Catalysts for hydrotreating Synthoil
by Mark Douglas Anderson
A thesis submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE
in Chemical Engineering
Montana State University
© Copyright by Mark Douglas Anderson (1978)
Abstract:
Synthoil was hydrotreated with eight commercial and six MSU catalysts in four batch runs and 15
continuous runs. The liquid products were analyzed for sulfur and nitrogen content, and the extent of
hydrocracking was determined by performing ASTM-D86 distillations.
Batch runs were used for screening catalysts. Continuous runs were performed to determine the effect
of LHSV, hydrogen:oil ratio, temperature, and deactivation on catalyst performance. The standard run
conditions were 450°C, 800 psig, LHSV of 1.0, and a H2:oil ratio of 10,000 scf/bbl. A run using two
separate catalytic steps was performed at 410°C.
The extent of hydrocracking and heteroatom removal was shown to be directly proportional to
temperature and inversely proportional to LHSV.
Catalyst deactivation during the 12 hour runs was a serious problem which could be lessened by
decreasing the temperature from 450°C to 410°C. MSU catalysts were poisoned more rapidly than
commercial catalysts.
The two-step run at 410°C gave results that were comparable to those obtained in one step at 450°C.
Shell 324 (Ni-Mo) removed 43% of the nitrogen in Synthoil, and MSU STK-5-2-6 (Co-Ni-Mo)
removed 70% of the sulfur. Hydrocracking Synthoil at 450°C increased the distillate yield below 700°F
from 44% by volume for the feedstock to an average value of 60% for the products. STATEMENT OF PERMISSION TO COPY
In p re s e n tin g t h i s t h e s is in p a r t ia l f u l f i l l m e n t o f th e r e q u ir e ­
ments f o r an advanced degree a t Montana S ta te U n iv e r s it y ,
th e L ib r a r y s h a ll make i t
f r e e ly a v a ila b le f o r in s p e c tio n .
I agree t h a t
I fu rth e r
agree t h a t p e rm is s io n f o r e x te n s iv e co p y in g o f t h i s t h e s is f o r s c h o la r ­
l y purposes may be g ra n te d by my m a jo r p r o fe s s o r , o r , in h is absence,
by th e D ir e c to r o f L ib r a r ie s .
I t is und e rsto o d t h a t any co p y in g o r
p u b lic a t io n o f t h i s t h e s is f o r f in a n c ia l g a in s h a ll n o t be a llo w e d
w ith o u t my w r it t e n p e rm is s io n .
S ig n a tu re
Date
I 9? 8
1X -
CATALYSTS FOR HYDROTREATING SYNTHOIL
by
MARK DOUGLAS ANDERSON .
A t h e s is s u b m itte d in p a r t ia 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 degree
of
MASTER OF SCIENCE
in
Chemical E n g in e e rin g
A pproved:
0fT?
C h a irp e rs o n , Graduate-^Cbriinit te e
Head, M a jo r DepartruerilT^
~
G raduate Dean
MONTANA STATE UNIVERSITY
Bozeman, Montana
A u g u st, 1978
iii
ACKNOWLEDGMENTS
■
The a u th o r w ishes to th a n k th e s t a f f o f th e Chemical E n g in e e rin g
D epartm ent a t Montana S ta te U n iv e r s it y f o r t h e i r h e lp and encouragem ent.
S p e c ia l th a n ks go to D r. L lo y d Berg f o r h is guidance d u rin g th e co urse
o f t h is
p r o je c t .
The a u th o r would l i k e to acknowledge th e Departm ent o f Energy f o r
t h e i r f in a n c ia l s u p p o rt w hich made t h i s p r o je c t p o s s ib le .
•
S p e c ia l a p p r e c ia tio n goes to Jim T i l l e r y and th e la t e S ila s Huso
f o r t h e i r h e lp in th e m aintenance o f th e equipm ent.
The a u th o r w ould
l i k e t o th a n k Gary Hass and Steve Kujawa f o r t h e i r many s u g g e s tio n s .
A f i n a l th a n ks goes to Ron N ovich who com pleted m ost o f the
a n a ly t ic a l w o rk.
TABLE OF CONTENTS
Page
ii
VITA . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ACKNOWLEDGMENTS
iff
TABLE OF CO NTENTS.................................................
•' i v
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . .
vf
LIST OF FIGURES .................................................................................................
v ii
ABSTRACT . . .
v iiT
..................
. . . . . . . . . . . . . . . . . .
INTRODUCTION
'I
BACKGROUND ..........................
. . . . .
3
S y n th o il Process
.................. . . . . . . . . . . . . . .
Chemical P r o p e rtie s o f S y n t h o il.. . . . . . . . . . . .
H y d r o r e fin in g C o a l. L iq u id s
. . . . . . . . .
..................
RELATED RESEARCH . . ..................
3
5
10
? .
18
■ Oklahoma S ta te U n iv e r s it y . . . . . . . . . . . . . . .
UOP . ....................... . . . . . . . . . . . . . . . . . . .
■ DOW . . . . . . . . .
.....................................................
RESEARCH. OBJECTIVE .
v
.
.
18
18
19-
21 '
'
MATERIALS, EQUIPMENT, AND PROCEDURES . . . . . . . . . . . .
22
M a te r ia ls . . . . . . . . . . . . . . . . . . . . . . .
Equipment and Procedures
. . .
........................... . . . . .
22
RESULTS AND DISCUSSION . . . . . .
22
...................................
35
Batch Runs . . . . . .
. . ..............................
C ontinuous Runs . . . . . . . . . . . . . . . . . . . .
SUMMARY AND CONCLUSIONS
35
40
. . ' ...........................'.........................- . . .
RECOMMENDATIONS FOR FUTURE STUDIES . . ......................
72
'
74
V
. Page
LITERATURE CITED
.
76
APPENDICES . .
J
. . . . . . . . . . . . . . . . . . . . . . .
80
A ppendix
A ppendix
A ppendix
A ppendix
A.
B.
C.
D.
Batch Run C a ta ly s t D e s c rip tio n s
. . . . . .
Batch Run Data . . . . . . . . . . . . . . .
C ontinuous Run C a ta ly s t D e s c rip tio n s . . . .
C ontinuous Run Data . . . . .
...........................
.81
82
.8 3
86.
■v i
.
LIST OF TABLES
T ab le
I.
II.
III.
. Page
Chemical C o m po sition o f S y n th o il and Feed Coal . .
T y p ic a l Compounds Found in S y n th o il
„
6
.8
. . . . . . . . .
A ro m a tic Compounds C o n ta in in g S u lf u r , N itro g e n ,
and O x y g e n ...................... ..................................................
9
IV .
U pgrading S y n th o il a t OSU
...........................
18
V.
U pgrading S y n th o il a t UOP
. . . . . . . . . . . . . .
19
V I.
U pgrading S y n th o il a t DOW
...................
20
V II.
V III.
IX .
. . . . . . . . .
A n a ly s is o f Feed Coal to S y n th o il Process
. . . . . .
.23
S y n th o il A n a ly s is
. . . . .
24
. . . .
. . . -.
Batch Run Data Summary . . .
.-.
...................
.•
. . . . . . . . .
. 37
X.
E f f e c t o f LHSV bn C a ta ly s t Perform ance . . . . . . . .
43
X I.
E f f e c t o f H g iO il R a tio oh C a ta ly s t Perform ance . . . .
49
E f f e c t o f Tem perature on C a ta ly s t Perform ance
. . . .
51
E f f e c t o f D e a c tiv a tio n on C a ta ly s t Perform ance . . . .
55
Two-Step H y d ro tr e a tin g Run Data
64
X II.
X III.
XIV .
XV.
Summary o f Best R e s u lts
. . . . . . . . . . .
...........................................................
.
70
V ii:
LIST OF FIGURES
F ig u re
Page
3
1.
S y n th o il Process S chem atic ...............................
2.
C o ntinuo us R e a cto r S chem atic . . . . . . .
3.
E f f e c t o f T em perature on H y d ro c ra c k in g in th e
Batch A u to c la v e
.............................................................
4.
E f f e c t o f LHSV on S u lf u r Removal
........................................
45
5.
E f f e c t o f LHSV on N itro g e n R e m o v a l.............................................
46
6.
E f f e c t o f LHSV on H y d r o c r a c k i n g ....................
47
7.
E f f e c t o f T em perature on H y d r o c r a c k in g ....................................
52
8.
E f f e c t o f C a ta ly s t D e a c tiv a tio n on S u lf u r
Removal
..............................................................................
. 9.
10.
.
.......................
.
27
E f f e c t o f C a ta ly s t D e a c tiv a tio n on N itro g e n
Removal . .. ...............................................................................
5
E f f e c t o f C a ta ly s t D e a c tiv a tio n on H y d ro c ra c k in g
a t High T e m p e r a t u r e ............................................................... ....
. .
11.
E f f e c t o f T em perature on C a ta ly s t D e a c tiv a tio n
12.
E f f e c t o f C a ta ly s t D e a c tiv a tio n on H y d ro c ra c k in g
a t Low T em perature ......................................... . . . . . . . . .
59
. . . . . .
61
. . .
62
13.
S u lf u r Removal in Two-Step H y d ro tr e a tin g Run . . . . . .
66
14.
N itro g e n Removal in Two-Step H y d ro tr e a tin g Run ..................
67
15.
H y d ro c ra c k in g in Two-Step H y d r o tr e a tin g Run" ....................... .
68
v iii
ABSTRACT
S y n th o il was h y d ro tre a te d w ith e ig h t com mercial and s ix MSU c a ta ­
ly s t s in fo u r ba tch ru n s and 15 c o n tin u o u s ru n s . The l i q u i d p ro d u cts
were a n a lyze d f o r s u l f u r and n itr o g e n c o n te n t, and th e e x te n t o f h y d ro ­
c ra c k in g was d e te rm in e d by p e rfo rm in g ASTM-DB6 d i s t i l l a t i o n s .
Batch runs were used f o r s c re e n in g c a t a ly s t s .
C ontinuous runs were
perform ed t o d e te rm in e th e e f f e c t o f LHSV, h y d ro g e n :o il r a t i o , tem per­
a t u r e , and d e a c tiv a tio n on c a t a ly s t p e rfo rm a n ce . The s ta n d a rd run con­
d it io n s were 450°C, 800 p s ig , LHSV o f 1 .0 , and a H g zo il r a t i o o f
10,000 s c f / b b l . A ru n u s in g two s e p a ra te c a t a l y t i c ste p s was perform ed
a t 410°C.
The e x te n t o f h y d ro c ra c k in g and he te ro a to m removal was shown to be
d i r e c t l y p r o p o r tio n a l to te m p e ra tu re and in v e r s e ly p r o p o r tio n a l to
LHSV. .
C a ta ly s t d e a c tiv a tio n d u rin g th e 12 hour runs was a s e rio u s p ro b ­
lem w hich c o u ld be le sse n e d by d e c re a s in g th e te m p e ra tu re from 450°C to
410°C. MSU c a t a ly s t s were poisoned more r a p id ly than com m ercial
c a t a ly s t s .
The tw o -s te p ru n a t 41O0C gave r e s u lt s t h a t were com parable to
th o s e o b ta in e d in one s te p a t 4 5 0 °C.
S h e ll 324 (N i-M o) removed 43% o f th e n itr o g e n in S y n t h o il, and
MSU S T K -5-2-6 (C o-N i-M o) removed 70% o f th e s u l f u r .
H y d ro c ra c k in g
S y n th o il a t 450°C in c re a s e d th e d i s t i l l a t e y ie ld below 700°F from 44%
by volume f o r th e fe e d s to c k to an average v a lu e o f 60% f o r th e p ro d u c ts .
INTRODUCTION
The U n ite d S ta te s is c u r r e n t ly fa c in g a s e rio u s energy c r i s i s .
W h ile th e demand f o r energy is
f o u r p e r c e n t, do m e stic o i l
o f 0 .5 m i l l i o n
in c re a s in g a t an annual r a te o f th re e to
p ro d u c tio n is d e c re a s in g a t an annual r a te
b a r r e ls p e r day.
T h is d is c re p a n c y between s u p p ly and
demand has fo rc e d th e U.S. to r e ly h e a v ily on fo r e ig n o i l
an e s tim a te d annual c o s t o f 40 b i l l i o n
d o lla r s
The o u tlo o k f o r th e f u tu r e is no b r ig h t e r .
by th e y e a r 2000, o i l
to 20 m i l l i o n
sources a t
(I).
It
is e s tim a te d t h a t
p ro d u c tio n in th e non-com m unist w o rld w i l l be 15
b a r r e ls p e r day s h o r t o f demand ( 2 ) .
A lte r n a te energy sources such as n u c le a r f i s s i o n , n u c le a r f u s io n ,
s o la r , w in d , and geotherm al pow er, are b e in g deve lop ed b u t a re n o t ex­
pected to make a s i g n i f i c a n t c o n t r ib u t io n in th e n e a r f u t u r e .
I t is e s tim a te d t h a t dom estic coal re s e rv e s co m prise 80 p e rc e n t o f
th e U n ite d S ta te s ' t o t a l energy fro m o i l ,
gas and c o a l.
T h is v a s t ,
ene rg y so urce c o u ld l a s t up to 100 y e a rs ( T ) .
Combustion o f coal in c o n v e n tio n a l power p la n ts is tro u b le d by
t r a n s p o r t a t io n and p o llu t io n problem s w h ich make i t
method o f e x t r a c tin g energy fro m c o a l.
an u n d e s ira b le
T h e re fo re , a method o f c o n v e rt­
in g co a l to c le a n fu e ls w hich c o u ld be tra n s p o r te d and r e fin e d in
e x is t in g f a c i l i t i e s
is needed.
A lth o u g h com m ercial co a l c o n v e rs io n processes a re b e in g o p e ra te d
in Europe and South
A f r i c a , coal c o n v e rs io n processe s in th e U n ite d
S ta te s rem ain in th e developm ent sta g e ( I ) .
The U n ite d S ta te s Departm ent o f Energy (D .O .E .) is c u r r e n t ly
d e v e lo p in g co a l g a s i f i c a t io n and liq u e f a c t io n processe s f o r th e c o n v e r­
s io n o f coal to c le a n f u e ls .
G a s if ic a t io n processes under developm ent
in c lu d e th e HYGAS, B i-Gas and Synthane p ro ce sse s.
L iq u e fa c tio n
processes in c lu d e th e S o lv e n t R e fin e d Coal (SRC), Exxon Donor S o lv e n t
(EDS) 5 H -C o a l, and S y n th o il processes ( 3 ) .
The p r o d u c t. o f th e S y n th o il process was o r i g i n a l l y in te n d e d f o r
use as a c le a n b o i le r f u e l , b u t a t p re s e n t c o s t j i t
to c le a n up th e s ta c k gases than i t
is . t o
is more econom ical
burn a c le a n f u e l
(4 ).
. Syn-
th o .il has a p o t e n t ia l use as a s y n th e tic crude o i l , b u t b e fo re i t can
be r e fin e d in c o n v e n tio n a l p e tro le u m r e f i n e r ie s , i t
must be c a t a l y t i -
c a l l y upgraded o r h y d ro re fin e d ( 4 ) .
T h e re fo re , th e o b je c t o f t h is re s e a rc h is to d e v e lo p a c a t a ly s t
w hich w i l l
h y d r o tr e a t S y n t h o il, in c re a s in g th e hydrogen c o n te n t and
re d u c in g th e s u l f u r and n itr o g e n c o n te n t, to produce a more s u ita b le
sou rce o f c le a n d i s t i l l a t e
f u e ls .
BACKGROUND
S y n th o il Process
The S y n th o il process is a c a t a l y t i c coal liq u e f a c t io n process
w h ich c o n v e rts h ig h - s u lf u r co a l to a lo w - s u lf u r , lo w -a s h s y n t h e t ic
fu e l o i l .
A s ch e m a tic o f th e process is shown in F ig u r e I .
RECYCLE GAS
C O M PR ESSO R
RECYCLE H2 RICH GAS
HIGH PRESSURE
OIL A N D GAS
SEPARATIO N
COAL
r
C O AL
PREPA­
R A T IO N
JT
FIXED BED
REACTOR
840 °F
2000-4000 PSIG
I
HYDROCARBON
GASES
LOW PRESSURE
OIL A N D GAS
SEPARATIO N
VENT
GAS
Y
SOLIDS
SLURRY
PREPA­
R A T IO N
S O L ID /L IQ U ID
SEPARATIO N
-------- > -
PYROLYZER
PREHEATER
CARBONACEOUSw
RESIDUES 7
GASIFIER A N D
SHIFT
CONVERTER
M A K E U P H2
SL U R R Y
FEED
PUMP
NO NPO LLUTING
FUELOIL
RECYCLE OIL
4
I
H 2O
ASH
PRODUCT
O IL
F ig u re I .
S y n th o il
Process S ch em a tic
4
The coal is crushed and d r ie d and then mixed w ith process p ro d u c t
o il
to fo rm a s lu r r y o f abo ut 40 p e rc e n t c o a l.
The s lu r r y is combined
w ith hydrogen and fe d to a f i r e d p re h e a te r.
The pre h e a te d s lu r r y is th e n v i o l e n t l y p ro p e lle d th ro u g h a f ix e d bed c a t a l y t i c r e a c to r where liq u e f a c t io n and d e s u lf u r iz a t io n o c c u r.
The c a t a ly s t is a c o b a lt-m o ly b d a te c o m b in a tio n on a s ilic a - a lu m in a
s u p p o rt.
A f t e r le a v in g th e r e a c t o r , th e liq u id s . a n d u n re a cte d s o lid s are
s e p a ra te d , and p a r t o f th e l i q u i d p ro d u c t is re c y c le d as s lu r r y o i l .
The r e s u lt in g s o lid s are s e n t to a p y r o ly z e r to re c o v e r more l i q u i d
p ro d u c t, and th e re m a in in g carbonaceous re s id u e is fe d t o a g a s i f i e r
and s h i f t c o n v e rte r to produce hydrogen.
The process o ff- g a s e s a re se p a ra te d in t o f i v e stre a m s :
ammonia, hydrogen s u l f i d e , hydroca rbo n gases, and h ydrog en.
w a te r,
Elem ental
s u l f u r is re co ve re d from th e hydrogen s u l f i d e , and th e hydrocarbon
gases a re fe d to th e g a s i f i e r and s h i f t c o n v e rte r .
The hydrogen p ro ­
duced in t h i s u n i t is mixed w ith th e excess hydrogen fro m th e r e a c to r
and re c y c le d
(5 )..
Work on t h i s process began in 1969 a t th e P itts b u r g h Energy Re­
search C e nte r (PERC).
The i n i t i a l
b e n c h -s c a le process u n i t used a
5 /1 6 - in c h in t e r n a l d ia m e te r r e a c to r t h a t processed f i v e pounds o f
s lu r r y p e r hour ( 5 ) .
•
5 .
L a t e r 5 a I / 2 - t o n p e r day p la n t was c o n s tru c te d u s in g two i n t e r ­
c o n n e c tin g 1 4 .5 f o o t le n g th s o f 1.1 in c h in s id e d ia m e te r s t a in le s s
s te e l p ip e ( 5 ) .
T h is u n i t was l a s t o p e ra te d in August o f 1976 ( 6 ) .
A 1 0 -to n p e r day process developm ent u n it is e xpe cted t o be com­
p le te d by 1979, b u t an o p e ra tin g c o n t r a c to r has n o t y e t been s e le c te d
(3 ).
Chemical P r o p e rtie s o f S y n th o il
S y n th o il is an e x tre m e ly complex m ix tu re o f p o ly c y c lic a ro m a tic
compounds.
Exxon Research and E n g in e e rin g Company (ER&E) has r e c e n t ly
p u b lis h e d a d e t a ile d s tu d y o f th e chem ical n a tu re o f S y n t h o il, and some
o f th e r e s u lt s fro m t h i s
s tu d y are p re se n te d in th e f o llo w in g p a ra ­
g ra p h s. ; The f o llo w in g in fo r m a tio n was ta ke n ^from th e Summary o f th e .
f i n a l r e p o r t p repa red by ER&E (7).
T a b le I g iv e s a summary o f th e a n a ly s is o f a West V i r g in i a
Mine feed coal and l i q u i d
Ir e la n d
p ro d u c t FB-46 made from th e co a l u s in g th e
S y n th o il p ro c e s s .
The sample o f S y n th o il used in t h i s
re se a rch p ro d u c t was a ls o p ro ^
duced from coal from th e Ire la n d M ine, so i t s
a n a ly s is s h o u ld be s im i­
l a r to t h a t o f p ro d u c t FB-46.
Coal liq u i d s a re g e n e r a lly se p a ra te d in t o th e se th re e f r a c t io n s :
o il,
a s p h a lte n e s and re s id u e .
t h a t is s o lu b le in c y c lo h e x a n e .
O il is d e fin e d by Exxon as th e f r a c t io n
A sp h a lte n e s a re d e fin e d as cyclo hexan e
in s o lu b le s -b e n z e n e s o lu b le s and th e re s id u e f r a c t io n
is
in s o lu b le in
6
T a b le I .
Chemical C o m po sition o f S y n th o il and Feed CoaV
C lasses o f Components
W eight P e rce n t in Sample
W. Va.
S y n th o il
Ire la n d
FB-46
Feed Coal
Batch 55
0.660
69.49
0.114
5 .2 7
P a r a ffin s
0.037
1 .19
Naphthenes
0.077
4 .0 7
0.312
33.67
H ydrocarbons
0.260
3 1 .6 3
Thiophenes
0.027
0.5 6
Furans
0.025
' 1.4 8
0.234
30.56
' 0.066
15.29
D i-oxygen compounds
0.012
2 .0 7
N itro g e n compounds
0 . 010.
7 .2 5
O il
« S a tu ra te s
"• A ro m a tics
• P o la rs
Mono-oxygen compounds
•O ther
• Residue
A sp h a lte n e s
Residue
^ Data ta k e n from R eference 7.
0.006
• 0 .4 2
0.139
5.5 3
0.150
17.22
95.77
9 .0 4 .
•
7
benzene.
T a b le I shows t h a t in liq u e f a c t io n , a l l b u t abo ut 9 p e rc e n t
o f c o a l's r e s id u a l m a te ria l is c o n v e rte d to o i l s o r a s p h a lte n e s .
The o i l
f r a c t io n can be f u r t h e r se p a ra te d in t o s a t u r a te , a ro m a tic
and p o la r compounds.
ty p e s id e n t i f i e d
T able I I l i s t s
some o f th e s p e c if ic compound
in each o f th e s e f r a c t io n s .
Exxon found 13 compound ty p e s and 225 carbon number homologs in
th e s a tu r a te f r a c t io n .
A bout 80% o f th e s a tu ra te s in p ro d u c t FB-46 a re
naphthenes.
The a ro m a tic f r a c t io n o f S y n th o il c o n ta in s condensed r in g s t r u c ­
tu re s c o n ta in in g up to 8 r in g s .
1150 carbon number hom ologs.
Exxon is o la t e d 135 compound types and
P o ly c y c lic r in g s c o n ta in in g oxygen,
n itr o g e n ,a n d s u l f u r were a ls o i d e n t i f i e d .
a re l i s t e d
Some o f th e s e compound ty p e s
in T a b le I I I .
The p o la r f r a c t io n c o n ta in s one to e ig h t r in g h y d ro x y a ro m a tic s and
d ih y d ro x y a ro m a tic s , and a ro m a tic p y r r o le s and p y r i d in e s .
A to ta l o f
158 compound ty p e s and 1150 homologs were fo u n d .
A sp h a lte n e s a re complex r in g systems c o n ta in in g 7 t o 11 a ro m a tic,
r in g s and I t o 4 n a p h th e n ic r in g s p e r m o le c u le .
A p p ro x im a te ly 80 p e r ­
c e n t o f th e carbon is lo c a te d in a ro m a tic r in g s ^ and th e average a lk y l
group is
le s s th a n 2 carbons in le n g th .
There a re I t o 3 oxygen atom s,
1 /2 to I n itr o g e n atom s, and 0 .0 3 t o 0 .1 6 s u l f u r atoms p e r m o le cu le ( 7 ) .
8
T a b le I I .
T y p ic a l Compounds Found in S y n th o il
.F ra c tio n
I
T y p ic a l Compounds
O il
'
P o la r
n a p hth ale nes
acenaphthenes
flu o re n e s
phenanthrenes
. pyrenes
. flu o r a n th r e n e s
benzanthracenes
chrysenes
benzopyrenes
m
.
CM
naphthenes
I
A ro m a tic
n - p a r a f f in s , C ^ ■
J
S a tu ra te s
b e n zo p e ryle n e s
coronenes
t e t r a l in s
te tra h y d ro a c e n a p h th e n e s
h e x a h y d r o fluorenes
d ib e n zo th io p h e n e s
p h e n a n th re n o th io p h e n e s
d ib e n z o fu ra n s
p h e n a n th re n o fu ra n s
I - 8 r in g h y d ro x y a ro m a tics and d i h y d ro x y a ro m a tic s
a ro m a tic p y r r o le s , p y r i d in e s
A sp h a lte n e s
^Taken fro m R eference 7.
a ro m a tic p h e n o ls , p y r r o le s
9
I
T a b le I I I .
A ro m a tic Compounds C o n ta in in g S u lf u r , N itro g e n and Oxygen
H eteroatom
S u lf u r
T y p ic a l Compounds"
benzothiophenes
d ib e n z o th io p h e n e s
■ ph e n a n th re n o th io p h e n e s
N itro g e n
p y r r o le s
p y r i d in e s
q u in o lin e s
c a rb a z o le s
a c r id in e s
Oxygen .
d ib e n z o fu ra h s
p h e n a n th re n o fu ra n s
hydroxybenzenes
h y d r o x y indanes . '.
t e tr a lin s
Taken fro m R eference 7.
10
The f o llo w in g tra c e m e ta ls have been found in S y n t h o il:
Fe, T i , K, Na, Mg, Ca, Pb, V, and N i.
S i, A l ,
The c o n c e n tra tio n s o f these
m e ta ls range fro m 1348 ppm f o r Si down to I ppm f o r N i.
I t i s b e lie v e d
t h a t th e h ig h s i l i c o n and aluminum c o n c e n tra tio n s o r ig in a t e from th e
S i- A l c a t a ly s t used in th e S y n th o il process ( 8 ) .
.
H y d r o r e fin in g Coal L iq u id s
As m entioned in th e I n t r o d u c t io n , b e fo re S y n th o il can be processed
in t o c le a n d i s t i l l a t e
f u e ls in c o n v e n tio n a l p e tro le u m r e f i n e r i e s , i t
must be c a t a l y t i c a l l y h y d ro tre a te d .
r e f i n in g
(4 ).
The process is
known as h yd ro ­
H y d ro r e fin in g is n e ce ssary because S y n th o il c o n ta in s
e x c e s s iv e c o n c e n tra tio n s o f r e s id u a l c a rb o n , p o ly n u c le a r a ro m a tic s ,
com plex h e te ro c y c le s c o n ta in in g s u l f u r , n itr o g e n and oxyge n, and ash .
(9 ).
The b a s ic g o a ls o f h y d r o r e fin in g a re to s a tu r a te and p a r t i a l l y
c ra c k p o ly n u c le a r a ro m a tic s and to remove s u l f u r , n itr o g e n and o x y g e n ,
T h is r e s u lt s in a h ig h e r hydrogen to carbon r a t i o , p ro lo n g e d c a t a ly s t
life
in subsequent p ro c e s s in g , and reduced c o n c e n tra tio n s o f p o t e n t ia l
a i r p o llu t a n t s .
The f o llo w in g s e c tio n s w i l l d is c u s s c a ta ly s ts in g e n e r a l, s p e c if ic
r e a c tio n s t h a t o c c u r in h y d r o r e f in in g , and c a t a ly s t p r e s u lf id in g ,
p o is o n in g , and t e s t in g .
11
C a ta ly s ts in g e n e r a l.
C a ta ly s ts a re u s e fu l in h y d r o r e fin in g be­
cause th e y a llo w r e a c tio n s to proceed by lo w e rin g th e a c t iv a t io n e n e r­
g ie s o f th e r e a c tio n ste p s and p r o v id in g a lt e r n a t e r e a c tio n paths ( 10 ) .
The a c t i v i t y and s e l e c t i v i t y o f a c a t a ly s t is d e te rm in e d by th e f o ll o w ­
in g p r o p e r t ie s :
n a tu re o f th e s u p p o rt, chem ical c o m p o s itio n , s u rfa c e
a c i d i t y , t o t a l s u rfa c e a re a , pore volum e , and p o r e - s iz e d i s t r i b u t i o n
among o th e rs
(9 ).
l y s t p o is o n s .
A c t iv ity
is a ls o in flu e n c e d by p re tre a tm e n t and c a ta ­
The e f f e c t s o f th e se p r o p e r tie s on c a t a l y t i c a c t i v i t y a re
d is c u s s e d in th e f o llo w in g s e c tio n s .
. R e a c tio n s .
Three im p o rta n t r e a c tio n s t h a t o c c u r in h y d r o r e fin in g
a re h y d ro c ra c k in g , h y d r o d e s u lfu r iz a tio n
(HDN).
(HDS), and h y d ro d e n it r o g e n a t ion
E ffe c ts o f c a t a ly s t p r o p e r tie s on th e se r e a c tio n s and sim p le
mechanisms a re d is c u s s e d .
I.
H y d ro c ra c k in g .
H y d ro c ra c k in g c a t a ly s t s a re im p o rta n t because
th e y prom ote s a tu r a tio n and p a r t ia l c ra c k in g o f p o ly n u c le a r a ro m a tic
compounds.
H y d ro c ra c k in g is b e lie v e d to proceed th ro u g h a m u lt i- s t e p
mechanism in v o lv in g h y d ro g e n a tio n , is o m e r iz a tio n , c r a c k in g , and re h y d ro ­
g e n a tio n .
These r e a c tio n s produce s a tu ra te d c y c li c and branched com­
pounds and reduce coke d e p o s itio n caused by p o ly n u c le a r a ro m a tic s ( 9 ) .
The m a jo r it y o f c u r r e n t ly used h y d ro c ra c k in g c a t a ly s t s are based on
c r y s t a l l i n e s ilic a - a lu m in a c o m b in a tio n s im pregn ate d w ith c o b a lt , m olyb­
denum, n ic k e l o r tu n g s te n in v a ry in g p r o p o r tio n s . - These c a t a ly s t s a c t
12
as h ig h te m p e ra tu re a c id s w h ich accou nts f o r t h e i r a c t i v i t y
(1 1 ) .
Pore
s iz e d i s t r i b u t i o n and s u rfa c e area a re a ls o im p o rta n t param eters ( 9 ) .
2.
H y d ro d e su lf u r i z a tio n (HDS).
li q u i d s because i t
p o is o n .
S u lf u r is u n d e s ira b le in coal
i s r e a d ily adsorbed on th e c a t a ly s t and a c ts as a
S u lf u r p re s e n t in f u e ls a ls o a c ts as an a i r p o llu t a n t ( 9 ) .
S tu d ie s o f d ib e n z o th io p h e n e , a c o n s t it u e n t o f S y n t h o il 5 have shown
t h a t s u l f u r e x t r a c t io n o cc u rs p re d o m in a te ly b e fo re th e a ro m a tic r in g s
a re c o m p le te ly s a tu r a te d .
S u lf u r i s removed as HgS.
The HDS r e a c tio n
was found to be f i r s t o rd e r w ith re s p e c t to th e s u lf u r - c o n t a in in g com­
pound (1 2 ) .
In g e n e r a l, as th e m o le c u la r w e ig h t o f th e compound i n ­
c re a s e s , th e d i f f i c u l t y o f HDS and HDN in c re a s e s .
remove th a n n itr o g e n
S u lf u r is e a s ie r t o
( 11 ) .
The m ost common HDS c a t a ly s t s a re Co-Mo c o m b in a tio n s on alum ina
o r s ilic a - a lu m in a s u p p o rts .
HDS a c t i v i t y
in c re a s e s w ith in c re a s in g
s u rfa c e area and average pore s iz e ( 11 ) .
3.
H y d ro d e n itro g e n a tion (HDN).
B a sic n itr o g e n compounds are
u n d e s ira b le because th e y r e a c t w ith th e a c id c e n te rs o f th e c a t a ly s t
and i n h i b i t c r a c k in g .
They a ls o a c t as coke p re c u rs o rs and, i f
p re s e n t in f u e ls , a c t as a i r p o llu t a n t s
( 11 ) .
S tu d ie s on th e HDN o f q u in o lin e , a c o n s t it u e n t o f S y n t h o il, have
shown t h a t com ple te h y d ro g e n a tio n must o c c u r b e fo re th e C-N bond is
broken (1 2 ) .
N itro g e n i s removed as NHg.
13
The most common HDN c a ta ly s ts , a re N l-M o 1 N I-W o r Ni-Co-Mo com bi­
n a tio n s on alum ina o r s ilic a - a lu m in a s u p p o rts .
T h e s e ,c a ta ly s ts must be
p r e s u lfid e d f o r p ro p e r a c t i v i t y .
P r e s u lf id in g .
H y d ro r e fin in g c a t a ly s t s a re p r e s u lfid e d to in c re a s e
h y d ro g e n a tio n a c t i v i t y and decrease th e i n i t i a l r a t e o f carbon d e p o s i­
t io n by m in im iz in g h y d ro c ra c k in g .
P r e s u lfid a t io h decrea ses HDS1 b u t
most HDS c a t a ly s t s a re s u lfid e d in th e r e a c to r by fe e d s c o n ta in in g
more th a n one p e rc e n t s u l f u r ( 9 ) .
C a ta ly s t p o is o n in g .
by f o u r mechanisms:
C a ta ly s t d e a c tiv a tio n o r p o is o n in g can o c c u r
a d s o rp tio n o f s u l f u r and n itr o g e n compounds, coke
d e p o s itio n , d e p o s itio n o f o rg a n o m e ta llic compounds, and s in t e r in g .
S u lf u r and n itr o g e n p o is o n in g have a lre a d y been b r i e f l y d is c u s s e d , so
t h i s s e c tio n w i l l
c o n c e n tra te on th e problem s o f c o k in g and organo­
m e ta ll ic compounds.
I.
C o kin g .
S in t e r in g w i l l
n o t be d is c u s s e d .
C a ta ly s t p o is o n in g due t o coke d e p o s itio n d u rin g th e
h y d r o r e f in in g o f coal li q u i d s is a s e rio u s problem .
T h is is ,because o f
th e h ig h c o n c e n tr a tio n o f p o ly n u c le a r a ro m a tic compounds, e s p e c ia lly
th o s e c o n ta in in g n itr o g e n , found in th e s e liq u id s
(9 ).
Coking o ccu rs when th e f r e e - r a d ic a ls t h a t a re form ed d u rin g h y d ro ­
g e n a tio n and h y d ro c ra c k in g r e a c tio n s a re n o t quenched w ith hydrogen b u t
r e a c t w ith o th e r f r e e - r a d ic a l c o n ta in in g fra g m e n ts .
The r e s u lt is
14 .
r e p o ly m e r iz a tio n o r co n d e n sa tio n o f la r g e p o ly n u c le a r compounds t h a t
a re r e s is t a n t to f u r t h e r fra g m e n ta tio n ( 9 ,1 3 ) .
,
A lth o u g h t h i s ty p e o f p o is o n in g is n o t perm anent, c o k in g o ccu rs
r a p id ly and causes th e c a t a ly s t to lo s e 70 to 90 p e rc e n t o f i t s
ity .
a c t iv ­
T h is lo s s o f a c t i v i t y is caused by th e lo s s o f pore volume and
s u rfa c e area as th e carbon is d e p o s ite d th ro u g h o u t th e pore s t r u c t u r e .
These d e p o s its te n d to f i l l
up pores t h a t have a ra d iu s s m a lle r than
O
30 A.
R e g e n e ra tio n can r e s to r e 90 to 94 p e rc e n t o f th e c a t a ly s t 's
v ir g in a c t iv it y
(1 4 ).
Coking can be reduced by u s in g more a c t iv e c a t a ly s t s a t a lo w e r
te m p e ra tu re to p re v e n t f r e e - r a d ic a l fo rm a tio n ( 9 ) .
p e tro le u m r e s id u a l o i l s ,
In a s tu d y o f
in c re a s in g th e hydrogen p re s s u re decreased th e
amount o f c o k in g b u t d id n o t decrease th e r a te o f fo rm a tio n ( 11) .
2.
Q rg a n o m e ta llic compounds.
P o is o n in g by th e d e p o s itio n o f
O rg a n o m e ta llic compounds o ccu rs a t a much s lo w e r r a t e th a n c o k in g , b u t
it
is
ir r e v e r s ib le .
I r r e v e r s i b i l i t y occu rs because perm a n e n tly bound
m etal o x id e s a re form ed d u rin g c a t a ly s t re g e n e ra tio n (1 4 ) .
The ash in S y n th o il c o n ta in s f o u r known c a t a ly s t p o is o n s .
They
a re Fei N i, T i , and V (1 1 ,1 4 ).
C a ta ly s t t e s t i n g .
r e a c to r ty p e s :
C a ta ly s t t e s t in g ta k e s p la c e in th re e general
d i f f e r e n t i a l , p u lse d m ic ro , and i n t e g r a l .
15
W h ile d i f f e r e n t i a l re a c to rs a re u s e fu l f o r o b ta in in g k in e t i c d a ta s
and p u lse d m ic ro re a c to rs f o r s c re e n in g c a t a ly s t s s in t e g r a l re a c to rs can
be used f o r both purp o se s.
S ince in t e g r a l r e a c to rs o p e ra te a t h ig h
c o n v e rs io n le v e ls , th e y more n e a rly s im u la te th e r e a l c a t a l y t i c
process ( 9 ) .
A tr ic k le
liq u id
bed r e a c to r is a f ix e d bed in t e g r a l
r e a c to r in which
and gas flo w c o n c u r r e n tly down th ro u g h th e r e a c t o r .
W h ile t h i s
ty p e o f r e a c to r is u s e fu l in c a t a ly s t s c re e n in g , r e s is ta n c e t o hea t and
mass t r a n s f e r can g iv e m is le a d in g r e s u lt s .
C a t a ly t ic r e a c tio n s in v o lv e s e v e n .s te p s ( 1 5 ) :
1.
D if f u s io n o f r e a c ta n ts th ro u g h th e e x te r n a l f i l m
to th e
c a t a ly s t s u rfa c e .
2.
D iff u s io n o f r e a c ta n ts th ro u g h p o re s .
3.
A d s o rp tio n o f re a c ta n ts on a c t iv e s it e s .
4.
R e a c tio n .
5.
D e s o rp tio n o f p ro d u c ts .
6.
D iff u s io n o f p ro d u c ts th ro u g h p o re s .
7.
D if f u s io n o f p ro d u c ts th ro u g h th e e x te r n a l f i l m .
.
I f h e a t and mass t r a n s f e r l i m i t a t i o n s are s i g n i f i c a n t , th e r e a c tio n
w ill
n o t be c o n t r o lle d by ste p s 3 , 4 , and 5 making i t
o b se rve th e k in e t i c e f f e c t o f c a t a ly s t s
( 10 ) .
d i f f i c u l t to
■
16
Three ty p e s o f t r a n s p o r t l i m i t a t i o n s t h a t o c c u r a r e :
tic le ,
in te rp h a s e and i n t e r p a r t i c l e .
in t r a p a r ­
These l i m i t a t i o n s and th e methods
o f t e s t in g f o r them a re d iscu sse d below .
I f i n t r a p a r t i c l e t r a n s p o r t li m i t a t i o n s are s i g n i f i c a n t , th e c a ta ­
l y s t e ffe c tiv e n e s s f a c t o r n w i l l be in v e r s e ly p r o p o r t io n a l' t o th e c a ta ­
l y s t d ia m e te r.
In c re a s in g c o n v e rs io n w ith d e c re a s in g p a r t i c l e s iz e is
a p o s it iv e t e s t f o r t h i s l i m i t a t i o n
(1 6 ) .
In te rp h a s e t r a n s p o r t l i m i t a t i o n s a re severe in
because o f th e l i q u i d
f ilm
t r ic k le
bed r e a c to r s
w h ich su rro u n d s th e c a t a ly s t p e l l e t T
I f con­
v e rs io n in c re a s e s w ith in c re a s in g mass flo w r a te a t a c o n s ta n t l i q u i d
h o u r ly space v e l o c it y , in te rp h a s e li m i t a t i o n s a re im p o r ta n t (1 6 ).
I n t e r p a r t i c l e li m i t a t i o n s can le a d t o r a d ia l te m p e ra tu re g r a d ie n ts
in th e c a t a ly s t bed.
To p re v e n t d e v ia tio n s from id e a l p lu g flo w due to
c h a n n e llin g and a x ia l d is p e r s io n , th e c a t a ly s t bed s h o u ld be d ilu t e d
w ith i n e r t p a r t ic le s .
Hears (16) sugg ests th e f o llo w in g c r i t e r i o n
d ilu t io n :
I
= c a t a ly s t + d ilu e n t bed le n g th
dp = p a r t i c l e d ia m e te r
b
3
3
= cm in e r t : c m
c a t a ly s t r a t i o
6
= r e l a t i v e e x p e rim e n ta l e r r o r in c o n v e rs io n
fo r
17
T h is d is c u s s io n o f h y d r o r e fin in g i l l u s t r a t e s
th e p roblem o f o b ta in in g c le a n d i s t i l l a t e
Because o f t h i s c o m p le x ity , i t
th e c o m p le x ity o f
f u e ls fro m coal li q u i d s .
is e s s e n tia l t h a t c a t a ly s t p r o p e r tie s
and o p e ra tin g c o n d itio n s a re w e ll d e fin e d and c a r e f u l l y c o n t r o lle d .
RELATED RESEARCH
S y n th o il has been c a t a l y t i c a l l y
upgraded by a t le a s t th re e o th e r
groups o f in v e s tig a t o r s th ro u g h th e s u p p o rt o f th e U,S> Departm ent o f
Energy.
In g e n e ra l, th e se in v e s t ig a t o r s used more s e v e re p ro c e s s in g
.
c o n d itio n s and o b ta in e d b e t t e r r e s u lt s than were o b ta in e d in t h is
in v e s t ig a t io n .
T h is r e la t e d re s e a rc h was com pleted by th e School o f
Chemical E n g in e e rin g a t Oklahoma S ta te U n iv e r s it y , UOP, and Dow . T h e ir
p ro c e s s in g c o n d itio n s and r e s u lt s a re summarized below .
Oklahoma S ta te U n iv e r s it y
A S y n th o il l i q u i d was tr e a te d a t OSU under a v a r ie t y o f r e a c to r
c o n d itio n s in a o n e -s te p c a t a l y t i c process (1 7 ).
The c a t a ly s t s used
w ere Co-rMo and Ni-Mo c o m b in a tio n s on S i- A l s u p p o rts .
The p ro c e s s in g
c o n d itio n s and he te ro a to m removal r e s u lt s from one ru n a re p re se n te d
below in T a b le IV .
T a b le IV.
U pgrading S y n th o il a t OSU
T L°C)
T
Feed
P ro d u c t
UOP
427
C a ta ly s t:
Ni-Mo
P (.p s ig )
LHSV ( h r - 1)
——
1500
1 .0
.
.
w t.
%S
Wt.
%N
1.02
. 1.19
0.12
0.58
..
S y n th o il was tr e a te d in a tw o -s te p c a t a ly t ic p ro ce ss a t UOP u sin g
c a t a ly s t s c o n ta in in g group V I and group V I I I m e ta ls on h ig h s u rfa c e
19
area r e f r a c t o r y s u p p o rts U 8 J.
and h yd ro cra cke d (S tep I I ) ,
B e fo re being h y d r o tre a te d (S tep I )
th e S yn th o iT was f i l t e r e d
and washed to remove NH4C l.
to remove ash
The o p e ra tin g c o n d itio n s f o r Steps I and
I I were in th e f o llo w in g ra n g e s:
Tem perature:
P re s s u re :
:
375-450°C .
2000-3000 p s ig
.2 5 - 1 .0 h r " 1
LHSV:
T h e ir r e s u lt s a re summarized in T ab le V--
T a b le .V .
U pgrading .S y n th o il a t UOP
Wt. % S
.W t..% N
Feed
.5 5
S tep I P ro d u c t
.02
.376
S tep I I
—
.076
P ro d u ct
.1.46
DOW
S y n th o il was s tu d ie d by Dow to d e te rm in e i t s
p e tro c h e m ic a l fe e d s to c k (1 9 ) .
s u i t a b i l i t y as a ■
The f i r s t ste p was t o d i s t i l l
S y n th o il p ro d u c t to o b ta in th e 350-650°F f r a c t io n
(S te p I ) .
the
T h is
d i s t i l l a t e was then hydrocracked (S te p T I ) and th e n h y d ro tre a te d
(S te p I I I ) .
The p ro d u c t fro m S tep I I I was then c a t a l y t i c a l l y re fo rm e d
to produce a maximum y i e l d o f a ro m a tic s .
r e s u lt s a re p re se n te d in T ab le V L
T y p ic a l c o n d itio n s and
20
.T a b le V L
U p g ra d in g S y n t h o il a t Dow
C a ta ly s t
Step I
Step I I
S te p .III
—
T ( 0C)
P ( p s ig )
■
—
LHSV
—
W t. %
S
W t. %
N '
.28
.74
HT-400 (Co-Mo)
510
2500
1.0
.015
.06
.HDS-9A (N i-M o)
.360.
1000
2.0
.0001
.0003
These r e s u lt s show t h a t S y n th o il must be h y d r o tre a te d under
se ve re c o n d itio n s in a m u lt i- s t e p pro ce ss b e fo re Tow le v e ls o f s u l f u r
and n itr o g e n c o n te n t can be a c h ie v e d .
become v e ry e x p e n s iv e .
T h is ty p e o f p ro c e s s in g c o u ld
.
RESEARCH OBJECTIVE
The o b je c t o f t h is re s e a rc h p r o je c t was to c a t a l y t i c a H y h y d ro t r e a t S y n th o il t o produce cle a n d i s t i l l a t e
f u e ls .
T h is means t h a t th e
s u l f u r and n itr o g e n c o n te n t o f S y n th o il sh o u ld be re d u c e d 5 and t h a t th e
p e rce n ta g e o f low b o i li n g compounds sh o u ld be in c re a s e d .
The re s e a rc h p la n c o n s is te d o f t e s t in g com m ercial and "in -h o u s e "
h y d r o tr e a tin g c a t a ly s t s in a c o n tin u o u s t r i c k l e
e ffe c ts o f liq u id
bed r e a c t o r .
The
h o u rly space v e l o c it y , h y d r o g e n :o iI. r a t i o , tem per­
a t u r e , and c a t a ly s t d e a c tiv a tio n were s tu d ie d in t h i s r e a c t o r . .
I t is hoped t h a t t h i s
in v e s t ig a t io n w i l l g iv e some d ir e c t io n to
f u t u r e s tu d ie s on th e h y d r o tr e a tin g o f S y n t h o il.
MATERIALS, EQUIPMENT, AND PROCEDURES
M a t e r ia ls
Coal a n a ly s is .
A 5 5 -g a llo n drum o f c e n tr ifu g e d S y n th o il
(FB-49C)
was re c e iv e d fro m th e P itts b u r g h Energy Research C e n te r (PERC),
P itts b u r g h , P e n n s y lv a n ia .
T h is sample o f S y n th o il was made from co a l fro m th e P itts b u r g h
Seam o f th e I r e la n d Mine in West V i r g in i a .
co a l is p re se n te d in T a b le
S y n th o il a n a ly s is .
V II
The a n a ly s is o f t h is feed
.
The S y n th o il sample used in t h i s re se a rch was
produced a t PERC u s in g th e 1 /2 - to n /d a y u n i t .
were 4 ,0 0 0 p s ig , 450°C, and a l i q u i d
The o p e ra tin g c o n d itio n s
feed r a te o f 2 5 - lb / h r .
The c a ta ­
l y s t was 1/ 8 " p e lle t s o f c o b a lt molybdenum on a s ilic a - a lu m in a s u p p o rt
T able
V I I I g iv e s th e a n a ly s is o f t h is
p ro d u c t .
Equipm ent and Procedures
C a ta ly s t p r e s u l f i d in g .
A ll o f th e c a t a ly s t s te s te d were p r e s u l­
fid e d in a s e p a ra te s u l f i d in g a p p a ra tu s .
The s u l f i d in g a p p a ra tu s was a two f o o t le n g th o f one in c h I .D .
s te e l p ip e t h a t was heated w ith an e l e c t r i c p ip e h e a te r.
A f t e r being, f i l l e d
w ith c a t a ly s t and 1 /4 - in c h i n e r t sp h e re s, th e
r e a c to r was heated to 350°C.
D u rin g th e h e a tin g s te p , a stream o f 10%
hydrogen s u lfi.d e in hydrogen was passed th ro u g h th e r e a c to r a t abo ut
a tm o s p h e ric p re s s u re .
23
T a b le V I I ■.
A n a ly s is o f Feed Coal t o S y n th o il
P roxim ate A n a ly s is , W t. P e t,
P ro cess
(as re c e iv e d )
I „6
M o is tu re
V o la t il e M a tte r
Fixed Carbon .
4 1 .6
,
Ash
4 8 .6
8.1
U ltim a te A n a ly s is , W t. P e t.
Hydrogen
5 .3
Carbon
73 .8
N itro g e n
1 .4
Oxygen
7 .6
S u lf u r
3 .8
. 8.2
Ash
C a l o r i f i c v a lu e , B tu/1 b > - l3,400
24
■Table V I I I
.
S y n t h o il A n a ly s is
P h y s ic a l P ro p e rtie s
V is c o s it y , SSF @ ISO0 F
5 0 .5
1 .103
S p e c if ic G r a v ity
U ltim a te A n a ly s is , VJt. P c t.,
87.62
Carbon
Hydrogen
Oxygen
7 .9 7
.
2.08
.
N itro g e n
0.97
S u lf u r
0 .4 3
Ash
1 .50
S o lv e n t A n a ly s is , VJt. P e t.
O rg a n ic Benzene In s o lu b le s
(Ash F re e )
4.2
A sp h a lte n e s (P entane In s o lu b le s
from Benzene S o lu b le s )
22.5
O ils (Pentane S o lu b le s from
Benzene S o lu b le s )
71.8
25
The f lo w o f th e HgS m ix tu re was m a in ta in e d f o r 12 hours a t 350°C ■
and c o n tin u e d f o r about one hour a f t e r th e h e a te r was tu rn e d o f f .
A f t e r th e flo w was stopped and th e r e a c to r was a llo w e d to c o o l, th e
c a t a ly s t was removed and s to re d in se a le d c o n ta in e r s .
Batch r u n s .
Batch runs were made in a P a rr s e r ie s 4000 p re s s u re
r e a c tio n a p p a ra tu s ( 2 0 ) .
T h is a p p a ra tu s was heated in a r o c k in g a u to ­
c la v e h e a te r.
B atch ru n s were perform ed by c h a rg in g th e 500 ml a u to c la v e w ith
150 ml o f S y n th o il and 25 ml o f s u lf id e d c a t a ly s t .
The head o f th e
r e a c to r was secured to th e body by a screw cap equipped w ith e ig h t cap
screw s.
A copper g a ske t was used between th e head and th e body t o p re ­
ve n t le a k a g e .
A f t e r th e cap screws were to rq u e d down, th e p re s s u re
gauge was connected to th e head.
The a u to c la v e was th e n p re s s u riz e d w ith 2000 ± 100 ps'ig o f h y d ro ­
gen u s in g a Haskel gas b o o s te r (2 1 ) and checked f o r le a ka g e .
I t was
then in s e r te d in t o th e r o c k in g a u to c la v e h e a te r and secured w ith a
r e t a in in g b o l t lo c a te d in i t s
base.
An ir o n - c o n s ta n ta n therm oco uple
was in s e r te d in t o a h o le in th e r e t a in in g
b o l t , and th e te m p e ra tu re was
re co rd e d on a Honeywell te m p e ra tu re re c o r d e r .
The ro c k e r and h e a te r were then a c t iv a t e d , and th e te m p e ra tu re was
‘
c o n t r o lle d m a n u a lly w ith a P o w e rsta t v a r ia b le tra n s fo r m e r.
Tem perature
and p re s s u re re a d in g s were ta ke n a t 15 m in u te in t e r v a ls u n t i l
26
c o m p le tio n o f th e ru n .
A p p ro x im a te ly one hour was re q u ire d to h e a t th e
a u to c la v e t o th e run te m p e ra tu re o f 450°C.
The a c tu a l run tim e a fte r-
p re h e a tin g was one h o u r.
A t th e end o f th e r u n , th e a u to c la v e was removed fro m th e h e a te r
and a llo w e d to co o l o v e r n ig h t a t room te m p e ra tu re .
A f t e r c o o lin g , th e
f i n a l p re s s u re was re co rd e d and s lo w ly vented to p re v e n t lo s s o f l i q u i d
p ro d u c t.
The p ro d u c t was se p a ra te d fro m th e c a t a ly s t and s to re d in
g la s s b o t t le s .
C ontinuous r e a c t o r .
The c o n tin u o u s t r i c k l e
bed r e a c to r was de­
s ig n e d and b u i l t by th e Chemical E n g in e e rin g Departm ent a t Montana
S ta te U n iv e r s it y p r io r to th e b e g in n in g o f t h is in v e s t ig a t io n .
The
c o n tin u o u s r e a c to r a p p a ra tu s is shown in F ig u re 2.
The r e a c to r c o n s is ts o f a one in c h I .D . s ch e d u le -8 0 In co n e l p ip e
th re e f e e t lo n g .
The r e a c to r f i t s
in t o an aluminum b lo c k w hich Ts
wrapped w ith th re e s e ts o f n i chrome h e a tin g w ir e s .
Power to the h e a t­
in g w ire s is c o n t r o lle d by th re e P o w e rsta t v a r ia b le tra n s fo r m e rs .
aluminum b lo c k is en clo se d by a m etal s h e ll f i l l e d
The
w ith z o n o lite
in s u la t io n .
A 1 /4 - in c h s t a in le s s s te e l tu b e ru n s down th e m id d le o f th e r e a c ­
t o r and se rve s as a th e rm o w e ll.
Three chrom e!-a lu m e l therm ocouples
measure th e te m p e ra tu re a t th e end o f th e pre h e a t s e c t io n , and a t two
p o in ts in th e c a t a ly s t s e c tio n .
The te m p e ra tu re s a re re c o rd e d on a
Leeds and N o rth ru p m u lt ip o in t r e c o r d e r .
2
7
NaOH
SCRUBBER
F ig u re 2,
C ontinuous R eactor Schem atic
28
The to p o n e - t h ir d o f th e r e a c to r is f i l l e d
a c t as a p re h e a tin g zone.
w ith i n e r t p a cking t o .
The m id d le o n e - t h ir d is f i l l e d
w ith a 1:1
m ix tu re o f I / 1 6 - in c h c a t a ly s t e x tru s io n s and 1/ 8 - in c h i n e r t p a r t ic le s .
The re m a in in g s e c tio n is f i l l e d
w ith 1 /4 - in c h i n e r t p a c k in g .
S y n th o iT is pumped in t o . t h e to p o f th e r e a c to r th ro u g h a I / 8 - in c h
s t a in le s s s te e l fe e d li n e by a M ilto n Roy Model A c o n t r o lle d volume
p is to n pump.
To p re v e n t S y n th o il fro m f r e e z in g , th e fe e d r e s e r v o ir ,
pump check v a lv e c a s in g , and fe e d lin e s a re wrapped w ith C ole-Farm er
h e a tin g c o rd s .
The te m p e ra tu re o f th e S y n th o il is m a in ta in e d .a t abo ut .
SO0 C to p e rm it easy pumping.
'
T e c h n ic a l grade hydrogen flo w s th ro u g h a m ic ro m e te rin g v a lv e in t o
a Brooks Thermal Mass Flowm eter and in t o th e to p o f th e r e a c to r .
S y n th o il and hydrogen flo w c o n c u r r e n tly down th ro u g h th e r e a c to r
and in t o th e g a s - liq u id s e p a ra to r.
w hich is p e r io d ic a lly dumped.
The l i q u i d flo w s in t o th e c a tc h p o t
Both th e g a s - liq u id s e p a ra to r and c a tc h ­
p o t a re wrapped w ith h e a tin g co rd s to f a c i l i t a t e
l i q u i d p ro d u c t c o l le c ­
t io n .
The gas strea m is co o le d and th e n flo w s th ro u g h a Grove back p re s ­
su re r e g u la t o r .
The gases a re th e n scrubbed in a sodium h yd ro x id e s o lu ­
t io n b e fo re b e in g vented to th e atm osphere.
A w et t e s t m eter can be
connected beh ind th e s c ru b b e r to m o n ito r th e flo w r a t e o f th e e x it in g .
gas.
2
9
C ontinuous r u n s .
T h is s e c tio n w i l l d is c u s s th e te c h n iq u e s t h a t
were used in o p e ra tin g th e c o n tin u o u s r e a c to r .
Some o f th e equipm ent
and methods were changed a f t e r th e f i r s t s ix runs i n o rd e r t o a ch ie ve
b e t t e r c o n tr o l o f r e a c to r c o n d itio n s .
These changes w i l l be d is c u s s e d .
The r e a c to r c o n ta in e d th re e zones: th e p re h e a tin g , c a t a ly s t and
bottom zones.
For th e f i r s t s ix r u n s , th e p re h e a tin g zone c o n s is te d o f
50 ml o f I / 4 - in c h i n e r t N o rton Denstone spheres fo llo w e d by 100 ml o f
1 /8 - in c h i n e r t N orton Denstone bed s u p p o rt p a r t ic le s .
The c a t a ly s t
zone c o n s is te d o f 70 ml o f I / 1 6,-inch c a t a ly s t e x tr u s io n s mixed w ith
70 ml o f 1 /8 - in c h i n e r t s u p p o rt p a r t ic le s .
th e same in a l l r u n s .
The c a t a ly s t s e c tio n was
The re m a in d e r o f th e r e a c to r was th e n f i l l e d
w ith 50 ml o f 1 /8 - in c h p a r t ic le s and 30 ml o f I / 4 - in c h s p h e r e s .' In th e
l a s t n in e runs, th e p re h e a tin g zone c o n s is te d o f .130 ml o f 1 /4 - in c h
spheres and 20 ml o f 1 /8 - in c h p a r t ic le s .
The s e c tio n f o llo w in g th e
c a t a ly s t bed c o n s is te d o f 20 ml o f 1/ 8 - in c h p a r t ic le s and 60 ml o f
1 /4 - in c h sp h e re s.
in g .
These changes were made to f a c i l i t a t e
r e a c to r c le a n ­
The p r e h e a tin g , c a t a ly s t , and bottom zones o c c u p ie d about 14, 13
and 8 in ch e s o f r e a c to r le n g th , r e s p e c t iv e ly .
A c o n ic a l p ie c e o f s te e l
mesh a t th e bottom o f th e r e a c to r s u p p o rte d th e r e a c t o r p a ckin g .
A f t e r th e r e a c to r was f i l l e d ,
i t was in s e rte d in t o th e h e a tin g
b lo c k and th e fe e d lin e s and s e p a ra tio n a pp aratu s were co nn ecte d.
p re v e n t le a k a g e , a l l th re a d e d f i t t i n g s were se a le d w ith t e f l o n ta p e
and S ilv e r Goop.
To
3
0
A f t e r th e r e a c to r a p p a ra tu s was assem bled, i t was p re s s u riz e d w ith
hydrogen and checked f o r le a k s .
The r e a c to r was l e f t f o r about fo u r
hours a t o p e ra tin g p re s s u re to d e te c t any unknown le a k s .
I f th e r e a c t o r was found to c o n ta in no le a k s , i t was d e p re s s u riz e d
and th e h e a te rs were tu rn e d on.
H e a tin g th e r e a c to r to o p e ra tin g tem­
p e ra tu re r e q u ire d abo ut 12 h o u r s .’
For th e f i r s t s ix ru n s , th e hydrogen flo w was c o n t r o lle d by u s in g
a c a lib r a t e d m ic ro m e te rin g v a lv e .
T h is v a lv e was c a lib r a t e d p r io r to .
each ru n by p a s s in g hydrogen th ro u g h th e packed, p re s s u riz e d r e a c to r
system to a w et t e s t m e te r.
manner f o r each ru n .
A c a l ib r a t io n cu rve was o b ta in e d in t h is
T h is method was n o t v e ry s a t is f a c t o r y f o r o b t a in ­
in g r e p r o d u c ib le flo w r a te s .
A hydrogen mass flo w m e te r was o b ta in e d and used in th e l a s t n in e
ru n s .
A f t e r b e in g c a lib r a t e d to lo c a l a tm o sp h e ric p re s s u re , th e m e te r
was used to c o n tr o l th e hydrogen flo w r a t e .
The l i q u i d
flo w r a te was m o n ito re d w ith th e use o f a 100 ml b u re t
connected in p a r a lle l to th e feed r e s e r v o ir .
The flo w r a te was d e te r ­
mined by c lo s in g th e v a lv e a t th e bottom o f th e feed r e s e r v o ir and t im ­
in g th e change in th e l i q u i d volume o f th e b u re t w ith a s to p w a tc h .
Due
to pumping r a te f lu c t u a t io n s , th e f lo w r a te had to be de te rm in e d e v e ry
20 m in u te s to in s u re a c o n s ta n t r a te .
•
.
When th e r e a c to r reached run te m p e ra tu re , the. h e a tin g cords were
tu rn e d on to h e a t th e l i q u i d feed system and c a tc h p o t.
A f t e r about a
.
31
h a l f h o u r, th e pump was a c tiv a te d w ith th e feed l i n e d is c o n n e c te d fro m
th e r e a c t o r .
T h is was done to obse rve t h a t th e pump was o p e ra tin g
s a t is f a c t o r ily .
The l i q u i d
feed l i n e was then connected to th e r e a c t o r i n l e t and
pumping commenced.
The r e a c t o r was then s lo w ly p re s s u riz e d w ith h y d ro ­
gen w h ile m o n ito r in g th e pump to in s u re c o n tin u e d o p e r a tio n .
A f t e r th e
o p e ra tin g p re s s u re had been re a ch e d , th e pump and th e hydrogen v a lv e
were a d ju s te d t o g iv e th e d e s ire d flo w r a te s .
The l i q u i d c a tc h p o t was em ptied by f i r s t c lo s in g th e i n l e t v a lv e
t o th e c a tc h p o t.
A f t e r th e c a tc h p o t p re s s u re was v e n te d , th e l i q u i d
o u t l e t v a lv e was opened and th e l i q u i d was c o lle c t e d .
The o u t le t v a lv e
was th e n c lo s e d , and th e c a tc h p o t was re p re s s u riz e d w ith n itr o g e n be­
fo r e ope nin g th e c a tc h p o t i n l e t v a lv e .
The r e a c to r p re s s u re rem ained
n e a r ly c o n s ta n t d u rin g p ro d u c t c o l le c t io n .
A f t e r s te a d y te m p e ra tu re and flo w c o n d itio n s were o b ta in e d , 150 to
200 ml o f l i q u i d were c o lle c t e d .
T h is sample was c o n s id e re d to be un­
s te a d y w ith re s p e c t to c a t a l y t i c a c t i v i t y .
About 150 ml o f th e f i r s t
p ro d u c t was then c o lle c t e d , and th e c o n d itio n s were changed.
About
150 ml o f unsteady s ta te m a te ria l was c o lle c t e d b e fo re c o lle c t io n o f
th e second p ro d u c t was begun.
th ir d
used.
p ro d u c t.
T h is w i l l
T h is p ro ce d u re was re p e a te d f o r th e
In seven runs o n ly one s e t o f o p e ra tin g c o n d itio n s was
be d iscu sse d in th e R e s u lts and D is c u s s io n s e c tio n .
3
2
The lo n g e s t runs la s te d f o r 12 to 14 h o u rs , b u t some runs ended
p re m a tu re ly , due to r e a c to r p lu g g in g .
The r e a c to r shut-dow n p ro ced ure
is d e s c rib e d below .
A t th e end o f th e ru n , th e pump was s h u t o f f and th e fe e d r e s e r v o ir
was d ra in e d .
W hile t h is was h a p pening, th e r e a c t o r h e a te rs were tu rn e d
o f f , and th e r e a c to r was s lo w ly d e p re s s u riz e d .
The l i q u i d c a tc h p o t was
then d r a in e d , and th e s e p a ra tio n a p p a ra tu s was d is c o n n e c te d from th e
re a c to r.
The fe e d r e s e r v o ir was f i l l e d
w ith a b o u t 400 ml o f 30 w e ig h t
m otor o i l w hich was pumped th ro u g h th e h o t r e a c t o r t o c le a r o u t any
re m a in in g S y n t h o il.
d u rin g t h i s
s te p .
C a u tio n :
The room must be th o r o u g h ly v e n t ila t e d
A f t e r t h i s s te p , a l l
h e a tin g c o rd s were tu rn e d o f f
and th e r e a c to r was removed from th e aluminum b lo c k .
speed up c o o lin g .
T h is was done to
The th e rm o w e ll was c a r e f u ll y removed from th e h o t
r e a c to r to f a c i l i t a t e
r e a c to r c le a n in g .
A f t e r th e r e a c to r reached room te m p e ra tu re , to lu e n e was pumped
th ro u g h th e r e a c to r to lo o se n th e p a c k in g .
U nless p lu g g in g had
o c c u rre d d u rin g th e r u n , . t h e p a ckin g w ould e a s ily f a l l
to r.
o u t o f th e re a c ­
In some ru n s , p lu g g in g p re ve n te d th e removal o f th e th e rm o w e ll,
and th e p a ckin g had to be d r i l l e d o u t.
The pump was cle aned by c y c lin g to lu e n e th ro u g h th e pump and fe e d
lin e s
lin e .
f o r s e v e ra l h o u rs .
Acetone was th e n c y c le d t o d ry th e pump and
The re m a in in g p ie ce s o f equipm ent were a ls o cle a n e d w ith to lu e n e
and a ce to n e .
3
3
A n a ly t ic a l te c h n iq u e s .. A l l p ro d u c ts from b a tch o r c o n tin u o u s ru n s
were an a lyze d t o d e te rm in e th e e x te n t o f h y d ro c ra c k in g , d e s u lf u r iz a t io n ,
and d e n itr o g e n a tio n .
1.
ASTM d i s t i l l a t i o n .
The e x te n t o f h y d ro c ra c k in g was d e te r ­
mined by p e rfo rm in g an ASTM D-86 d i s t i l l a t i o n
t io n a p p a ra tu s (22 ) .
in a L a b - tin e d i s t i l l a ­
The r e s u lt s were n o t c o rre c te d fro m lo c a l atm os­
p h e ric p re s s u re (630-640 mm Hg; to one atm osphere.
S in ce th e r e s u lt s were o n ly d e s ire d as a q u a li t a t iv e com parison o f
p ro d u c ts , two m o d ific a tio n s were made in t h is p ro c e d u re .
t h a t th e sample s iz e was reduced fro m 100 ml to 50 m l.
The f i r s t was
A ls o , the
samples were d r ie d f o r s e v e ra l hours a t IOO0C b e fo re d i s t i l l a t i o n .
, The d a ta were p lo t t e d as te m p e ra tu re versus c u m u la tiv e volume p e r­
cent d is tille d
o il.
on a p l o t c o n ta in in g th e d i s t i l l a t i o n
c u rv e f o r S y n th -
The e n d p o in t was taken as th e te m p e ra tu re when d e co m p o sitio n
began to o c c u r o r 700°F, w h ich e ve r o c c u rre d f i r s t .
The d a ta fro m th e d i s t i l l a t i o n
p e rc e n t d i s t i l l e d
cu rve s were broken in t o th e volume
in each o f th e f o llo w in g te m p e ra tu re ra n g e s:
0 -4 2 5 °F , 425-600°F and 600-700°F.
The t o t a l volume p e rc e n t d i s t i l l e d
under 700°F was r e fe r r e d to as th e y i e l d .
2.
S u lf u r a n a ly s is .
The s u l f u r c o n te n t o f th e samples was
d e te rm in e d by th e q u a rtz tube com bustion method u s in g a Bico-Brown
S h e ll d e s ig n s u l f u r d e te rm in a tio n a p p a ra tu s (2 3 ,2 4 ) .
The presence o f
c h lo r id e s a n d /o r n itr o g e n in th e samples i n t e r f e rre d w ith th e normal
34
sodium h y d ro x id e t i t r a t i o n , so a g r a v im e tr ic proced ure u s in g barium
c h lo r id e to p r e c ip it a t e th e s u lf a t e was used.
J h e a n a ly s is o f th e S y n th o il fe e d showed t h a t i t
w e ig h t p e rc e n t s u l f u r (2 5 ) .
c o n ta in e d 0.4 4
The a n a ly s is s u p p lie d by PERC in d ic a te d a
s u l f u r c o n te n t o f 0.41 w e ig h t p e rc e n t.
sented as w e ig h t p e rc e n t d e s u lf u r iz a t io n
S u lfu r removal d a ta are p re ­
(% DeS) based on th e h ig h e r
v a lu e o f 0 .4 4 .
3.
N itro g e n a n a ly s is .
The n itr o g e n c o n te n t o f th e samples was
d e te rm in e d by th e Macro K je ld a h l method u s in g 0 .5 grams o f sample and
4 0 .0 grams o f p o tassium s u lf a t e to in s u re com plete d ig e s t io n
(2 6 ,2 7 ,2 8 )
The n itr o g e n c o n te n t o f S y n th o il was found to be 1 .06 w e ig h t p e r­
c e n t (2 5 ) .
N itro g e n removal d a ta a re p re se n te d as w e ig h t p e rc e n t
d e n itro g e n a tio n
It
(% DeN) based on t h i s v a lu e . .
is b e lie v e d t h a t th e s e th re e a n a ly t ic a l te c h n iq u e s p ro v id e a
q u ic k , r e l i a b l e and in e x p e n s iv e method o f com paring p ro d u c ts .
■ RESULTS AND DISCUSSION
S y n th o il was h y d ro tre a te d w ith 14 d i f f e r e n t c a t a ly s t s in fo u r
b a tc h runs and 15 c o n tin u o u s ru n s .
The l i q u i d
p ro d u c ts were analyzed
f o r s u l f u r and n itr o g e n c o n te n t, and ASTM d i s t i l l a t i o n s were perform ed
t o d e te rm in e th e e x te n t o f h y d ro c ra c k in g .
Appendices A and C c o n ta in th e c a t a ly s t d e s c r ip tio n s , and th e b a tc h
and c o n tin u o u s ru n da ta and a n a ly t ic a l r e s u lt s a re c o n ta in e d in Appen­
d ic e s B and D.
Batch ru n s a re d iscu sse d f i r s t ,
fo llo w e d by th e d i s ­
c u s s io n o f th e c o n tin u o u s ru n s .
;
■
■
Batch Runs
The purpose o f b a tc h runs was t o screen c a t a ly s t s f o r t h e i r a c t i v ­
it y
b e fo re p e rfo rm in g c o n tin u o u s t e s t s .
r e l a t i v e l y h ig h a c t i v i t y
I f th e c a t a ly s t e x h ib ite d
in th e b a tch t e s t , i t was f u r t h e r te s te d in
th e c o n tin u o u s r e a c t o r .
A p re v io u s in v e s t ig a t o r used S y n th o il to s cre e n 25 c a t a ly s t s in
th e b a tch a u to c la v e
(2 5 ).
'
These p re v io u s s c re e n in g ru n s were used in
t h i s in v e s t ig a t io n as a b a s is f o r choosing, c a t a ly s t s to be te s te d in
th e c o n tin u o u s r e a c t o r .
C o n se q u e n tly, o n ly f o u r a d d it io n a l c a t a ly s t s
were te s te d in th e b a tch r e a c to r .
Three M .S .U . c a t a ly s t s and one com m ercial c a t a ly s t were te s te d in
th e P a rr a u to c la v e .
These c a t a ly s t s a re d e s c rib e d in Appendix A.
usual c o n d itio n s were as f o llo w s :
The
36
I n it ia l
Hg P re s s u re :
2000+100 p s ig
Run T em perature:
4 5 0 + 5 °C
H eat-up Tim e:
I hour
Run Tim e:
. I hour
. The th re e MSU c a t a ly s t s were te s te d a t th e usual o p e ra tin g c o n d i­
t io n s in runs B33, B34, and B35.
Run BR I , u s in g Cyanamid c a t a ly s t
HDS-20A, was made a t ab o u t 550°C due to a therm oco uple m a lfu n c tio n .
The p ro d u c ts from th e s e runs a re compared in T able IX .
The batch run
d a ta and a n a ly t ic a l r e s u lt s a re g iv e n in Appendix B.
. The d a ta in T a b le IX show t h a t MSU c a t a ly s t STK-10 (Mo, Co, N i,
Fe) gave a h ig h e r degree o f d e s u lf u r iz a t io n and h y d ro c ra c k in g than
c a t a ly s t S T K -I2 (Mo, N i, Z n ).
g e n a tio n and h y d ro c ra c k in g .
T h is shows t h a t Co and Fe im prove h y d ro ­
The p ro d u c t from run B34 was l e f t on a
h o t p la te f o r ab o u t one hour, making i t
u se le ss f o r he te ro a to m a n a ly s is .
D u ring run BR I , th e therm oco uple m a lfu n c tio n e d and began g iv in g
re a d in g s t h a t were about IOO0C lo w e r than th e a c tu a l c o n d itio n s .
Con­
s e q u e n tly , . th e a u to c la v e was heated to a t le a s t 550°C and had a r e s i ­
dence tim e above 450°C o f about two h o u rs .
D u rin g h e a tin g o f th e a u to c la v e to run te m p e ra tu re , th e p re ssu re
and te m p e ra tu re a re d i r e c t l y r e la t e d because th e r e a c tio n s do n o t o ccu r
a t th e lo w e r te m p e ra tu re s .
C o n se q u e n tly, th e te m p e ra tu re o f run BR I
c o u ld be e s tim a te d by u s in g th e te m p e ra tu re versus p re s s u re r e la t io n s h ip
o b ta in e d fro m p re v io u s batch t e s t s .
3
7
T able IX .
' C a ta ly s t
o'
0
1
Run
f i)
Batch Run Data Summary' '
% DeS
% DeN
Y ie ld
I
B33
S T K -I0
450±5
36
23
450+5
( 2) .
( 2)
62
450±5
17
22
60
550+
86 .
62 "
.
67
(12% Mo, 1.7% Co,
2.6% N i,. 0.9% Fe)
B34
STK-14
(17.4% Mo, 2.3% N i,
1.8% Cu)
B35
STK-12
.
(18% Mo, 2% N i,
1.7% Zn)
BRl
HDS-20A
•
77
(5% Co, 16.2% Mo)
( I ) S y n th o il c o n ta in s 0.44% s u l f u r , 1.06% n itr o g e n , and 44% is
d i s t i l l e d under 700°F.
(2 ) Not analyzed..
38
The e f f e c t s o f t h i s extrem e te m p e ra tu re were s i g n i f i c a n t .
T ab le
IX shows t h a t s u l f u r and n itr o g e n removal were two t o th re e tim e s
h ig h e r th a n had been o b ta in e d in p re v io u s batch t e s t s .
As would be
e x p e c te d , th e e x te n t o f h y d ro c ra c k in g was a ls o v e r y h ig h .
shows th e d i s t i l l a t i o n
F ig u re 3
cu rve s f o r S y n th o il and p ro d u c ts B33 and BR!.
T h is f ig u r e shows t h a t 35 p e rc e n t o f p ro d u c t BR! was d i s t i l l e d below
425°F compared t o 11 p e rc e n t f o r p ro d u c t B33 and 4 p e rc e n t f o r
S y n t h o il.
U n fo r tu n a te ly , th e s e extrem e c o n d itio n s c o n v e rte d ab o u t 50 p e rc e n t
o f th e o r ig in a l charge in run BRl to gas o r co ke.
liq u id
T h is seve re lo s s o f
p ro d u c t is o b v io u s ly n o t d e s ir a b le i f th e p ro d u c t is
as a so urce o f d i s t i l l a t e
in te n d e d
f u e ls .
I t is im p o rta n t to n o te t h a t even a f t e r b e in g tr e a te d a t th e se
e x tre m e ly seve re c o n d it io n s , th e l i q u i d p ro d u c t s t i l l
c o n ta in e d h ig h
c o n c e n tra tio n s o f s u l f u r and n itr o g e n , 600 ppm and 4000 ppm, re s p e c - ■
t iv e ly .
T h is p o in ts o u t th e need f o r more a c t iv e c a t a ly s t s w hich can
remove th e s u l f u r and n itr o g e n from th e complex h e te r o c y c le s .
The p re v io u s s c re e n in g runs in d ic a te d t h a t com m ercial Co-Mo and
Ni-Mo c a t a ly s t s had th e h ig h e s t d e s u lf u r iz a t io n and d e n itro g e n a tio n
a c t iv ity .
The th re e MSU c a t a ly s t s screened in t h i s
in v e s t ig a t io n had
r e l a t i v e l y low a c t i v i t i e s and were not. te s te d f u r t h e r .
3
9
TEMPERATURE, DEGREES F
SYNTHOIL
30
.
40
90
VOLUME PERCENT DISTILLED
F
IG
U
R
E3
. E
F
F
E
C
TO
FT
E
M
P
E
R
A
T
U
R
EO
NH
Y
D
R
O
C
R
A
C
K
IN
GINT
H
EB
A
T
C
H
A
U
T
O
C
L
A
V
E
100
40
C ontinuo us Runs
Seven com m ercial c a t a ly s t s and th re e MSU c a t a ly s t s were te s te d in a
t o t a l o f 15 c o n tin u o u s ru n s .
Three o f th e com m ercial c a t a ly s t s te s te d
were cobalt-m olybdenu m on alu m in a and f o u r were n icke l-m o lyb d e n u m on
a lu m in a .
Al I o f th e MSU c a t a ly s t s te s te d were c o b a lt-n ic k e l-m o ly b d e n u m
c o m b in a tio n s on s ilic a - a lu m in a s u p p o rts .
by Kujawa (2 9 ).
These c a t a ly s t s were p re p a re d
C a ta ly s t p r o p e r tie s a re g ive n in A ppendix C.
The ru n s were made to d e te rm in e th e e f f e c t o f process v a r ia b le s on
s u l f u r re m o v a l, n itr o g e n re m o v a l, and h y d ro c ra c k in g .
w ere:
c a t a ly s t p r o p e r t ie s , l i q u i d
The v a r ia b le s
h o u rly space v e l o c i t y , h y d ro g e n :o iI
r a t i o , te m p e ra tu re , and c a t a ly s t d e a c tiv a tio n .
The r e a c to r was o p e r­
a te d in th e f o llo w in g range o f c o n d itio n s :
T em perature:
410-450°C
P re s s u re :
800 p s ig
LHSV:
1 .0 - 2 .0 h H
H2 : 0 i I R a tio :
500 0-10,000 s c f / b b l
t
The r e a c to r was o p e ra te d a t n e a rly is o th e rm a l c o n d it io n s .
The
te m p e ra tu re c o u ld be m a in ta in e d t o w it h in ±5°C o f th e d e s ire d v a lu e .
The l i q u i d
flo w r a te was s e t between 70 and 140 m l/ h r depending
on th e d e s ire d LHSV.
Pumping r a te f lu c t u a t io n s were u s u a lly le s s th a n
6 p e rc e n t o f th e d e s ire d v a lu e .
The r e a c to r p re s s u re was m o n ito re d d u rin g th e ru n .
I f th e p re s ­
su re . in c re a s e d more th a n 25 p s ig d u rin g th e ru n , p lu g g in g was in d ic a te d
and th e run was sto p p e d .
41
The hydrogen f lo w r a te co u ld n o t be m o n ito re d in th e f i r s t s ix
runs because a hydrogen flo w m e te r was n o t a v a ila b le .
In s te a d , a
m ic ro m e te rin g v a lv e was c a lib r a t e d p r i o r to each ru n f o r th e packed,
p re s s u riz e d r e a c t o r .
D u rin g th e r u n , th e v a lv e w o u ld be p la ce d a t th e
p ro p e r s e t t in g a c c o rd in g to t h i s c a l ib r a t io n c u rv e .
However, t h is
method was u n r e lia b le because as soon as S y n th o il was pumped in t o th e
r e a c t o r , th e p re s s u re dro p a cross th e r e a c to r w o uld in c re a s e .
T h is
meant t h a t le s s hydrogen was p ro b a b ly b e in g p u t th ro u g h th e r e a c to r
th a n was d e s ire d .
A ls o , any changes in th e p re s s u re o f th e hydrogen"
i n l e t l i n e would change th e flo w r a t e .
A hydrogen flo w m e te r was used in th e l a s t n in e ru n s .
T h is p ro ­
v id e d a method o f o b ta in in g s te a d y , r e p r o d u c ib le hydrogen flo w r a te s .
The f o llo w in g s e c tio n s w i l l d is c u s s th e c o n tin u o u s ru n s a c c o rd in g
to t h e i r p u rpo se.
The e f f e c t s o f LHSV, Hg=Oil r a t i o , te m p e ra tu re ,
c a t a ly s t d e a c t iv a t io n , and c a t a ly s t p r o p e r tie s on c a t a ly s t perform ance
a re d is c u s s e d .
The c o n tin u o u s run d a ta and a n a ly t ic a l r e s u lt s are
g iv e n in A ppendix D.
E f f e c t o f L iq u id H o u rly Space V e lo c it y (LHSV).
LHSV i s d e fin e d
as th e l i q u i d flo w r a te in ml per hour d iv id e d by th e volum e o f c a ta ­
l y s t in m l.
As LHSV in c re a s e s , th e re s id e n c e tim e o f th e l i q u i d in
th e c a t a ly s t zone d e cre a se s.
{
42
The f i r s t s ix runs were made to d e te rm in e th e e f f e c t o f LHSV on
c a t a ly s t p e rfo rm a n ce .
However, two o f th e ru n s , CR! and CR5, were
ended a f t e r a b o u t f o u r hours o f o p e ra tio n due to r e a c t o r p lu g g in g .
In
b o th o f th e s e r u n s , th e r e a c to r te m p e ra tu re reached a t le a s t 455°C, and
th e space v e l o c it y was abo ut 2 .0 .
A f t e r th e s e r u n s , th e r e a c to r pack­
in g was cemented in t o th e r e a c to r by coke d e p o s its .
Runs CR2, CR3, and CR4 showed t h a t as LHSV is
d e cre a se s.
in c re a s e d , c o n v e rs io n
However, th e r e s u lt s were in flu e n c e d by c a t a ly s t d e a c tiv a ­
t io n because two o r th re e d i f f e r e n t space v e l o c it ie s were te s te d in
each ru n .
The r e s u lt s o f th e se runs a re p re se n te d in T a b le X.
F ig u re s 4 , ' 5 ,
and 6 show th e e f f e c t o f LHSV on s u l f u r re m o v a l, n itr o g e n re m o v a l,
and h y d ro c ra c k in g , r e s p e c t iv e ly .
The ru n s a re d is c u s s e d in d e t a il
below .
Run CR2 was made w ith S h e ll 324 (N i-M o ).
T h is c a t a ly s t showed
v e ry h ig h d e n itro g e n a tio n and h y d ro c ra c k in g a c t i v i t y . . However, i t
is
im p o rta n t to remember t h a t c a t a ly s t a c t i v i t y changes s i g n i f i c a n t l y
d u rin g such a s h o r t ru n .
T h is f a c t can be observed by com paring
p ro d u c ts CR2-2 and CR2-3.
F ig u re s 4 and 5 show t h a t s u l f u r and n itr o g e n removal decrease
F ig u re 6 shows th e
a t a b o u t th e same r a te as th e LHSV is
in c re a s e d .
e f f e c t o f th e LHSV on h y d ro c ra c k in g .
T h is f ig u r e shows t h a t as th e
LHSV was in c re a s e d from 1 .2 to 2 .0 , th e y i e l d o f p ro d u c ts t h a t w e re .
4
3
T able X.
Run,
C a ta ly s t
E f f e c t o f LHSV on C a ta ly s t P e r fo r m a n c e ^
. % DeN
P ro d u ct
H rs . on
O il
I
4
1.2
36
43
74
CR2,
2
6 .5
2.0
32
35
65
S h e ll 324
3
7
2.0
30
35
58
CR3,
2
4
1.6
57
6
64
HDS-9A
3
7 .5
1.0
64
14
65
CR4,
2
5
1 .5
. 50
8
63 .
HR-811
3
8
1.1
45
7
60
4
10
2.0
43
0 .
56
I
5
1 .5
52 .
8
63
CR6 ,
.
LHSV
% DeS
.
K F -I53
(1 ) C o n d itio n s :
T = 450±5°C
P = 800 p s ig
Hg=Oil R a tio = 10,000 s c f /b b l 2
(2 ) Y ie ld = Volume p e rc e n t d i s t i l l e d
below 700°F
Y ie ld
^
4
4
d is t ille d
below 600°F decreased from 48 p e rc e n t to 40 p e rc e n t.
d i s t i l l a t e y ie ld was reduced from 74 p e rc e n t to 58 p e r c e n t.
T o ta l
P a rt o f
t h i s d e cre a se , how ever, was p ro b a b ly due to c a t a ly s t p o is o n in g .
Run CR3 was made u s in g Cyanamid c a t a ly s t HDS-9A (N i-M o ).
T h is
c a t a ly s t gave h ig h s u l f u r removal b u t r e l a t i v e l y lo w n itr o g e n re m o va l.
T h is c a t a ly s t shows th e h ig h e s t s e n s i t i v i t y to LHSV o f th e th re e c a ta ­
l y s t s te s te d .
Run CR4 was made w ith Houdry c a t a ly s t HR-811 (N i- M o ) .
T h is c a ta ­
l y s t e x h ib ite d lo w a c t i v i t y and lo w s e n s i t i v i t y to LHSV.
T a b le X and F ig u re s 4 and 5 show th e e f f e c t o f c a t a ly s t d e a c t i­
v a tio n in t h i s ru n .
P ro d u ct CR4-2 c o n ta in e d le s s s u l f u r and n itr o g e n
th a n p ro d u c t CR4-3 even though i t
ity .
was made a t th e h ig h e r space v e lo c ­
T a b le X shows t h a t h y d ro c ra c k in g , is a ls o a f fe c te d by c a t a ly s t
d e a c tiv a tio n f o r th e s e two p ro d u c ts .
In run CR4, th e r e a c to r reached a te m p e ra tu re o f 5 5 0 °C d u rin g p re ­
h e a tin g .
The r e a c to r was a llo w e d to cool to th e norm al te m p e ra tu re o f
450°C b e fo re th e run was s t a r t e d .
I t was fe a re d t h a t th e c a t a ly s t may
have been s in te r e d a t t h i s te m p e ra tu re .
Run CR6 was made w ith K e tje n c a t a ly s t K F -I53 (N i-M o ) w h ich has th e
same m etal lo a d in g as HR-811 .
As T ab le X shows, th e s e two c a t a ly s t s
e x h ib ite d n e a r ly th e same a c t i v i t y a t a space v e l o c it y o f 1 .5 .
T h is
su g g e sts t h a t HR-811 was n o t s i n t e r e d . s i g n i f i c a n t l y d u rin g p re h e a tin g .
4
5
100
O
HDS-9A
A
HR-811
□
Shell 324
80
8
20
-L-0
1.5
LIQUID HOURLY SPACE VELOCITY
F
IG
U
R
E4
.
E
F
F
E
C
TO
FL
H
S
VO
NS
U
L
F
U
RR
E
M
O
V
A
L
2,0
4
6
O
HDS-9A
A
HR-Sll
□
Shell 324
20 ____
LIQUID HOURLY SPACE VELOCITY
F
IG
U
R
E5
* E
F
F
E
C
TO
FL
H
S
VO
NN
IT
R
O
G
E
NR
E
M
O
V
A
L
4
7
TEMPERATURE, DEGREES F
SYNTHOIL
Shell 324
LHSV= 1.2
LHSV= 2.0
90
VOLUME PERCENT DISTILLED
F I G U R E 6.
EFFECT OF LHSV ON HYDROCRACKING
100
48
O nly one u s a b le p ro d u c t was o b ta in e d fro m ru n CR6 due to r e a c to r p lu g ­
g in g .
These ru n s showed t h a t c a t a ly s t perform ance i s
in v e r s e ly p ro p o r­
t io n a l to LHSV and t h a t c a t a ly s t d e a c tiv a tio n must be in v e s tig a t e d .
A lth o u g h Ni-Mo c a t a ly s t s a re u s e fu l f o r rem oving n itr o g e n from , p e t r o l ­
eum p ro d u c ts , th e y a re n o t e f f e c t i v e f o r rem oving n itr o g e n from
S y n t h o il.
O f th e f o u r c a t a ly s t s te s te d in th e f i r s t s ix ru n s . S h e ll
324 gave th e b e s t n itr o g e n rem oval and h y d ro c ra c k in g w h ile HDS-9A
gave th e b e s t s u l f u r re m o val.
It
is d i f f i c u l t to a d e q u a te ly compare c a t a ly s t s to e x p la in t h e i r
r e l a t i v e a c t i v i t y because n o t a l l o f th e c a t a ly s t p r o p e r tie s were sup­
p lie d by th e ve n d o rs .
Im p o rta n t p r o p e r tie s t h a t need to be known
a re t o t a l p o re .v o lu m e , t o t a l s u rfa c e a re a , and p o r e - s iz e d i s t r i b u t i o n .
E f f e c t o f Hp =O il r a t i o .
Two ru n s were made in an a tte m p t t o d e t e r ­
mine. th e e f f e c t o f th e hydrogen flo w r a te on s u l f u r and n itr o g e n
rem oval and h y d ro c ra c k in g .
The r e s u lt s o f th e se ru n s a re in c o n c lu s iv e
b u t a re p re s e n te d ■in T ab le X I.
Run CR8 was made using. Harshaw HT-400 (C o-M o), and Run CRlO was
made u s in g MSU c a t a ly s t S T K -5 -2 -1 . (C o -N i-M o ). ■
T a b le XI shows t h a t in bo th r u n s , d e s u lf u r iz a t io n , d e n itro g e n a tio n
.
and h y d ro c ra c k in g decrease r a p id ly w ith tim e r a t h e r th a n as a f u n c t io n
o f hydrogen flo w r a t e .
P re vio u s re s e a rc h by Runnion a t MSU (25)
4
9
T able X L
E f f e c t o f Hg =O il R a tio on C a ta ly s t P e r f o r m a n c e ^
Run,
C a ta ly s t
Temp. ( 0C)
LHSV
CR 8
450-455',
HT-400
1.2
.
P ro d u c t,
H rs . on
O il
1.1
Y ie ld
80
16
67
2, 9
7,500
64
6
54
10 , 000 ^
32
I
50
5
7,500
75
16
68
2, 9
10,000
57
4
60
5,000
18
0
56
I,
GO
STK-5-2-1
% DeN
5,000
GO
442-445,
% DeS
5
L
3 , 12.5
CR 10
H2 =Oil .
R a tio
( s c f/b b l)
..
•
(1 ) P re ssu re = 800 p s ig
(2 ) P lu g g in g was o c c u r r in g , and Hg f lo w r a te f lu c t u a t e d
u n c o n tr o lla b ly .
suggested t h a t c a t a ly s t a c t i v i t y is o p tim iz e d a t a Hg: O iI r a t i o o f
10,000 s c f / b b l.
The r e s u lt s o b ta in e d in th e se two ru n s a re to o in c o n ­
s is t e n t to v e r i f y t h i s c o n c lu s io n .
In run CR8 , th e te m p e ra tu re reached 455°C w hich a p p a r e n tly caused
e x c e s s iv e c o k in g w h ich poisoned th e c a t a ly s t and s lo w ly plugged th e
re a c to r.
D u rin g c o lle c t io n o f p ro d u c t CR8-3, th e hydrogen flo w r a te
f lu c t u a t e d u n c o n tr o lla b ly .
T h is e x p la in s th e la c k o f h y d ro g e n a tio n
a c t i v i t y f o r t h i s p ro d u c t. . I t appears t h a t c a t a l y t i c a c t i v i t y was
changing q u ite r a p id ly d u rin g th e c o lle c t io n o f th e f i r s t two p ro d u c ts ,
because th e b e s t r e s u lt s were o b ta in e d a t th e lo w e r hydrogen flo w r a t e .
5
0
In run CR10, c a t a ly s t d e a c tiv a tio n aga in c o n t r o lle d th e e x te n t o f
h y d ro g e n a tio n in th e f i r s t two p ro d u c ts .
As th e h y d r o g e n :o il r a t i o
was decreased fro m 10,000 to 5 ,000 s c f / b b l f o r th e l a s t p ro d u c t,
s u l f u r rem oval decreased by 68 p e rc e n t.
Most o f t h i s decrease was
p ro b a b ly due to th e decreased hydrogen flo w r a t e , b u t c a t a ly s t d e a c t i­
v a tio n c o u ld have a ls o c o n tr ib u te d .
N itro g e n rem oval was n e g lig ib le
a t . t h e end o f bo th ru n s . ■
These r e s u lt s i l l u s t r a t e
d u rin g th e s e 12 hour ru n s .
how im p o rta n t c a t a ly s t d e a c tiv a tio n is
T h is problem w i l l be d is c u s s e d l a t e r .
E f f e c t o f te m p e ra tu re on c a t a ly s t p e rfo rm a n ce .
Three ru n s were
made to d e te rm in e th e e f f e c t o f te m p e ra tu re on c a t a ly s t perform ance.
I t was found t h a t s u l f u r re m o v a l, n itr o g e n re m o v a l, and h y d ro c ra c k in g
a ll
in c re a s e w ith in c re a s in g te m p e ra tu re .
The d a ta fro m th e se runs are.sum m arize d in T a b le X I I .
F ig u re 7
shows th e e f f e c t o f te m p e ra tu re on h y d ro c ra c k in g .
Run CR9 was made u s in g S h e ll 324 a t two te m p e ra tu re s , 420°C and
445°C.
The da ta in T able X I I show t h a t as th e te m p e ra tu re was i n ­
c re a s e d , s u l f u r removal and h y d ro c ra c k in g im proved.
However, n itr o g e n
removal a c t u a lly decreased by 14 p e rc e n t due to c a t a ly s t p o is o n in g .
C a ta ly s t d e a c tiv a tio n p ro b a b ly decreased th e n e t e f f e c t o f te m p e ra tu re
on s u l f u r re m o va l.
51
T a b le X I I .
E f f e c t o f Tem perature on C a ta ly s t P erform ance
' Run,
C a ta ly s t,
P re ssu re
P ro d u c t,
Mrs. on
O il
CR9
I, 4
420
1.1
68
26
58
S h e ll 324
2, 6
420
1.1
61
21
55
1000 p s ig
3 , 1 1.5
445+5
1.1
66
18
65
CR! I ,
I,
3
445+5
1 .1
91
31
69
I,
3 :3
410
1.2
45
13
66
Temp. ( 0C)
LHSV
% DeS
% DeN
.
Y ie ld
S T K -5 -2 -2 ,
800 p s ig
CRl 5,
S T K -5 -2 -2 ,
800 p s ig
To a v o id th e u n c e r t a in ty caused by c a t a ly s t d e a c t iv a t io n , p ro d u c ts
C R ll- I and CR!5-1 a re compared in T ab le X I I .
Runs CR!! and CR!5 were
made w ith th e same c a t a ly s t , S T K -5 -2 -2 , a t d i f f e r e n t te m p e ra tu re s .
The
f i r s t p ro d u c ts fro m each run a re compared so th e e f f e c t o f te m p e ra tu re
on i n i t i a l
c a t a ly s t a c t i v i t y can be obse rve d .
T a b le X II shows t h a t as th e te m p e ra tu re was decreased from 445°C
t o 410°C, s u l f u r and n itr o g e n removal decreased by 51 and 58 p e rc e n t,
r e s p e c t iv e ly .
F ig u re 7 shows t h a t as th e te m p e ra tu re was decrea sed, th e
d i s t i l l a t e y i e l d below 4 2 5 °F decreased by 7 p e rc e n t.
y ie ld below 600°F was decreased by 16 p e rc e n t.
The d i s t i l l a t e
5
2
SYNTHOIL
TEMPERATURE, DEGREES F
Catalyst:STK-5-2-2
4l0 °C
90 ioo
VOLUME PERCENT DISTILLED
F
IG
U
R
E7 •
E
F
F
E
C
TO
FT
E
M
P
E
R
A
T
U
R
EO
NH
Y
D
R
O
C
R
A
C
K
IN
G
53
U n fo r tu n a te ly , h ig h e r te m p e ra tu re s a ls o in c re a s e th e c o n v e rs io n
o f l i q u i d to g a s , r a te o f coke d e p o s itio n , and th e chance o f r e a c to r
p lu g g in g .
A t a te m p e ra tu re o f 450°C, as much as 20 p e rc e n t o f th e l i q u i d
may be c o n v e rte d to gas.
As th e te m p e ra tu re is decreased by 40°C ,
c o n v e rs io n drops to le s s th a n 10 p e rc e n t.
R e a cto r p lu g g in g is a ls o s t r o n g ly in flu e n c e d by te m p e ra tu re .
Of
th e 11 c o n tin u o u s runs t h a t were made a t a te m p e ra tu re o f 450°C o r
h ig h e r , f o u r were ended p re m a tu re ly due t o r e a c to r, p lu g g in g .
f o u r , two were ended a f t e r le s s th a n f o u r hours o f o p e r a tio n .
O f th e s e
F iv e
o f th e ru n s made a t t h i s te m p e ra tu re showed no s ig n s o f p lu g g in g a f t e r
12 hours o f o p e r a tio n .
None o f th e f o u r runs made a t 420°C o r lo w e r
showed any s ig n s o f p lu g g in g .
T h e re fo re , though d e c re a s in g th e o p e ra tin g te m p e ra tu re decreases
in it ia l
liq u id
c a t a ly t ic a c t iv it y ,
p ro d u c t is l o s t .
r e a c t o r p lu g g in g is a vo id e d and le s s
The e f f e c t o f te m p e ra tu re on c a t a ly s t d e a c t i­
v a t io n i s d is c u s s e d i n a l a t e r s e c tio n .
E f f e c t o f c a t a ly s t d e a c t iv a t io n .
C a ta ly s t d e a c tiv a tio n occurs
r a p id ly w ith S y n th o il because o f th e h ig h c o n c e n tra tio n s o f p o ly n u c le a ra ro m a tic compounds and com plex h e te ro c y c le s c o n ta in in g s u l f u r and
■n itr o g e n .
As th e te m p e ra tu re is in c re a s e d , more f r e e - r a d ic a ls are
form ed and more c o k in g o c c u rs .
.
5
4
Runs CR7, C R ll 9 and CR!2 were made a t 45G°C t o obse rve c a t a ly s t
d e a c tiv a tio n .
I t was found t h a t th e MSU c a t a ly s t s . used in ru n s CRll
and CR!2 were more s u s c e p tib le to c a t a ly s t d e a c tiv a tio n th a n th e com­
m e rc ia l c a t a ly s t used in run CR7.
N itro g e n rem oval was n e g lig ib le
in a l l th re e ru n s .
F ig u re s 8 , 9 , and 10 show th e e f f e c t o f c a t a ly s t d e a c tiv a tio n on
s u l f u r re m o v a l, n itr o g e n re m o v a l, and h y d r o c r a c k in g 9 r e s p e c t iv e ly .
The
d a ta fro m th e s e runs a re summarized in T a b le X I I I .
Run CR7 was made w ith Houdry c a t a ly s t HR-801
a tu r e o f 450°C.
(Co-Mo.) a t a tem per­
The run la s te d f o r 14 hours w ith no s ig n s o f p lu g g in g .
S u lf u r rem oval decreased by 14 p e rc e n t in 10 hours w h ile n itr o g e n
rem oval decreased by 37 p e rc e n t.
N itro g e n removal was o n ly abo ut
6 p e rc e n t a f t e r 14 h o u rs.
T h is c a t a ly s t has a lo w e r i n i t i a l
a c t i v i t y th a n th e two MSU c a ta ­
l y s t s , b u t as F ig u re s 8 and 9 show, i t
is . much more r e s is t a n t to c a ta ­
l y s t d e a c tiv a tio n .
R u ns.C R ll and CR!2 were made a t 445°C in an a tte m p t to reduce
c o k in g and th e chance o f p lu g g in g , th e r e a c t o r .
in it ia l
In s p it e o f t h e i r h ig h
a c t i v i t y , th e s e c a t a ly s t s showed v e ry l i t t l e
s t a b i l i t y under
th e s e c o n d itio n s .
Run CR!! was made w ith MSU c a t a ly s t S T K -5-2-2 (C o -M i-M o).
T h is
c a t a ly s t had a v e ry h ig h i n i t i a l a c t i v i t y in a l l r e s p e c ts , b u t a f t e r
55
T a b le X I I I .
Run,
C a ta ly s t
E f f e c t o f D e a c tiv a tio n on C a ta ly s t Perform ance
% DeS
P ro d u ct
H rs . on O il
CR7,
I
3
1.1
59
. 9
57
HR-801
2
5
1.1
55
8
53
4
9
1.1
—
6 .4
6
13
1.1
51 ’ ■
5 .7
60
C R ll,
I
3
1.1 ■
91
31
69
S T K -5-2-2
2
5
1.1
80
3
7
1.1
65
7
62
5
11
1.1
43
0
59
I
2
4 .3
1.2
77
23
72
6 .3
1.2
71
12
60
CRl 2,
S T K -5-2-6
(I)
.
LHSV
% DeN
.
16
Y ie ld
.
54
79
.
C o n d i t i o n s : T = 445±5°C
P = 800 p s ig
Hg=Oil R a tio = 10,000 s c f /b b l
12 h o u rs , s u l f u r rem oval had dropped to 43 p e rc e n t, and th e r e was no
n itr o g e n re m o v a l.
D u rin g c o lle c t io n o f p ro d u c t CRlI - 2 , th e r e a c to r te m p e ra tu re
jumped IO 0C and th e n g r a d u a lly re tu rn e d to i t s o r ig in a l v a lu e .
T h is ,
" h o t s p o t" caused th e d i s t i l l a t e y i e l d to in c re a s e fro m 69 p e rc e n t to
79 p e rc e n t as shown in T a b le X I I I . ' The f r a c t io n b o i li n g in th e 425600°F range in c re a s e d from 15 to 20 p e rc e n t.
-
F ig u re 10 shows th e e f f e c t o f c a t a ly s t d e a c tiv a tio n on h y d ro c ra c k ­
in g in ru n C R !!.
T h is f ig u r e shows th e d i s t i l l a t i o n
cu rv e s f o r th e
56
f i r s t and l a s t p ro d u c ts fro m t h i s ru n .
In e ig h t h o u rs , th e t o t a l
d i s t i l l a t e y i e l d decreased from 69 to 59 p e rc e n t.
tille d
The f r a c t io n d i s ­
below 4 2 5 °F decreased fro m 15 to 10 p e rc e n t.
Run CR!2 was made w ith MSU c a t a ly s t ST K -5-2-6 (C o-N i-M o) a t th e
same c o n d itio n s as ru n CRTl.
The i n i t i a l
a c t i v i t y o f t h i s c a t a ly s t is
. com parable to S T K -5 -2 -2 , b u t i t appears t o be a l i t t l e
more s ta b le
w ith re s p e c t t o s u l f u r re m o va l.
T a b le X I I I shows t h a t t h i s c a t a ly s t has h ig h h y d ro c ra c k in g a c t i v ­
i t y w h ich caused th e r e a c t o r t o become plugged a f t e r e ig h t hours o f
o p e r a tio n .
S u lf u r removal and n itr o g e n removal decrea sed by 8 and 48
p e rc e n t, r e s p e c t iv e ly ,in 2 hours in d ic a t in g a r a p id r a t e o f coke depo­
s it io n .
As A ppendix C shows, th e s u p p o rt used f o r S T K -5 -2 -6 has la r g e r
pores th a n th e s u p p o rt used f o r S T K -5 -2 -2 .
T h is c o u ld be th e reason
t h a t th e fo rm e r was s l i g h t l y more s ta b le than th e l a t t e r .
I t is o b v io u s fro m th e s e ru n s
t h a t th e MSU c a t a ly s t s were much
to o u n s ta b le to be o f any im p o rta n c e .
T h is r a p id d e c lin e in a c t i v i t y
c o u ld be due to an u n fa v o ra b le p o r e - s iz e d i s t r i b u t i o n due to th e
method o f p r e p a r a tio n .
I t is a ls o a p p a re n t t h a t th e h ig h te m p e ra tu re
i s c a u s in g e x c e s s iv e c o k in g w h ich causes c a t a ly s t p o is o n in g and r e a c t o r
p lu g g in g .
The e f f e c t o f te m p e ra tu re on c a t a ly s t d e a c tiv a tio n is d i s ­
cussed in th e n e x t s e c tio n .
5
7
HR-801
STK-5-2-2
PERCENT DESULFURIZATION
STK-5-2-6
I
i
I i
I
TOTAL HOURS ON OIL
F
IG
U
R
E8
.
E
F
F
E
C
TO
FC
A
T
A
L
Y
S
TD
E
A
C
T
IV
A
T
IO
NO
NS
U
L
F
U
RR
E
M
O
V
A
L
58
HR -801
STK-5-2-2
PERCENT DENITROGENATION
STK-5-2-6
TOTAL HOURS ON OIL
F
IG
U
R
E9
.
E
F
F
E
C
TO
FC
A
T
A
L
Y
S
TD
E
A
C
T
IV
A
T
IO
NO
NN
IT
R
O
G
E
NR
E
M
O
V
A
L
5
9
SYNTHOIL
TEMPERATURE, DEGREES F
Hours on Oil
Catalyst:STK-5-2-2
Temperature:
C
90 100
VOLUME PERCENT DISTILLED
FIGURE 10.
EFFECT OF CATALYST DEACTIVATION ON HYDROCRACKING
AT HIGH TEMPERATURE
60
E f f e c t o f te m p e ra tu re on c a t a ly s t d e a c t iv a t io n .
Runs CRll and
CRTS were made w ith th e same c a t a ly s t and o p e ra tin g c o n d itio n s b u t a t
\
d i f f e r e n t te m p e ra tu re s .
T h is was done to d e te rm in e i f th e amount o f
carbon laydown c o u ld be decreased a p p re c ia b ly by d e c re a s in g th e tem­
p e ra tu re from 445°C to 410°C.
The da ta f o r th e se ru n s a re g iv e n in
T able X I I and Appendix D.
F ig u re 11 shows how th e s u l f u r and n itr o g e n rem oval decreased as
a fu n c t io n o f tim e a t th e two te m p e ra tu re s .
T h is f ig u r e shows t h a t a t
th e lo w e r te m p e ra tu re th e r a te o f c a t a ly s t p o is o n in g was s i g n i f i c a n t l y
lo w e r.
.
-
In f a c t , a f t e r a b o u t 6 h o u rs , th e b e s t n itr o g e n rem oval was g iv e n
a t th e lo w e r te m p e ra tu re .
I t a ls o appears t h a t th e s u l f u r removal
cu rve s would c ro s s a f t e r abo ut 20 hours o f o p e r a tio n „
F ig u re 12 g iv e s th e d i s t i l l a t i o n
p ro d u c ts ta k e n in run CR!5.
cu rve s f o r . r u n C R ll.
cu rve s f o r th e f i r s t and la s t
F ig u re 10 shows com parable d i s t i l l a t i o n
These two f ig u r e s show t h a t as te m p e ra tu re is
decre a se d , th e r a te o f decay o f h y d ro c ra c k in g a c t i v i t y , d e cre a se s.
e ig h t hours a t th e h ig h e r te m p e ra tu re , th e t o t a l d i s t i l l a t e
creased by 14 p e rc e n t.
In
y ie ld de­
In e ig h t h o u r s ,a t th e lo w e r te m p e ra tu re , t h e .
decrease was o n ly 6 p e rc e n t.
These two ru n s show t h a t c a t a ly s t s t a b i l i t y was g r e a t ly enhanced by
d e c re a s in g th e ru n te m p e ra tu re fro m 445°C to 410°C.
However, s u l f u r
61
O
% DeS
A
% DeN
iao 0C
"PERCENT HETEROATOM REMOVAL
Catalyst:STK-5-2-2
— -A —
TOTAL HOURS ON OIL
F
IG
U
R
E1
1
.
E
F
F
E
C
TO
FT
E
M
P
E
R
A
T
U
R
EO
NC
A
T
A
L
Y
S
TD
E
A
C
T
IV
A
T
IO
N
6
2
SYNTHOIL
TEMPERATURE, DEGREES F
Hours on Oil
Catalyst: STK-5-2-2
90
IOO
VOLUME PERCENT DISTILLED
FIGURE 12.
EFFECT OF CATALYST DEACTIVATION ON HYDROCRACKING
AT LOW TEMPERATURE
63
and n itr o g e n rem oval and h y d ro c ra c k in g are more d i f f i c u l t a t th e lowerte m p e ra tu re .
T w o -s te p -h y d ro tre a tin g r u n .
Runs CRl3 and CR!4 were made to d e te r
mine i f adequate s u l f u r and n itr o g e n removal c o u ld be o b ta in e d in a two
s te p h y d r o tr e a tin g run a t a te m p e ra tu re o f 410°C.
Run CR!3 t r e a te d S y n th o il w ith S h e ll 344 (C o-M o).
A f t e r two hours
o f o p e r a tio n , th e p ro d u c t from t h i s run was c o lle c t e d t o be used as a
fe e d s to c k f o r ru n CR!4 .
Small samples were taken d u r in g run CRl3 f o r
s u l f u r and n itr o g e n a n a ly s is , and th e n e t p ro d u c t was th o ro u g h ly mixed
and sampled f o r s u l f u r , n itr o g e n , and h y d ro c ra c k in g a n a ly s is .
The n e t p ro d u c t fro m t h i s
run was then h y d ro tre a te d w ith S h e ll
324 (N i-M o) in run CR!4 a t th e same c o n d itio n s as in run CR!3,
T h is
run o n ly la s te d e ig h t hours due to th e lim it e d amount o f fe e d s to c k .
T able XIV p re s e n ts th e s u l f u r and n itr o g e n c o n te n t and d i s t i l l a t e
y i e l d f o r each o f th e p ro d u c ts .
th ro u g h 15.
These da ta a re p lo t t e d in F ig u re s 13
In F ig u re s 13 and 14, s u l f u r and n itr o g e n removal d a ta
a re p lo t t e d based on th e s u l f u r and n itr o g e n c o n te n t o f S y n th o il f o r
run CRl3.
For run CR!4 , th e se d a ta a re based on th e s u l f u r and n i t r o ­
gen c o n te n t o f th e fe e d s to c k and o f S y n t h o il.
The d i s t i l l a t i o n
cu rve s
f o r th e n e t p ro d u c t fro m CR!3 and p ro d u c t CRl4 -4 a re shown in F ig u re
15.
64
T a b le X IV .
Two-Step H y d ro tr e a tin g Run D a t a ^
P ro d u ct
CR! 3 ,
’
S h e ll 344
H rs . o n .O il
%N
Y ie ld
I
■ 4
.21
2
8
.22
——
3
13
.23
1 .0 4
——
net
2 -1 3 .5
.21
3
S h e ll 324
3
5
4
7
.
.93
—
LO
CO
CTi
2
'
56
O
<3-
CR! 4 ,
(I)
%S
LO
CO
Run,
C a ta ly s t
.65
66
.145
.68
5 7 ^
.150
.75
65
C o n d i t i o n s : T = 410±5°C
P = 850 p s ig
LHSV = I . 1 -1 .2
Hg=Oil R a tio = 7500 s c f /b b l
(2 ) T em p e ra tu re .d ro p p e d t o 405 °C-
In F ig u re 13 , th e m id d le cu rve shows t h a t a f t e r 13 h o u rs , th e Co-Mo
c a t a ly s t was rem oving 48 p e rc e n t o f th e s u l f u r .
rem oval decreased s lo w ly w ith tim e .
A t 410°C , s u l f u r
D u rin g th e second run , th e Ni-Mo
c a t a ly s t o n ly removed an a d d it io n a l 29 p e rc e n t o f th e s u l f u r a f t e r 7
h o u rs .
T h is c a t a ly s t was a ls o r e l a t i v e l y s ta b le .
The n e t e f f e c t o f
th e tw o -s te p process i s shown in th e upper cu rve in F ig u re 13.
T h is
shows t h a t a f t e r 7 hours o f o p e r a tio n , abo ut 66 p e rc e n t o f th e s u l f u r
in S y n th o il was removed.
A f t e r 7 hours o f o p e ra tio n a t 4 5 0 °C in run
C R !I, 65 p e rc e n t o f th e s u l f u r was removed.
6
5
F ig u re 14 g iv e s th e n itr o g e n d a ta f o r th e se tw o runs in th e same
form as F ig u re 13.
I t shows t h a t th e Co-Mo c a t a ly s t in th e f i r s t s te p
removed a maximum o f 12 p e rc e n t o f th e n itr o g e n i n . S y n t h o il.
In th e
second ru n , th e Ni-Mo c a t a ly s t removed an a d d it io n a l 20 p e rc e n t a f t e r
7 hours o f o p e r a tio n .
The n e t e f f e c t o f th e two ru n s was a n itr o g e n .
removal o f 29 p e rc e n t a f t e r 7 hours o f o p e r a tio n .
In ru n CR2 a f t e r
I hours o f o p e ra tio n a t 450°C, n itr o g e n removal was 35 p e rc e n t.
N itro g e n removal was more s e n s itiv e to c a t a ly s t d e a c tiv a tio n than s u l­
f u r re m o v a l.
However, compared to th e MSU c a t a ly s t te s te d a t 450°C 9
n itr o g e n removal was more s ta b le in th e tw o -s te p r u n .
F ig u re 15 shows th e d i s t i l l a t i o n
run CR!3 and p ro d u c t CR14-4.
tille d
curves f o r th e n e t p ro d u c t from
T h is f ig u r e shows t h a t th e amount d i s ­
in th e 425 t o 600°F range was in c re a s e d by a b o u t 17 p e rc e n t in
run CR!4 r e l a t i v e to th e fe e d s to c k .
T o ta l d i s t i l l a t e y i e l d was i n ­
creased fro m 56 p e rc e n t f o r th e fe e d s to c k to 65 p e rc e n t f o r p ro d u c t
CR!4 -4 .
In run CR3 a f t e r 7 .5 hours a t 450°C, th e t o t a l d i s t i l l a t e
y ie ld was a ls o 65 p e rc e n t.
T h e re fo re , tw o -s te p p ro c e s s in g a t 41O0C g iv e s p ro d u c ts th a t a re
com parable to th o s e made a t 450°C in one s te p .
how ever, p ro lo n g s c a t a ly s t l i f e
The tw o -s te p p ro c e s s ,
because o f th e lo w e r te m p e ra tu re .
66
IOO
Run CR13:Synthoil on Shell 3UU
O
Q Run CRlUrProduct CRl3 on Shell 32U
A
Run CR lU data based on S content of Synthoil
PERCENT DESULFURIZATION
80
---------A
60
Uo
□
0l i l i l i l i l i t
O
2
U
6
8
10
lU
TOTAL HOURS ON OIL
F
IG
U
R
E1
3
.
S
U
L
F
U
RR
E
M
O
V
A
LINT
W
O
-S
T
E
PH
Y
D
R
O
T
R
E
A
T
IN
GR
U
N
6
7
O
Run CR13:Synthoil on Shell 344
□
Run CR14!Product CR13 on Shell 324
A. Run CRl4 data based on N content of Synthoil
TOTAL HOURS ON OIL
F
IG
U
R
El4.
N
IT
R
O
G
E
NR
E
M
O
V
A
LINT
W
O
-S
T
E
PH
Y
D
R
O
T
R
E
A
T
IN
GR
U
N
6
8
SYNTHOIL
TEMPERATURE, DEGREES F
O Run CR13:Shell 3UU
Q Run CR14:Shell 324;
Feedstock- Product
CRl 3
90
100
VOLUME PERCENT DISTILLED
F
IG
U
R
E1
5
. H
Y
D
R
O
C
R
A
C
K
IN
GINT
W
O
-S
T
E
PH
Y
D
R
O
T
R
E
A
T
IN
GR
U
N
69
Comparison o f c a t a ly s t s .
Due to th e problem s o f r e a c to r p lu g g in g
and r a p id c a t a ly s t d e a c tiv a tio n , i t
is d i f f i c u l t to a c c u r a te ly d e te r ­
mine w h ich c a t a ly s t is th e b e s t f o r h y d r o tr e a tin g S y n t h o il,
t e s ts by Kujawa (29) and Hass (30) a t MSU show t h a t f i l m
A ls o ,
and pore d i f ­
fu s io n l i m i t a t i o n s a re s i g n i f i c a n t enough to in flu e n c e c a t a l y t i c e f f e c ­
tiv e n e s s .
T h is means t h a t th e r e a c tio n s may have been c o n t r o lle d by
d i f f u s io n r a th e r th a n by th e k in e t i c e f f e c t s o f th e c a t a ly s t s .
In
s p it e o f th e se u n c e r t a in t ie s , th e b e s t r e s u lt s a re summarized below .
The h ig h e s t c a t a l y t i c a c t i v i t i e s were o b ta in e d a t th e se c o n d itio n s
Tem perature
= 450±5°C
P ressure
= 800 p s ig
LHSV
= 1.1 ± .1 h r " 1
Hg=Oil R a tio = 10 ,0 0 0 s c f /b b l
The b e s t d e n itro g e n a tio n and h y d ro c ra c k in g were g iv e n by S h e ll 324
(N i-M o ).
Four c a t a ly s t s , in c lu d in g two MSU c a t a ly s t s , gave com parably
h ig h d e s u lf u r iz a t io n .
I t is
im p o rta n t to remember t h a t a l l o f th e se
r e s u lt s were o b ta in e d d u rin g tim e s o f t r a n s ie n t c a t a l y t i c a c t i v i t y .
The b e s t r e s u lt s a re pre se n te d in T able XV.
In g e n e r a l, th e b e s t n itr o g e n removal was o b ta in e d by Ni-Mo c a ta ­
l y s t s , and th e b e s t s u l f u r removal was o b ta in e d by Co-Mo o r Co-Ni-Mo
c a t a ly s t s .
These r e s u lt s p re s e n t no s u r p r is e s .
H y d ro c ra c k in g a c t i v i t y
d id n o t d i f f e r much between c a t a ly s t s b u t was more dependent on
te m p e ra tu re .
T ab le XV.
Summary o f Best R e s u lts
Wt. % DeS .
Wt. IDeN
Y ie ld
36
43
74
6
70
■ 12
S T K -5-2-2
(C o-N i-M o)
7
65
CR 8
HT-400
(Co-Mo)
9
CR 3
HDS-9A
(N i-M o)
8
Run
C a ta ly s t
Mrs. on O il
CR 2
S h e ll 324
(N i-M o)
4
CR 12
ST K -5-2-6
( C o -N i-Mo)
CR 11
64
.
.
64
.
..
60
7
62
6
54
■ 14
.
65
In o r d e r . t o a d e q u a te ly compare c a t a ly s t s , co m p le te in fo r m a tio n i s
needed on th e c a t a ly s t s ' p r o p e r tie s .
Data on s u rfa c e a re a , pore volum e,
and p o r e - s iz e d i s t r i b u t i o n were n o t a v a ila b le f o r some o f th e commer­
c ia l c a t a ly s t s .
A lth o u g h th e pore volume and s u rfa c e area da ta were
known f o r th e s u p p o rts o f th e MSU c a t a ly s t s , th e se p r o p e r tie s w e re ,
unknown f o r th e im pregnated c a t a ly s t .
I t is g e n e r a lly accepted t h a t c a t a ly s t s w ith la r g e pores are
needed to h y d r o tr e a t c o a l- d e r iv e d li q u i d s because o f th e s iz e o f th e
com plex a ro m a tic compounds.
Using th e c y li n d r ic a l
pore a ssu m p tio n , an ,
average pore d ia m e te r ( P .D .). can be c a lc u la te d i f
th e t o t a l s u rfa c e
area and po re volume are known (see A ppendix C ).
S h e ll 324 had th e
.
71
O
h ig h e s t average pore d ia m e te r, 125 A, and showed h ig h a c t i v i t y .
How­
e v e r, i t would be more d e s ir a b le to know th e p o r e - s iz e d i s t r i b u t i o n
so
t h a t a c c u ra te com parisons c o u ld be made.
■ In sum m ation, even i f
th e b e s t r e s u lt s shown in T a b le XV c o u ld be
o b ta in e d f o r a lo n g p e rio d o f tim e , th e p ro d u c t w ould be u n d e s ira b le
as a so urce o f c le a n d i s t i l l a t e
f u e ls .
The h y p o th e tic a l
:
" b e s t" p ro d u c t
would c o n ta in 0 .1 3 p e rc e n t s u l f u r and 0 .6 0 p e rc e n t n itr o g e n .
Less than
50 p e rc e n t o f t h i s
The
p ro d u c t would be d i s t i l l a b l e
below 600°F.
r e s u lt s o b ta in e d by th e in v e s tig a t o r s d e s c rib e d in th e R e lated Research
s e c tio n were much b e t t e r , b u t th e y were o b ta in e d under more seve re
p ro c e s s in g c o n d it io n s .
T h e re fo re , i f
d is tilla te
S y n th o il is to be processed in t o a source o f c le a n
f u e ls in one c a t a l y t i c s te p under c o n d itio n s s im il a r to
th o se used in t h i s
in v e s t ig a t io n , more a c t iv e c a t a ly s t s a re needed.
These c a t a ly s t s sh o u ld be e f f e c t iv e a t r e l a t i v e l y lo w te m p e ra tu re s to
m in im iz e c o k in g and th u s p ro lo n g c a t a ly s t l i f e .
SUMMARY AND CONCLUSIONS
1.
A t a te m p e ra tu re o f a b o u t 550°C in th e ba tch a u to c la v e , th e
e x te n t o f h y d ro c ra c k in g and h eteroatom removal was two to th re e tim e s
h ig h e r th a n a t 450°C.
However, a b o u t h a lf o f th e o r ig i n a l l i q u i d was
c o n v e rte d to coke o r gas a t t h is extrem e te m p e ra tu re .
2.
H y d ro tr e a tin g S y n th o il a t 450°C in th e c o n tin u o u s r e a c to r
can r e s u l t in seve re c a t a ly s t d e a c tiv a tio n and r e a c to r p lu g g in g .
3.
The e x te n t o f h y d ro c ra c k in g and h eteroatom rem oval is
v e r s e ly p r o p o r tio n a l to l i q u i d
in ­
h o u r ly space v e lo c it y and d i r e c t l y
p r o p o r tio n a l to te m p e ra tu re .
4.
The r a t e o f c a t a ly s t d e a c tiv a tio n due to carbon d e p o s itio n
is s t r o n g ly dependent on te m p e ra tu re .
5.
t h e r e fo r e ,
N itro g e n rem oval is more d i f f i c u l t than s u l f u r re m o v a l, and,
is more s e n s it iv e t o changes in LHSV, te m p e ra tu re , and
c a t a ly t ic a c t iv it y .
6.
a c t iv ity ,
The MSU Co-Ni-Mo c a t a ly s t s te s te d e x h ib ite d h ig h i n i t i a l
b u t v e ry lo w r e s is ta n c e to d e a c tiv a tio n a t 450°C compared
to a com m ercial Co-Mo c a t a ly s t .
7.
H y d ro tre a tin g S y n th o il in two s e p a ra te c a t a l y t i c steps a t
410°C r e s u lt e d in p ro d u c ts t h a t were com parable to th o s e produced in
one s te p runs a t 450°C.
lo w e r te m p e ra tu re .
C a t a ly t ic a c t i v i t y was more s ta b le a t th e
■
73
8.
In g e n e ra l, Co-Mo and Co-Ni-Mo c a t a ly s t s had th e h ig h e s t
d e s u lf u r iz a t io n a c t i v i t y , and Ni-Mo c a t a ly s t s had th e h ig h e s t d e n it r o g e n a tio n a c t i v i t y . .
9.
The b e s t n itr o g e n re m o v a l, 43%, Was o b ta in e d w ith S h e ll 324
(N i-M o ) a f t e r f o u r hours o f r e a c to r o p e ra tio n a t th e c o n d itio n s g iv e n
on page 69.
10.
The b e s t s u l f u r re m o v a l, 70%, was o b ta in e d w ith MSU c a t a ly s t
S T K -5-2-6 (C o-N i-M o) a f t e r seven hours o f r e a c to r o p e ra tio n a t th e
c o n d itio n s g iv e n on page 69.
11.
On th e ave ra g e , th e d i s t i l l a t e y ie ld below 700°F was i n ­
creased from 44% f o r S y n th o il to ab o u t 60% f o r th e p ro d u c ts .
, 12.
More d e t a ile d c h a r a c t e r iz a t io n o f c a t a ly s t s s h a ll be a v a i l ­
a b le t o p ro v id e a b e t t e r u n d e rs ta n d in g o f c a t a l y t i c a c t i v i t y .
.
1.
RECOMMENDATIONS FOR FUTURE STUDIES
Due to c a t a ly s t d e a c tiv a tio n , o n ly one s e t o f o p e ra tin g
c o n d itio n s shou ld be used in each f u t u r e 12 hour ru n .
2.
The te m p e ra tu re sh o u ld be o p tim iz e d to m axim ize c a t a ly t ic ,
a c t i v i t y w h ile m in im iz in g gas fo rm a tio n and carbon d e p o s i­
t io n .
3.
The h y d r o g e n :o iI r a t i o
sh o u ld be o p tim iz e d by v a ry in g o n ly
th e hydrogen flo w r a te in th re e o r more in d iv id u a l ru n s.
4.
A minimum p re s s u re o f 1000 p s ig sh o u ld be used.
I f p r a c t i­
c a l, th e r e a c to r system sh o u ld be m o d ifie d to han dle p re s ­
sures o f 1500 p s ig o r h ig h e r.
5. .
.
A lo n g e r r e a c to r sh o u ld be used so t h a t th e c a t a ly s t bed
w i l l occupy 24 to 30 in c h e s .
The lo n g e r c a t a ly s t bed w i l l
e n a b le h ig h e r l i q u i d flo w ra te s to be used, and f i l m
i n t e r p a r t i c l e d if f u s io n
6.
li m i t a t i o n s w i l l
and
be reduced.
C h ro m a to g ra p h ic a n a ly s is o f th e e x i t gases sh o u ld be p e r­
form ed so t h a t a m a te ria l balance may be made on th e r e a c to r
7.
C o n ve rsio n o f th e r e s id u e and a s p h a lte n e f r a c t io n s to o i l s
c o u ld be d e te rm in e d by s o lv e n t e x t r a c tio n te c h n iq u e s .
The
amounts o f s a tu r a te , a ro m a tic , and p o la r compounds in th e
o i l f r a c t io n c o u ld be de te rm in e d by c la y - g e l p e r c o la tio n
m ethods.
75
MSU p repa red c a t a ly s t s sh o u ld be a n a ly z e d f o r t o t a l s u rfa c e
area and t o t a l pore volum e to d e term ine w h at e f f e c t s th e s e
p r o p e r tie s have on c a t a ly s t perform an ce.
LITERATURE CITED
LITERATURE CITED
1.
N a tio n a l Academy o f S c ie n c e s , Assessment Of T echnology f o r th e
L iq u e fa c tio n o f COal: Summary, DOE R eport FE/12 1 6 -2 , December
1.977, p p . 1 -1 6 .
2.
Workshop on A lte r n a te Energy S t r a t e g ie s , "E n e rg y: G lo b a l
P ro sp e cts 1 9 8 5 -2 0 0 0 ," Tim e, May 23, 1977, 109, p. 63.
3.
A s s is ta n t S e c re ta ry o f Energy T e ch n o lo g y, F o s s il Energy Research
' and Development Program o f th e U.S. Departm ent o f E n e rg y, DOE
R e port ET-0013 ( 7 8 ) , March 1978, pp. 65-67 .
' '
"
4.
De R o sset, Armand J . - e t a l . , C h a ra c te riz a tio n o f Coal L iq u id s ,
ERDA R e port FE -2010-09, March 1977, pp. 2 -1 0 .
5.
W h ite , P h i l l i p C. and Z a h ra d n ik , R. L . , Coal L iq u e f a c t io n , ERDA
Q u a r te r ly R e p o rt, A p r il- J u n e 1976, pp. 11-15.
6.
Salmon, R ., Oak Ridge N a tio n a l L a b o ra to ry , E v a lu a tio n o f th e
S y n th o il P ro ce ss, V o l. I I , ERDA R eport 0RNL-5210, June 1977,
pp. 4 -1 8 .
7.
A c z e l, Thomas e t a l . , Chemical P ro p e rtie s o f S y n th o il P roducts
and Feeds, Summary o f F in a l R e p o rt, DOE R eport MERC-8007-1,
F e b ru a ry 1977, pp. 4 -1 8 .
,
8.
C a lle n , R. B. e t a l . , "U p g ra d in g Coal L iq u id s to Gas T u rb in e F u e ls .
I . A n a ly t ic a l C h a ra c te riz a tio n o f Coal L iq u id s , " I n d u s t r ia l and
E n g in e e rin g C h e m is try , P ro d u ct Research and D evelopm ent, V o l. 1 5 ,
No. 4 , 1976, p. 227.
9.
U.S. Energy Research and Development A d m in is tr a tio n , S c i e n t i f i c
Resources R e le va n t to th e C a t a ly t ic Problems in th e C onversion o f
C o a l, D iv is io n o f F o s s il Energy Research, 1976.
10.
S m ith , J . M ., Chemical E n g in e e rin g K in e t ic s , 2nd E d it io n , McGrawH i l l , I n c . , New Y o rk , NY, 1970.
11.
Thomas, C h arles L . , C a t a ly t ic Process and Proven C a ta ly s ts ,
Academic P re ss, New Y o rk, NY, 1970.
12.
G ates, Bruce G. e t a l . , K in e tic s and Mechanisms o f D e s u lf u r iz a t io n
and D e n itro g e n a tio n o f C o a l-D e riv e d L iq u id s , DOE R e port F E -2028-9,
A ugust 25, 1977, pp. 1 -6 . .
78
13.
R u e th e r, John A . , . " K in e t ic s o f H e te ro g e n e o u sly C a ta lyze d H y d r o li­
q u e fa c t io n , " I n d u s t r ia l and E n g in e e rin g C h e m is try , Process Design
and D evelopm ent, V o l. 1 6 , No. 2Y'1~9775 pp. 249 -2 53. -
14.
Ocampo, A q u ile s e t a l . , " D e a c tiv a tio n o f H y d ro d e s u lfu r iz a tio n
C a ta ly s ts under Coal L iq u id s .
1. Loss o f H yd ro g e n a tio n A c t i v i t y
Due to Carbonaceous D e p o s its .
2. Loss o f H yd ro g e n a tio n A c t i v i t y
Due to A d s o rp tio n o f M etal l i e s , " I n d u s t r ia l and E n g in e e rin g
C h e m is try , P ro d u c t Research and Developm ent, V o l. 17, No. I , 1978,
pp. 5 6 -6 7 .
15.
L e v e n s p ie l, O ctave, Chemical R e a ctio n E n g in e e rin g , 2nd E d it io n ,
John W ile y and Sons, I n c . , New Y o rk, NY, 1972.
16.
H e a rs, David E ., "T e s ts f o r T ra n s p o rt L im ita t io n s in E xp erim e ntal
C a t a ly t ic R e a c to rs ," I n d u s t r ia l and E n g in e e rin g C h e m is try , Process
Design and D evelopm ent, V o l . ' 10, No. 4 , 1971, pp. 541-547.
17.
C rynes, B. L . , C a ta ly s ts f o r U pgrading C o a l-D e riv e d L iq u id s , ERDA
R e p o rt FE -2011-8, June 1977, pp. 1 -9 .
18.
De R o sse t, A. J . e t a l . , C h a r a c te r iz a tio n o f Coal L iq u id s , ERDA
R e p o rt FE -2010-09, March 1977.
19.
P e te rs , B. C ,,. Chem icals fro m C o a l. In te r im R e p o rt f o r USBM
S y n t h o il, DOE R eport F E -I5 3 4 -4 9 , O ctober 1977.
20.
P a rr In s tru m e n t Company, I n s t r u c t io n s f o r th e S e rie s 4000 P ressure
R e a ctio n A p p a ra tu s , P a rr Manual No. 141.
21.
Haskel E n g in e e rin g and S upply Company, O p e ra tin g and M aintenance
. I n s t r u c t io n s f o r Haskel A ir D riv e Gas B o o ste r Com pressor, PM 3 .
22.
Am erican S o c ie ty o f T e s tin g and M a te r ia ls , "S ta n d a rd Method o f
T e s t f o r D i s t i l l a t i o n o f P e trole um P ro d u c ts , " 1974 Annual Book o f
' ASTM S ta n d a rd s , P a rt 23, ASTM D e s ig n a tio n D86.
23.
P e te rs , E. D. e t a l . , "D e te rm in a tio n o f S u lf u r and H alogens, Im­
proved Q uartz Tube Combustion A p p a ra tu s ," A n a ly t ic a l C h e m is try ,
V o l. 24, No. 4 , A p r il 1952, pp. 710-714.
24.
Am erican S o c ie ty f o r T e s tin g and M a te r ia ls , "S ta n d a rd Method o f
T e s t f o r S u T fu r in P e trole um O ils (Q u a rtz Tube M e th o d ), " . 1974
Annual Book o f ASTM S ta n d rd s , P a rt 23, ASTM D e s ig n a tio n D1551.
7
9
25.
R u nnion, K. N ., " C a t a ly t ic H yd ro g e n a tio n o f S y n t h o il31' u n p u b lis h e d
M.S, t h e s is , Montana S ta te U n iv e r s it y , 1 977.
26.
F r i t z , J . S. and Schenk, G. H ., Q u a n tita tiv e A n a ly t ic a l C h e m is try ,
3rd E d it io n . (B o sto n , 1 9 7 4 ), pp. 4 4 -6 9 , 191-193.
27.
Lake, G. R. e t a l . , " E f f e c ts o f D ig e s tio n Tem perature on K je ld a h l
A n a ly s is ," A n a ly t ic a l C h e m is try , V o l. 2 3 , No. 1 1 , November 1951,
pp. 1634-1638.
28.
Am erican S o c ie ty f o r T e s tin g and M a te r ia ls , "S ta n d a rd Method o f
T e s t f o r T o ta l N itro g e n in O rga nic M a te ria ls by M o d ifie d K je ld a h l
M e th o d ," 1974 Annual Book o f ASTM S ta n d a rd s, P a rt 30, D e s ia n a tio n
E258.
'
— -----
29.
Kujawa, S. T . , " C a ta ly s ts f o r H y d ro tr e a tin g COED P y r o ly s is O i l , "
u n p u b lis h e d d is s e r t a t io n f o r th e P h .D ., Montana S ta te U n iv e r s it y ,
1978.
30.
Hass, G. R ., " C a t a ly t ic H yd ro g e n a tio n o f S o lv e n t R e fin e d C o a l,"
u n p u b lis h e d d is s e r t a t io n f o r th e P h .D ., Montana S ta te U n iv e r s it y ,
1978.
APPENDICES
APPENDIX A
BATCH RUN CATALYST DESCRIPTION
Run
B33
C a ta ly s t
D e s c r ip tio n ^
MSU STK-IO
• 1 2.0 % MoOg , 1.7% CoOs
(1 /1 6 " e x tr u s io n s )
.
2 .6 % N iO , 0.9%
• FegO3 on a lu m in a ^ ^
B34
MSU S T K -I4
■ 1 7.4 % MoO3 , 2.3% NiO,.
1.8 % CuO on a lu m in a ^ ^
( 1 /1 6 " e x tru s io n s )
B35
BRl
MSU STK- 12
' 1 8 .0 % MoO3 , 2.0% NiO,
(1 /1 6 " e x tr u s io n s )
1.7% ZnO on a lu m in a ^ ^
Cyanamid HDS-20A
1 6.2 % MoO3 , 5.0% CoO
(1 /1 6 " t r i l o b e )
on alu m in a
IT)
A l l c a t a ly s t s p r e s u lfid e d
(2 )
N o rto n 6176 alu m in a s u p p o rt (see Appendix C)
:
APPENDIX B
BATCH RUN DATA
Run(T)
C a ta ly s t^ ^ )
H9 T a k e -u p (^ )
ip s ig j
V o l. %
D is tille d
M t. %
D is tille d
44
43
0.44
1.0 6
——
S y n th o il
Wt. % W t. %
S
N
B33
STK-IO .
725
67
65
0 .2 8
0.8 2
B34
S T K -I4
775
62
63 '
(4 )
(4 )
B35
S T K -I2
800
60
58
0.3 7
0 .8 3
BRl
HDS-20A
1075
77
76
0.0 6
0 .4 0
1.
Run c o n d it io n s :
T = 450±5°C e xce p t B R l, T = 550±°C.
2.
C a ta ly s t p r o p e r tie s g iv e n in Appendix A.
3.
Hg Take-up = I n i t i a l Hg p re s s u re - F in a l Hg p re s s u re measured
a t room te m p e ra tu re .
4.
P ro d u ct c o u ld n o t be a n a ly z e d .
ASTM D i s t i l l a t i o n s
V o l. % D i s t i l l e d
BRl
S y n th o il
435
260
490
519
330
570
580
586
400
632
618
625 .
636
446
682
50
660
663
673
503
—
60 '
680
696
700
583.
--
L B34.
. 420
390
.. 504
509
30
560
40
10
20
. .
Tem perature ( 0 F)
B35 .
B33
70
.
——
——
'
— —
-
— —
r- •”
APPENDIX C
. CONTINUOUS RUN CATALYST DESCRIPTIONS
Co-Mo C a ta ly s ts
Run
CR I ,
C a ta ly s t
S h e ll 344
% CoO
2 .4
% MoOg
9 .9 .
CR 13
CR 7
S .A .
P0V.
P.D.
(m2/ g )
(cc/g)
(R)
195
.
0 .5
.
IOQ
'
Houdry .
3 .0 ..
1 5 .0
300
3 .0
1 5 .0
220
HR-801
CR 8
Harshaw
HT-400
..
0 .5 5
IOO
84
Ni-Mo C a ta ly s ts
Run
C a ta ly s t
% NiO
% MoO3
S .A .
.
(Hi2Zgl)
CR 2 ,
P.V.
P.D.
( c c /g )
(%)
0 .5 0
125
S h e ll 324
2 .7
13.2
160
Cyanamid
3 .5
18 .0
—
3 .0
1 5 .0
300
...
.
3 .0
15 .0
180
■
0.5 0
CR 9 ,
CR 14
CR 3
"
'—*
'
HDS-9A
CR 4
Houdry
—
--
HR-811
CR 5 /
K e tje n
CR 6
K F -I53
no .
MSU Co--Ni-Mo C a ta ly s ts
% CoO
% NiO
STK-5-2-1
0.75
0.48
2 3 .9
ST K -5-2-2
1.15
0 .26
13.1
B
ST K -5-2-6
1.10
0 .2 0
1 5 .5
C
. Run .
C a ta ly s t
CR 10
CR 11
..
.
% MoO3
S upport
.
A
CR 15
CR 12
85
A
N orton
99.85
O
% A l 2O3
Name
% Na2O
PO
S u p p o rt
CO
S u p p o rt Data
0.014
• S .A .
.
p.v. •
P.D.
(m*1
23
/g )
4
( c c /g )
(R)
250
0.9 0
152
0.1 2
.
1.3 3
■ 0.01
240
0.7 0
117
0.37
0 .1 0
200
.0 .7 3
146
6176
K e tje n -
B
98.66
.
003
C
K e tje n 006
Notes
1.
Al I c a t a ly s t s were p r e s u lfid e d .
2.
A ll com m ercial c a t a ly s t s were su p p o rte d on 1 /1 6 -in c h alum ina
e x t r u s io n s .
3.
A ll MSU c a t a ly s t s were su p p o rte d on 1 /1 6 - in c h e x tr u s io n s .
4.
S.A. = t o t a l s u rfa c e area
P.V. = t o t a l pore volume
P.D. - mean pore d ia m e te r
(4 0 ,0 0 0 ) ( P .V .) /( S .A .) .
APPENDIX D
C ontinuous Run Data
Run:
CR I
C a ta ly s t:
S h e ll 344 (Co-Mo)
P re s s u re :
800 p s ig
P ro d u ct
Hrs on
O il
T
(OC)
LHSV
H2 : 0 i l
R a tio ( s c f / b b l )
W t. %
S
W t. %
N
1-2
2 .0
455
2 .0 8
10,000
.3 4
.80
1-3
3 .0
460
2 .0 8
10,000
— —
— ■*-
Note - P lu g g in g o c c u rre d a f t e r 3 .5 hours on o i l .
ASTM D i s t i l l a t i o n :
V o l. %
T ( 0 F)
D is tille d
Temp. Range ( 0 F)
V o l. %
IBP
320
IBP-425
15
25
489
425-600 •
29
50
615
6 00 -7 0 0
26
55
655
Recovery
60
674
Y ie ld
70
63
680
W t. %
72
70
F in a l
D is tille d
0
87
Run:
CR 2
C a ta ly s t:
S h e ll 324 (N i-M o)
P re s s u re :
800 p s ig
P ro d u ct
Hrs on
O il
T
( 0 C)
LHSV
2-1
4 .0
450+5
1 .2
2-2
6 .4
445+5
2 .0
2-3
7 .0
450
2 .0
H2 :Oi I
R a tio ( s c f/ b b T )
.
■W t .
%
W t. :
S
N
10,000
.2 8
.60
10,000
.30
...6 9
10,000 .
.31
.6 9
V o l. %
D is tille d
2-1
2 -2
2 -3
IBP
330
CO
^sJ
O
ASTM D i s t i l l a t i o n :
341
10
400
445
430
20
470
508
30
518
560
40
565
.6 0 6
600
50
61.0
645
650
60
655
680
700
62
— —
65
—
70
690
71
F in a l
Tem perature (0F )
.
—
F in a l
.
487
540 .
F in a l
88
V o l. % D i s t i l l e d
2-2
Temp. Range ( 0F)
2-1
2-3
-IBP-425
13
7
9
425-600
' 35
32
31
600-700
. . 26
,2 6
18
R ecovery
_3
Y ie ld
77
65
62
78
57
57
Wt. % D i s t i l l e d
CR. 3
C a ta ly s t:
HDS-9A (N i-M o ;
P re s s u re :
800 p s ig
T ( 0C)
LHSV
. 3-1
2 .5
450±5
1 .6
10,000
3-2
3 .8
445±5
1 .6
10,000
.19
3-3
7 .5
450
1.0
10,000
.16
.91
10.8
450
1.6
I T , 400
.29
P ro d u c t
3-4
.
H9 : O il R a tio
^ ( s c f / b b l)
Wt. %
S
Mrs. on
O il
O
O
Run:
' _4
.
--
Wt. %
. N ■
.90
.1.03 .
89
ASTM U is t i I l a t i on:
V o l ..% D i s t i l l e d
3-2
Temperature ( 0F)
3-3
3-4
IBP
300
330
10
450
440
455
20
511
■ 495
512
,3 0
568
521
558
40
617
570
596
50
660
628 .
632
60
690
674
642
64
F in a l
--
F in a l
66
706
76
F in a l.
Temp. Range ( 0F)
3-2
.
V o l. 7o D i s t i l l e d
3-3
8
328
3-4
IBP-425
8
425-600
29
.3 6
35
600-700
27
21
23
Recovery
——
i i
—— -
Y ie ld
64
76
64
71
61
Wt. % D i s t i l l e d
60
.
6
90
Run:
CR 4
C a ta ly s t:
HR-811 (Ni-M o)
P re s s u re :
800 p s ig
P ro d u c t
Hrs. on
Oi I
T ( 0C)
.LHSV
H9 : O il R a tio
^ (s c f/b b l)
4-1
3 .3
445±5
1 .5
.
4 -2
5 .0
450
1 .5
10,000
4 -3
7 .8
445±5
1.1
10,000
4-4
10.0
450
2 .0
' Wt. %
. S
10,000
'
W t:. %
N
.98
.
1 0 ,0 0 0 .
.22
.97
.24
. .98
.2 5 .
1.06
Notes
C a t a l y s t prehe ate d to 550°C
I.
2. • C o nversion o f l i q u i d t o gas ~:20%
ASTM D i s t i l l a t i o n :
V o l. % D i s t i l l e d
___________ Temperature ( 0F)
4-2
4-3
IBP
330
270
10
455
466
20
517
30
564
577
40
615
605
50
643
625
56
—
60
675
63
F in a l
.
_______
4 -4
300
.
'
532
;
470
540
578
643
..
680
F in a l
F in a l
91
V o l. % D i s t i l l e d
4-3
Temp. Range ( 0F)
4-2
4-4
IBP-425
6
7
6
425-600
31
30
26
600-700
26
23
24
Y i e ld
63
60
56
54
53
Wt. % D i s t i l l e d
Run:
.
CR 5
C a ta ly s t:
Temp:
K F - I 53 (Ni-M o)
450°C
P re s s u re :
800 p s ig
Hg: O i l R a t i o :
LHSV:
59
10,000 s c b /b b l
2 .0
R e a cto r plugged a f t e r 3 hours o f o p e r a tio n - no p ro d u c ts
c o lle c te d .
92
Run:
CR 6
C a ta ly s t:
KF-153 (Ni-Mo)
P re s s u re :
800 p s ig .
P ro d u c t
Hrs. on
on
T ( uC)
H9: O il R a tio
LHSV
n s c f/b b l
Wt. %
S
Wt. %
H
6-1
5
450±5
1 .5
10,000
.21
.98
6 -2
8 .3
455+5
1 .0
10,000
.28
1.04
Notes
I.
P lu g g in g o c c u rre d d u r in g c o l l e c t i o n o f 6 -2 . .
2.
C o nversion o f l i q u i d
t o gas
% 20%
. -
ASTM D i s t i l l a t i o n :
6-1
V o l. % D i s t i l l e d
T ( 0F)
IBP
363
IBP-425
10
444
. 425-600
7 .
33
20
500 ■
. 600-700
23
30
40
555
600
50
640
60
658 '•
63
F in a l
. Temp. Range ( 0F)
Y i e ld
w t.
%
■ D i s t i ll e d
V o l.
%D is tille d
63
60
93
Run:
CR 7
.C a ta ly s t:
HR-801 (Co-Mo)
'P re s s u re :
800 p s ig
Tem perature:
LHSV:
450°C
1.15
Hg: O il R a tio :
C o nversion o f
10,000 s c f / b b l
l i q u i d t o gas:
^ 12%
H r s . on O il
P ro d u c t
Wt. % S
'W t.
N
%
7-1
3
.18
.97
7-2
5
.20
.9 8
7-4
9
---
.99
7-6
13
.2 2
. 1.00
ASTM D i s t i l l a t i o n :
Temperature I ° F }
V o l. % D i s t i l l e d
7-1
7-2
IBP
267
296
TO
390
20
7-4
7 -6
391
312
426
439 '
428
488
502
499
499'
30
555
575
561 •
547
40
615
. 639
611
50
670
687
674
647
53
—
700
—
r*~
57
60
.
700
.
——
.
.
589
700
700
9
4
V o l. % D i s t i l l e d
7-2
7-4
Temp. Range ( 0F)
7-1
7-6
IBP-425
'13
10
7
9
425-600
24
24
31
33
600-700
20
19
16
18
Recovery
10
12
Ii
'JL
Y ie ld
67
65
68
• 68
64
63
65
67
716
730
750
730
Wt. % D i s t i l l e d
E n d p o in t (0 F)
Run:
CR 8
C a ta ly s t:
HT-400 (Co-Mo)
P re s s u re :
800 p s ig
Tem perature:
P rodu ct
450-455 0C
H r s . on
LHSV
Hg: O il R a tio
(s c f/b b l)
O il
.
Mt. %
W t. %
S
N
8-1
5
1 .2
5,000
.09
.89
8 -2
9
1.2
7,500
.16
1 .0 0 •
1 .2
10,000
.30
1.05
8 -3
12.5
.
Note - P lu g g in g o c c u rre d d u r in g c o l l e c t i o n o f 8-3 -
f l o w unsteady.
ASTM D i s t i l l a t i o n :
V o l . % D i s t i l l ed
Temperature ( 0 F)
8-2
8-1
.'IB P
300
-
-
8 -3
340
336
10. .
395
440
. 452
20
470
505
52T
30
530
555
589 .
40
582
620
657
685
700
50
.
623
53
—
60
667
.
—™
700
V o l. % D i s t i l l e d
8-2
Temp. Range (0 F)
8-1
8-3
IBP-425
13
.9
7
425-600
31
27
24
600-700
23
18
Recovery
—
8
12
F in a l
67
62
62
62
60
724
723
Wt. % D i s t i l l e d
E n dpoint ( 0 F)
66
671
•
.
19
96
Run:
CR 9
C a ta ly s t:
S h e ll 324 (Ni-M o)
P re s s u re :
1000 p s ig .
LHSV:
1.1
Hg: O il R a tio :
10,000 s c f / b b l
P ro d u ct
IH rs . on
O il
T (0 C)
Wt. %
S
Wt. %
N
4
420
.1 4
CO
9 -2 .
6
420
.17
.8 4
445±5
.15
11.5
9-3
CO
9-1
‘
-
Note - Conversion t o gas ~
1% 0 420°C
"
Conversion t o gas ^ 12% 0 445°C •
ASTM D i s t i l l a t i o n
Temperature ( 0 F)
V o l. % D i s t i ll e d
9-1
9-2
. 9-3
IBP
310
330
301
10
410
434
20
1 480
.502
481
30
553
561
529
40
610
626
576
50
660
671
623
700
56
'
405 .
——
60
700
681
65
— —
700
9
7
VoK % D i s t i l l e d
9 -2
Temp. Range ( 0F)
9-1
9 -3
IBP-425
12
10
13
425-600
26
25
32
600-700
20
20
20
9
12
8
67
67
73
. 62
65
71
707
720
719
Recovery
Y i e ld
Wt. % D i s t i l l e d
E n d p o in t ( 0 F)
Run:
CR 10
C a ta ly s t:
STK-5-2-1
P re s s u re :
800 p s ig
Temperature!:
LHSV:
Product.
(Ni-Co-Mo)
440-445 0 C
1.1
H r s . on
O il
Wt. %
S
. .11
W t. %
N
i
H9 : O il R a tio
K s c f/b b l)
■
S
10-1
5
7,500
10-2
9
10,000
.19
1 .0 2
10-3
13
5,000
. 36
1.06
.
98
ASTM D i s t i l l a t i o n :
V o l. % D i s t i l l e d
10-1
.
.
Temperature ( 0 F)
10-2 ;
10-3
IBP
290
300
294
10
405
447
423
20
475
502
■ 495
30
535
543
549 .
40
587
601
605
50
635
659
658
60
675
700
64'
690
.
Temp. Range ( 0 F)
10-1
V o l. % D i s t i ll e d
10-2
.
10-3
IBP-425 .
12
9
10
425-600
30
28
28
600-700
26
23
■ 18
Recovery
-- -
9
Y ie ld
68
69.
56
68
67
58
691
724
658
Mt. % D i s t i l l e d
E n d p o in t ( 0 F)
9
9
Run:
. CR 11
C a ta ly s t:
STK-5-2-2 (Ni-Co-Mo)
P re s s u re :
800 p s ig
LHSV:
1.1
Hg: O il R a tio :
10,000 s c f / b b l
H r s . on
O il
P ro d u ct
Wt.- %
S
T ( 0C)
• M t. %
N
11-1
3
445+5
.04
.73
11-2
5
442-455
.09
.8 9
11-3
7
• 442-445'
.15
.9 9
.11-5
11
445 •
.25
1 .06
Notes
1.
Conversion o f l i q u i d t o gas ~ 16%.
2.
During c o l l e c t i o n o f 11-2 te m p e ra tu re s u d d e n ly jumped t o
455°C then decreased back t o 445°C.
ASTM D i s t i l l a t i o n :
V o l; % D i s t i ll e d
IBP
10
20
30 .
40
50
60
67
70
78
-
________ _________Tem perature
11-2
11-3
11-1
320
399
449
500
561
603
681
700
250
355
423
470
515
565
625
670
700
.
11-5
313
423
310
420
491
493
540
548
591
643
700
598
633
700
100
Temp. Range ( 0 F)
11-1
V o l. % D i s t i ll e d
1 1 -2
. I T-3
IBP-425
15
20
425-600
35
36
. 600-700.
19
23
4
73
Recovery
.
Y i e ld
Wt. % D i s t i l l e d
72
E n d p o in t ( 0 F)
723
Run:
CR 12
C a ta ly s t:
STK-5-2-6 (Ni-Co-Mo)
P re s s u re :
800 p s ig
T em perature:
LHSV:
.
11-5
io .
10
30
32
22
17
4
6
11
83
68
70
88
64
67
704
700
727
•
•
.
'
445±5°C
1 .2
H2 : O il R a tio :
10,000 s c f / b b l
P ro d u ct
12-1
.
12-2
H r s . on O il
Wt.' % ■
S
4 .3
.11
.8 2
6 .3
.13
.9 3
Notes
1.
P lu g g in g o c c u rre d a f t e r 7 .5 hours o f o p e r a t i o n .
2.
Conversion o f l i q u i d t o gas ^ 11%.
M t. %
N
ASTM DISTILLATION:
V o l. % D is t i ll e d
Temperature (0 F)
T'2-l
12-2
IBP
260
299
10
.420
. 417
20
467
491
30
525
540
40
575
589
50
620
643
60
660
68
692
•
700
V o l. % D is t i ll e d
Temp. Range ( 0 F)
12-1
12-2
IBP-425
14
11
425-600
31
31
600-700
27
18
Recovery
—
13
Y ie ld
72
73
73
71
692
760
Wt. % D i s t i l l e d
E n dpoint
102
Run:
CR 13
C a ta ly s t:
S h e ll 344 (Co-Mo)
P re s s u re :
850 p s ig
Tem perature:
410±5°C
Hg: O il R a t io :
LHSV:
7500 s c f / b b l
1 .2
.P ro d u ct
H r s . on O il
13-1
■4
.21 .
.9 3
8
.2 2
.9 3
13
-23
1.04
2 -1 3 .5
.21
13-2 .
13-3
13
Wt. % N
W t. % S
:
.9 3 5
Note - C onversion o f l i q u i d t o gas n, 5%.
ASTM D i s t i l l a t i o n :
V o l. % D i s t i l l e d
13
Temp.
( 0 F)
Temp. Range ( 0F)
.10
IBP
299
IB P -4 2 5
10
423
425-600
20
511
600-700
30
576
Recovery .
40
631
Y i e ld
6 98
Wt. %
700
D is tille d
50
52
.
V o l. %D is t ille d
■-
;
;
. 24
18
6 .
58
56
■
.
103
Run:
CR 14
C a ta ly s t:
S h e ll 324
Feedstock: P ro d u ct from Run CR 13.
P re s s u re :
850 p s ig
Tem perature: ■ 410±5°C
1.1
H2 : O il R a t io :
P rodu ct
13 (Feed)
7500 s c f / b b l
H r s . on O il
—
14-2
3
14-3
5
14-4
...
.
7
W t.
W t. % S
no
O
LHSV:
.
.9 3 5
.1 4 0
.65
.145
.68
.15
.75
Notes
1.
C onversion o f l i q u i d t o gas ~ 6%.
2.
Run ended a f t e r 8 hours due t o e x h a u s tio n o f fe e d s to c k .
%N
.
104
ASTM D i s t i l l a t i o n :
V o l. % D i s t i l l e d
Temperature ( 0 F)
14-3
14-2
14-4
300 ..
357
TO
401
416
20
487
494
... 510
30
536
552
561
40
588
609
609
50
653
661
666
55
—
700
—
60
695
61
700
IBP
311
■
.
700
14-2
V o l. % D i s t i l l e d
14-3
12
11
425-600
29
27
600-700 '
20
Recovery
5
Temp. Range ( 0 F)
IBP-425
.
Y ie ld
VJt. % D i s t i l l e d
E n dpoint ( 0F)
. 1 9 .
.
441 .
5
14-4
9
.
28
22
6.
66
62
65
64
59
63
700
729
700
1
0
5
Run:
CR 15
C a ta ly s t:
STK-5.-2-2
P re ssu re :.
800 p s ig
Tem perature:
LHSV:
410±5°C
1 .2
H g ^ il
R a tio :
10,000 s c f / b b l
P ro d u ct
■ Wt. % S
H rs . on O il
Wt. % N
15-1
3 .3
.2 4
.92
15-3
7 .3
.2 8
.96
15-5
11.3
.3 3
.99
N o te :
Conversion o f l i q u i d t o gas % %
ASTM D i s t i l l a t i o n :
V o l. % D i s t i ll e d
Tem perature ( 0F)
15-3
15-1
. ..
15-5
IBP
292
291
10
402
.4 1 0
20
473
489
508
. 30
527
. 541
571
40
590
592
631
50
619
630
682
56
—
.60
689
63
700
-------
.
:
673
303
449 .
-
700
106
Ib -I
V o l. % D i s t i l l e d
. lb - 3
15-5
IBP-425
14
12
8
425-600
28
30
27
600-700
21
23
21
Recovery
_3
Y ie ld
66
65
62
67
62
60
Temp. Range ( 0F)
'
Wt. % D i s t i l l e d
_6
Notes on Appendix D
1.
C a t a ly s t d e s c r i p t i o n s i n Appendix C,
2.
Mrs. on o i l = t o t a l number o f hours o f o i l - c a t a l y s t c o n t a c t a t th e
tim e o f p ro d u c t c o l l e c t i o n .
3.
E n dpoint f o r d i s t i l l a t i o n s
n oted.
4.
R ecovery: volume p e rc e n t recovered a f t e r s to p p in g d i s t i l l a t i o n
th e volume p e r c e n t d i s t i l l e d above 700°F.
5.
C onversion o f l i q u i d t o gas = volume o f l i q u i d fe d t o r e a c t o r (volume o f p ro d u c ts c o l l e c t e d + e s tim a te d r e a c t o r h o ld - u p )
6.
S y n th o il c o n t a in s 0.44% s u l f u r and 1.06% n i t r o g e n .
i s 700°F o r lo w e r u n le s s o th e r w is e
ASTM D i s t i l l a t i o n :
....
Temp. Range ( 0F)
.
V o l. % D i s t i ll e d
IBP-425
4
425-600
20
600-700
20
Y ie ld
Wt. .% . D i s t i l le d
..
44
43
or
MONTANA STATE
IfS jS S
3 1762 10011899 9
An227
cop.2
DATE
Anderson, Mark Douglas
Catalysts for hydrotreating Synthoil.
I S S U E D TO
* ■
Z