a s e i n te m p e ra tu re in c r e a s e s th e r a t e o f d e s u l f u r i z a t i o n .
I n o rd e r t o o b ta in some ty p e o f te m p e ra tu re -c o n v e rs io n c o r r e l a t i o n , an
A rrh e n iu s -ty p e te m p e ra tu re p l o t was made (F ig u re 12) .
Two r a t e c o n s ta n ts ,
k. and k _, were e s tim a te d f o r each cu rv e by draw ing ta n g e n ts to th e c u rv e s
I
j
i n F ig u re s 6 , rI 3 B3 and 9; th e i n i t i a l r a t e c o n s ta n ts , k ^ , were o b ta in e d
by draw ing ta n g e n ts t o th e cu rv es where th e y i n t e r s e c t e d th e o r ig i n , and
th e r a t e c o n s ta n ts a t a c o n ta c t tim e o f 3 ( h r ) (IQOg) , kq, w ere o b ta in e d by
ft3
draw ing ta n g e n ts t o th e c u rv e s where th e y c ro s se d th e a b s c is s a v a lu e o f
3.
The u n i t s o f k a re
and i t should be remembered t h a t k
( h r ) (IOOg)
i s r e s t r i c t e d by th e o p e r a tin g c o n d itio n s a s m entioned b e f o r e .
The lo g a rith m s of t h e k v a lu e s a r e p l o t t e d v e rsu s r e c ip r o c a l a b s o lu te
te m p e ra tu re s f o r each charge o i l i n F ig u re 1 2 .
I t may be seen from t h i s
f i g u r e t h a t th e s lo p e s o f th e k^ p l o t s a r e g r e a t e r t h a t th e s lo p e s o f th e
k^ p l o t s f o r a l l f o u r o i l s .
These d if f e r e n c e s i n s lo p e s i n d i c a t e t h a t an
in c r e a s e i n te m p e ra tu re has l e s s e f f e c t on in c r e a s in g d e s u lf u r iz a ti o n a s
—18—
th e d e s u lf u r iz a ti o n becomes more co m p lete.
T h is i s p ro b a b ly due. t o a p r e ­
ponderance o f th e l e s s r e a c t i v e , o r more r e f r a c t o r y , s u l f u r compounds r e ­
m ain in g i n th e o i l .
The e f f e c t s .of,-.hydrogen., c o n c e n tra tio n ..,in .th e . t r e a t .- .g a s .,..t r e a t - g a s , ...
r a t e , p r e s s u r e , hydrogen p a r t i a l p r e s s u r e , and o i l p a r t i a l p re s s u re on th e
d e s u lf u r iz a ti o n o f th e Aramco o i l were s tu d ie d a t 650 F , and th e e f f e c t s
o f p re s s u re and g a s - r a t e a t 700 F .
m ethane.
The d ilu e n t i n th e t r e a t - g a s was
A ll th e d a ta w ere compared a t a c o n s ta n t c o n ta c t tim e of
2 ( h r ) (IOOg) s in c e most o f th e d a ta w ere o b ta in e d n e a r t h i s v a lu e .
The
ft3
c o n v e rsio n v a lu e s a t th e c o n ta c t tim e o f 2 were ta k e n from th e c u rv e s of
F ig u re s 10 and 1 1.
The d a ta a re t a b u la te d i n T able XLI„
F ig u re 13 shows t h a t a t a giv en p r e s s u r e and gas r a t e , an in c r e a s e
i n hydrogen c o n c e n tra tio n in c r e a s e s d e s u l f u r i z a t i o n , which i s th e same a s
say in g t h a t a t a c o n s ta n t o i l p a r t i a l p r e s s u r e , an in c r e a s e i n hydrogen
p a r t i a l p r e s s u r e in c r e a s e s d e s u lf u r iz a ti o n (F ig u re 1 4 ).
However, when
o p e ra tin g a t 400 p s ig and a gas r a t e o f 2000 f t ^ / b b l , in c r e a s in g th e
hydrogen c o n c e n tra tio n above 60% a p p e a rs t o have no e f f e c t on in c r e a s in g
d e s u lfu riz a tio n .
F ig u re s 13 and 14 a ls o show t h a t a t c o n s ta n t p r e s s u r e ,
in c r e a s in g th e gas r a t e from 1000 t o 2000 f t " / b b l in c r e a s e s d e s u lf u r iz a ti o n .
The e f f e c t o f in c r e a s in g c o n v ersio n w ith an in c r e a s e i n hydrogeti p a r t i a l p r e s s u r e i s a ls o in d ic a te d i n F ig u re 1 5 , i n which t h e l o g
A is
A—x
p l o t t e d v e rs u s th e r a t i o o f hydrogen p a r t i a l p r e s s u r e t o o i l p a r t i a l p re s ­
s u re a t 200 p s ig .
T h is p l o t h o ld s f o r g as r a t e s o f 1000 and 2000 f t ^ / b b l
o f 100% H2 , 60% H2 - 40% CH^, and 30% H2 - 70% CH^, in d i c a t i n g t h a t th e
r a t i o o f th e hydrogen p a r t i a l p r e s s u r e to th e o i l p a r t i a l p r e s s u r e i s more
im p o rta n t th a n th e a b s o lu te v a lu e o f th e hydrogen p a r t i a l p r e s s u r e .
S im ila r
d a ta s c a t t e r e d q u ite b a d ly a t UOO p s ig (T ab le XC¥),
When com paring d e s u lf u r iz a ti o n a t d if f e r e n t, p r e s s u r e s th e r e a c tio n
a p p e a rs more com plex.
I n F ig u re 16 th e lo g
A i s p l o t t e d v e rs u s r e A-x
a c t o r p r e s s u r e 5 a l l th e d a ta a re compared a t a c o n s ta n t c o n ta c t tim e ,
( r e c i p r o c a l v ap o r r a t e ) o f 2
( h r ) ( l0 0 g )
(T ab le XLI) ,
F ig u re 16 shows'
ft^
t h a t w here 100% hydrogen t r e a t - g a s was u s e d , and where 60% Hg - 40% CH^
3
t r e a t - g a s a t 1000 f t / b b l was u s e d , an in c r e a s e i n p re s s u re d e c re a se d
d e s u lfu riz a tio n .
(T h is d e c re a s e i n d e s u lf u r iz a ti o n w ith ah in c r e a s e in
p r e s s u r e may a p p e a r c o n fu sin g a t f i r s t s in c e i t i s g e n e r a lly a c c e p te d
t h a t an in c r e a s e i n p r e s s u r e in c r e a s e s d e s u l f u r i z a t i o n , w hich i s t r u e i f
t h e d a ta a t d i f f e r e n t p r e s s u r e s a r e compared a t c o n sta n t sp ace v e l o c i t i e s
(T ab le XE).
The in c r e a s e i n d e s u lf u r iz a ti o n w ith p re s s u re a t c o n s ta n t
. sp ace v e l o c i t y i s due t o an in c r e a s e i n c o n ta c t tim e w ith an in c r e a s e i n
O
p r e s s u r e . F o r in s ta n c e , 200 p s ig , 650 F , 1000 f t V b b l , and a space v e lo c ­
i t y o f 2 g /h r / g g iv e s a c o n ta c t tim e o f 3 ,6 ( h r ) (IQOg).,, w h ile 400 psig, and
t h e same c o n d itio n s g iv e a c o n ta c t tim e o f 7 .3 5 ffcr) (IOOg) . However, when
ft3
t h e d a ta a t d i f f e r e n t p r e s s u r e s a r e compared a t c o n s ta n t c o n ta c t tim e th e
e f f e c t s o f p re s s u re may show up a s h av in g an a d v e rse e f f e c t on d e s u lf u r iz a ­
tio n .)
S ince b o th hydrogen p a r t i a l p r e s s u r e and o i l p a r t i a l p re s s u re i n ­
c re a s e w ith r e a c t o r p r e s s u r e , and s in c e i t h a s been shown t h a t d e s u l f u r i ­
z a tio n in c r e a s e s w ith in c r e a s e d hydrogen p a r t i a l p r e s s u r e , and y e t de­
s u l f u r i z a t i o n d e c r e a s e s , th e n some ty p e o f p r e f e r e n t i a l a d s o r p tio n o f o i l
-
m olecule s i s i n d ic a te d .
20 -
I n o th e r w ords, th e d e c re a se i n d e s u lf u r iz a ti o n
w ith an in c r e a s e i n p r e s s u r e a t c o n s ta n t c o n ta c t tim e i s a t t r i b u t e d to
th e in c r e a s e i n o i l p a r t i a l p r e s s u r e ,
.F ig u re I ? , which i s a p l o t o f
l o g A v s , o i l p a r t i a l p r e s s u r e , shows t h i s a d v e rse e f f e c t o f in c r e a s in g
A-x
o i l p a r t i a l p r e s s u r e when u s in g 100% hydrogen o r when o p e ra tin g a t 1000
f t 3/ b b l of 60% H2 - 40% GH,.
I f a d ilu e n t i s u sed i n th e t r e a t - g a s (60% H^ - .40% CH^ and 30% H2 70% CH^) an in c r e a s e i n p r e s s u r e in c r e a s e s d e s u lf u r iz a ti o n (e x c ep t f o r
1000 f t ^ / b b l o f 60% Hg - 40% CH^) a s in d ic a te d i n F ig u re s 16 and 17,
T h is change i n th e e f f e c t of p re s s u re may be e x p la in e d by r e f e r r i n g to
F ig u re 13.
T h is f i g u r e shows t h a t f o r a g iv en c o n ta c t tim e when o p e ra tin g
O
a t 650 F and a gas r a t e o f 2000 f t / b b l , an in c r e a s e i n p r e s s u r e w i l l i n ­
c re a s e d e s u lf u r iz a ti o n when th e c o n c e n tra tio n o f hydrogen i n th e t r e a t - g a s
i s l e s s th a n a p p ro x im a te ly 85%S b u t, when th e c o n c e n tra tio n o f hydrogen
i n th e t r e a t - g a s i s g r e a t e r th a n 85%, an in c r e a s e i n p r e s s u r e w i l l de­
c re a s e d e s u l f u r i z a t i o n .
Iihen o p e ra tin g a t a 650 F and a g as r a t e o f 1000
f t ^ / b b l , 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 d e s u lf u r iz a ti o n when th e
hydrogen c o n c e n tra tio n i s l e s s th a n a p p ro x im a te ly 55%S and w i l l d e c re a se
d e s u lf u r iz a ti o n i f th e hydrogen c o n c e n tra tio n i s g r e a t e r th a n 55%«
These
v a lu e s o f 85% and 55% may v a ry w ith d i f f e r e n t d ilu e n ts i n th e t r e a t - g a s .
The cu rv e i n F ig u re 16 a t 1000 f t ^ / b b l o f 60% H2 - 40% CH^ i s above th e
55% v a lu e , and t h e r e f o r e an in c r e a s e i n p r e s s u r e d e c re a s e s d e s u l f u r i z a t i o n .
The r e s u l t s o f t h e p r e s s u r e e f f e c t s may be e x p la in e d w ith th e f o l ­
low ing a ssu m p tio n s; The d e s u lf u r iz a ti o n r e a c tio n i s th e r e s u l t o f th e
—21*-
s u l f u r - b e a r in g compound r e a c tin g w ith hydrogen atoms which a r e form ed by
a c t i v a t e d a d s o r p tio n o f hydrogen m o le c u le s on th e c a t a l y s t „ I f th e o i l
m o le c u les a r e p r e f e r e n t i a l l y a d so rb e d , th e r e would be l e s s s u rfa c e f o r th e
a d s o r p tio n o f t h e hydrogen m o le c u le s .
The r e s u l t o f a d e c re a s e i n d e s u l­
f u r i z a t i o n w ith in c r e a s in g o i l p a r t i a l p r e s s u r e co u ld be e x p la in e d t h i s
way.
The d e c re a se i n d e s u lf u r iz a ti o n w ith an in c r e a s e i n p r e s s u r e may
a ls o be due t o more l i q u i d b e in g p r e s e n t a t th e h ig h e r p r e s s u r e s , and th u s
a h ig h e r d e n s it y o f l i q u i d o i l m o le c u les p e r c a t a l y s t s i t e , . H ow ever,,-the '
a d v e rse e f f e c t o f p r e s s u r e on d e s u lf u r iz a ti o n a t c o n s ta n t c o n ta c t tim e
h a s been n o te d i n s im ila r c a t a l y t i c d e s u lf u r iz a ti o n r e a c tio n s where th e
p ro c e s s was a v ap o r p h ase o p e ra tio n (6 , 7 ) °
The r e s u l t s in d i c a t e t h a t a t
a c o n s ta n t p r e s s u r e an in c r e a s e i n hydrogen p a r t i a l p r e s s u r e in c r e a s e s
d e s u l f u r i z a t i o n , and t h i s i s p ro b a b ly due t o th e h ig h e r hydrogen concen­
t r a t i o n s p re v e n tin g th e o i l m o lecu les from b e in g so r e a d i l y a d so rb e d .
If
a d ilu e n t i s p r e s e n t i n th e t r e a t - g a s , i n t h i s case m ethane, i t w i l l com­
p e te w ith th e hydrogen f o r th e c a t a l y s t s i t e s and th e amount o f hydrogen
ad so rb ed w i l l be d e c re a s e d .
The e f f e c t o f in c r e a s in g t o t a l p re s s u re w i l l
th e n in c r e a s e d e s u lf u r iz a ti o n ( i f i t i s below th e c o n c e n tra tio n s m entioned)
s in c e th e in c r e a s in g e f f e c t o f th e hydrogen p a r t i a l p r e s s u r e i s more p ro ­
nounced th a n th e d e c re a s in g e f f e c t o f t h e o i l p a r t i a l p r e s s u r e (T able
H I).
I t i s n o t known w h eth er th e m ethane a c t u a l l y com petes f o r th e c a t ­
a l y s t s i t e s o r m erely " s h ie ld s " th e hydrogen from th e c a t a l y s t ,
The c o m p o sitio n s o f th e f o u r o i l s u sed and th r e e sam ples o f th e de­
s u lf u r iz e d Aramco o i l w ere d eterm in ed by mass sp e c tro m e te r a n a ly s e s .
The
-2 2 -
a ro m a tic f r a c t i o n s were s e p a ra te d from th e s a tu r a te f r a c t i o n s by s i l i c a
g e l p e r c o la ti o n .
These a n a ly s e s a r e ta b u la te d i n T a b le s XLII and XL?.
E s s e n t i a l l y no s u l f u r was p r e s e n t i n th e s a t u r a t e f r a c t i o n s and where
s m a ll amounts a re i n d i c a t e d , th e y were n e g le c te d .
The mass sp e c tro m e te r
c o u ld n o t a n a ly z e f o r th io p h e n e s , and so , p resu m ab ly , th e s u l f u r n o t ac­
co u n ted f o r by b en zo th io p h en e s and d ib e n z o th io p h e n e s i s i n th e form of
th io p h e n e and i t s hom ologues.
F o r c o n v en ie n c e, th e BT and DBT w i l l be. r e ­
f e r r e d t o a s a ro m a tic s u l f u r i n t h i s p a p e r, and th e s u l f u r unaccounted f o r
by th e mass s p e c tro m e te r a n a ly s is w i l l be r e f e r r e d t o a s th io p h e n e s .
A rom atic s u l f u r compounds a re h a rd e r t o remove th a n a l i p h a t i c s u lf u r
compounds, and i t was b e lie v e d t h a t th e more arom atic, th e charge o i l , and
hence th e more a ro m a tic t h e .s u l f u r compounds, th e more d i f f i c u l t i t would
be t o d e s u l f u r i z e i
th e MCO i s
A 50-50 w t.$ b le n d o f MCO and ERD was d e s u lf u r iz e d ;
a ro m a tic and h as 2 .6 6 w t.$ s u l f u r , w h ile th e ERD i s o n ly
30% a ro m a tic and has 1 .0 w t„% s u l f u r .
The r a t e o f d e s u lf u r iz a ti o n of th e
b le n d was e x p e c te d t o be l e s s th a n th e r a t e o f th e RED and g r e a t e r th a n
th e r a t e of th e MCO; i n s t e a d , th e r e v e rs e was n o te d .
Ifilhen th e co m p o sitio n s
o f th e o i l s were examined i t was seen t h a t 82% o f th e s u l f u r i n th e MCO
was a ro m a tic s u l f u r , BT, w hereas 68% o f th e s u l f u r i n th e RED was a ro m a tic
b u t was a com bination o f BT and DBT.
I t a p p e a rs th e n t h a t th e a r o m a tic ity
o f th e s u l f u r compounds i n th e o i l i s n o t so much th e c r i t e r i a f o r d e s u l­
f u r i z a t i o n , b u t more e x p l i c i t l y th e ty p e o f a ro m a tic s u l f u r compounds i n ­
v o lv e d .
S in ce BT i s common t o b o th th e MCO and RRD b u t DBT i s o n ly p r e s ­
e n t i n th e RED, th e d e c re a s e i n th e r a t e o f d e s u lf u r iz a ti o n o f th e b len d
-2 3 i s e v id e n tly due to th e p re se n c e o f th e DBT„ A sm all amount o f DBT i s
a p p a r e n tly q u ite e f f e c t i v e i n r e ta r d in g th e d e s u lf u r iz a ti o n r a t e because
th e DBT i n th e a ro m a tic f r a c t i o n o f th e b le n d was a p p ro x im a te ly 0 .7 2 w t.%•
When com paring th e e s tim a te d r a t e c o n s ta n ts o f th e f o u r o i l s i n T ab le
X o r th e lo g
A v a lu e s a t c o n s ta n t c o n ta c t tim e in . T ab le XVjl i t i s seen
A-x
t h a t th e o i l s d e s u lf u r iz e w ith in c r e a s in g d i f f i c u l t y a s f o llo w s : MCOj, RRD,
Aramco, Husky.
The DBT c o n te n t o f th e o i l s in c r e a s e s i n t h i s same o rd e r •
(T ab le X I I l ) w ith th e e x c e p tio n o f th e Aramco5 which h as 0 .6 $ more DBT
th a n th e Husky.
However5 th e Husky o i l i s o n ly s l i g h t l y more d i f f i c u l t
t o d e s u lf u r iz e th a n th e Aramco and i s p ro b a b ly due t o th e la r g e q u a n tity
o f BT (1 0 .4 "wt,$ ) a s s o c ia te d w ith th e DBT ( 6 .8 w t.$ ) 5 ( th e Aramco has 7»8
w t.$ BT and 7 .4 w t.$ DBT) .
A lthough th e p re s e n c e of a l l th e v a rio u s s u l f u r compounds i n th e
c h arg e o i l e f f e c t s th e r a t e o f d e s u l f u r ! Z a tio n 5 th e p re se n c e o f DBT seems
t o p a r t i c u l a r l y l i m i t th e r e a c tio n r a t e and th e d eg ree o f d e s u lf u r iz a ti o n
can be app ro x im ated from th e DBT c o n te n t o f th e o i l .
The c o r r e la tio n be­
tw een d e s u l f u r i z a t i o n and DBT c o n te n t was made by com paring th e degree o f
d e s u l f u r i z a t i o n a t c o n s ta n t c o n ta c t tim e f o r th e f i v e ch arg e o i l s a t 6005
6505 and 700 F 5 200 p s i g 5 and 1000 f t ^ / b b l o f hydrogen ( th e d a ta f o r th e
MCO was compared o n ly a t 600 and 650 F ) .
The c o n ta c t tim e s ( l/V .R .) of
1 .0 sind 3 .0 ( h r ) (lOOg) were compared f o r each o i l ; th e d a ta a r e ta b u la te d
ft^
i n T able XV. F ig u re 17 shows t h a t th e d eg ree o f d e s u lf u r iz a ti o n can be '
e s tim a te d from th e DBT c o n te n t o f o i l s b o ilin g in th e 400-700 F ra n g e .
C o r r e la tio n i s q u ite good a t th e low er c o n v e rs io n s , b u t some s c a t t e r i n g
—24—
i s evid en ced a t th e h ig h e r c o n v e rsio n s .
The e f f e c t s o f th e s u l f u r compounds i n th e o i l a re ta b u la te d below
i n T able XVI.
When 49$ o f th e i n i t i a l s u lf u r h%d been removed (Aramco-5,
Sample 2 7 ), 79$ o f th e th io p h e n e s , 60$ o f th e BT, and"35$ o f th e DBT had
been removed.
When 89$ o f th e i n i t i a l s u l f u r had been removed (Aramco-5,
Sample 1 2 ), a l l t h e th io p h e n e s , 91$ o f . t h e BT5 and 63$ o f th e DBT had been
rem oved.
These v a lu e s in d i c a t e t h a t t h e th io p h e n e s a r e more r e a c tiv e th a n
t h e BT3 more r e a c tiv e th a n th e DBT.
TABLE XVI
COMPARISON OF SULFUR REMOVAL FROM ARAMCO LIGHT WAXY DISTILLATE
Run .
Sample
Wt .$ S i n Sample $ o f I n i t . S (1 .2 7 w t.$ ) Removed
A rtim atic F r a c tio n (Wt.$ )
B enzothiophenes
D ibenzothiophenes
S u lf u r
$ S a s BT
$ S a s DBT
$ S a s "T hiophenes"
$ BT removed
% DBT removed
$ "T hiophenes" removed
Aramco-9
26
. 0 .0 9
93
Aramco-5
12
0 .145
89
Aramco-5
27
0 .6 5
49
0 .6 *
1 .3
0 .3 6
37
63
0
92
82
100
0 .7
2 .7
0 .6 1
23
77
0
91
63
100
3 :1
4*8
2 .0 1
36
43
21.
60
35
79
-KThis v a lu e u n c e r ta in
I t i s n o t . known. e x a c tly why th e s e compounds, .re a c t a t. d i f f e r e n t ra te s.j..
i t may be due t o s t e r i c h in d ra n c e o r t o an in c r e a s e i n s p e c i f i c a d so rb a b i l i t y w ith in c r e a s in g m o le c u la r w eight o f th e s u lf u r - b e a r in g compounds.
At 700 F th e p l o t of t h e lo g
A v s . c o n ta c t tim e (F ig u re 8) f o r th e
A—x
'
MGO i s n e a r ly a s t r a i g h t l i n e , which i s ap p ro a ch in g a f i r s t - o r d e r r e a c tio n .
-2 $ -
T h is c o u ld be e x p ec te d s in c e 82% o f th e s u l f u r i s p re s e n t a s BT5 th e r e ­
m ainder b e in g th io p h e n e s .
At t h i s te m p e ra tu re th e th io p h e n e s a r e c o n v ert
ed v e ry r e a d i l y and t h e d e s u lf u r iz a ti o n would be t h a t o f one compound.
The d e s u lf u r iz a ti o n o f BT h as been shown t o be a p s e u d o - f ir s t- o r d e r r e ­
a c ti o n (5 , 8 ) .
-2 6 -
SUMMARY
I f th e e f f e c t s o f th e v a r ia b le s in v o lv e d i n th e c a t a l y t i c hydro­
d e s u l f u r i z a t i o n of p e tro le u m f r a c t i o n s b o ilin g i n th e ran g e o f 400 to
700 F a r e e s ta b lis h e d , an a n a ly s is of th e ty p e s and q u a n t i t i e s o f th e
s u l f u r compounds i n th e f r a c t i o n w i l l p e rm it th e p r e d ic tio n o f th e con­
v e r s io n t o be e x p e c te d a t a g iv en s e t o f o p e ra tin g c o n d itio n s „ Thiophene
and i t s homolo g u e s a re more e a s i l y removed th a n b e n zo th io p h en e s which a re
more e a s i l y removed th a n d ib e n z o th io p h e n e s .
The p re se n c e o f d ib e n z o -
th io p h e n e s , even i n sm a ll q u a n t i t i e s , a p p e a rs t o p a r t i c u l a r l y r e t a r d th e
r a t e o f d e s u l f u r i z a t i o n o f o i l s i n th e 400 t o 700 F ra n g e .
W ith th e know­
le d g e o f th e d ib e n zo th io p h en e c o n te n t i n th e charge, o i l , i t i s p o s s ib le
t o e s tim a te th e d eg ree o f d e s u l f u r i z a t i o n .
The e f f e c ts ^ o f th e o p e r a tin g v a r ia b le s may be summarized a s fo llo w s :
1.
A.s c o n ta c t tim e i n c r e a s e s , c o n v e rsio n in c r e a s e s b u t th e
r a t e o f r e a c tio n d e c r e a s e s .
2.
An in c r e a s e i n te m p e ra tu re w i l l in c r e a s e th e r a t e of
r e a c t i o n ; how ever, t h i s in c r e a s in g e f f e c t o f te m p e ra tu re
i s l e s s pronounced a t h ig h e r c o n v e rs io n s .
T em peratures
I
o f 700 F and lo w er a r e c o m p atib le w ith p ro lo n g ed c a t a l y s t
a c tiv ity .
3.
At a c o n s ta n t p r e s s u r e an in c r e a s e i n hydrogen p a r t i a l
. p r e s s u r e in c r e a s e s d e s u l f u r i z a t i o n , b u t th e r a t i o o f
hydrogen p a r t i a l p r e s s u r e t o o i l p a r t i a l p r e s s u r e a p p e a rs
more im p o rta n t th a n the. a c t u a l v a lu e of, hydrogen p a r t i a l
-2 7 -
p re ssu re .
.4»
I f th e e f f e c t s o f p re s s u re a r e compared a t c o n s ta n t space
v e l o c i t y , 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 d e s u l f u r i ­
z a tio n .
However, i f d e s u lf u r iz a ti o n i s compared a t a p p a re n t
c o n s ta n t c o n ta c t tim e , p r e s s u r e may o r may n o t have an i n ­
c re a s in g e f f e c t on d e s u l f u r i z a t i o n .
The d e c re a se i n de­
s u l f u r i z a t i o n w ith an in c r e a s e i n p r e s s u r e a t c o n s ta n t
c o tita c t tim e i s a t t r i b u t e d t o an in c r e a s e i n o i l p a r t i a l
p r e s s u r e ; how ever, th e p resen ce, o f a d ilu e n t i n th e t r e a t gas may re d u c e th e hydrogen p a r t i a l p re s s u re t o a p o in t
where in c r e a s in g th e t o t a l p r e s s u r e i s more b e n e f i c i a l
from th e s ta n d p o in t o f in c r e a s in g hydrogen p a r t i a l p r e s ­
s u re th a n i s th e a d v e rse e f f e c t o f in c r e a s in g o i l p a r t i a l
p r e s s u r e , and an in c r e a s e i n p r e s s u r e th e n in c r e a s e s
de s u l f u r i z a t i o n .
~
28 —
ACKNOWLEDGMENT
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
R ese arch and E n g in e e rin g Company who sp o n so red t h i s r e s e a r c h , and th e
members o f i t s s t a f f , Mr. John W eikart and D r. S. B. Sw eets e r , w ith
whom s e v e r a l i n t e r e s t i n g d is c u s s io n s w ere h e ld .
The g u id an ce o f D r. L loyd Berg and th e a s s is ta n c e o f R. L. Jaco b so n ,
R. A. Mahugh, and M. K. O pprecht a r e g r a t e f u l l y acknow ledged.
-2 9 -
LITERATURE CITED
(1 )
B erg, C ly d e ; B ra d e ly , 'W. E ., S t i r t on, R. I . , F a i r f i e l d , R. G .,
L e f f e r t , C. Be, B a lla r d , J , He, Cheme E n g r, P ro g , I , No, I ,
1 -12 ( 1947 )
(2 )
C o rrig a n , Thomas E e, Cheme E n g re, A p r il (1955)
(3 )
Emmett, P a u l He, and o th e r s , " C a ta ly s is 11- V ole I , New York,
R ein h o ld P u b lis h in g C o rp o ra tio n (1954)
(4 )
Esso R esearch and E n g in eerin g . C o ., "Esso B lue Book", U ttpublished
P a p e r, L in d en , New J e r s e y
( 5)
E sso R esearch and E n g in e e rin g C o ., U npublished P a p e r, L in d en ,
New J e r s e y (1957)
(6 )
Jac o b so n , Re L ., P h eD. T h e s is , M ontana S ta te C o lleg e (1958)
(7 )
K irs c h , F ,
Heinemann, H ein z; S tep h en so n , De H ., I n d e Eng. Chem,
4 9, 646 (1957)
(S)
S e y f r ie d , ¥ , D», Chem. E n g r. News 27, 2482 (1949)
(9 )
¥ i l s o n , ¥,. Ae, V oreck, ¥„ E ,, & M alo, R. Ve, I n d . Eng, Cheme 49,
657 (1957)
-3 0 -
APPENDIX
T able I
Charge O il In s p e c tio n D ata . . . . . . .
T ab le I I
T a b u la te d D ata From Runs H usky-1, - 2 , -3
33
T ab le I I I
T a b u la te d D ata From Run Husky-5
W ith 50 Grams o f C a ta ly s t ...........................
34
T ab le IV
T a b u la te d D ata From
Run Aramco-2 . . . .
35
T ab le V
T a b u la te d D ata From
Run Aramco-9 . . . .
36
TablS VI
T a b u la te d D ata From Runs A ram bq-I,
—3)
- 5 ) —10, —12, —13, -14 . . . . . . .
37
T ab le H I
T a b u la te d D ata From
Run C a r te r - 1 . . . .
40
T a b le H I I
T a b u la te d D ata From
Run C a r te r - 2 . . . .
41
T ab le IX
T a b u la te d D ata From
Run Carter-i-3 . . . .
42
T ab le X
T a b u la te d D ata F o r A rrh en iu s-T y p e P l o t s
T ab le XI
T a b u la te d D ata From
T ab le X II
T a b u la te d D ata F o r P re s s u re and Hydrogen
C o n c e n tra tio n S tu d y . . . . . . . . . .
45
T a b le X I lI
Mass S p e c tro m e te r A n aly ses o f Charge O ils
46
T a b le XTV
Mass S p e c tro m e te r A n aly ses o f D e s u lfu riz e d
Aramco l i g h t Waxy D i s t i l l a t e . . . . . .
47
T ab tild ted Data F o r D ibenzothiophene
C o r r e la tio n ...............................................
4#
Schem atic Flow Diagram o f th e De­
s u l f u r i z a t i o n System . ............................... .
49
E f f e c t o f T em perature on P e rc e n tag e
V aporized of Charge O ils . . . . . . . .
50
E f f e c t of T em p eratu re> P r e s s u r e , and
T r e a t-g a s R ate on P e rc e n ta g e V aporized
f o r Aramco Charge O il. . . . '..................
51
T ab le XV
F ig u re I
F ig u re 2
F ig u re 3
page 32
43
Runs Aramco-4, - 1 1 , -15 44
—31—
APPENDH (G o n t0)
F ig u re 4
T e s tin g f o r D iff u s io n
F ig u re 5
C a ta ly s t D e a c tiv a tio n . . . . . . . . .
F ig u re 6
E f f e c t o f C o n tact Time on D e s u lf u r iz a tio n
o f Husky No. 350 B urner O i l ......................
54
E f f e c t o f C o n ta ct Time on D e s u lf u r iz a tio n
o f C a r te r E a ilr o a d D ie s e l O il . . . . .
55
E f f e c t o f C o n tact Time on D e s u lf u r iz a tio n
o f G a rte r Medium C ycle O il and o f 50 Wt
Blend R a ilro a d D ie s e l and Medium C ycle O il
56
F ig u re 7
F ig u re 8
F ig u re 9
F ig u re 10
page 52
E f f e c t o f C o n ta ct Time on D e s u lf u r iz a tio n
o f Aramco L ig h t Waxy D i s t i l l a t e
53
57
E f f e c t o f C o n tact Time, P r e s s u r e , Hydrogen
C o n c e n tra tio n , and T r e a t- g a s R ate on Des u l f u r i z a t i p n o f Aramco L ig h t Waxy
D i s t i l l a t e § t 650 F . . . . . . . . .
.
58
E f f e c t o f C o n ta ct Time> P r e s s u r e , and T r e a tg as R ate on D e s u lf u r iz a tio n o f Aramco
L ig h t Waxy D i s t i l l a t e a t 700 F . . . . .
59
F ig u re 12
E f f e c t o f T em perature oh D e s u lf u r iz a tio n
60
F ig u re 13
E f f e c t o f Hydrogen C o n c e n tra tio n on
D e s u lf u r iz a tio n . . . . . . . . . . . .
61
E f f e c t o f Hydrogen P a r t i a l P re s s u re
on D e s u lf u r iz a tio n .......................................
62
E ff e c t o f Hydrogen. & O il P a r t i a l
P r e s s u r e s on D e s u lf u r iz a tio n ..................
63
E f f e c t o f R ea c to r P r e s s u r e on
D e s u lf u r iz a tio n . . . . . . . . . . . . .
64
F ig u re I ?
": >
E f f e c t o f O il P a r t i a l P r e s s u r e on
D e s u lf u r iz a tio n
V ......................
65
F ig u re 18
E f f e c t o f D ibenzothiophene on
D e s u lf u r iz a tio n . . . . " . . =.
66
F ig u re I l
F ig u re 14
V ',;.
F ig u re 15
F ig u re 16
•
TABLE
I
CHARGE OIL.INSPECTION DATA
Charge O il
Aramco L ig h t
Waxy D i s t i l l a t e
G ra v ity 0A , ? . ! .
3 4 .6 -
Husky N o.350
B urner O il
C a r te r ER
D ie s e l O i l .
C arter-W editm
C ycle O il
$0Wt/6 C a rte r
ER D ie s e l
$OWt^ C a r te r
MCO
.3 0 .6
3 4 .4
1 6.7
458
526 .
547 ..
$68
582
591
601
611
623
638
663
———
674
406
45347-3
48$
497
511
527
$42
556
$70
58$
596
620
468 .
488
494
499
$02
$06
$08 '
$12
$16
521
$28 .
#5
546 .
392
471
483
499
509
$18
"52$
534
542
551
567
573
579
'2 .1 1
1 .0
2 .6 6
1 .7 6
2$
V ol. % D i s t i l l e d
a t 0F
I .B .P .
.5
IO
20
30
40
50
60
70
80
90
95
E .P .
Wt. % S u lf u r
301
401
446
499
530
555
578
" 602
629
656
687
689
693
1 .2 7
,
TABLE I I
• TABULATED DATA FROM RUNS HUSKY-1, - 2 , -3
HUSKY-1 (200 p s lg )
Temp
°F
Sample
No.
' 2
6
io
U
651
650
648
.
649
18
22
650
649
26
650
30
652
650
650
34
38
4
8
13
18
22
26
3 ■
7
11
15
19
23
605
603
600
601
601
648
700
702
702
646
702
702
T o ta l
H rs .
.
Space
V e lo c ity
( g /h r /g )
F t3/ b b l
T re a t Gas
(100% H2 )
50
82
90.
107
2.0
iooo
1 .0 1
990
3.92
1.48
128
7 .9 7
1 .9 9
138
170
3.29
1020
1010
1000
1005
915
1065
1010
in
183
200
228
260
270
280
289
305
317
345
360
376
386
391
1 .1 7
2 .4 8
1.9 5
1 .9 6
1 .0 0
3 .0 0
3.95
7.94
1.98
1.95
1.03
2.95
2.02
3.93
7 .8 7
1020
Avg .Wb.
%S
i n P ro d .
(A-x)
0 .#
0.30
0.97
0.32
3.98
7.03
2.18
1 .3 2
O.63
1.6
3.35
0.78
0 .3 5
0.68
0.60
HUSKY-2 (200 p s ig )
1000
1.15
1000
0.83
1000
1 .3 1
1010
1 .4 6
1010
1 .7 4
1010
0.58
HUSKY-3 (200 p s ig )
1020
0.215
970
0 .1 2 4
1020
0.38
990
1020
1020
A
- togIO
(A-x)
A = In it.S
A / (A-x)
0 .6 0 .
0 .8 4 7
0.338
0.608
0.203
4 .0 6
-
0 .5 2 4
0 .4 3 2
I
Vapor
ra te
3
(---h r - l—
O77=
O4----e / f t4)_
3 .#
7.85
1 .9
5 .1
0.95
3.85
2.7
7.4
2 .7 1
6.03
3 .1 1
- 0.78
0.492
3 .1
3.52
0 .546
3.8
1 .8 4
2 .5 4
1 .6 1
1 .4 5
1 .2 1
3 .6 4
Oi 263
0.405
4 .3
0.207
2.85
2 .1
. 0 .1 6 1
0.083
0 .5 6 1
9.81
0.992
0,653
0.477
• 1 7 .0
5;55
3 .2 3
4 .4 2
■ 1 .2 3 1
0.745
0 .5 1
0 .646
O.863
2,45
0.39
8.4
1.05
3.8
3.45
7.05
2 .3
3.9
1.75
0.85
-
TABLE I I I
TABULATED DATA FRCM RUN HUSKY-5 H TH 50 GRAMS OF CATALYST
(200 p s ig )
Sample
No.
2
6
10
U
18
22
25
29
33
Temp.
0F
650
650
651
650
651
651
650
650
648
T o ta l
H rs e
67.
131
147
165
197
227
235
240
272
Space
V e lo c ity
( g /h r /g )
1.99
1 .0 0
3 .0 4
4 .0 0
F t3Zbbl
T re a t Gas
(100% H2 )
'
1000
1000
Avg .W t.
%$
i n P ro d .
(A-x)
0.585
A
(A-x)
A = in it S
3 .6
6 .6
2 .3 8
1 .9 5
logIO
A / (A-x)
0.556
0.-820
7.90
1000
1000
1000
1010
0 .3 2 0
0 .887
1 .0 8
0 .6 4 0
0 .4 9 0
1 .3 9
1.52
0.634
0.182
1 5 .4 4
-2.02
1040
990
1.65
0.673
1 .2 8
3 .1 4
0.107
0.497
1.99
1 ,5 0
990
3.30
4 .3 1
0.376
. 0.290
0 .518
I .
Vapor
ra te
a
(h r-lO O e /fV )
3.85
7.75
2 .6
1.95
3 .8 5
5.15
0.95
0 .4 4
3 .8
TABLE IV
TABULATED DATA FROM RUN ARAMCO-2
(200 p s ig )
Sample
No o
h
5
8
9
12
15
19
25
30
34
37
Temp,
op
650
650
851
. 853
844
851
846
847
847
847
846
T o ta l
H rs .
43
47
59
63
75
87
103.
127
147
' 163
175
Space
V e lo c ity
(g /h r/g ).
1 ,9 8
1 .9 5
2 .0 2
2 .0
1 .9 3
2 ,0
2 .0
1 .9 8
2 .0
1 .9 1
1 .93
F t3/ b b l
T re a t Gas
( 1 0 # H2 )
1000
1010
990
1000
1020
1000
1000
1000
1000
1020
1020
Avg. Wt.
56 S
i n P ro d ,
(A-.x)
0 .3 1
0 .3 0
Go 27
0 .3 1
-0 .4 0
0 .4 4
0 .5 1
0 .5 8
0 .5 9
0 ,6 0
0 .6 2
# C onversion
x/A (100)
. 75.6
76.3
7 8 .8
7 5 .6
68.5
65.3
5 9 .8
54.3
53.6
5 2.7
5 1 .2
'
TABLE V
TABULATED.DATA FRCM RUN. ARAMCO-9
(200 p s ig )
Sample
No.
4
6
-B
13
17
21
26
30
Temp.
0F .
650
750
. 747
752
650
752
750
648
T o ta l
H rs .
65
72
77
87
105
121
139
155
Space
V e lo c ity
( g /h r /g )
F t3/ b b l
T re a t Gas
(100$ Hg)
Avg. Wt.
$ S
i n P ro d .
(A-x)
2 .6
9 .8 0
7 .9 3
4 .0 6
1 .9 9
1 .9 8
1 .5 1
1 .9 9
970
1020
1010
990
1000
1010
990
1000
0.217
0 .3 9 6
0 .3 5 9
0.204
0.277
0 .0 9 6
0.093
0 .3 6 0
' A .
(A—x )
A = In it S
lo g XO
A / (A-x)
5.8 5
3 .2 1
■ 3 .5 4
6.2 2
' 4 .5 8
13.23
13.65
3 .5 3
0.767
0 .5 0 8
0 .5 4 9
0 .7 9 4
0 .6 6 1
1.122
1.135
0 .5 4 8
<
- I .
Vapor
ra te . „
(h r-lO O s/ft^ )
3 .5 .
0.55
0 .7
1 .4
3 .5 5
2.85
3.8 5
3 .55
vi.
0
1
TABLE VI
TABULATED DATA FROM RUNS ARMCO-I5 - 3 , - 5 , - 1 0 , - 1 2 , - 1 3 , -1 4
x
ARMCO-I (400 p s ig )
Sample
No.
T o ta l
H rs .
Space
V e lo c ity
( g /h r /g )
700 _ .. .... 36 . .. .
702
60
702
66
696
91
700
99
698
109
700
127
4
8
11
18
24
29
33
"'8
13
17
23
31
37
45
50
I
2
3
4
5
6
7
12
Temp.
°F .
650
650
651
650
703
702
700
650
•
650
648
650
646
648 .
651
' 648
650
50
70
86
"98
124
137
145
165
29
37
45
53
61
69
• 77
97
2 .0 8
0 .9 2
3 .8
0 .9 0
5 .1
3 .7
2.06-
2 .0 2
1 .0 2
1 .5 ■
4 .0 5
2 .0 5
4 .0 3
7 .9
2 .0 1
.
2 .0 2
2 .0 2
2 .0 2
2 .03
2 .0 1
2 .0 3
1 .9 9
0 .9 9 '
F t3Zbbl
T re a t Gas
(100# H2 )
970 :
1040
920
1050
990
950
970
Avg. Wt,
%S
i n P ro d .
(A-x)
0:07
0 .0 2
0 .1 2
0 .0 2
0 .1 8
0 .1 4
0 .0 6
ARMC0-3-X2Q0-psig)
990
0 .3 0 9
980
0 .1 5 8
1000
0 .2 3 4
0.502
980
490
0 .1 5 6
990
0*253
1010
0 .4 5 4
1000
0 .2 7 7
ARMCO-5 (200. p s ig )
990
0.295
990
0.273
990
0.274
0.276
990
.. .1000
0.280
0.272
990
1000
0 .2 4 9
1000
O .I46
A
(A-x)
A=Xnit S
1 8 .2
63 .7
1 0 .6
63 .7
7 .1
9 .1
2 1 .2
Iog10
A /(A -x ).
1 .2 5 9 ,
1.802
1.025
1.802
0 .849
0.958
1 .326
I
Vapor
ra te
(h r -lO O e /f tr)
. 6 ,8
1 3 .0
3 .4 5
1 3 .0
2.7 5
3 .45
6 .8
4 .1 0
8 .0 3
5 .4 2
2 .5 3
8.1 3
5 .0 2
2 .8 0
4 .5 8
0 .612
0 .9 2
0.743
0.403
0 .9 1
0.701
0.448
0.661
3 .6
7.15
4 .7
1 .8
5.95
1 .6
0 ,7 5
3 .5 5
5 .1
8 .6 9
0.707
0 .938
3 .5 5
7 .05
TABLE VI ( C o a t.)
TABULATED DATA FBOM BUNS ARAMGO-I/ - 3 , - 5 , - 1 0 , - 1 2 , - 1 3 , -1 4
ARAMCO-5 (2 0 0 p s l g ) C o n t.
Sample
No.
17
21
27
31
36
43
47
51
56
61
65
68
72
76
80
84
88
9*
13*
17*
21*
25**
32*
37*
41**
Tgmp.
648
648
651
650
655
651
633
630
: 650
648
650
651
648
655
650
651
651
631
650
642
655
648
646
658
648
650
T o ta l
H rs .
• F t5Z bbl
Space
T re a t Gas
V e lo c ity
( g /h r /g )
(100# H2 )
. 980
990
1000
1000
1000
1010
1000
970
990
1030
1000
970
980
1000
1020
1000
1000
Avg. Wt.
%S
i n P ro d .
(A-x)
0.483
0 .2 1 9
0.645
0 .2 3 8
0 .370
0 .1 5 2
0.295
0 .231
0 .4 7 6
0 .2 0 2
0.365
0 .3 0
0.275
0.667
0 .1 5 6
0 .1 0
0.253
A
(A-x)
A = In it S
107
123
129
145
155
185
201
217
227
246
262
274
290
384
328
354
370
4.0 8
1 .5 2
7 .9 7
2 .0
3 .0 1
I .24
2 .5
2.0 5
4 .0 4
1 .4 5
3 .0
2 .5 8
2 .0 5
8 .0 2
1 .2 2
1 .0
2 .0 1
63
84
92
109
114
130
144
167
183
ABAMC0-10. (*400 p s ig , **200 p s ig )
1000
1 .9 9
0 .3 1 8
3 .9 9
960
- 0.122
10.40
1.0 5
1010
0.346
3 .9 5
3 .6 7
1010
1 .4 8
9 .27
0.137
8 .0 8
0 .6 1
2 .0 8
990
2 .0
1000
0.325
3 .9 1
■•1010
6.76
0 .1 8 8
1.95
1000
5.2 2
2 .4 9
0.243
1010
■0.263
1.9 5
4.8 3
2.6 3
5 .7 9
1 .9 7
5.33
3 .4 3
8.3 5
4 .3 1
5 .5
2 .6 ?
6.2 8
3 .4 8
4 .2 3
4 .6 2
1 .9
8 .1 4
1 2 .7
5 .0 2
..
10S io
A / (A-x)
I
Vapor
ra te
( h r - 1 0 0 g /f t5 )
0 .4 2
0 .762
0 .2 9 4
0 .727
0.535
0 .9 2 1
0 .6 3 4
0 .7 4
0 .4 2 6
0 .7 9 8
0 .5 4 1
0 .626
O.664
0.279
0 .9 1
1 .104
0 .7 0
1 .8
4 .7 5
0 .9
3 .5 5
2.35
5 .5
2.85
3 .6
1.63
4 .6
2.35
2 .9
3 .6
0 .9
5 .5
7.05
3 .5 5
.601
1.017
.565
.967
.318
.592
.830
.718
.684
3.5 5
1 4 .8
3 .6 5
9.85
1.85
3.5 5
7 .3
5 .9
3 .5 3
TABLE VI (C o n t. )
TABULATED DATA FROM RIMS ARAMCO-l, - 3 , - 5 , - 1 0 , - 1 2 , - 1 3 , - U
ARAMCO-12 (200 p s ig )
Sample
Noi
2
7
12
16
20
24
30 .
34
38,
42
Temp.
0F .
651
597
600
601
590
653
601
597
603
648
6
10
U
17
22
26
29
33
698
703
703
650
700
700
700
653
8
12
17
22
26
30
35
650
596
599
649 .
65 0 .
702
702
T o ta l
■H rs .
534
354
380
396
406
422
427
436
448
46I
Space
V e lo c ity
( g /h r /g )
F t3/ b b l
T r e a t Gas
(100# H2 )
1 .9 9
2 .0
0 .9 7
1 .4 9
3 .9 7
2 ,0 3
8 .0 6
2 .9 6
2 .4 8
1 .9 8
1000
1000
1010
lo o o
1000
990
990
IOlO
1006
1010
Avg.- Mt,
# .S
i n P ro d .
■(A -xj
0 .2 6
0 .622
0.420
0 .5 2 0
0 .8 5 1
0.253
0 .9 8
0 .7 6
0,646
0 .2 8 0
467
475
484
495
5U
526
545
559
7 .9 8
4 .0
3 .1
2 ,0 8
1 .9 8
2 .4 8
1.05
1 .9 3
ARAMCO-1 3 (200 p s ig )
1000
0.495
1000
0.266
970
0 .1 9
960
0 .3 2
I o io
0 .1 2 6
1000
0 .1 7 1
950
0.0258
1020
0 .2 8
69
101
121
137
-153
168
178
2 .0 8
0 .5 1
6 1 .0 2
1 .0
1.95
1 .9 9
4 .1 1
AEAMCO-U (200 p s ig )
960
0 .3 1
910
0 .2 5
980
0 .3 7
1000
O .U
0 ,2 7 .
. 1050
1000
. 0 .1 2
970
v 0 .2 8 !;
A
(A-x)
A = in it S
4 .8 8 __
2 .0 4
3 .0 2
2 .4 4 .
1 .4 9
5 .0 2
1 .3 0
1 .6 7
1 .9 7
4 .5 4
l o SlO
I
Vapor
A /(A-x)
0 .6 8 8
0 .3 1 0
0 .4 8 0
0 .3 8 ?
0.173
0 .7 0
0 .1 1 4
0 .222
0 .296
.0 .6 5 7
2 .5 6
4 .7 7
6 .6 8
3 .9 7
1 0 .0 6
7 .4 2
4 9 .2
4 .5 4
0 .408
0 .6 7 8
0.825 0 .599
1.003
0 .8 7 1
1 .6 9 2
0.657
4 .1
5 .0 8
3 .4 3
9 .0 6
4 .7
1 0 .6
■4.53
0.613
0 .706
0.535
Q.957
0.672
1.025
O.656
(h r -1 0 0 g /ft^ )
3 .5 5
4.05
7 .8
5 .3
2 .0
3 .6
1 .0
2 .6
3.25
■ 3 .5
0.75
1 .6
2.15
3 .6 5
3.15
2.5 5
6.65
3 .5
3.6 5
16 .2
8 .1
7.05
3 .5
3 .2
I .65
TABLE H I
TABULATED DATA FROM EUN ' CABTER-I
(200 p s ig )
Temp.
0F .
Sample
Noi
.
648
651
649
651
653
651
603
603
600
599
649
702
697
• 700
700
651
4
8
12
16
20
24
28
32
36
41
45
49
53
57
63
68
Z
T o ta l
H rs .
.
62
92
112
120
125 .
141
157
189
197
203
219
233
253
263
269
285
Space
V e lo c ity
( g /h r /g )
F t3Zbbl
T r e a t Gas
(100% % )
Avg. W t.
%S
i n P ro d .
(A-x)
1 .9 7
1 .0 2
1 .5 3
3 .9 2
7 .8 5
1 .9 6
1 .9 8
0.965
3 .9 4
7 .8 5
1 .9 6
1 .9 6
1 .4 9
3 .9 2
7 .8 6
. 1 .9 9
1015
980
980
1020
1020
1020
1010
1035
1015
1020
1020
1020
1010
1020
1020
1005
0 .1 1 4
0 .0 4 2
8.0727
0.2135
0 .385
0 .1 0 1
0 .2 7 8
0 .1 4 4
0 .4 5 2
0 .6 2 9
0 .0 8 1
0.0348
0.0 2 6 1
0 .0 9 8
0.213
0 .1 1 6
A
loS10
(A-x)
A = in it S A/(A- x )
8 .7 7
2 3 .8 0
13.75
4 .6 8
2 .6 0
9 .9 1
3 .5 9
6 .9 4
2 .2 3
1 .9 0
1 2 .3 4
2 8 ,7 0
3 8 .3 0
10.204
4 .6 9
8 .6 2
0.944
1.377
1.138
0.670
0.415
0.997
0.555
0.842
0 .348
0.279
i .091
1.458
1.583
1.009
0.672
0.936
I
Vapor
ra te
„
(h r-lO O e /ft^ )
3 .3 5
6 .8
4 .5 5
1.65
0 .8
3 .3 5
3 .8
7 .4 5
1 .9
0 .9
3 .3 5
2 .9
3 .9
1.45
0 .7
3 .4
.
TABLE H I I
RDK CARTER-2
(200 p s ig )
Sample
No6-
6
io
14
19
25
. 29
33
37
41
46
50
54
58
63.
64
68
72
Temp6
0F .
648
650
648
642
646
648
601
597
599
603
646
700
700
709
709
700
651
T o ta l
H rs ,
309
337
357
367
373
389
405 .
433
442
448
464
480
488
493
496
524
540
Space
V e lo c ity
( g /h r /g )
F t3Zbbl
T re a t Gas
(ioo# H2 )
1 .9 7
1 .0 3
1 .4 1
3 .9 8
7 .8 7
2 .0 0
2 .0 3
le©6
3 .9 8
8 ,0 7
2 .0 0
2 .0 2
4*03
8 .0 2
8*05
1 .0 2
2.0 3
1020
970
1060
1000
1020
1000
990
950
1000
990
iooo
990
990
1000
990
980
990
Avg. .Wfc.
%S
in . P ro d .
(A-x)
A
(A-x)
A = Iiiit S
0.085
... 3 1 .3 ...
0 .021
126.7
0.040
65.5
8 .5 6
0 .3 1 1
0.820
3 .2 5
2 1 .1
0.126
9 .2 0
0.289
0,3.24
2 1 .4
0 .8 6 0
3 .0 9
1 ,2 1 ■
2 .2 0
2 5 .8
0.103
0.027
9 8 .5
0 .3 0 1
8 .8 4
0.410
6 .4 8
. 5 .2 2 . .
0 .5 1 0
1 90.0
0 .0 1 4
1 3 .0
0.205
lo S lO
. A /(A-x)
1 .4 9 6
2.103
1,817
0 .9 3 3
0 ,5 1 2
1 .3 2 4
0 ,9 6 4
1 .3 3 1
0 .4 9 0
0.343
1,412
1 .9 9 4
0 ,9 4 7
0 .8 1 2
0 .7 1 8
2 ,279
1 .140
1 :.
Vap.br
ra te
(h r-lO O e /ft3 )
3 .2 5
6.65
4 .3
1 .6
0 .8
3 .3
3 .9
7 .9
1 .9
0 .9 7
3 .3
2 .7
1.35
0 .6 7
0.-68
5.45
3 .9
TABLE IX TABULATED DATA FEDH EUN CARTER-3
(200 p s ig )
T o ta l
H rs .
Sample
Temp.
No,
- - °F .
5
' 9
13
19
25
29
33
41
.45
650
649
650
• 647
645
650
701
700
647
.
.
131
159
175
188
193
210
226
263
279
Space
F t3Zbbl
V e lo c ity
T re a t Gas
( g / h r / g ) • (100# H5 )
1 .9 8
1 .0 6 1 .5 0
4 .0 1
7 .8 2
2 .0 2
1 .9 9
4 .0 4
1 .9 9
1010
940
1000
1000
1020
990
1000
990
1000
Avg. Wfc.
%S
i n P ro d .
(A-x),.
A
(A-x)
A = In it S
0 .1 4 2
0.022
0,062
0.303
0.585
0.152
0.034
0.145
0.158
1 2 .4
8 0 .2 . _
28 .5
5 .8 2
3 .0 2
1 1 .6
4 9 .0
1 2 .2
1 1 .2
4 ° g l0
A /(A-x)
1 .0 9 4
1 .905 _
1 .4 3 9
0.765
0.480
1.065
1 .690
1 .0 8 6
1.049
I .
Vapor
ra te
(----------™
h r - 1 0 0 z----rr*/ftn
3 .3
6.75
4.45
1.65
0 .8
3 .3 5
2 .85
1.45
3.3 5
TABLE Z
TABULATED BATA FOR.ARRHENIUS-TYPE PLOTS
1Og10K3
Temp. 0F
0R-1XlO'
Ki
1 oSio kI
0 .095
0 .3 4
0 .6 7
-1 .0 0 2
—0 .468
- 0 .1 7 4
0 .0 9 .
0 .2 2
0 .6 $
. - 1.045
-0 .6 $ 7
-0 .1 8 7
. 0 .0 5 2
0 .1 0 8
0.155
0 .2 6
0 .9 0
1 .5 4
-O .$8$
-0 .0 4 5
0 .1 8 8
0 .1 0 8
0 .1 6
0 .2 1 8
C a r te r R a ilro a d D ie s e l O il
-0 .9 6 6
600 , .
6$0
-0 .7 9 5
-0 .6 6 1
700
9*44
9,01
8.63
0 .4 0
1 .3 0
1 .8 $
-O i398
0 .1 1 4
0 .268
0 .1 8
0 .2 6
0 .5 3
C a r te r Medium Cycle O il
600
-0 .7 4 4
6$0
-0 .5 5 2
700
-0 .2 7 $
9.44
9.0 1
8.63
K3
Aramco L ig h t Waxy D i s t i l l a t e
600
0 .0 7
-1 .1 5 4
6$0
-0 ,8 7
0 .135
0.21$
700
-0 .6 6 7
9,4 4
9.0 1
8.63
Husky No. 350 B urner O il
600
—1 .2 8 4
6$0
-0 .9 6 6
700
-0 .8 0 9
9.4 4
9.01
8.63
TABLE Z t
TABULATED DATA FROM RUNS ARAMCO-A5 - I l 5 -1 5
ARAMCO-A (650°F )
Sample
No.
,
Space
V e lo c ity
( g /h r /g )
5
10
IA
3A
38'
A2
IB
22
26
30
2 .2 2
1 .9 8
1 .9 9
1 .9 6
1 .9 7
1 .9 6
2 . OA
2.03
2 .0
2 . OA
A
10
IA
18
22
28
32
36
AO
2 .0 6
0 .9 7
A. I l
1.A5
1 .9 8
7 .8 7
3 .0 8
2.A5
1 .9 7
A
8
12
16
20
: 2A
1 .9 6 .
1 .9 7
2 .0 1
1 .9 8 ■
1.96
1.95
P ress.
(p s ig )
200
11
. 11
ft
Il
Il
AOO
It
11
it
AOO
Il
11
U
200
AOO
11
11
200
200
Il
AOO '
If
100
200
F t3Zbbl
T re a t
Gas
910
1010
2000
1020
2030
1020
970
1970
1000
I960
T re a t Gas Avg .Wfc.
Comp.
%■ S
$HP-$CH.
i n Prod
1
(A_x)
100-0
Ti.335
60-AO
0.50A
' 0 .5 0
60-40
30-70
0 .7 7 4
30-70
0 .7 4 6
100-0
.0 .2 2 6
60-AO
0 .3 8
60—/$.0
0 .2 9 6
30-70
0 .582
30-70
0/5 6 4
970
1010
"970
1020
1000
1010
980
1010
1010
ARAMCO-■11 (650°F)
60—AO
0.A3
60-AO
0 .2 2
60—AO
0.565
60-AO
0 .2 6 9
100-0
0.207
60-AO
0 .7 7 8
60-AO
0 .4 7 7
60-AO
0 .4 2 6
100-0
0.2 5
1020
2030
1990
1010
1020
1025
■ A-,
( A
7
x
I
Vapor
ld g IO
)
A = In it S
A / (A-x)
3 .7 8
2 .5 2 .
2 .5 2
1 .6 4
1 .7 0
5 .6 2
3 .3 5
4 .2 9
2 .1 8
2 .2 9
0 .5 7 8
0.402
0 .4 0 2
0 .2 1 6
0.2 3
0.749
0.525
0 .632
0 .338
0 .3 6
( h r - 100e / f t 3 )
3 .7
3 .6
1.85
3 .5 2
1 .8 7 .
3 .5
7.45
3 .9
7*35
3 .9
2 .9 5
5.77
2.25
4 .7 2
6.13
1.632 .6 8
2 .9 8
5 .0 8
0 .4 7
0 .7 6 1
0 ,3 5 2
0*674
0.787
0.212
0 .4 2 8
0 .4 7 4
0 .7 0 6
7 .4
14.65
3 .7
9 .8
3 .5 5
1 .8
4.9 5
5.85
3.5.
ARAMCO-15 (650°F)
100-0
0 .276
4*6
H
0.226
5 .6 2
Il
0 .1 6 2
7 .8 4
0 .2 0 2
6 .3
Il
0 .4 2 6
■2 .9 8
0.276
4 .6
0.663
0 .7 5
0 .8 9 4
0.799
0.475
0.663
3 .5
1.85
3 .8
7 .3
1.75
3 .5
,
\
TABLE ZEI
TABULATED DATA FOB PBESSUBE AMD BYDBOGEM COMCEMTBATIOM STUDY
A ll D ata a t 650°F, C o n tact Time ( ! /V 0R0) = 2 h r (IOOg)
.04.3
Space
V e lo c ity
1.75
3.53
3.53
U
I!
it
7 .3 5
U
tl
3.75
tl
Il
. 1000
It
it.
it
2000
It
Il
1000
Il
Il
.2000
it
it
T r e a t-g a s
Gomp0
%EZ-%CE^
100-0
100-0
60-40
30-70
100-0
60-40
30-70
100—0
60-40
30-70
IOO-O
60-40
30-70
F t3/ h r
O il
Vapor
F t3Zbbl T o ta l
T r e a tp re ss.
g as .
.p s ia
o ’i i 5
0.383
0.084
0.413
Il
Il
0.063
Il
Il
it
Il
O
1.85
T re a t-g a s
B ate
f t 3/ b b l
115
215
it
Il
ii
It
U
It
0.054
If
it
0.445
415
0 .0 4 4
11
Il
0.455
Il
Il
it
tl
Il
Il
ii
it
ii
PpH2
( p s ia )
.
89
179
108
54
188
113
56
370
222
111
378
227
114
ppO il
(p s ia )
26
36
If
Il
27
ii
I'
45
Il
Il
37
Il
Il
ppCH^
ppH2 .
l o SiO
- (,psia).
p p O il
A / (A-x'
151
264
3 .4 2
4 .9 7
3 .0
1 .5
6.95
4 .2
2 .0 7
8 .2
4 .93
2 .4 6
1 0 .2
6 .1 4
3 .1
0 .5 4
0 .4 9
0 .2 5
0.14.
0 .7 7
0 .4 4
0 .2 5
0 .3 6
0 .2 3
0 .2 1
0 .6 4
0 .6 4
0 .3 9
—
3 .5 8
2 .5 8
5 .8
0 .7 8
0 .3 8
0.7 3
—
71
.125
—
75
132
—
148
259
—
700°F, C o n tact Time (1 /V .B .) = 2 h r ( IOOg)
ft3
3 .2
5 .8
6 ,6 5
1000
500
1000
100-0
it
tt
0 .1 1
0.39
0.137
0 .3 5 4
0 .4 2
0,073
215
215
415
168
155
354
47
60
61
TABLE XCII
MASS SPECTROMETER ANALYSES OF
OILS
SATURATE -FRACTIONS
Sample
Wt
o f T o ta l Sample
P a ra ffin s
Wfc0^
Non-condo N aphthenes "
2 Ring Cond= Naph=
"
3 E ing - 11
"
"
4 R in g ' »
"
"
5 R ing
"
v
»
6 R ing
"
"
"
Mono A rom atics
"
T o t a l :S u lf u r ( D i e t e r t ) "
%
G a rte r R=R=
D ifesel
70 c4
4 3 .9
2 3 ,1
18 .3
10.5.
1 .9
0 .3
2 .0
—
C a r te r Med
C ycle O il
2 1 .9
58.9
1 7 .4
1 3 .0
7 .6
. 1 .3
0 .3
1 .5
< .0 1
Husky #350
B urner O il
56
4 0 .0
2 2 .2
1 4 .9
1 1 .6
5 .6
3 .4
2 .3
Aramco L ig h t
Waiy D i s t i l l a t e
67
1
< .03
68
16
10
4
2
—
< .01
T
AROMATIC FRACTIONS
Wt S
o f T o ta l. Sample
2 9 .6
*78.1
44
A lk y l Benzenes
Wb S
Ih d a n s & T e t r a l i n s
"
D inaphthene/B enzenes "
N ap h th alen es
"
A cenaphthenes
"
A cenaphthylenes
"
P h e n a n th re n es
"
B enzothiophenes
*'
D ib enzqthiophenes
"
T o ta l S u lf u r ( D i e t e r t ) "
2 4 .4
2 0 .6
1 1 .3
1 5 .7
8 .1
6 .7
3 .2
7 .4
2 .6
3 .3 7
6 .0
6 .9
4 .1
4 7 .6
1 4.2
7 .4
1 .4
1 2 .4
1 7 .2
1 4 .0
13-. 5
1 2 .6
% o f - T o ta l. S u lf u r A ccounted
f o r by M .S. a n a ly s is
6 8 .4
82 -
■ ■ ■ ■ *
3 .4 6
33
29.8
6.8
.4 .9 2
17 i l
7 .6
13.3
6 .0
6 .2
4 .8
7 .8
7 .4
3 .9 4
7 6.3
8 1 .7
9.8 .
9 .4
6 .3
1 0 .4 ■
TABLE ZCV
MASS SPECTROMETER ANALYSES OF DESULFURIZED ARAMCO LIGHT MAXY DISTILLATES
SATURATE FRACTIONS
Run
Sample
Wfc.^ o f T o ta l Sample
P a ra ffin s
Non. Cond. Naph.
2 Ring Cond. Naph.
3 Ring "
"
4 Ring "
"
5 Ring. "
Aramco-9
26
78
Mt.%
It
Ii
it
it
ii
71
13
9+
4
1+
<1
S u lf u r (I n S a tu r a te F r a c tio n )
Arameo-5
12
77
69
14
10
5
1+
<1
Aramco-5
27
66
66
16
io+
5
2
<1
<0 . 005% -
AROMATIC FRACTIONS
Mt. % o f T o ta l Sample
-22
23
34
A lk y l Benzenes
Mt.%
it
in d a tts /T e tr a lih s
ii
D inaphthene/B enzenes
Il
N ap h th alen es
ii
A cenaphthenes
Il
A cenaphtylenes
P h e n a n th re n es
H
B enzothiophenes
D ib enzothiophenes
11
T o ta l S u lf u r ( D ie te r t)
% S u lf u r (T o ta l) i n P ro d u ct
33.3
34.8
19.4
3 4 .8
1 8 .6
7 .7
1 3 .0
6 .7
ii
% o f T o ta l S u lf u r A ccounted
f o r by M.S. a n a ly s is
1 7 .1
7.6
13.9
9.3
8 .7
1 1 .7
8 .9
8 .4
5 .3
4 .7
1 0 .4
0.6
1 .3
0.36
0.09
100
0 .7
2 .7
0 .6 1
0.145
100
6.9
-4.3
3 .1
4 .8
2 .0 1
0 .65
82
TABLE XV
Ta b u l a t e d d a t a f o e d ib e n z o t h io p h e n e c o r e e l a t io n
Charge
O il
Avg „
M.W.
Lo|
at
I
= 1 .0
V.R.
at
=3.0
Wt
D ibenzothiophene
in A rom atic F r a c tio n
o f Charge O il
V.R.
600°F
MCO
EED
Husky
Aramco
183
208
250
220
0 .3 3
0.77
0 .0
2 .6
0 .0 8
0 .0 9
0 .4 8
0 .2 2
0 .2 6
183
0 .6 4
1 .3 4
0 .0
197
208
250
220
0 .5 5
0 .4 8
0 .2 0
0 .2 9
1.09
0.93
0.46
2 .6
0.72
6.8
O.63
7 .4 .
183
0.87
2 .1 8
0 .0
197
208
250
220
0.76
0 .8 2
0 .4 5
0 .4 6
1.74.
1.43
0.21
6 .8
7 .4
650°F
MCO
50-50 Wfc
MCO-EED
EED
Husky
Aramco
700°F
MCO
50-50 W t.^
MCO-EED
EED
Husky
Arameo
0 .9
1 .0
v
2 .6
0 .7 2
6 .8
7 .4
— 49 —
T O FRANGIBLE
DISK
HYDROGEN IN
OIL IN
AIR
BURNOFF
"' ALUNDUM p e l l e t s
- HEATING COILS
CATA LYST
INSULATI ON
BACK P RES S UR E
VAUVE
CONDENSER
VENT
<
CONTR Oi-L ER
-----S I G H T
VENT
GLASS
-r
GAS
F ig u r e I .
METER
CAUSTIC
OIL
S c h e m a tic F low J ia g r n m o f flic L J e e u lf u r U a t in n
S y s te m
2 0 0 PSIG
VAPORIZED
IOOO F T ^ B B L
I
Vt
O
600
Figure
■&------------ 6 5 0
TEMP ERATURE
70 O
£ f i e c t or Temperature on lc r c e u ta g e V aporized o f Charge Oi l s
VAP ORI ZED
—------------ 6 5 0 —
TEMPERATURE
Fi gu re 3 .
f e e t o f Ie.:; ■r - t t u r e , P r e s s u r e , and Tr e a t—^as Iiate on P e r c e n t a g e Vapori zed
f o r AraiDcu J liirge O i l .
CX
O
0
G>
q
O /
vn
L 0G|
0
O
IOO
( RAMS
C MALYST
X
50
C RAMS
C ATALYST
_e
X
RECIPROCAL
Figure 4 .
VAPOR
T e s t i n g fo r D i f f u s i o n .
I
RATE
I0( IO
F T 3/B E
2
6 5 0 ° F , 2 0 0 PSI G,
S P t C E VELO CITY = 2 G
CONVERSION
D PSI G, IpOO F T3/E
- I O O ---------- 1 2 0 -----------IH OU R S ON S T R E A M
Ki-rure 5 .
C a t a l y s t Uva ct i v a v i o n
CONVERSION
L 06) q A-X
RECIPROCAL
Figu re R.
VAPOR
RATE
E f i e c t o f Co ntact Fiae on D e s u l f u r i z a t i o n of Dusky No. 350 Burner Oil
LOGi o A-X
C ONVE R S I ON
- 55 -
2 0 0 PSIG
innn FT-Jzi
1000
FT Vbbl
RECI PROCAL
Fi gu re 7 .
VAPOR
h2
RATE
L f f e e t of Contact 1'i.w* on D e s u l f u r i z a t i o n of
C a r t e r Hail road D i e s e l U i l .
0 N V E R S I ON
— 56 —
200
I000
RECI P ROCAL
I- i g n re 8 .
VAPOR
PSI G
F T 3ZBBL H
R ATE
i - f f e c t o f Co ntact fitni* on D e a u l f u r i z u t i o n o f Carter
iledium Cycle Oil and of 50 heig ht %. Blend ILiilroad
Dit-Hel uni Medium Cycle O i l .
CONVERSION
01Q O I
1000 F T 3ZBBL
RECIPROCAL
Kigure 0 .
VAPOR
RATE
LI f e e t o f Co ntact I'inie on Lm sulfnriAatioii of
Liati I l a t e .
ir.uico Li ;l:t
ity
C ONVERSION
O 0.6
------ 8 ---------- 10-----------12----RECIPROCAL
Kiirn re 1 0 .
VAP OR
RATE
L f f e c t o f C o n t a c t i i » > , K r e s u r e i Uydropen C o n c e n t r a t i o n , and T r e a t —g a s ICate
on UesuJ f u r i z u t i o n o f Ar-enro Liplst Lixy I J i s t i l l a t e at OoO K.
A-X
CONVERSl
- 59 -
RECIPROCAL
F i gu r e 11.
VAPOR
RATE
E f f e c t o f Co ntact l i m e , P r e e s n r e , and T r e a t - g a s
Kale on Desui f u r i z a t i o n of Araaco L i g h t Waxy
D i s t i l l a t e at 700 F.
145298
—
LOG
— 60
::
2 00) PSIG
loco
f t V bbl
R 'x IO
F i gu r e ] 2 .
L f f«.-cI, of femperature on D e s u l f u r i z a t i o n .
-J 0.4
\oqolI
ALL
POINTS
AT - ^ k
__4 0 ----------------- 5 0 ----------------- 6 0 ----------------- 7 0 ----------------- 8 0 -----HYDROGEN
F ig ur e 13»
CONCENTRATION
IN T R E A T - G A S
E f f e c t o f Hydrogeu C o n c e n t r a t i o n on U e a u l f n r i z u t i o n .
(VOLUME */•)
Ol
ALL
POINTS
AT J ^ . = 2 . 0 , 6 5 0 ° F
----------------------------- 2 0 0 --------------------1------------------- 3 0 0 ----------------------HYDROGEN P A R T I A L P R E S S U R E IN TRE AT- GAS ( P S l A )
Figu re 14.
L f f e c t o f Hydrogen P a r t i a l P r e s su re on U e s u l f u r i z a t i o n
— 63 ~
ALL POI NTS
AT -J - %2 D
2 0 0 PSIG
650" F
P A R T I A L P R E S S U R E HYDROGEN
P A R T I A L P R E S S U R E OIL
Figure 15.
E f f e c t of Hydrogeu & Oil P a r t i a l P r e s s u r e s on
Desulfurization,
LOG
— -O
650*F
IOQO F T 3
60%
IOOO FT
ALL POINTS AT - L - =2D
XD--------------------------------------3 0 0 -------REACTOR
P R E S S U R E ( P S I A)
Fi gu re H>.
L f f e c t o f Reactor P r e s s u r e on D e s u l f u r i z a t i o n ,
io r x
30
Fi gu re 17.
-----------3 5 --------
—1-----------40
OIL
PRESSURE
PARTI AL
o f O i l P c i r t i a l P r e s s u r e on D e s u l f u r i z a t i o n .
45
—
66
—
0 8 -----
x O/
WT. V. DlBENZOTHIOPHENE IN AROMATIC
Figu re 18.
FRACTION OF CHARGE
E f f e c t of Di be nz ot hi op hc ne on D e s u l f u r i z a t i o n .
OIL
MONTANA STATE UNIVERSITY I TRDAorcc
Il HI III Illl III
3
762 10009249 1
i
rV' 78
> -'
165^98
- cop .''
t p- ’ran . P . G .
Characterization of o i l s
Li /
for
/M ,
«»27*
P n
'tl-C i ) /
P - itfr x / c i t r
_______ TA:
j ’
/ ,
x x ■I
1 4 5 2 ^