Catalytic hydrogenation of PAMCO solvent-refined coal
by Lee Morgan Henton
A thesis submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE
in Chemical Engineering
Montana State University
© Copyright by Lee Morgan Henton (1978)
Abstract:
Catalytic hydrogenation of Pittsburgh and Midway Coal Company's Solvent-Refined Coal was
accomplished using commercial and lab-prepared catalysts.
Batch bomb tests indicated the relative activity of twenty-nine catalysts; five catalysts were used in the
operation of a continuous reactor.
Liquid hydrogenation products were analyzed by ASTM distillation quartz tube method for sulfur
content, and Macro Kjeldahl method for nitrogen content.
The Ketjen HC-5 catalyst (21% WO3 , 6.5% NiO on alumina) did the best desulfurization, 88%. The
Harshaw HT-400 (15% MoO3 3% CoU on alumina) did the best denitrogenation, 64%.
Temperature, liquid hourly space velocity, and hydrogen-to-oil flow rates were studied with the
continuous reactor; pressure and catalyst amount were held constant at 1000 psig and 70 ml,
respectively As temperature increases, hydrocracking and heteroatom removal increase.
Optimum space velocity varied between 1 and 2, depending on the catalyst. Heteroatom removal
decreased as space velocity increased„ A hydrogen-to-oil ratio of 10,000 SCF/bbl gave the best
hydrocracking and heteroatom removal results at 445° C and liquid hourly space velocity equals 1. -
STATEMENT OF PERMISSION TO COPY
In p re s e n tin g t h i s
re q u ire m e n ts f o r
o f th is
I
th e s is
p ro fe s s o r,
o r,
fu rth e r
fo r
in
in
p a r tia l fu lfillm e n t
o f th e
an a d va n c e d d e g re e a t M on ta n a S t a t e U n i v e r s i t y ,
I a gree t h a t th e L i b r a r y
in s p e c tio n .
th e s is
s h a l l make i t
fre e ly
a v a ila b le
a gree t h a t p e r m is s io n f o r
fo r
e x t e n s iv e c o p y in g
s c h o l a r l y p u r p o s e s may be g r a n t e d by my m a jo r
h is
absence,
by t h e
D ire c to r o f L ib r a r ie s .
u n d e r s t o o d t h a t any c o p y i n g o r p u b l i c a t i o n
o f th is
th e s is
It
is
fo r
f i n a n c i a l g a i n s h a l l n o t be a l l o w e d w i t h o u t my w r i t t e n - p e r m i s s i o n .
S ig n a tu re
Date
lI j
/ ^"7 3
_________
CATALYTIC HYDROGENATION OF PAMCO SOLVENT-REFINED COAL
by
LEE MORGAN HENTON
A t h e s is s u b m itte d i n p a r t i a l f u l f i l l m e n t
o f t h e r e q u i r e m e n t s f o r t h e d e g re e
of
MASTER OF SCIENCE
in
C h e m ic a l
E n g in e e rin g
A pproved :
C halrjm an,
Head,
Gradua4^e-jp€m m rttee
M a jo r
D e p a rtip e frt
L
bevVD
G r a d u a te
Dean
MONTANA STATE UNIVERSITY
Bozeman, M o n ta n a
M arch,
1978
iii
ACKNOWLEDGEMENT
The a u t h o r
th is
w is h a s t o
p r o j e c t by t h e
N a tio n a l
S c ie n c e
M o n ta n a S t a t e
s u p p o rt g iv e n
and C h e m ic a l E n g i n e e r i n g
D e p a r tm e n t o f
U n iv e rs ity .
w is h e s t o
d u rin g
th is
and Ken R u n n io n . f o r
th ro u g h o u t t h i s
re se a rch .
th a n k
D r.
L l o y d B e rg f o r
h is
encouragem ent
p ro je c t.
S p e c i a l t h a n k s go t o
H aas,
fin a n c ia l
E n e rg y R e s e a rc h and D e v e lo p m e n t A d m i n i s t r a t i o n ;
F o u n d a tio n ,
The a u t h o r
and g u i d a n c e
a c k n o w le d g e t h e
fe llo w
th e
re s e a rc h e rs
S te v e Kuj a w a ,
G ary
e x c h a n g e o f i d e a s and i n f o r m a t i o n
TABLE OF CONTENTS
Page
. VITA ■ .........................
'i i
ACKNOWLEDGEMENTS *
iii
L IS T OF TABLES .
.
v ii
L IS T OF FIGUR l S
c * * * * * * * * * * * * * * * * * * * * * * *
v ii. I
■x
ABSTRACT
INTRODUCTION
1
RESEARCH OBJECTIVE
3
BACKGROUND AND THEORY
............................................ ....
Coal L iq u e f a c t io n P rocesses
. . . . . . . . . . . . . . . . .
D i f f e r e n t Types
. . . . . . . . . . . . . . . . . . . . .
SRC I
. . . . . . . . . . . . . . . . . . . . . . . . .
S R C Il
. . . . . . . . . . . . . . . . . . . . . . . . .
4
4
4
F a c to rs in L iq u e fa c tio n
. . . . . . . . . . . . . . . . . . . .
C o a l S t r u c t u r e and C o m p o s i t i o n
. . . . . . . . . . . . .
SRC S t r u c t u r e and C o m p o s i t i o n
. . . . . . . . . . . . . .
D is s o lu t io n o f Coal
. . . . . . . . . . . . . . . . . . .
R e a c tio n to "P ro m p t” In te r m e d ia te s
. . . . ..............................
S l o w e r P r o g r e s s i v e and R e g r e s s i v e R e a c t i o n s
. . . . . . .
D e s u l f u r i z a t i o n R e a c t i o n S te p s . ....................................... . . . .
D e n itr o g e n a tio n R e a c tio n S te p s
. . . . . . . .
....................
C r a c k in g . R e a c t i o n s
. . . . . . . . . . . . . . . . . . .
7
8
10
1313
15
16
18
18
E f f e c t s o f V a r i a b l e s on C o n v e r s i o n and S u l f u r - N i t r o g e n Removal
S o lv e n t
. . . . . . . . . . . . . . . . . . .
....................
H ydrogen E f f e c t s
. . . . . . . . . . . . . . . . . . . .
T e m p e ra tu re E f f e c t s
. .
.............................. . . . . . . . .
P re ssu re E f f e c t s
. . . . . . . . . . . . . . . . . . . .
' H y d r o g e n S u l f i d e and O t h e r E f f e c t s
. . . . . . . . . . .
21
21
23
24
25
26
C a t a l y s i s ’ ............................................ .... ................................. .................................
F a c t o r s i n C a t a l y s t A c t i v i t y , S e l e c t i v i t y , and A c t i v i t y
M a in te n a n c e .
. . . . . . . . . . . . . • # * » . . ®
H
28
28
V
T a b le o f C o n te n ts c o n t ' d
Page
MATERIALS,
EQUIPMENT,
AND PROCEDURES
55
55
Coal C o m p o s itio n
SRC C o m p o s i t i o n
«
S o lv e n t
C o m p o s itio n
Feed t o
th e
P re s u lfid in g
0
6
0
e
e
6
«
6
#
e
C o n tin u o u s R e a cto r
R e a c to r
R o c k in g Bomb R e a c t o r
C o n tin u o u s R e a c to r
54
» » #
6
e
e
6
e
e
«
o
*
e
e
57
57
# # «
6
6
6
*
6
»
6
6
6
6
6
6
6
0
6
6
«
6
59
.
.
59
.
0
6
6
*
0
6
6
6
6
6
6
6
41
44
C o n t i n u o u s Runs
A n a ly t ic a l P rocedures
»
»
6 ,
0
6
0
*
6
6
6
*
6
47
48
RESULTS AND DISCUSSION
6
#
e
*
o
e
e
e
«
e
«
#
P r e l i m i n a r y Runs
. . .
#
»
#
0
6
0
6
6
0
# *
#
Feed S o l u t i o n
, . .
e
o
*
o
e
«
o
«
#
o
o
6
#
6
A n a ly tic a l D e fin itio n s
P r e l i m i n a r y C o n t i n u o u s Run
. . . .
Bomb Runs S t u d y i n g V a r i a b l e s O t h e r Than C a t a l y s t Type
C a t a l y s t S c r e e n i n g Bomb Runs
. . . . . . . . . . . .
C o m p a r is o n s o f Some N i- W , N i-M o and Co--Mo C a t a l y s t s . «
M e ta l C h lo rid e s
Fe and F e -C r C a t a l y s t s
................................................. .... . . .
O th e r E f f e c t s
.
C o n c l u s i o n s o f Bomb T e s t s
......................... . . . . . . .
C o n t i n u o u s Runs
. . . . . . . . . . . .
Summary o f R e s u l t s and C o n t i n u o u s Runs
H y d ro c ra c k in g
.
.................................. .... . .
H e t e r o a t o m Removal
. . . . . . . . . .
CONCLUSIONS
P
48
'4 8
49
• 50
55
56
64
65
65
67
67
67
68
69
72
vi
T a b le o f C o n te n ts c o n t ' d -
2
Page
RECOMMENDATIONS
S h o rt Ter m
Eong l e r r n
.
............................................ ....
.
.
.
.
.
.
.
.
.
.
.
.
LITERATURE CITED
APPENDICES
A p p e n d ix
.
A.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
D e s c rip tio n
o f C a ta ly s ts
A p p e n d ix C.
C o n t i n u o u s Runs:
A p p e n d ix
A v e ra g e P ore
L i s t o f Terms
.
.
.
.
.
.
.
.
.
* .
.
....................
. . . . . . . . . . . . . .
B a t c h Run D ata
A p p e n d ix E
.
.
. . . . . . . . . . . . . . .
A p p e n d ix B .
D,
.
84
.
. .
.............................
Used
84
86
.
. . . . . . .
.....................................................
C o n v e r s i o n o f SRC t o
D ia m e t e r C a l c u l a t i o n s e
.
»
e
e
'
e
»
e
o
e
84
91
92
95
L iq u id
1gQ
. . . . .
102
e
103
e
e
e
e
vii
L IS T OF TABLES
T a b le
. Page
1.
Mean A n a l y t i c a l
V a lu e s f o r
C h e m ic a l E le m e n ts i n
2.
T y p ic a l H y d ro g e n o ly s is M e ta ls
3.
C o a l A n a ly s e s t o
4.
SRC U l t i m a t e
5.
T y p i c a l Compounds i n
6.
S o lv e n t C o m p o s itio n
SRC P r o c e s s
A n a ly s is
.
.
Coal
11
28
.
.
.
. . . . . . . . . .
34
. . . . . . . . . . . . . . .
34
a C o a l-D e riv e d L iq u id
37
, D e s c r i p t i o n , C o n c e n t r a t i o n , and Makeup o f M o b i l ' s
GEC F r a c t i o n A n a l y s i s o f SRC
. . . . . . . . . . . .
38
8.
S o l v e n t R a t i o T e s t Runs .
55
9.
B a tc h
.
.
.
.
.
.
.
.
.
.
.
.
36
.
7.
. . . . . .
. . . . . .
. . . . . . . . . . . . .
C a t a l y s t s T e s t e d by M e t a l Type
. . . . . . . . .
Q u a lity
.
57
10.
B a t c h C a t a l y s t s Ranked by D i s t i l l a t e , C u r v e
.
59
11.
B e s t B a tc h
D e s u lfu riz a tio n s
. . . . . . . . . . . . .
65
12. . B e s t B a tc h
D e n itro g e n a tio n s
......................................
55
vL i i
L IS T OF FIGURES
Figure
•
Page
1.
SRC P r o c e s s S c h e m a tic
2.
A R e p re s e n ta tiv e o f B itu m in o u s Coal S tr u c tu r e
3.
Coal D is s o lu t io n
4.
C o n v e r s i o n o f B i t u m i n o u s C o a l w i t h R a p id H e a t i n g
a t 400°C .
. . . . .
....................................... . . . . . . .
Top i n T e t r a l i n ................................................. ....
B o tto m i n N a p h t h a l e n e ....................................... ....
A u t o c l a v e 1 and H e a r e r
6.
C o n tin u o u s R e a c to r
7.
P ro d u ct
8.
D is tilla tio n
.
1 Compared t o
D is tilla tio n
.
.
.
.
.
and R e a c t i o n M o d e l . . . . . . . . . .
5.
v9 .
6
» .
.
.
.
.
.
.
7 :2
.
.
.
.
.
.
.
S o lu tio n
.
.
.
.
.
.
.
.
.
.
*
.
14
17
.
.
.
.
3 :2 S o lu tio n
Feed
3 : 2 S o l u t i o n " Feed
10.
E f f e c t o f T e m p e r a t u r e on H y d r o c r a c k i n g by STK-7
11.
E f f e c t o f LHSV on H y d r o c r a c k i n g b y • H T -400
12.
E f f e c t o f H g ,R a tio
13.
P erce n t
D e s u lfu riz a tio n
vs.
14.
P erce n t
D e n itro g e n a tio n
15.
P erce n t
16.
on H y d r o c r a c k i n g
40
42
Feed . . . . . . . .
o f H T -4 0 0 P r o d u c t v s .
o f H T -500 P r o d u c t v s .
.
9
.■52
.
52
.
63
. . . .
70
. . . . . . .
7 -]
by STK 5 - 2 - 1
. . .
73
T e m p e ra tu re
. . . . . . .
74
vs.
T e m p e ra tu re
. . . . . . .
75
D e s u lfu riz a tio n
vs.
LHSV
. . . . . . . . . . .
76
P erce n t
D e n itro g e n a tio n
vs.
LHSV
.
17.
P erce n t
D e s u lfu riz a tio n
vs.
H ydrogen t o O i l R a tio
18.
P e rce n t
D e n itro g e n a tio n v s .
. . .................................
H ydrogen t o
O il
R a tio
.
. . .
^7
73
■.
79
ix
L is t o f
F ig u re
19.
20.
F ig u re s c o n t 'd
' . .
Page
P e rc e n t D e s u l f u r i z a t i o n v s . H ydrogen t o O i l R a tio
a t D i f f e r e n t L i q u i d H o u r l y Space V e l o c i t i e s
. . . .
P e r c e n t D a n i t r o g e n a t i o n vs." H y d r o g e n t o O i l . R a t i o
■ D i f f e r e n t L i q u i d H o u r l y Space V e l o c i t i e s
. .
at
. .
gg
.
81
X
ABSTRACT
C a t a l y t i c h y d r o g e n a t i o n o f P i t t s b u r g h and M idw ay C o a l C o m pany's S o l v e n t - R e f i n e d Coal- was a c c o m p l i s h e d u s i n g c o m m e r c i a l and
la b -p re p a re d c a t a ly s t s .
B a tc h bomb t e s t s i n d i c a t e d t h e r e l a t i v e a c t i v i t y o f t w e n t y - n i n e
c a t a l y s t s ; f i v e c a t a l y s t s w ere used i n t h e o p e r a t i o n o f a c o n t i n u o u s
re a c to r.
L i q u i d h y d r o g e n a t i o n p r o d u c t s w ere a n a l y z e d by ASTM d i s t i l l a t i o n
q u a r t z t u b e m eth o d f o r s u l f u r c o n t e n t , and M acro K j e l d a h l m ethod f o r
n itro g e n c o n te n t.
The K e t j e n HC-5 c a t a l y s t (21% VJO , 6.5% NiO on a l u m i n a ) d i d t h e
b e s t d e s u l f u r i z a t i o n , 88%.
The H a rsh a w H T-400 (15% MoO , 3% CoLI on
a l u m i n a ) d i d t h e b e s t d e n i t r o g e n a t i o n , 64%.
T e m p e r a t u r e , l i q u i d h o u r l y spa ce v e l o c i t y , and h y d r o g e n - t o - o i l
f l o w r a t e s w ere s t u d i e d w i t h t h e c o n t i n u o u s r e a c t o r ; p r e s s u r e and
c a t a l y s t am ount w ere h e l d c o n s t a n t a t 1000 p s i g and 70 ml-, r e s p e c t i v e l y
As t e m p e r a t u r e
in c re a s e .
in c re a s e s ,
h y d ro c ra c k in g
and h e t e r o a t o m r e m o v a l
Optimum space v e l o c i t y v a r i e d b e tw e e n 1 and 2, d e p e n d in g on t h e
c a ta ly s t.
H e t e r o a t o m r e m o v a l d e c r e a s e d as space v e l o c i t y i n c r e a s e d „
A h y d r o g e n - t o - o i l r a t i o o f 1 0 ,0 0 0 S C F /b b l gave t h e b e s t h y d r o ­
c r a c k i n g and h e t e r o a t o m r e m o v a l r e s u l t s a t 445 C and l i q u i d h o u r l y
space v e l o c i t y e q u a l s I .
INTRODUCTION
As o f
to ta l
1974,
p e tro le u m
e n e r g y consumed i n
re n e w a b le re s o u r c e
c o n s u m p tio n ,
la r g e
th e
s c a le
th e U n ite d
a ffo rd a b le
re s o u rc e s l i k e
Coal i s
S ta te s
( I ).
15% o f t h e
S in c e . o i l i s
and d i s c o v e r y o f new r e s e r v e s a r e l a g g i n g
t h e end o f
next f i f t y
and n a t u r a l g a s a c c o u n t e d f o r
ye a rs,
fu s io n
an i n t e r i m
a v ia b le
o il
is 'a p p r o a c h in g .
are n o t e x p e c te d t o
so u rce o f energy i s
c h o ic e .
a nonb e h in d
S in c e e x o t i c
be c o m m e r c i a l i n
needed.
P roven r e s e r v e s o f c o a l i n
th e
U n ite d
S t a t e s h o l d 3 t i m e s as much e n e r g y as known d o m e s t i c r e s e r v e s o f c r u d e
o il,
n a tu r a l gas,
The n a t u r e
tra n s p o rta tio n
fu e ls
o f c o a l makes i t
up t o
th e re fo re
have t o
fro m c o a l e c o n o m ic a lly
L iq u e fa c tio n
o p e ra te d i n
th e tic
fu e ls
fu e ls
o p e ra te d
crude o i l
to
m in e ra l
more s u l f u r
make d i s t i l l a t e
German l i q u i f i e d
co a l p la n ts
The B u r e a u o f M in e s o p e r a t e d
fro m
and
P ro c e s s in g t e c h ­
o rd e r to
1949 t o
fro m
1953;
1952 t o
w ere n o t e c o n o m i c a l l y c o m p e t a t i v e
Coal l i q u i d s
Much
.
n o t new.
d e m o n s tra tio n p la n t
(1 ,
syste m s;
Many c o a l s c o n t a i n
fe a s ib le .
of coal is
d is c o v e rie s
many u s e s .
e x is tin g
be d e v e l o p e d i n
a c o a l h y d ro g e n a tio n p la n t
p a te d need:
fit
fo r
made f r o m c r u d e o i l .
t h e . 1 9 2 0 ' s and 1 9 3 0 ’ s .
d e riv e d l i q u i d s
( 2).
u n s u ita b le
10% o f c o a l .
th a n c o m b u s tio n
n o lo g y w i l l
and b i t u m e n s
f u e l m ust be l i q u i d
ash a c c o u n t s f o r
n itro g e n
s h a le o i l s ,
U n io n C a r b id e
1 956.
in
a syn­
But c o a l-
lig h t
o f la rg e
3 ).
te c h n o lo g y
FMC COED p y r o l y s i s
is
a g a in b e in g
o il,
H -C o a l,
d e v e lo p e d t o
S y n th o il,
meet a n t i c i ­
and S o l v e n t -
2
R e fin e d C o a l are p r o d u c ts o f c u r r e n t te c h n o lo g y .
g iv e
la r g e
y ie ld s
T h e re fo re ,
o f h ig h
q u a lity
liq u id
th e o b je c t o f t h i s
fu e l,
re se a rch
These s t i l l
h ow ever.
is
fu e l.
- .
t o ,upgrade P i t t s b u r g h
and M id w a y C o a l C o m p a n y's SRC ( S o l v e n t - R e f i n e d C o a l )
d is tilla te
do n o t
in to
a c le a n
RESEARCH 0B3ECTIVE
The o b j e c t o f t h i s
S o lv e n t-R e fin e d
re se a rch
is
c a ta ly tic
C oal (a n u pgrade d c o a l p r o d u c t )
c o n v e r s i o n o f PAMCO's
to
c le a n
d is tilla te
fu e ls . .
A number o f c o m m e r c i a l and l a b - p r e p a r e d
to
h y d ro tre a t
te m p e ra tu re
b o ilin g
a s o lu tio n
o f S o lv e n t-R e fin e d
and p r e s s u r e .
fra c tio n s
th a n th e
p ro d u c t c o n te n t i s
a ls o
The p r o d u c t
o p e ra tio n
h o u rly
a ls o
c a ta ly s ts .
o f a c o n tin u o u s t r i c k l e - b e d
s tu d ie d in
th e
a t h ig h
s h o u l d h a ve more l o w -
re d u ce d s u l f u r
a u to c la v e
P ro m is in g c a t a l y s t s
space v e l o c i t y ,
were used
and n i t r o g e n
d e s ire d .
The r e s e a r c h p l a n i n c l u d e d
tre a tin g
C o a l (SRC)
s o lu tio n
fe e d s o l u t i o n ;
c a ta ly s ts
te s t
w ere e m p lo y e d i n
re a c to r.
h y d ro g e n -to -o il r a t i o ,
c o n tin u o u s r e a c t o r .
s c re e n in g
E ffe c ts
o f h yd ro -
th e
of liq u id
and t e m p e r a t u r e were
BACKGROUND AND THEORY
Coal L i q u i f a c t i o n
P rocesses
D iffe re n t
b e in g
T ypes -
d e v e lo p e d i n
th e
F our t y p e s o f l i q u e f a c t i o n
U .5 .:
T rd p sch c o a l g a s - t o - l i q u i d
p y ro ly s is ,
s y n th e s is ,
■ E xam ples o f t h e p y r o l y s i s
G u lf O i l ' s
tre a tin g
coker
d is tilla te
and a c h a r p r o d u c t
p r o c e s s e s a re
d i r e c t h y d ro g e n a tio n ,
F is c h e r-
and s o l v e n t h y d r o g e n a t i o n .
ty p e
p rocess.
a re :
F M C s COED p r o c e s s and
P ro d u c ts are
a ta r
o il
fo r
h y d ro -
( I ).
D i r e c t h y d r o g e n a t i o n p r o c e s s e s i n c l u d e H y d r o c a r b o n R e s e a rc h
In c .'s
H-COAL, P i t t s b u r g h
E n e rg y R e s e a rc h C e n t e r ' s
C o a l D e v e lo p m e n t C o m p a n y's Z i n c C h l o r i d e
T e c h n o lo g y 's
R is e r C ra c k in g o f c o a l.
va ry w id e ly .
Coal s lu r r y
bed o f c a t a l y s t
tu rb u le n tly
re a c ta n ts
in
th ro u g h
coal p a rtic le s
is
and h y d r o g e n g a s p a s s t h r o u g h
a fix e d
a m o lte n
le s s
p r o c e s s and I n s t i t u t e
Types o f c o n t a c t in g
t h e H-COAL p r o c e s s ;
th ro u g h
S y n t h o i l , Conoco
c a ta ly s t
s a lt
th a n
bed;
coal
s lu rry
bed f o r
10 s e c o n d s i n
th e R is e r
and c a t a l y s t s
an e b u l l a t i n g
and h y d r o g e n p a s s
S y n th o il.
re s id e n c e tim e
o f Gas
fo r
Conoco p a s s e s
p u lv e riz e d
C ra c k in g t u b u la r
re a c to r.
F is c h e r-T ro p a c h
h ig h te m p e ra tu re
s u lfu r
to
and n i t r o g e n
make s h o r t c h a i n
S o lu tio n
s y n th e s is in v o lv e s r e a c tin g
make CO and H^ g a s .
com pounds,
a lc o h o ls
th e n i t
The ga s i s
re a c ts over
and h y d r o c a r b o n s
ste'.am and c o a l a t
fir s t
p u rifie d
a c a t a l y s t bed t o
( 'I ) .
h y d ro g e n a tio n p ro c e s s e s in c lu d e
of
PAMCO1s S o l v e n t -
5
R e fin e d Goal
p ro ce ss,
" C le a n
( SRC), C o n s o l ' s C re sa p p r o j e c t ,
M o rg a n to w n E n e r g y R e s e a rc h C e n t e r ' s " T w o - S t e p , "
and t h e
F u e l s W est" p r o c e s s s p o n s o r e d by S o u t h e r n C a l i f o r n i a
M o b il O i l ,
EPRI ,
th e r e c y c le
p rocess
and Conoco C o a l .
s o lv e n t a n d /o r
s u lfu r
v a rie s
and t h e
th a n t h a t o f th e
s u b s ta n tia lly
o rig in a l
n itro g e n
to
to
th e
o rig in a l
th e
s o lv e n t in
and pumped t o
d is s o lv e r
is
th e
o b je c t o f t h i s
The r a w g a s i s
The c o a l s l u r r y
as m ost o f t h e
u n d is s o lv e d
c o a l m a tte r i s
s o lid s
(ash
c o a l b e in g
d is s o lv e r.
th e
s till
le s s
s o lv e n t-
(5 ).
s lu rrie d
w ith
a r e m ix e d , , heate.d ,
liq u id .
coal s lu rry .
and h y d r o g e n i s
s e p a ra to r
and c o a l r e s i d u e )
&
s lig h tly
The p r o d u c t f r o m t h e
rem ove i m p u r i t i e s
le a v in g
th e
th e s is re se a rch .
s e p a r a t e t h e r a w g a s e s fr o m t h e
tre a te d to
o rig in a l
s o lid
Coal I p ro c e s s
H y d r o g e n and s l u r r y
h ig h p re s s u re
re p o rt.
p r o c e s s s c h e m a tic o f P i t t s b u r g
w ith p u lv e r iz e d
a m ix t a n k .
fla s h e d to
re d u c e d fro m th e
o f th e p ro d u c t i s
and M idw ay C o a l C o m p a n y 's S o l v e n t - R e f i n e d
s ta rts
th is
a t room t e m p e r a t u r e ,
c o a l . ■ The u p g r a d i n g o f t h e
1 shows a s i m p l i f i e d
The p r o c e s s
a s o lid
in
o f th e c o a l re m a in s i n
h y d ro g e n -to -c o a l r a t io
c o a l p r o d u c t f r o m SCR I i s
F ig u re
re c y c le
a c c o rd in g
t h e one o f i n t e r e s t
c o a l m a jo r p r o d u c t i s
and ash c o n t e n t
H ow ever, th e
p ro d u c t,
re fin e d
The m ethod o f h y d r o g e n a d d i t i o n
s o lu tio n
The SRCI p r o c e s s i s
The s o l v e n t - r e f i n e d
c o a l.
coal
E d is o n ,
(4 ).
SRC I -
w ith
E x x o n 's donor s o lv e n t
is
a t h ig h
F iltra tio n
re c y c le d .
te m p e ra tu re ,
s e p a ra te s th e
fro m th e h o t l i q u i d .
The
HYDROGEN
M Y M O C A R 3 0 N O AS
FIR E D PREHEATER
D IS­
SOLVER
S00° F
100M m
SLURRY MIX TANK
£50° F
SULFUR
COAL
SEPARATOR
HYDROGEN
SOLVENT RECYCLE
SLURRY
SOLIDS
COAL'
G ASIFIER
AND
SH IFT
CONVERTER
,FILTEF,*
SOLVENT
RECOV­
ERY
U N IT
COAL
STEAM
LIQUID FUEL TO SOLIDIFICATION
SRC I P r o c e s s
S c h e m a tic
7
s o lid
c o a l re s id u e
hydrogen f o r
is
re a c te d
b o ilin g
■lower b o i l i n g
la r g e
m a te ria l is
s o lid
" s o lv e n t-re fin e d
SRC I I
fro m th e
(5 ,
" re c y c le
m ake-up
th e
SRC 11 l i q u i d s
SRC I I
re c y c le
and g a s e s ,
w ith
le s s
u n it.
s o lv e n t.
T h is
p r o d u c t and a
The s o l i d
fin a l
s o lid
In s te a d ,
liq u id
s o lid
is
p ro d u c t,
c o a l process c a lle d
SRC I p r o c e s s a r e t h a t :
th e
s o lv e n t."
a s o lv e n t re c o v e ry
amount o f l i q u i d
p ro d u c t;
b)
SRC I I .
y ie ld s
may be more f e a s i b l e
can
The
a)
ash i s
it
does n o t use a
some o f t h e h o t p r o d u c t
f o r . use as t h e p r o c e s s s o l v e n t
If
fro m
in
e n te rs
a t room t e m p e r a t u r e .
s o lv e n t- r e fin e d
tw o m a in c h a n g e s f r o m t h e
d iv e rte d
y ie ld
6 ).
- More l i q u i d s
but re ta in e d
filte r
a s m a ll
m a te ria l
c o a l"
be made by a m o d i f i e d
lig h t
to
s e p a ra te d fro m th e
m a te ria l y ie ld s
amount o f
moved,
steam and a i r
th e p ro c e s s .
The h o t l i q u i d
The l o w e r
w ith
not re ­
s tr e a m i s
( 6 ).
are h ig h
enough,
u p g ra d in g
th a n u p g ra d in g th e
th e
a s h -fre e
s o lid
SRC I .
F a c to rs in
L iq u e fa c tio n
A good many f a c t o r s
rank o f c o a l in flu e n c e s
s u lfu r,
n itro g e n ,
in flu e n c e
what p r o d u c ts
oxygen,
ash,
c o n t a m i n a n t s may be c a t a l y t i c ,
w ith th e c a t a ly s t
o r p lu g g in g
A m y ria d o f o t h e r
c o a l-to -liq u id
c o n v e rs io n .
are p o s s ib le .
C o a ls v a r y i n
and t r a c e
m e ta l c o n te n t.
b u t some i n h i b i t
c a ta ly s is
The
Some o f t h o s e
by r e a c t i n g
h e te ro g e n e o u s c a t a l y s t p o re s .
fa c to rs
in flu e n c e
c o a l c o n v e rs io n
and t y p e s
8
o f p ro d u c ts .
L e n g th o f p r o c e s s in g tim e
be v e r y i m p o r t a n t .
n a tu re ,
The i n f l u e n c e
of
c o n fig u ra tio n
s o lu tio n
v a rie s ,
s tru c tu re
a ro m a tic r i n g
fo r
d e riv e d
(9 ).
is
2 .2 0
a ro m a tic ity
p o is o n c a t a l y s t s ,
is
and r e a c t o r
and t y p e o f p r o c e s s i n g .
F ig u re
2 shows a r e p r e s e n t a ­
Coal s t r u c t u r e
is
" c o n s is ts o f
tie d
to g e th e r
of
Illin o is
1 .5 5
No.
6 is
and a r e f i n i n g
C o a l ' s l o w H/C r a t i o
is
a n o th e r
0 .8 6 ,
in d ic a tio n
s ig n ific a n t
a m ounts o f o x y g e n ,
th e s e im p a rt u n d e s ira b le
s u lfu r
q u a litie s
to
fu e l p ro d u c ts ,
o r become c o m b u s t i o n p o l l u t a n t s .
phenol s tru c tu re s
and n o t h e t e r o c y c l i c .
In
u s e s o f u p g r a d e d c o a l when t h e p r e s e n c e o f o x y g e n i s
fu e ls ) ,
" it
is
d iffic u lt
d e s ira b le
to
m in im iz e h y d ro g e n c o n s u m p tio n "
is
le s s
and i n o r g a n i c
s u lfu r
iro n
FeS^,
s u lfid e ,
of
and n i t r o g e n .
in
• S u lfu r
w h ile
n a p h th a
le a s t
to
by
l o w e r t h a n m ost f u e l m a t e r i a l s
Rem oval o f o x y g e n i s
(lo w grade
n itro g e n
n a tu re ,
p re s s u re -a n d
o f c o a l c om pared t o p e t r o l e u m .
Compounds c o n t a i n i n g
u s u a lly
6 ' s r a tio
a g e n ts ,
th a n 6 o r 7 r in g s
The H/C r a t i o
No.
Coal c o n ta in s
a b le
o f no l a r g e r
fro m p e tr o le u m .
fra c tio n
tim e
(7 ).
C o a l ' s H/C r a t i o
o il
c a ta ly s t
and C o m p o s i t i o n -
c lu s te rs
r e s id u a l h e a tin g
th e
and r e a c t i o n ,
b itu m in o u s c o a l
lin k a g e " ( 8).
o f re d u c in g
d e p e n d in g on t h e
Coal S t r u c t u r e
b rid g e
s o l v e n t c h e m i c a l and p h y s i c a l
s o l v e n t r a t i o , - am ount and t y p e
te m p e ra tu re
tiv e
of
and t y p e o f p r o c e s s a p p e a r t o
d iffic u lt
rem ove o n l y
c o a l.
am ount i s
s u lfu r
a c c e p tand
( 10) ,
th a n n itr o g e n
are fo u n d i n
and a s m a l l
b e ca u se o x y g e n atom s a re
t o rem ove
M ost i n o r g a n i c
p re se n t
(1 0 ).
s u lfu r
as s u l f a t e
O rg a n ic
is
io n .
'
H
H
I
I
0
1
H
H
S
I
H
H
H
I
z^ . / H H
H
C =O
,H
F ig .
2.
A R e p re s e n ta tiv e o f B itu m in o u s Coal S tr u c tu r e
(? )
10
O rg a n ic
s u lfu r
c o a ls ranges
is
is
m o s tly h e t e r o c y c l i c ; t o t a l
fro m
a c a ta ly s t
s e v e ra l p e rce n t to
p o is o n
and p o l l u t a n t ;
1-2 w e ig h t p e rc e n t i n
m ost c o a l s
An a n a l y s i s o f
h a l f o f th e
10~15/£.
it
is
N itro g e n ,
p re s e n t in
ta b le "
( 11) ,
as com p a re d t o
f r o m K e n t u c k y No.
9 c o a l.
fa c tio n
and r e a c t i o n s .
s u lfid e ,
d is trib u te d
U ltim a te
K e n t u c k y No.
te riz a tio n
M a te ria ls
fro m th e
9 a re g iv e n in
shows a v e r ­
PAMCO1s SRC I
liq u e ­
in
s u rfa c e
a c id ity "
(10)
tra c e
m e t a l s w e re v a r i a b l y
.
( 12) .
s o lv e n t- r e fin e d
th e M a te r ia ls
and C o m p o s i t i o n -
fr a c tio n
is
c o a l and i t s
so u rce c o a l,
s e c tio n ta b le s .
A l t h o u g h no compound b re a k d o w n
c o a l h a s been p u b l i s h e d
by s o l u b i l i t y
I
SYNTHOIL p r o c e s s w ere c o n t a m i n a t e d w i t h
and s i l i c o n ;
a n a ly s e s o f
o f s o lv e n t-re fin e d
of
" S m a ll a m ounts o f T iO ^ on a s i l i c a
th e c a t a ly s t
SRC S t r u c t u r e
T a b le
T r a c e m e t a l s may enhan ce o r i n h i b i t
a lu m in u m ,
th ro u g h
s u lfu r ,
c o n c e n tra tio n s
v a lu e s i n
o r a l u m i n a s u p p o r t can c a u s e a m a rke d i n c r e a s e
fe rro u s
lik e
in
100 c o a l s " r e v e a l e d t h e p r e s e n c e o f w e l l o v e r
age c o a l m e t a l c o n c e n t r a t i o n s
Aged c a t a l y s t p e l l e t s
c o n c e n tra tio n
( 11) .
e le m e n ts o f th e p e r i o d i c
c a ta ly s ts
s u lfu r
in
p ra c tic e d
th e l i t e r a t u r e ,
ch a ra c­
by s e v e r a l p e o p l e
(see
s e c tio n ).
The s u l f u r
and ash l e v e l s
c o a l, b u t th e n itr o g e n
80% and d e - a s h i n g
le v e l
a b o u t 97L
/a.
is
o f SRC a r e much l e s s t h a n i t s
n o t re d u c e d .
D e s u lfu riz a tio n
is
p a re n t
about
11
T a b le
I
M ean analytical values for chem ical
elem ents in coal ( 1 1 )
C o n s ti­
tu e n t
As
B
Be
Br
Cd
Co
Cr
Cu
F
Ga
Ge
Hg
Mn
Mo
Ni
P
Pb
Sb
Se
Sn
V
Zn
Zr
■
<•-
Al
Ca
Cl
Fe
,• •*
; •
K
Mg
Na
Si
Ti
moisture
ash
M ean,
ppm
14.02
102.21
1.61
15.42
2.52
9.57
13.75
15.16
60.94
3.12
6.59
0.20
49.40
7.54
21.07
71.10
34.78
1.26
2.08
4.79
32.71
272.29
72.46
12 900
7700
1400
19 200
1600
500
500
24 900
700
9.05%
11.44%
V a lu e In
o s h -fre e ,
s o lv e n t r e fin e d
K e n tu c k y
N o. 9 c o a la
S td .
dev.
17.70
54.65
0.82
5.92
7.60
7.26
7.26
8.12
20.99
1.06
6.71
0.20
40.15
5.96
12.35
72.81
43.69
1.32
1.10
6.15
12.03
694.23
57.78
4500
5500
1400
7900
600
400
400
8000
200
5.05%
2.89%
1
6.2
0.8
;. . /
/ c
1.7
.
:
...
^
.
.
.
2.8
65
167
196
2.6
96
0.00%
0.051%
Source: Illinois State Geological Survey a Data obtained by Manahan's research
group, prim arily by neutron activation analysis.
■ ' '• .. - N.".---•
V.
v; ...-WJ'* --
f
12
The H/C atom r a t i o
vs.
0 ,8 3 7 ,
e n tly
o f SRC i s
even t h o u g h h y d r o g e n i s
h y d ro g e n fro m th e
lo w e r th a n th e p a r e n t c o a l ,
consumed i n
c o a l goes t o
th e p ro c e s s .
d e s u lfu riz a tio n
0 /7 6 9
A ppar­
( m a k in g H^S)
and
m a k in g h y d r o c a r b o n g a s e s .
A g ra d ie n t e lu t io n
and H-COAL p r o d u c t s
was p e r f o r m e d by a M o b i l O i l team ( 1 3 ) ,
a n a ly s is c o n s is te d o f
s o lu b ility
s e p a ra tin g
SRC i s
H-COAL,
a s p h a lte n e ,
a s p h a lte n e
th e
liq u id s
in to
th irte e n
SYNTHOIL,
The
d iffe re n t
fra c tio n s .
S o lv e n t-re fin e d
SYNTHOIL,
c h r o m a t o g r a p h i c a n a l y s i s o f SRC,
c o a l has much more a s p h a l t e n e c o n t e n t t h a n
o r p e tr o le u m re s id u u m .
w h ile
E ig h ty -o n e
12 w e i g h t p e r c e n t L i g h t
w e ig h t p e rc e n t
A r a b i a n R esiduum i s
(1 3 ).
S e v e r a l g e n e r a l t r e n d s w ere l e a r n e d fr o m c h a r a c t e r i z i n g
o f th e
th irte e n
fr a c tio n s
" a r e more a r o m a t i c t h a n t h e
(and t h e r e f o r e
s iz e s )
s m a lle r th a n p e tro le u m
(c )
N itro g e n
fra c tio n s ,
do
th e m s e lv e s :
lig h t
a) The p o l a r ,
fra c tio n s ,
of coal liq u id
but s u lfu r
r e s i d u a c o m p o n e n ts o f t h e
c o n te n t i s
n e a rly
heavy f r a c t i o n s
b ) The m o l e c u l a r w e i g h t s
c o m p o n e n ts a r e
and o x y g e n c o n t e n t o f SRC i s
each
s ig n ific a n tly
same f r a c t i o n .
h ig h e s t i n
c o n s ta n t in
th e
a ll
a s p h a lte n e
fr a c tio n s
(1 3 ).
•
13
D is s o lu tio n
o f Coal -
s o lv e n t c o a l - I i q u e f a c tio n ,
c o a l --------- >
tio n
A c c o rd in g
o ils
a s p h a l t e n e - —'— ^
o f c o a l ta k e s p la c e
o i l ' (4 )„.
a t h ig h
an a u t o c l a v e )
The s l o w e s t r e a c t i o n
is
fro m
25 t i m e s
H ow ever, r e c e n t
v e rte d to
ene t o
o il
o il
s te p .
have l e d t o
th e
ve ry
as f a s t
s tu d ie s
h e a te d i n
c lu s te rs
appear s
a)
th re e
a n d 're s id u e
th e
420°D and 80 ■
th e
(14-’) f
c o a l — ------
■■
c o a l can s o m e tim e s be c o n ­
and s h o r t r e s i d e n c e
ve ry
tim e
c o n v e rs io n .
a s o lv e n t to
are r a p i d l y
o ils ,
s o lu b le
ty p e s o f
(to w a rd o i l )
R e a c tio n to
"p ro m p t"
( 8).
ben ze n e b u t n o t p e n t a n e ;
s lo w p r o g r e s s i v e
in
(up t o
" d e p o ly m e riz a ­
s lo w a s p h a l t ­
e x p e rim e n ts
F ig u re
3 d is p la y s
(4 ).
The f i r s t
fa c to r
known t h a t
w it h o u t g o in g th ro u g h - th e
b u t n o t b e n z e n e ; and d) r e s i d u e ,
S e m i- c o k e
a s equen ce o f r e a c t i o n s :
th e presence o f s o lv e n ts "
show t h a t
R a p id h e a t i n g
b o n d s b e tw e e n r i n g
in te rm e d ia te s
is
t r a d i t i o n a l m odel o f
a s p h a l t e n e ---------> o i l , w i t h
q u ic k ly ,
When c o a l i s
in
in
a new m odel f o r ; c o a l - t o - o i l
new m odel
s o lu b le
It
in
te m p e ra tu re s
in
b e in g
W e lle r 's
appear l a s t
a tm o s p h e r e i n i t i a l l y
a s p h a lte n e
to
broken.
in
p e n ta n e ; b)
a s p h a lto ls ,
not in c lu d in g
e a s ily -b ro k e n
a s p h a lte n e s ,
s o lu b le
in
In te rm e d ia te s -
f i r s t , c o a l r e a c tio n ,
b reak-up
ra p id
(to
0
in to
re la tiv e ly
s e m i-c o k e )
re a c tio n s .
(4 ).
Time i s
h e a tin g
p y rid in e
ash.
s p e c ie s th e n p ro c e e d w it h
and r e g r e s s i v e
Only, w i t h
th e
F our t y p e s o f p r o m p t
do n o t r e a c t p r o g r e s s i v e l y
"P ro m p t"
in te r m e d ia te s .
c)
4D0°C,
th e
th e im p o rta n t
fo u r
s p e c ie s o f
and q u e n c h in g
are th e
14
PRODUCT
OIL
COAL
SEMI - COKE
► RESIDUE
A w o r k i n g model of reaction paths in donor solvent
liquefaction of a bituminous vitrinite.
The curved lines
at the left represent rapid cleavage of scissile bonds to
yield prompt liquefaction int e r m e d i a t e s .
These comprise
a large number of distinct species forming a hierarchy of
increasing polarity toward the bottom of the f i g u r e , and
also a prompt residue.
Relatively slow progressive
r e a c t i o n s , indicated by solid lines,
intermediates
to oil.
convert
the prompt
The progressive reactions compete
w i t h relatively slow regressive r e a c t i o n s , indicated by
dot-dash l i n e s , that lead to s e m i - c o k e .
F ig . 3
Coal
D is s o lu tio n
and R e a c t i o n M o d e l ( 4 ) .
15
"p ro m p t"
in te rm e d ia te s
n o tic e d .
The r a p i d r e a c t i o n s
presence o r
c a ta ly s t;
are t h e r m a l;
a b se n ce o f - h y d r o g e n ;
c)
b)
hydrogen donor p r o p e r t i e s
"The i n i t i a l
m o le c u la r w e ig h t
some f r a g m e n t s h a v i n g
w e ig h ts g r e a te r
f r a g m e n t s a r e b e tw e e n 300 and 9 0 0 "
c o a ls v a ry
fro m
2000 t o
w e ig h ts r a n g in g
up t o
1 2 ,0 0 0 ;
th e
o f th e
tim e
th a n
u s in g h yd ro g e n o n ly
" E a rly
d is s o lu tio n
c o a l" ; s in c e
th e
in c re a s e
a ro m a tic ity
in
c o a l's
hydrogen i s
makes sen se
"P rom pt l i q u e f a c t i o n
c y c lic
a ro m a tic
S lo w e r
s tru c tu re s "
P ro g re s s iv e
y ie ld e d
se ve ra l
is
b im o d a l,
and t h e
a d d itio n a l
w ith
re m a in in g
w e i g h t , o f m ost
and r e s i d u a l o i l s
have m o l e c u l a r
(1 5 ).
fro m th e
p ro d u c ts
th e
The m o l e c u l a r
F o r t y p e r c e n t o f t h e o x y g e n and s u l f u r
q u ic k ly ,
(4 ).
2 050,
a)
absence o f a s o l i d
s o lv e n t
d is trib u tio n
(4 ).
ta rs
m illio n s
do n o t depen d o n :
th e presence or
M o b i l O i l d a t a on s h o r t r e a c t i o n
fa c ts ,
th e y
in
coal is
rem oved
c o a l.
a r e more a r o m a t i c t h a n t h e
consumed i n
o rig in a l
h e te ro a to m , re m o v a l,
th e
(4 ).
in te r m e d ia te s c o n ta in r e l a t i v e l y
fe w p o l y ­
(4 ).
and R e g r e s s i v e R e a c t i o n s -
z a t i o n s ca n be made a b o u t t h e p r o d u c t s f r o m
S e ve ra l g e n e r a li­
s lo w r e a c t i o n s
o f th e prom pt
in te rm e d ia te s .
"At l o n g e r t i m e s ,
as does a l s o
th e
te m p e ra tu re s
a ls o
th e
a ro m a tic c o n te n t
( o f th e p ro d u c t)
number o f p o l y c o n d e n s e d a r o m a t i c r i n g s " ( 4 ) .
in c re a s e
t h o s e tw o v a l u e s .
0
in c re a s e s ,
H ig h e r
16
The H/C r a t i o
d e c r e a s e s as r e a c t i o n
Though much h y d r o g e n can be consum ed,
o f g a s and r e - h y d r o g e n a t i n g
L ittle
h yd ro g e n goes to
A s p h a lto ls
re s u lts
if
it
gen d o n o r
'g e ts
s o lv e n t i s
p o in t
s o lv e n t).
(4 ). '
"C o ke f o r m a t i o n
donor
s o lv e n t"
o f th e
(4 ).
s o lv e n t
is
m ost i m p o r t a n t
R e g re s s iv e r e a c t i o n s p re d o m in a te i f
n o t u se d ..
re a c tio n s
th e p ro d u c tio n
ahead' o f h y d ro g e n a tio n o f c o a ly ( s ic )
fro m th e
s lo w r e a c t i o n s .
in c re a s e .
( re c y c le
a r e t h e m ain s o u r c e o f s e m i - c o k e .
th e rm a l c ra c k in g
th e re g r e s s iv e
fo r
s tru c tu re s
h e te ro a to m re m o va l
The h y d r o g e n d o n o r c a p a b i l i t y
th e
and s e v e r i t y
goes m o s t l y
h y d ro a ro m a tic
m a t t e r by h y d r o g e n t r a n s f e r
d u rin g
tim e
A donor
le a d in g
to
s o lv e n t
coke.
a p p a re n tly
a h yd ro ­
suppresses
F ig u re 4 i l l u s t r a t e s
th e
( 4 ).
A b o u t 90/o o f a b i t u m i n o u s c o a l was c o n v e r t e d t o
s o lu b le s
when h e a t e d r a p i d l y
5 m in u t e p e r i o d
is
A fte r
5 m in u te s ,
th e
re a c tio n s
m a rk e d ly
fir s t
c o m p e te .
In t h i s
te tra lin ,
D e s u lfu riz a tio n
o ccu rs at le s s
th e
te tr a lin
or n a p h th a le n e .
re a c tio n to
s lo w e r p r o g r e s s in g
second tim e re g im e ,
n a p h th a le n e ,
s o lv e n t t e t r a l i n .
c o n tin u e d i n
e ith e r
th e re g im e o f r a p i d
decreased in
gen d o n o r
in
"p ro m p t"
S te p s -
hydro
s ta b le
in
th e h y d ro ­
lig h te r
n a p h th a le n e
have t e s t e d m o d e l com pounds t o
p ro d u c ts
(4 ).
d e s u lfu riz a tio n
severe c o n d it io n s th a n h y d r o d e n itr o g e n a tio n
e ra l in v e s tig a to rs
in te rm e d ia te s .
and r e g r e s s i v e
P ro g re s s iv e r e a c t io n s to
R e a c tio n
That
p y rid in e -s o lu b le s
w h ile re m a in in g
b u t c o k e . w a s fo r m e d i n
p y rid in e -
(HDS)
(H D N ).
d e te rm in e ste p
Sev­
17
IO O
,
ASPHALTENES
; ZL
I
._____ i —
.,-ZLv' "
_____J
I s
a
, , . . , . , 0IL
5----------- ------------------------
40
60
Time, Minutes
X
80
GAS
Conversion, % of Coal
(Ivloisfure-and-Ash-Free)
Conversion, % of Coal
(Moisture-and-Ash-Free)
PROMPT RESIDUE
Time, Minutes
F ig . 4.
C o n v e rs io n o f B itu m in o u s C oal w it h
H e a tin g a t 400°C .
Top - i n
B o tto m -
T e tra lin
i n N a p h th a le n e
»
R a p id
18
sequences i n
rin g
s u lfu r
s a tu ra tio n
is
r e m o v a l fr o m
a ro m a tic s ;
n o t n e ce ssa ry
fo r
coal o ils
t h o u g h no n i t r o g e n
D e n itro q e n a tio n
in
th re e
-D e s u lfu riz a tio n
('1 7 ,1 8 ).
A ro m a tic n i t r o g e n
is
rem oved
1)
E q u ilib r iu m h y d ro g e n a tio n o f th e .-n itr o g e n - c o n ta in in g
r i n g t o . .h y d rd a ro m a tic s t r u c t u r e .
2)
C ra c k in g o f r i n g ,
3)
E lim in a tio n
d e te rm in in g
(1 0 ,1 9 ).
s te p
D iffic u lty
o f 3 -rin g
w ith
n itro g e n
o f am ine g r o u p
of
D e la w a re
com pounds was s l o w co m p a re d t o
t i o n -o f th e
U n iv e rs ity
o u te r
rin g s
was s t i l l
re s e a rc h e rs lik e w is e
t r e a t th a n
as ammonia,
rem oval in c re a s e s
U n iv e rs ity
r a p id
is
fo u n d " r e a l "
a m odel raw a n th ra c e n e o i l
NH^.
th e r a t . e -
as t h e
number o f r i n g s
th o u g h hyd ro g e n a ­
O klahom a S t a t e
liq u e fie d
c o a l s much h a r d e r
(1 8 ).
C r a c k i n g R e a c t i o n s - The g o a l o f c o a l h y d r o c r a c k i n g
s e le c tiv e ly
h ydrogen .
c ra c k th e
coal
s tru c tu re
H y d ro g e n g e n e r a t i o n
te c h n o lo g y .
is
"The f u n c t i o n
w ith
.
fo u n d d e n i t r o g e n a t i o n
q u in o lin e ,
(1 9 ).
- -
b e c o m in g an -NH .
th e h y d ro a ro m a tic r i n g ,
o f n itro g e n
a compound i n c r e a s e s .
liq u id
was
s te p s :
b re a k in g
to
16).
s u p p o r t beds f r o m 3 1 6 - 4 2 7 ° C ,
R e a c tio n S te p s - -
The s e c o n d s t e p ,
in
o ccu rs.
passed over i n e r t
re m o va l o c c u rre d
a ro m a tic
C-S bond b r e a k i n g - ( 1 0 ,
Some t h e r m a l r e m o v a l o f s u l f u r
o b served f o r
th e y c o n c lu d e
is
to
a minimum c o n s u m p tio m o f
an e x p e n s i v e p a r t o f c u r r e n t c o a l
o f hydrogen i s ' t o
'h e a l'
th o s e carbon
19
bonds in v o lv e d
in
a C-C bond s c i s s i o n
h e te ro a to m re m o v a l"
a b le
fo r
h y d ro c ra c k in g
lo s s
is
it.
(20,
fu lly
and i n
s te p
s tru c tu re
m ost f a v o r ­
th a t in
w h ic h t h e
w h ic h h y d r o g e n a t i o n , c a u s e s
a n o n a ro m a tic r i n g
cracked p ro d u c ts
a r e more f a v o r e d t h a n h y d r o ­
a t te m p e ra tu re s
above 3 5 0 °C .
are v e ry lo w ,
But th e r a te s
A c tiv a tio n
but a c tiv a tio n
m o le c u la r w e ig h t , u n r e a c tiv e
reduces l i q u i d
e n e rg ie s
fo r
c ra c k in g
s o lid
tio n s ,
as h y d r o g e n i s
c o n d e n s a tio n r e a c t io n s
Two p o s s i b l e
m in im iz e
co m pound s.
p ro d u ct y ie ld
c o k in g
u s u a lly
hydrogen donor o r
ra d ic a ls ;
s u p e rc ritic a l
to
h ig h
u n d e s ira b le
d e a c tiv a te s c a t a l y s t .
o f c o k e s a r e l o w e r t h a n o f t h e coke
are n o t s im p le p o ly m e r iz a ­
(1 0 ).
A ls o ,
la rg e r
th a n
a p p r o a c h e s may a v o i d c o k i n g :
th e rm a l fr e e
C o k in g i s
and p l u g s o r
re a c tio n s
e lim in a te d "
is
s te p s
(1 9 ,2 0 ).
H y d ro g e n -to -c a rb o n r a t i o s
"P y ro ly s is
fo r
e n e rg ie s o f th e h y d ro ­
C o k in g o c c u r s when c r a c k e d p r o d u c t s r e a c t i r r e v e r s i b l y
p re cu rso rs.
w h ic h ha s
10).
a r e b e tw e e n 20 and 35 k c l / m o l e
s in c e i t
one o f
Least fa v o re d i s
h y d ro g e n a tio n p r o d u c ts a re g r e a t e r .
g e n a tio n
and H^S f o r
h y d ro g e n a tin g
th a n h y d r o g e n a tio n i s
s a tu ra te d
By t h e r m o d y n a m i c s ,
g e n a tio n p ro d u c ts
"The h y d r o a r o m a tic
ra th e r
o f an a r o m a t i c r i n g .
a d o u b le bond"
fo rm
compounds a r e c r a c k e d by f i r s t
th e n c r a c k in g
n o n a ro m a tic r i n g
to
(1 0 ).
P o ly n u c le a r
th e r in g s ,
and a l s o
a c tiv a tio n
fo r
u s in g
c ra c k in g
(1 0 ).
re a c tio n s .
lo w t e m p e r a t u r e s t o
and q u e n c h i n g t h e r a d i c a l s
c a ta ly s is
e n ergy o f
fo r m e d by
20.
O th e r
U n s u b s titu te d
s tru c tu re
and c o m p o s i t i o n
a r o m a t i c s coke l e s s t h a n
fa c to rs
s u b s titu te d
because "T h e rm a l f r e e - r a d i c a l s a re i n v o lv e d
re a c tio n "
in c re a s e d th e
o f a n itro g e n
c o k in g r a t e
o f th e
n itro g e n
Gas and l i q u i d
p y r o l y z e s more e a s i l y
d iffe re n tly
to
in
ones,
c o k in g .
p o s s ib ly
th e c o k in g -c o n d e n s a tio n
(1 0 ),
S u b s titu tio n
p o s itio n
in flu e n c e
c o k in g ;
to o .
in
m e th y l g ro u p .
In
by 10 t i m e s i n
in
th e r i n g
in
liq u id
s o lu tio n ,
a p o ly n u c le a r
a ro m a tic
th e rm a l p y r o ly s is .
a ffe c ts
p hase r e a c t i o n s
gas th e y c a p tu re
.
atom i n
d iffe r
A ls o
th e r a t e .
a ls o
phase th a n v a p o r .
(1 0 ).
A n th r a c e n e '
Phenyl r a d ic a ls
phenyl ra d ic a ls .a d d to
a ro m a tic s ,
a h y d r o g e n atom fr o m a s u b s t i t u t e d
act
le a d in g
21
E ffe c ts
of
V a r i a b l e s on C o n v e r s i o n
S o lv e n t h y d ro a ro m a tic
fa c tio n
(8 ).
e n t was 20% c r e s o l -
cre so l
th e o ry
80% t e t r a l i n ,
s o lv e n t.
M ost c u r r e n t
th e
s o lv ­
s o lv e n t-to -c o a l r a t i o ,
in flu e n c e
g i v e n up t o
coal s o lv e n t-re fin in g
fra c tio n s
The
of
s ta b iliz e
and l i q u i d
th e
phase
fr o m t h e p r o c e s s as a
R e c y c le s o l v e n t c o m p o s itio n i s
b o th
s im ila r
to
coal
and c h e a p e r t h a n t e t r a l i n .
S o lv e n t n a tu re
tr ib u tio n .
a ffe c ts
liq u id
Though c o a l r a p i d l y
n a tu re
o f th e
depend on s o l v e n t
s o lu tio n
liq u e ­
o f coal
1 9 3 0 1s and 1 9 4 0 ' s ;
a 2 :1
and
bound h y d r o g e n s f r o m t h e t e t r a l i n
h y d r o g e n a t i o n p r o c e s s e s use m i d d l e
o f th e
th e
t e t r a h y d r o n a p h t h a le n e ) are e a s i l y
fra g m e n ts
in c re a s e s th e
was t h a t c o a l d e p o l y m e r i z e s u n d e r t h e
p o ly m e r r a d i c a l s .
re c y c le
at
a ro m a tic
s o lv e n t e x t r a c t io n
Germany d u r i n g
and h e a t ; t h e l o o s e l y
(1 ,2 ,3 ,4
and p h e n o l r i n g s
The P o t t - B r o c h e
p r o c e s s was o p e r a t e d i n
s o lu tio n
Removal
"T h e use o f c o n d e n s e d compounds h a v i n g
or h y d ro a ro m a tic
o f c o a l"
and S u l f u r - N i t r o g e n
breaks in t o
(4 ).
- re la tiv e
and p r o d u c t d i s ­
fra g m e n t m o le c u le s r e g a r d le s s
s o l v e n t , s u b se q u e n t s lo w e r
n a tu re
a c tiv ity :
c o a l c o n v e rs io n
Some f a c t o r s
s ta b iliz a tio n
c o rre la te
ease o f r e a c t i o n
w ith
w ith
re a c tio n s
co a l d is ­
a ty p ic a l
fre e
r a d i c a l , C C 1 ^ (2 0 )
-
n o n -p o la r
s o lu b ility
- p e n e tra tio n
C o n v e rs io n ,
va ry
w ith
s o lv e n t
o f c o a l f r a g m e n t s by s o l v e n t
p roduct d is t r ib u t io n ,
s o lv e n t-to -c o a l r a t io .
p a ra m e te r o f th e
and d i f f u s i o n
U n iv e rs ity
fo u n d h y d r o t r e a t m e n t o f so I v e n t - r e f i n e d
o f N o rth
(2 1 )
(2 0 ).
re s is ta n c e s
D a k o ta r e s e a r c h e r s
l i g n i t e , gave h i g h e s t , c o n v e r s i o n s '
22
in
a 1 :1 r a t i o
de cre a se
te tr a lin .
fro m t h a t r a t i o ,
p ro to n r a t i o
in
w ith
C o n v e rs io n d e c re a se d f o r
By NMR a n a l y s i s ,
o f p r o d u c ts in c re a s e d
th e
( 22) .
d e cre a se d ;
p ro d u ct
a ro m a tic /a lip h a tic
ra tio
!
V is c o s ity
of
a S R C -s o lv e n t s o l u t i o n
SRC c o n c e n t r a t i o n
in
th e
4 to
or
a r o m a tic /a lip h a tic
as s o l v e n t r a t i o
w h ic h no s o l v e n t was used had t h e h i g h e s t
an i n c r e a s e
20 t o
3 0 -5 0 / ra n g e ,
150 c e n t i s t o k e s
re s p e c tiv e ly
fo r
is
tra n s fe r
flu id s
changes o f th e
a lte rn a te
to
d i f f u s iv itie s
some o f t h e
In s titu te
a v a rie ty
and
by h i g h
h ig h
s o lv a tin g .p o w e r,
th a n l i q u i d s ,
and h i g h h e a t
(2 0 )
c o n d u c te d s u p e r c r i t i c a l c o a l
th e
T h e r m a l and c h e m i c a l
not a d is s o lu tio n
s u p e rc ritic a l
flu id s
o f u n ch a n g e d c o a l .
S q u ire s proposed ( 4 ) .
gave a t h e r m a l e f f e c t - m a te ria l to
S e c o n d a r y a l c o h o l s gave a c h e m i c a l e f f e c t
th e th e rm a l e f f e c t ,
s im ila r
p r o d u c t was c h a n g e d t o
and t e t r a l i n
d is s o lu tio n
s o lv e n ts .
o f common l i q u i d s .
c o a l were o b s e r v e d ,
a ll
coal
c o a l was chan g e d f r o m p y r i d i n e - i n s o l u b l e
d in e -s o lu b le .
and 5 0 / ,
t r a d i t i o n a l p o ly a ro m a tic
T h a t a g r e e s w i t h ' t h e m odel o f c o a l d i s s o l u t i o n
N e a rly
fro m
(1 0 ).
S t a n f o r d R e s e a rc h
u s in g
s o l v e n t m e d ia f o r
are c h a r a c t e r iz e d
h ig h e r
p ro p e rtie s
d is s o lu tio n
40,
v a rie s
-
an a t t r a c t i v e
heat c a p a c itie s ,
d e p e n d e n t on t h e
K in e m a tic v i s c o s i s t y
(2 3 ).
S u p e rc ritic a l
ve ry
c o n c e n t r a t i o n s o f 30 ,
The use o f s u p e r c r i t i c a l
re a c tio n
is
to
t e t r a lin — s ig n ific a n tly
p y rid in e -s o lu b le ' m a te r ia l.
each c o n v e r t e d
and above
more c o a l
Is o p r o p y l a lc o h o l
about 5 0 / o f th e c o a l to
0
over
p y r i­
p y rid in e -
23
s o lu b le s
in
re a c tio n
a t 3 3 5 °C ,
90 m i n u t e s ,
and 1000 p s i g
o f e ith e r
N2 9r H2.,
The b e s t c o n v e r s i o n
p o ta s s iu m
is o p ro p o x id e
was 97% s o l u b l e
0.4% ( 2 0 ) .
in
was added t o
p y r id in e ; s u lfu r
N e ith e r
as i s o p r o p y l
was o b t a i n e d
by t h e
th e
c a p a c ity "(2 0 ).
Im p o rta n t to
o f th e
coal is
m e th a n o l u n d e r
s o lu b ility
e x tra c te d
(th e
e x p e rim e n ts
o f th e
-
u s e fu l in
c o a l p ro c e s s e s f i n d
u r e due t o
p a rtia l
th e
th e
is
coal is
showed t h e
re a c tio n s
se c o n d -s te p
" s o lv a tio n
h y d ro g e n a tio n "
(8 ).
in
th e
(th e
benzene,
or
n o t needed
S o lv e n t-re fin e d
PAMCO1s s o l v e n t - r e f i n e d
d e c lin e )
c o a l d u rin g
d e c lin e d
as i t
was a t t r i b u t e d
th e
s o lu tio n
s o lv e n t p ro c e s s e s h y d ro g e n a te th e
0
fra c tio n
in c r e a s e s under hydrogen p r e s s ­
a b s e n c e o f Hg . . .
S e ve ra l o th e r
" n o m a jo r
A ls o ,
S q u ire s m odel ( 4 ) ,
used i n
s o lv e n t to
s ta te .
s lo w e r r e a c t i o n s .
( o f c o a l)
in c re a s in g
t h e r m a l change
A l t h o u g h t h e p r e s e n c e o f Hg i s
w o rk f o u n d t h a t " s o l v e n t e f f i c i e n c y
o f Hg f r o m t h e
is
t h a t "some
(2 0 ).
b e n c h -s c a le
th e
d o n a tio n ,
a ffe c te d ,
2.2% t o
same e f f e c t s
p o s tu la te d
s u p e rc ritic a l
c o n d itio n s "
th e r a p id th e rm a l f i r s t - s t e p
hydrogen i s
The c o a l p r o d u c t
th e
by s u p e r c r i t i c a l i s o p r o p a n o l ,
re a c tio n )
H y d ro g e n E f f e c t s
fo r
th a t
was n o t d e p e n d e n t on a t t a i n i n g
th ough p y r i d i n e
It
s o l v e n t , such as h y d r i d e
n o te i s
amount o f
c o n t e n t was r e d u c e d f r o m
se co n d a ry b u t a n o l.
c h e m ic a l a c t io n
e ffe c t
is o p ro p y l a lc o h o l.
m e th a n o l nor t - b u t a n o l e x h i b i t e d
a lc o h o l o r
d is s o lu tio n
when a c a t a l y t i c
s o lv e n t
to
coal
was r e ­
a tra n s fe r
p ro ce ss"
(8 ).
s e p a ra te ly
fro m
24
th e
s o lu tio n
Hg d i r e c t l y
p ro c e s s ,
to
th e
but " s a tis fa c to ry
d is s o lv e r"
In h y d r o tr e a tin g
re s u lts
a r e o b t a i n e d by a d d in g
(8 ).
SRC f i l t r a t e
under
se ve re c o n d i t i o n s ,
fo u n d h y d r o g e n c o n s u m p t i o n was 2 5 0 0 -3 0 0 0 S C f / b b l
c lu d e d fro m h i s
c ra c k in g
was k i n e t i c a l l y
c o n v e rtib le
A ls o ,
v a ria tio n
fro m 8 t o
He a l s o c o n ­
d a t a t h a t h y d r o g e n a t i o n was e q u i l i b r i u m
1 9 6 3 -1 9 6 8 w o rk w i t h
fo r
(2 3 ).
lim ite d
coal liq u e fa c tio n
fra c tio n s
in
H
flo w
e ffe c t
lim ite d ,
D u r in g C o n s o l i d a t e d
in
m o lte n s a l t s ,
ra te
ra te s
may have l i t t l e
e ffe c t.
h y d r o g e n a t i o n o f CDED t a r
c o n s ta n ts
q u in o lin e .,
over
a fix e d
p re ssu re ;
p re ssu re
(1 0 ,
a m o d e l'c o m p o u n d f o r
s te p s e x h ib it e d
c ra c k in g
18).
D u r in g
n itro g e n
a p o s itiv e
s t e p s ' s h o w .a n e g a t i v e
and de~
d e n itro g e n a tio n
of
r e m o v a l'fro m -c o a l s tu d ie s ,
o r d e r w i t h r e s p e c t t o Hg
or
zero o r d e r
fo r
Hg
(1 6 ).
H y d ro g e n ga s g e n e r a t e d i n
fo rm s th a n o t h e r s .
fa c tio n
w ith
s itu
is
more a c t i v e
fo r
some, c o a l
ERDA1s COSTEAM p r o c e s s makes h y d r o g e n d u r i n g
by r e a c t i o n
w orks b e t t e r
o f c a r b o n m o n o x id e and w a t e r ;
lig n ite
th e
liq u e ­
COSTEAM p r o c e s s
and l o w r a n k , m a t e r i a l s t h a n w i t h
b itu m in o u s
c o a l.
T e m p e ra tu re
c o k in g ,
I
bed
(2 7 ).
of coal liq u id s
h y d ro g e n a tio n
(2 6 )..
R ate ch a n g e s
P resence o f gaseous h yd ro g e n enhances d e s u l f u r i z a t i o n
n itro g e n a tio n
but
C o a l's
o f c o a l w ere i n d e p e n d e n t o f p r e s s u r e
12 M S C F /b b l d u r i n g
had no s i g n i f i c a n t
(2 4 ),
deRosset
E ffe c ts -
h e te ro a to m re m o v a l,
T e m p e ra tu re a f f e c t s
and c r a c k i n g
in
gas p r o d u c t io n ,
coal liq u e fa c tio n
25
p ro ce sse s.
In
PAMCD1s SRC p r o c e s s ,
d e p e n d e n t on t e m p e r a t u r e
coke f o r m a t io n
te m p e ra tu re
th a n th e
to ta l
liq u id
are f a v o r e d
of to ta l
te m p e ra tu re
at
p r im a rily
In
a d d itio n ,
a g iv e n p re s s u re
a p p ro x im a te ly
c o n v e rs io n
is
u s u a lly
gases"
n o t in c re a s e d
re m o v a l fro m c o a l l i q u i d s
te m p e ra tu re s th a n
s u lfu r
re m o v a l.
and n i t r o g e n
lig n ite .
H ite s h u e
(28)
n o te s
O
above 450 C.
u s u a lly re q u ir e s
h ig h e r
m odel compound
363°C t h a n f r o m 3 2 5 - 3 4 2 ° C
re m o va l u s u a lly
in c re a s e
w ith
(1 9 ).
te m p e ra tu re o f
re a c tio n .
P re ssu re
tu re
w i l l g e n e ra lly
v e rs io n
u s u a lly
s o lv e n t- r e fin e d
y ie ld
E ffe c ts
or
An i n c r e a s e
in
p re ssu re
n o t c h ange t h e g a s c o n v e r s i o n ,
in c re a s e s
lig n ite
more l i q u i d
2500 p s i g
-
H o w e v e r,
a t a g i v e n te m p e r a ­
b u t th e l i q u i d
con­
b a tc h h y d ro g e n a tio n o f
on H arshaw H T -400 c o b a l t m o l y b d a t e was fo u n d t o
p ro d u ct
1000 p s i g
(2 8 ,2 9 ).
at
(2 9 ).
.
"H eavy l i q u i d s
D e n itro g e n a tio n o f th e
i n c r e a s e d .more f r o m 342 t o
w ith
was 50/6 l e s s
s o lv e n t-re fin e d
(2 9 ).
In l i g n i t e
lin e a rly
gas f o r m a t io n
h y d ro g e n a tio n o f
expense o f th e
(-2 8 ).
w ill
i n c r e a s e s much more
and h e a v y ends w ere f o r m e d a t 4D 0°C :
a t th e
s u lfu r
is
(8 ).
c o n v e rs io n p ro d u c ts
At a g i v e n p r e s s u r e ,
a t 450°C f o r
N itro g e n
B o th
in
c o n v e rs io n in c r e a s e s
(2 2 ).
More m i d d l e o i l s
q u in o lin e
tim e "
f r o m 5 7 5 O- 4 5 0 ° C ,' b u t t h e g a s f r a c t i o n
a t 4D0°C t h a n
liq u id
an i n c r e a s e
t h e ga s f r a c t i o n
liq u e fa c tio n ,
re s id e n c e
s o lu tio n
was o b s e r v e d above 4 4 0 °C .
G e n e ra lly ,
in c re a s e
and l i q u i d
"d e g re e o f
1750 p s i g ' i n i t i a l
c o ld p r e s s u r e th a n a t
26
The h i g h e s t p r e s s u r e s
th e lo w e s t
re fin e d
lig n ite
fo r
over
(3 0 ).
up t o
in c re a s e d .
S u lfu r
ra w a n t h r a c e n e o i l
1500 p s i g ,
and n i t r o g e n
does n o t i n h i b i t
and O t h e r
E ffe c ts -
in
is
HDN; h o w e v e r ,
h y d ro d e s u lfu riz a tio n
B o th
s u lfu r
o rd e r k in e c tic s
w ith
(3 1 ).
The p r e s e n c e o f s m a l l
u n til
it
in
a d d itio n
r e a c h e s 2-3% m ole
(HDN) o v e r
a h e te ro ­
a r e more a c t i v e
th a n th e o x id e
HDNe
rem o ve d as H^S,
h ig h
(10,
n itro g e n
a c tiv ity
s u lfu r
in
c o n c e n tra tio n
o f th e c a t a ly s t
a fe e d s to c k
in
( ID ),
d o e s n 't
a fe e d i n h i b i t s
18).
and' n i t r o g e n r e m o v a l r e a c t i o n s p r o c e e d by f i r s t th e
The l o w e s t l i q u i d
th e b e s t re p o r te d
o ff
o f coal liq u id s ;
2) H^S h e l p s t h e h y d r o c r a c k i n g
s u lfu r
in c re a s e d w ith ■
tw o w ays:
1) S u lf id e d m e ta l c a t a l y s t s
in h ib it
q u in o lin e
H^S e n h a n c e s "h y d r o d e n i t r o g e n a t i o n
fo r m f o r
re m o va l in c re a s e d
above w h ic h r e m o v a l l e v e l e d
h y d ro d e s u lfu riz a tio n
geneous m e ta l c a t a l y s t
S in c e
s o lv e n t-
a t 7 0 0 ° F and l o w spa ce v e l o c i t i e s
a m ounts o f H^S p r o m o t e s d a n i t r o g e n a t i o n
c o n c e n tra tio n .
y ie ld
c o a l m odel com pounds o r
N it r o g e n re m o v a l fro m
H y d ro g e n S u l f i d e
it
h y d ro g e n a tio n o f
rem oval in c re a s e d f o r
as p r e s s u r e
c a ta ly s t
w ere fo u n d t o
(2 9 ).
w ith p re s s u re
p re ssu re
te m p e ra tu re
a m ounts o f vacuum b o t t o m s f o r
H e te ro a to m
m ix tu re s
a t a g iv e n
liq u id
o b t a i n e d by d e R o s s e t f o r
c o n c e n tra tio n
h o u rly
o f each t y p e o f compound ( 1 6 ,
spa ce v e l o c i t i e s ,
c o n v e rs io n s
and HDN.
LHSV, g e n e r a l l y
Best r e s u lts
SRC a t t h e ..most s e v e r e c o n d i t i o n s :
were
4 5 0 °C ,
17 ).
g iv e
27
•UHSV=^-,
o il
and 3000 p s i g
H
over
showed i n c r e a s e d n i t r o g e n
te m p e ra tu re s
200 ml o f c a t a l y s t
a p p ro p ria te
(1 8 ).
t h e t y p e s o f c o a l used d e t e r m i n e d t h e
re s u lts .
s e v e rity
I n t h e German p l a n t s ,
o f th e o p e r a tin g
con­
Brow n c o a l c o u l d be h y d r o g e n a t e d a t much l o w e r p r e s s u r e
h a rd e r c o a l
(3 2 ).
c a ta ly tic
th a n
(3 ).
F in a lly ,
io n s
Ram a n t h r a c e n e
r e m o v a l as LHSU d e c r e a s e d a t
Coal ra n k in flu e n c e s l i q u e f a c t i o n
d itio n s .
(2 4 ),
b e n e fic ia tio n
U n b e n e fic ia te d
FeS i n
th e ro c k
of coal
a ffe c ts
coal re a c ts b e s t:
and ash m ix e d w i t h
c a ta ly tic
th is ' is
th e c o a l.
c o a l convers­
p ro b a b ly
due t o
28
CATALYSIS
C a ta ly s ts
by a l l o w i n g
are im p o r t a n t i n
a lte rn a te
co a l h y d ro tre a tin g .
m echanism p a t h s
-and h e t e r o a t o m r e m o v a l r e a c t i o n s ;
tio n
e n e rg ie s th a n
th e
u n c a ta ly z e d p a th s ,
fo r
C a ta ly s ts
w ork
h y d r o c r a c k in g , h y d ro g e n a tio n ,
a lte rn a te .p a th s
so c a t a l y s t s
have l o w e r
a c tiv a ­
in c re a s e r e a c tio n
ra te s .
H y d ro c ra c k in g
c ra c k h ig h
a te s
m o le c u la r
c a ta ly s ts
M a in t e n a n c e -
C a ta ly s t
A c tiv ity ,
S e le c tiv ity ,
m ost o f t e n
a r e . . a f f e c t e d by s u p p o r t t y p e
and s t r u c t u r e ,
a c id ity ,
s iz e , p lu g g in g ,
a r e a ,, p o r e
A lu m in a o r
s ilic a -a lu m in a
e a r t h p r o m o t e r s a re o f t e n
S u p p o rts o f t e n
tio n
in
(3 1 ).
T a b le
d e te rm in e
th e
w ith
used f o r
or
used i n
h y d ro tre a tin g ,
s u rfa c e
and p o i s o n s .
w ith o u t
h y d ro c ra c k in g
a lk a lin e
c a ta ly s t
c r a c k i n g , and l o a d e d m e t a l s
and r a r e
s u p p o rts .
a ffe c t
hydrogen a­
h y d r o g e n o ly s is are l i s t e d
(1 0 ).
T a b le
II.
T y p ic a l H y d ro g e n o ly s is M e ta ls
B re a k in g o f
M e ta l
Bond Type'________________________________
C-C
C-N
C-O
r „ q
Group V I I I
"
"
"
"
.
u n s a tu r- •
and A c t i v i t y
m e ta l lo a d in g ,
T y p i c a l c a t a l y s t m e t a l s u se d f o r
II
They m ust b o t h
(3 3 ,3 5 ).
H e te r o g e n e o u s c a t a l y s t s ,
s u rfa c e
fu n c tio n a l.
w e i g h t h y d r o c a r b o n s ;and . h y d r o g e n a t e
( c o k e p r e c u r s o r ) fo r m e d
F a c to rs in
m ust be d u a l
11
II
0
Re
"
"
11
W
"
"
11
Mo
M
11
11
Cu
11
11
Ag
11
29
H e te ro g e n e o u s c a t a l y s t s
H^S) t o
n ic k e l
s in c e
be m ost a c t i v e .
a c id ity
fo r
to
go t o
...
of
a c a ta ly s t
as s p l i t t i n g
fo u n d t h a t p r e f e r r e d
p o s s ib le
w ith
a C r^O ^ -
c o n tro lle d
rin g
d e s ira b le
c ra c k in g
m o d e ra te ly
a c id ity
p ro v id e
a c id ic
o f th e
D e s u lfu riz a tio n
re a c tio n s
c a ta ly s ts
to
w ith
c o b a lt,
T h is i s
a Yfo s u l f u r
im p o r ta n t.
c a ta ly s ts
and
fo rtu n a te
r e a c ta n t con­
c a ta ly s t
s u rfa c e
a c tiv ity
is
o c c u r on s t r o n g l y
a re a i s
fo u n d by M o n ta n a S t a t e
w h ile
c a ta ly s ts "
w ith
th o s e w ith
(3 4 ).
It
a c id ic
ha s been
o f p h e n a n th re n e i s
s tre n g th .
e n h a n c in g t h e
"T h e re ­
s e le c tiv ity
(1 0 ).
fo r
th e p e tro le u m
S tu d ie s i n
a ls o
it
a re
a p p e a rs
a la r g e
number o f o n l y
u p g ra d in g
SRC f o u n d t h a t
a f f e c t e d carbon d e p o s itio n
i
e le c tr o p h ilic
s ite s "
in d u s try
t'h s r e fo r e ,
i n f l u e n c e d by a c i d i t y
s ite s ,
(1 0 ).
a ls o .— "h y d ro g e n a tio n
w h ile
d e s u lfu riz a tio n
( 1 0 .) .
im p o rta n t to
U n iv e rs ity
s u p p o rts -w e re
lo w a c i d i c
a s u p p o rt t h a t c o n ta in s
(3 5 ).
C a t a l y s t w ork done
on b a s i c
n i t r o g e n o u s .p o is o n s ,;
s ite s "
H ig h s u r f a c e
In
o x id e s .
may be an a p p r o a c h t o
o c c u r s on w e a k ly e l e c t r o p h i l i c
(3 7 ).
m olybdenu m ,
c e n te r r i n g ' c ra c k in g
re a c tio n s "
a c id ic
s e n s itiv e
to
is
A l^ O ^ c a t a l y s t
a c id ity
S tro n g ly
"e x tre m e ly
in
p re h y d ro g e n a tio n r e a c t io n s ,
re c e n tly
o f c e n te r
s u lfid e s
th e . c o n c l u s i o n
s u p p o rt are p r e f e r r e d
fo re ,
o f tu n g s te n ,
(tre a te d
(1 0 ).
Germany " l e d
s u ita b le
s u lfid e d
s u p p o rts th a n t h e i r
m ost m e t a l c a t a l y s t s
S u rfa c e
in
S u lfid e s
a r e more a c t i v e - b n
c e n tra tio n
are u s u a l l y
(3 6 ),
a s e r ie s o f in -h o u s e c a t a ly s t
c o a l p ro d u c t c a ta ly s ts ,
and U n i v e r s i t y
o f N o rth
as
D a k o ta
s u p p o r ts im p re g n a te d w it h
N i-M o
30
a t th e
U n iv e rs ity
w ere h i g h e s t
fo r
o f N o rth
D a k o ta ,
c a ta ly s ts
a c tiv itie s
c o n ta in in g
per u n it
T iO ^ ( 0^ and I j
m e r c i a l N i-M o c a t a l y s t on a l u m i n a had much h i g h e r
te r
o v e ra ll
a c tiv ity
P ore s i z e
m o le c u le s
(1 0 ).
in
th e
A lth o u g h
p ro b a b ly
(3 5 )
(3 8 );
Exxon g o t t h e
2 0 0 -3 5 0 ' A r r a n g e ,
to
to o
p resent
A° b i g
and H S
(l0 ) j
s iz e
to
p lu g
c a ta ly s ts
A s p h a lte n e
s m a ll p o re s
on 100 A ° . .
be o p tim u m i n
h is
coal
b e s t a s p h a lte n e re m o v a l w ith
th e ir
and f o u l i n g .
S u lfu r
s u ffe r
6 0-80
pore
s iz e
c a ta l­
A° and 40 A° ( 3 9 ) .
because o f t h e i r
d e a c tiv a tio n
a ll
a c tiv ity
and n i t r o g e n
o f 5-13
s u p e rio r
A ° ( 3 3) i s
h u rts
ha s been, n o t e d f o r
w h ic h c o n t a i n
d e g r a d a t i o n ,from b o t h
p o is o n
c o n c e n tra tio n s ;
h y d r o g e n a t i o n c o m p o n e n ts and n i t r o g e n
COED t a r ,
a r e a and b e t ­
s m a ll,
above p a r t p e r m i l l i o n
C a ta ly s t
s u rfa c e
enough t o
te s tin g
h e l d hope as c a t a l y s t s
MH
area
b u t a com­
h e te ro g e n e o u s c a t a l y s t s .
as c o m p a re d w i t h
H e te ro g e n o u s c a t a l y s t s
p o is o n in g
is
f o u n d 200 A° p o r e
z e o lite s
re s is ta n c e
lim it
be 4 0 - 5 0
E n g e lh a rd I n d u s t r i e s
t r e a t m e n t w o rk
y s ts
c o n s tra in ts
W e lle r
);
s u rfa c e
(3 7 ).
are r e p o r t e d t o
s u p p o rts ;
of
s u lfu r
some c a t a l y s t s
s u lfu r
and n i t r o g e n
when
u s u a lly h u rts
th e c ra c k in g
p ro c e s s in g
'
SRC,
a t about
c o m p o n e n ts
S y n th o il,
I
(3 3 )
and
c o n c e n tra ­
tio n .
■ E a s ily
s u lfu r-p o is o n e d c a ta ly s ts
s u lfu r-re s is ta n t
m olybdenu m ,
a c tiv ity
c a ta ly s ts
a r e m o lybdenu m ,
and n i c k e l - t u n g s t e n
lo s s fo r
p la tin u m
in c lu d e
(4 0 ).
p la tin u m
tu n g s te n ,
N itro g e n
on s i l i c a - a l u m i n a
a ls o
(3 3 ).
ir o n ,
and p a l l a d i u m ;
n ic k e l-
causes' i r r e v e r s i b l e
31
A lk a li
in g .
s a lts
For e x a m p le ,
d u rin g
and t i t a n i u m
s o d iu m i o n s ca u s e i r r e v e r s i b l e
c a t a ly s t re g e n e ra tio n ;
in c re a s e s
s u rfa c e
a c id ity
F o u lin g r e s u l t s
c o v e rin g
a ll
to
T iO ^ d e p o s i t i o n
co a l p rocess­
s u rfa c e
a re a lo s s
on s i l i c a - a l u m i n a
.
(1 0 ).
fr o m e i t h e r
c a ta ly s t re a c tio n
c o n trib u te
compounds a r e p o i s o n s i n
c a ta ly s t
c o k e •fo rm a tio n
s u rfa c e s .
M e ta ls ,- ash,
d e g ra d a tio n
or tra c e
c o n ta m in a n ts
and a s p h a l t e n e s may
as o b s e r v e d i n
SRC u p g r a d i n g
(1 0 ,2 4 ).
Homogeneous c a t a l y s t s ,
are
m o lte n - s a l t s ,
s u g g e s t e d as more e f f e c t i v e
in
a v o id in g
and s u p e r c r i t i c a l c a t a l y s i s
mass t r a n s f e r
lim ita tio n s
o f th r e e - p h a s e h e te ro g e n e o u s c a t a l y s i s .
L e w is a c i d - t y p e
th e se in c lu d e
b e in g
m e ta l h a lid e s ,
u se d f o r
"c h lo rid e
e s p e c ia lly
coal liq u e fa c tio n
to - c a ta ly s t r a tio s .
c h lo rid e s
compounds a r e u s u a l l y
a r e tw o r e s t r a i n i n g
re a c ts
w ith H S
c h lo rid e s .
re se a rch
C a ta ly s t re c o v e ry
fa c to rs
good hom ogeneous c a t a l y s t s :
in
.Z in c
b o th -s m a ll
and c o r r o s i v e
in
and NH^ d u r i n g
and l a r g e
c u r r e n t p r o c e s s e s have been d e v e l o p e d ; f o r
is
.
c o a l-
p ro p e rtie s o f
m e ta l c h lo r id e
liq u e fa c tio n
c h lo rid e
use.
Z in c
re a c tio n s ,
99.9% c a t a l y s t
but
re c o v e ry
( 3 , 8 , 26 ).
Much w o rk i s
c o n tin u in g
in
h e t e r o g e n e o u s and homogeneous c a t a l y ­
s is o f c o a l c o n v e rs io n .
Good s o u r c e s i n c l u d e
R esearch I n s t i t u t e
U n iv e rs ity
D e v e lo p m e n t
(2 6 ),
S ta te U n iv e r s it y
(2 0 ),
H ite s h u a
(3 6 ),
(2 8 ),
o f N o rth
E n g le h a rd
R a p o p o rt
(4 0 ),
D a k o ta ( 2 9 ) ,
In d u s trie s
and p a t e n t s by M o b i l O i l
(4 1 ),
S ta n fo rd
Conoco C o a l
(3 5 ),
M o n ta n a
Exxon ( 3 9 ) ,
32
U n iv e rs a l
O il
P r o d u c ts - ( 4 2 ) ,
and A t l a n t i c
G iv e n any one p a r t i c u l a r
may be r a t e - d e t e r m i n i n g .
c a ta ly s ts
F ilm
are
D iffu s io n
o f re a c ta n ts
2.
D iffu s io n
o f re a c ta n ts in
3.
A d s o r p t i o n on
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 iffu s io n
o u t o f p o re s
7,.
D iffu s io n
away f r o m c a t a l y s t
re s is ta n c e
p a s t th e
d e c r e a s e d by u s i n g
a d iffe re n t
is
v a rie d
If
th e
is
cu rve s c o in c id e ,
c o n v e rs io n
u s in g h e te ro g e n e o u s
te s te d
film
is
w ill
in c re a s e
e x te rio r
po re s
e x te rio r.
w ith
th e r e a c ta n t
d iffu s io n
re s is ta n c e
h a v in g le s s p o re l e n g t h
by m a kin g tw o s e r i e s o f r u n s ,
The l i q u i d
C o n v e rs io n i s
d iffu s io n
te s te d
If
pore
W, o f c a t a l y s t .
d iffe re n t
c o n tro llin g .
c a ta ly s t
c a ta ly s t p a r tic le s
is
p lo tte d
each a t .
fe e d r a t e ,
F,
v e r s u s W/F.
not r a te -c o n tro llin g .
by m a k in g tw o r u n s a t t h e - s a m e c a t a l - ■
s iz e p e l l e t s .
a c o n s ta n t w e ig h t o f c a t a l y s t / f e e d
not ra te
processes
c a t a ly s t s u rfa c e
each s e r i e s o f r u n s .
b u t u s in g
to
c a ta ly s t p a r t ic le ;
s m a lle r
d iffu s io n
P o re d i f f u s i o n
is
d iffu s io n
can be d e c r e a s e d by i n c r e a s i n g
c o n s ta n t'w e ig h t,
in
y s t - charge,
The p a t h s . f o r r e a c t i o n
1.
d iffu s io n
F ilm
s y s te m ,
(4 3 ).
as f o l l o w s :
mass f l o w r a t e
is
c a ta ly s t
R ic h fie ld
ra te
ra tio ,
pore r e s is ta n c e
is
d e c re a s in g p e l l e t
The same c o n v e r s i o n
W/F,
means p o r e
c o n tro llin g ,
s iz e
(4 4 ).
at
d iffu s io n
th e n th e
MATERIALS,
C oal C o m p o s itio n
T u jo
It
is
Sample
i"
used t o
The c o a l i s
x 0
a v e ra g e 1p ro x im a te
T a b le 3
s o lid
t a k e n Oune 13,
The c o a l t y p e
u se d i s
cans o f
and Midmay M i n i n g
110,
C o l o n i a l M in e .
AND PROCEDURES
_
1 0 -g a llo n
fro m P i t t s b u r g h
EQUIPMENT,
d rie d
to
S o l v e n t - R e f i n e d C o a l mere r e c e i v e d
C o m p a n y 's F t .
p la n t.
1975.
make t h e
SRC mas K e n t u c k y # 9 fro m
mashed and s i z e d
a t t h e m in e ;
<( Yfo m o i s t u r e b e f o r e
and u l t i m a t e
L e m is p i l o t
use.
a n a l y s e s as r e c e i v e d
th e
th e
s iz e
The 1975 y e a r l y
are l i s t e d
in
Table
3
Coal Analyses to SRC Process
P ro x im a te w t . p e r c e n t
as r e c e i v e d
M o is tu re
2 .2 5
Ash
1 0 .5 0
V o la tile s '
3 6 .7 5
F i x e d C arbon
5 0 .5 0
U ltim a te
w t.
p e rce n t
as r e c e i v e d
M o is tu re
2 .2 5
C
' 7 0 ,1 0
H
4 .8 9
N
1 .3 7
• S
3 .5 1
Cl
0 .0 4
Ash
1 0 .5 0
0
7 .3 4
by d i f f e r e n c e
SRC C o m p o s i t i o n
The u l t i m a t e
is
g i v e n b e l o w "i n
a n a ly s is o f th e
T a b le
T a b le 4 .
SRC sam ple as r e p o r t e d
4 .
SRC U l t i m a t e
A n a ly s is
C
67.33%
H
5 ,6 0 %
N'
2 .2 8 %
S
0 .6 8 %
0
4 .1 1 %
Ash
0 .3 3 %
by PAMCO
35;
I
No c o m p l e t e compound a n a l y s i s i s
fo r
S o lv e n t-R e fin e d
5
lis ts
tio n
a r e known f o r
none o f w h ic h u s u a l l y
com pounds i n
p ro c e s s o f th e
in
th e p ro d u c t
th e ir
la rg e
fo llo w s
fra c tio n s .
(2 5 ):
C
number o f com­
e x c e e d s 2% c o n c e n t r a t i o n .
T a b le
f r o m U n io n C a r b i d e c o a l h y d r o g e n a ­
1 9 4 0 1s and 1 9 5 0 ' s ,
M o st c u r r e n t c o a l p r o d u c t s a r e c h a r a c t e r i z e d
b ility
th e l i t e r a t u r e
C o a l,
C o a l-d e riv e d l i q u i d s
pounds p r e s e n t ,
a v a ila b le
A .3.
in s o l.
by t y p e s o f s o l u ­
de R o s s e t o f UOP c h a r a c t e r i z e d
'
B enzene i n s o l .
89.4/a
3 4 .7 ^
D M F /X yle n e i n s o l .
0 .1 5 ^ -
Ash c o n t e n t
0.11%
an SRC sam ple
as
36>
T a b le
5.
\
T y p i c a l Compounds i n
A r o m a t i c In d a n e and H y d r o a r o m a t i c :
T e tra h y d ro n a p h th a le n e
N a p h t h a le n e
1- M e t h y ! n a p h t h a l e n e
2 - M e th y !n a p h th a le n e
2 , 3 - D im e th y ln a p h th a le n e
2 . 6 - D im e th y !n a p h th a le n e
2 . 7 - D im e th y ln a p h th a le n e
A c e n a p h th e n e
D ip h e n y l
F lu o re n e
9 , 1 0 -D ih y d ro a n th ra c e n e
A n th ra c e n e
P h e n a n th r e n e
and t h e f o l l o w i n g b a s e s :
P y rro le
P y rid in e .
2 - M e th y l p y r i d in e
3M e th y lp y rid in e
. A -M e th y lp y rid in e
2 - E th y l p y r i d i n e
3 - E th y lp y rid in e
A -E th y lp y rid in e
2 - M e th y 1 - 6 - e t h y l p y r i d in e
3M e th y I - 6 - et h y l p y r i d i n e
■A - M e t h y l - 2 - e t h y l p y r i d i n e
2 ,3 ,A -T rim e th y lp y rid in e
2, 3 , 5 - T r i m e t h y l p y r i d i n e
2 , 3 , 6 - T rim e th y lp y rid in e
2, A, 5 - T r i m e t h y l p y r i d i n e .
2 ,A ,6 -T rim e th y lp y rid in e
A n ilin e
2 - M e th y I a n i l i n e
3 - M e th y I a n i l i n e
A -M e th y la n ilin e
2 -E th y la n ilin e
• 2 ,3 -D im e th y la n ilin e
2 ,A -D im e th y la n ilin e
a C o a l-D e riv e d L iq u id
(1 3 )
A r o m a t i c and H y d r o a r o m a t i c
c o n tin u e d :
C h ry s e n e
P e ry le n e
P ic e n e
A lip h a tic :
ri-U n d e ca n e
_n-Dode cane
n i-T rid e c a n e
B -H e p ta d e ca n e
H e te ro c y c lic :
D ib e n z o fu ra n
B e n z o th io p h e n e
D ib e n z o th io p h e n e
2, 3 - D i m e t h y ! p y r i d i n e
2, A - D i m e t h y l p y r i d i n e
2, 5 - D im e t h y l p y r i d i n e
2, 6 - D im e t h y l p y r i d i n e
3, A - D im e th y lp y r id in e
3, 3 - D im e th y lp y r id in e
2 -ri-P ro p y lp y rid in e
2 - M e th y l- A - e th y lp y r id in e
2 .5 D im e th y la n ilin e
3 ,A -D im e th y la n iiin e
3 . 5 - D im e th y la n ilin e
1- Napht h y I am ine
. .
2N a p h th y la m in e
In d o le
2M e th y lin d o le 3 - M e th y lin d o le
C a rb a z o le
Q u in o lin e
2 - M e th y I q u i n o l i n e
7 -M e th y lq u in o lin e
Is o q u in o lin e
1- M e t h y I i s o q u i n o l i n e
3M e th y lis o q u in o lin e
37
M o b i l O i l (13) L s e d g r a d i e n t e l u t i o n
iz e
SRC i n t o
13 d i f f e r e n t
c h a ra c te riz a tio n
of
fra c tio n s .
a .W ils o n v ille ,
c h ro m o to g ra p h y to
T a b le
7
g iv e s
c h a ra c te r
and e x p l a i n s
a
A labam a SRC.
S o lv e n t C o m p o s itio n
The s o l v e n t
u se d i n
M o b il O i l re s e a r c h e r s
(A ),
a p p ro x im a tio n o f a r e c y c le
th e p r o je c t i s
one f o r m e r l y
The c o m p o s i t i o n
s o lv e n t
used by
mas c h o s e n due t o
w h ic h m ould be u se d i n
its
an SRC
p ro ce ss.
T a b le
6.
S o lv e n t C o m p o s itio n
(4 )
43/£ t e t r a l i n
3 8 ^ m e th y l n a p h th a le n e
17% m -p C r e s o l
2% gamma p i c o l i n e
C o n ta in s
Feed t o
,
th e
.36% S and .59% N
C o n tin u o u s R e a c to r '
The SRC s o l u t i o n
by p r e s s u r e - t e m p e r a t u r e
s o lv e n t-to -S R C
8 h o u rs,
th e
tre a tm e n t in
c o n tin u o u s r e a c t o r
mas p r e p a r e d
b a tc h
ft 1 . 5 : 1
c h a r g e mas p r e s s u r e d t o
0
t o 400 C and h e l d t h e r e
fo r
fe e d t o
fo r
a u to c la v e s .
2000 p s i g
o n e -h a lf h o u r.
d e p r e s s u r iz e d - a n d e m p tie d o f
in itia lly ,
The bomb mas a i r
s o lu tio n .
h e a te d
c o o le d
T a b le
7.
D e s c r i p t i o n , C o n c e n t r a t i o n , and Makeup o f
M o b i l ' s GEC F r a c t i o n A n a l y s i s o f SRC
Concn in GKC fraction (wt %)
Description
GEC JTncUon
I.
2.
Satoratcs
M N A -D N A oil
3. I’NA oil
4. PNAsoftresin
Colorless oil or white wax. melting
slightly above room temperature.
Very soluble in paraffinic solvents.
Very light yellow heavy oil,
sometimes with waxy solids, easily
melted. Very soluble in aromatic
solvents.
Bright yellow-orange oil.
Usually a tacky orange-red semisolid.
slow to turn fluid at elevated
• temperature, but pours readily at
200 0F.
5. Hard resin
6. PoIarresin
Bed brown powders which turn tacky
slightly above 100 °F. Extremely
viscous Iinuide at 240 eF.
7. Eluted asphaltenes Dark lirown powder. Behavior
intermediate between resins and
polar asphaltenes. Very soluble in
methylene chloride.
8-12. Polar asphaltenes Black powder, very friable. Very high
softening point. Poorly soluble in
methylene chloride, very soluble in
T i IF.
13. Nonelulcd
Among others, can he strongly acidic.
components (carboxylic acids),
inorganic solids (carbon, catalysts
fines, etc.).
Hydrocarbon
type
Satu­
rate
Paraffins
Olefins
Naphthenes
Monnaromatics
Diaromatics
Triaromatics
Tetraaromatics
Pcniaammatics
Aromatic sulfur
compounds
Unidentified
aromatics
37.9
Total
MNADNA
a
PNA oils
0.0
0.0
b
b
PNA snft
resin
0.0
.
b
Cl.O
1.1
0.0
0.0
0.0
0.0
0.0
0.0
44.7
25.4
9.1
0.5
7.2
5.5
0.0
7.7
59.8
15.5
8.3
4.2
2.6
0.0
9.6
11.4
15.7
27.1
18.2
9.8
0.0
7.G
1.9
8.2
100.0
100.0
100.0
100.0
% Insufficient sample.
h
Analysis not applicable.
GEC FR AC TIO N VLflV1BER
39
• P re s u lfid in g
R e a c to r
C o m rn e rica l c a t a l y s t s
fid e d .
S u lfid in g
are d r ie d
the" c a t a l y s t s
at
in c re a s e s c ra c k in g
a c tiv ity .
w ith
is
s u p p o rt sp h e re s,
th e r e a c to r
• is
fo r
th e n
s u l­
and d e n i t r o g e n a t i o n
o n e -fo u rth
one i n c h
a fo o t in to
in c h
t h e n more i n e r t
o f h y d r o g e n and 5 - 1 0 ^ h y d r o g e n
in e rt
I . D, s t e e l
it.
a lu m in a
sp h e re s.
s u l f i d e ■f l o w s t h r o u g h
t w e l v e h o u r s a t 350°.C and a t m o s p h e r i c p r e s s u r e .
m a in ta in e d w ith
s to re d in
a tiuo f o o t l o n g
th e rm o w e ll e x te n d in g
lo a d e d w ith
scrubbed w ith
c a ta ly s t is
is
th e n c a t a l y s t ,
A m ix tu re
is
re a c to r
a q u a r te r in c h
The p i p e
o u tg a s
a day,
.
The s u l f i d i n g
p ip e ,
IOQ0 C f o r
w a te r
a c o n tro lle r
c o o le d w ith
s e a le d j a r s
to
and s o d iu m h y d r o x i d e .
and e l e c t r i c
The t e m p e r a t u r e
p ip e h e a t e r .
c o n t i n u e d ga s f l o w .
S u lfid e d
p r e v e n t exposure to
a ir
The
The
c a ta ly s ts
are
and w a t e r .
R o c k in g Bomb R e a c t o r
A P arr s e r i e s 4000 p r e s s u r e r e a c t i o n
b a tc h ru n s
( 4 6 .■),
D e ta ils
o f th e h e a te r
The P a r r bomb was c h a r g e d w i t h
a ly s t.
T w e n ty m l.
a p p a r a t u s was u se d t o
and bomb a r e shown i n
s o lv e n t,
o f h e te ro g e n e o u s c a t a l y s t o r
s o lid
make
F ig u re 5
SRC, and c a t ­
10 m l , o f p o w d e rs and
s a l t s . w ere u s e d .
A p r e s s u r e head and c o p p e r g a s k e t f i t
An e i g h t - b o l t
s c r e w cap s e c u r e d t h e h e a d ;
c o n n e c t e d .to t h e h e a d .
on t h e
a p re ssu re
t o p o f t h e bomb.
gauge b l o c k was
40
B re a th e r
Tube /
A u to c la v e
body
T h e r m o c o u p le h o l e
Gauge b l o c k
i
I
F ig u re
5.
A u to c la v e
and H e a t e r
4 1.
The bomb mas p r e s s u r i z e d
a H a s k e l ga s c o m p r e s s o r
t h e bomb was p l a c e d i n
h e a t e r base and i n t o
(4 7 ).
If
hydrogen to
no l e a k s
a b o u t 2000 p s i g
a p p e a re d i n
th e r o c k e r - h e a t e r .
A b o lt
t h e bomb b o t t o m s e c u r e d i t .
t h e r m o c o u p l e was i n s e r t e d
The e l e c t r i c
w ith
w ith
d riv e
a P o w e rs ta t v a r ia b le
in to
a h o le o f th e
ro cke r
tra n s fo rm e r;
m in u te s ,
screw ed th r o u g h
th e
An i r o n - c o n s t a n t a n
s e c u rin g
was s t a r t e d ;
fiv e
w ith
b o lt.
h e a t i n p u t was c o n t r o l l e d
te m p e ra tu re
was g r a p h e d by a
H o n e y w e ll te m p e r a tu r e r e c o r d e r .
In itia l
r u n s w ere c o n d u c t e d f o r
o n e - h a lf hour a t 4 15-420 °C .
S u b s e q u e n t r u n s w e re a t & 3 5 -4 4 5 ° C s i n c e
50 m i n u t e s h e a t - u p
A fte r
w ere r e q u i r e d
th e ru n ,
p ro d u c t.
About
re a ch ru n te m p e ra tu re .
t h e bomb c o o l e d i n
p r e s s u r e was b l e d o f f g r a d u a l l y
liq u id
to
no c o k i n g was o b s e r v e d .
over
a ir
to
room t e m p e r a t u r e .
10 m i n u t e s t o
P r o d u c t s w ere s t o r e d i n
m in im iz e
g la s s b o t t le s
Gas
lo s s o f
u n til
a n a ly s e s
w ere p e r f o r m e d .
C o n tin u o u s R e a c to r
is
. •
The r e a c t o r
s y s te m i s
The r e a c t o r
is
packed w ith
s e c tio n ;
th e
c a ta ly s t
F i g u r e 6.
a o n e - i n c h 0 . D. t h r e e - f o o t l o n g
a s e c tio n ' o f i n e r t N o rto n
m id s e c t i o n
s u p p o r t ; th e b o tto m
s ta in le s s
shown i n
h o ld s
s e c tio n
is
D e n sto n e s u p p o r t i n
a 5 0 - 5 0 m ix o f a c t i v e
fille d
s t e e l th e r m o w e ll e x te n d s
w ith
fro m th e
and s u p p o r t .
0
In c o n e l p ip e .
in e rt
to p
It
th e to p
c a t a l y s t and i n e r t
s u p p o rt.
A 1 /4 “
down t h r o u g h
th e packed
42
Temp
Record­
er
Thermowel I
B a ll Check
Heater
Feed
R eservoir
& Feed
Lines
V ariable
Transformers
Micro
, M etering
Valve
C a ta lyst'
Inconel
Reactor
Aluminum
H eating
Jackets
G as-Liquid
Separator
Gas
I
Outlet
= : Gas I n l e t
L iq u id
Catchpot
'^ P r e s s u r e Release
liq u id O u tle t
FIGURE 6
Continuous Reactor
Hydrogen
..43
The r e a c t o r p i p e
is o th e r m a l o p e r a tio n .
b lo c k
fits
in
an a lu m in u m b l o c k ,
Three n ic h ro m e h e a t in g
a r e c o n t r o l l e d by m anual v a r i a b l e
c o n ta in e r
w ith
z o n o lite
in s u la tio n
to p ,
m id d le ,
and b o t t o m p a r t s
th e rm o c o u p le s are c o n n e c te d to
w i r e s w ra p p e d a ro u n d t h e
tra n s fo rm e rs .
in s id e
o f th e
A s h e e t m e ta l
e n c lo s e s th e
T hree c h ro m e -a lu m e l th e rm o c o u p le s i n
th e
w h ic h f a c i l i t a t e s
a lu m in u m b l o c k .
th e th e rm o w e ll m o n ito r
a c tiv e
c a ta ly s t
s e c tio n ;
th e
a L eeds and N o r t h r o p t e m p e r a t u r e
re c o rd e r.
T e c h n ic a l grade hydrogen flo w s
a b a ll
check v a lv e ,
th ro u g h
a N upro m e t e r i n g v a l v e ,
and p a s t a p r e s s u r e gauge i n t o
th e
to p o f th e
re a c to r.
A s o lu tio n
re s e rv o ir
th ro u g h
of
1 /8 "
s o lv e n t- r e fin e d
s ta in le s s
s te e l
a H ills -M c C a n n a c h e m ic a l p r o p o r t io n in g
and pump a r e a l l
p lu g g in g
lin e s
e le c tric a lly
a l y s t bed and i n t o
and i n t o
pump.
The r e s e r v o i r , t u b i n g ,
h e a te d to p r e v e n t th e
th e g a s - l i q u i d
down i n t o
th e
t h e r e a c t o r - by
fe e d s to c k
and c a t c h p o t i s
p re s s u re re le a s e
v a lv e
c lo s e d .
downward t h r o u g h
s e p a ra to r.
are scru b b e d ,
liq u id
Ta e m pty t h e c a t c h p o t ,
a ra to r
a g la s s
tu b in g
and h y d r o g e n f l o w
G rove b a c k - p r e s s u r e r e g u l a t o r ,
drop
pumped f r o m
fr o m
o r pump c h e c k v a l v e s .
The SRC s o l u t i o n
L iq u id s
coal is
th e c a t ­
Gases p a s s t h r o u g h t h e ■
and v e n t e d i n t o
a hood.
c a tc h p o t.
t h e v a l v e b e tw e e n t h e
P ressure i s
and p r o d u c t i s
(I
le t
c o lle c te d
g a s -liq u id
se p ­
d o w n .th ro u g h th e
fro m
th e b o tto m o f th e
44
c a tc h p o t.
n itro g e n
A fte r
th ro u g h
t h e p r o d u c t dump, t h e c a t c h p o t i s
t h e ga s i n l e t
and t h e p a t c h p o t i s
The c y c l e
is
re -o p e n e d ,
re p e a te d f o r
v a lv e .
w ith
The v a l v e
b e tw e e n t h e
no d i s r u p t i o n
ecery l i q u i d
r e - p r e s s u r iz e d w ith
s e p a ra to r
o f s y s te m p r e s s u r e .
s a m p le .
/
C o n t i n u o u s Runs
The f o l l o w i n g
p ro je c t.
d e s c rib e s th e
One p r e l i m i n a r y
r u n had m i n o r
and t h e r m o c o u p l e p l a c e m e n t ,
c o n d u c t e d as o u t l i n e d
A ru le
re a c to r
w ith
d iffe re n c e s
b u t th e r e s t o f th e
in
c a ta ly s t
th a t
th e rm o w e ll i n
100 m l.
p la c e .
1 / 4 " spheres i n e r t
N o r t o n D e n s to n e s u p p o r t
amount
c o n t i n u o u s r u n s w ere
of
s m a ll p e l l e t s
The r e a c t o r
was f i l l e d
9 ^-1 6 "
of
as f o l l o w s :
120 m l.
1 3 .5 "
p re h e a t
s e c tio n
5 0 - 5 0 m ix o f c a t a l y s t
140 m l.
and i n e r t D e n s to n e
(70 m l. a c t i v e c a t a l y s t )
14"
re a c tio n
s e c tio n
1 /8 ”
8"
D e n s to n e
f ill
15 m l.
1 /8 " e x tr u s io n s
i n e r t N o r t o n D e n s to n e
su p p o rt
in e rt
th e
h e re .
o f thum b i s
th e
b e s t p ro c e d u re d e v e lo p e d d u r in g
80 m l.
R e s t', was f i l l e d w i t h 1 / 4 "
s p h e r e s and s t e e l s c r e e n .
to h o ld p a c k in g m a t e r ia l
i n n la r.e
T h e r m o c o u p le s w e re p l a c e d i n
tu re s
in
th re e p a rts
o f th e r e a c t o r .
th e th e rm o w e ll to
The f i r s t
m e a su re te m p e r a ­
was 1 0 ^ ”
in to
45
th e packed m a t e r ia l
se c o n d mas 20 1 / 4 "
th ird
mas 28 1 / 4 "
(n e a r th e b o tto m o f th e p re h e a t s e c t i o n ) .
in to
in to
The r e a c t o r
p ro d u c t
s e p a ra tio n
t h e bed ( j u s t
mas p l a c e d i n
and c o l l e c t i o n
s y s te m mas p r e s s u r i z e d
The r e a c t o r
ho u rs.
th e b e d .( c e n te r o f th e r e a c t io n
and t e s t e d
mas h e a t e d t o
a lu m in u m b l o c k .
fo r
N o rth ru p
and i n d i c a t e d
s e c tio n ).
Feed l i n e s
p i e c e s mere c o n n e c t e d ;
■
and
t h e mhole
le a k s .
s te a d y
s ta te
Power i n p u t mas m a n u a l l y c o n t r o l l e d
a b le t r a n s f o r m e r s
s e c t i o n ) . . The
b e lo m end o f r e a c t i o n
th e
The
by t h r e e
te m p e ra tu re re c o rd e r p r in t e d
te m p e ra tu re
w ith
th re e
a m p m e te rs .
in
about 8
P o m e rs ta t v a r i ­
The L eeds and
bed t e m p e r a t u r e s
d u rin g
a fo u r-
m in u te c y c le .
H y d ro g e n f l o w
to
th e r e a c t o r
mas c o n t r o l l e d ' by a m i c r o z
m e te rin g v a lv e .
E x p e rie n c e
m e te rin g v a lv e
is
o ff-g a s e s
s im ila r
o ff-g a s
to
fro m
showed t h a t c a l i b r a t i o n
u n re lia b le .
re a c to rs
A c h ro m a to g ra p h ic
th e o f f - g a s
a n a ly s is
a tte m p t o f
a t M o n ta n a S t a t e U n i v e r s i t y
be o v e r w h e l m i n g l y h y d r o g e n .
mas c o n n e c t e d a f t e r
o f th e m ic ro -
T h e re fo re ,
scrubber to
fo u n d t h e
a met t e s t m e te r-
m easure t h e h y d r o g e n f l o w
ra te .
A fte r
mas b e g u n .
v o ir.
s in c e
-
th e hydrogen r a t e
pum ping o f t h e
F lo w mas m ea su re d by t h e l e v e l
H y d r o g e n and l i q u i d
b o th te n d e d t o
10% o f t h e
mas s e t ,
flo w r a te s
flu c tu a te .
in
a g ra d u a te d g la s s r e s e r ­
w ere c h e c k e d e v e r y
F lo w s c o u l d u s u a l l y
d e s ire d h y d r o g e n - t o - o il r a t i o .
SRC s o l u t i o n
20 m i n u t e s
be c o n t r o l l e d
to
46
Once b o t h
re a c to r
F lo w r a t e s
was o p e r a t e d a t c o n s t a n t c o n d i t i o n s
beFore th e
F irs t
p a r a m e t e r s w e re c h a n g e d ,
P o t e n t ia l p lu g g in g
runs la s te d
a 60 m i n u t e t r a n s i t i o n
T ra n s itio n
From c a t c h p o t b e F o re sa m p le p e r i o d
Each sa m p le p r o d u c t was a b o u t 80 t o
m o n ito rin g ;
th e
F o r a t l e a s t 90 m i n u t e s
a t c o n s t a n t c o n d i t i o n s was a l l o w e d .
w e re c l e a r e d
w ere s t e a d i e d o u t ,
sample, p e r i o d b e g a n .
When o p e r a t i n g
p e rio d
and t e m p e r a t u r e
p e rio d p ro d u c ts
c o lle c tio n
began.
100 m l.
oF t h e r e a c t o r
From t w e l v e
to
s y s te m r e q u i r e d
tw e n ty h o u rs ,
w ith
c o n tin u o u s
Four to
n in e
sa m p le p r o d u c t s p e r r u n .
A F te r th e r u n ,
w ere h a l t e d .
lin e s
M o to r o i l
From t h e r e a c t o r ;
it
s o lu tio n ,
was pumped t h r o u g h
and l o o s e n r e a c t o r
The Feed l i n e s
h o t.
F e e d s to c k
th e
and pow er i n p u t
s y s te m t o
h e lp
c le a n
p a c k in g .
and b o t t o m c o l l e c t i o n
p i e c e s w e re d i s c o n n e c t e d
t h e r e a c t o r was re m o v e d From t h e
The t h e r m o w e l l m u st be p u l l e d
and t h e p a c k i n g
h ydrogen ,
u s u a lly
w h ile
become s t u c k
b lo c k w h ile
th e r e a c to r
and t h e p i p e
is
h o t,
s till
o th e rw is e
m ust be d r i l l e d
o u t.
A c e to n e i s
th e m .
A l l p ie c e s
pumped t h r o u g h
th e r e s e r v o ir
From t h e r e s e r v o i r
d i s m a n t l e d and c l e a n e d i F
n e ce ssa ry.
c a t c h p o t a re c le a n e d w i t h
a ce to n e ;
d is m a n tle d
and c l e a n e d .
to
and l i n e s
th e o u t l e t
to
c le a r
s i d e oF t h e pump a r e
The r e a c t o r p i p e ,
s e p a ra to r,
th e .b a c k p re ssu re r e g u la to r
is
and
47
A n a ly tic a l
P ro ce d u re s
P ro d u c ts fro m
d e te rm in e th e
was t o
and c o n t i n u o u s r u n s w ere a n a l y z e d t o
degree o f c ra c k in g .,
W a te r i n
so D r i e r i t e
th e b a tc h
th e
d e n itro g e n a tio n ,
sam ple i n t e r f e r e d
w ith
( a n h y h d r o u s CaSO^) was u s e d .
d ire c tly
add Jf te a s p o o n o f
th e
and d e s u l f u r i z a t i o n
d is tilla tio n
The o n l y e f f e c t i v e
D r ie rite
to
100 m l.
a n a ly s is ,
m ethod
s a m p le s i n
s e a le d j a r s .
An i n d i c a t i o n
d is tilla tio n
o f c ra c k in g
m ethod D-86 (• 48 ) .
o f d is tilla b le s
a llo w s c a lc u la t io n
I
in
c o m b u s t i o n m e th o d ,
fe re n ce o f t i t r a t i o n
s a m p le s (
s a m p le s i s
te m p e r ­
ASTM m ethod D1551
d e t e r m i n e d by t h e
( 4 9 ,' 5 0 ).
th e
ASTM D15 5 1 .
s u lfa te
in te r­
A g ra v im e tric
u s in g b a riu m c h l o r i d e
was
51 ).
in
s a m p le s was d e t e r m i n e d by t h e M acro
ASTM E 258 ( 5 2 , 53 -).
C h ro m a to g ra p h ic a n a l y s i s o f c o n tin u o u s r e a c t o r
been s u c c e s s f u l l y
vs.
c a t a l y s t r u n s had h y d r o g e n c h l o r i d e
W e ig h t p e r c e n t n i t r o g e n
K j e l d a h l m e th o d ,
th e
m e a su re m e n t i n
p r o c e d u r e w h ic h p r e c i p i t a t e d
th o se
am ounts
o f c ra c k in g .
S am ples f r o m m e t a l c h l o r i d e
used f o r
curve s o f p e rc e n t d i s t i l l e d
W e ig h t p e r c e n t s u l f u r
q u a rtz -tu b e
T h i s m ethod d e t e r m i n e s t h e
a t t e m p e r a t u r e s b e tw e e n 70 and 7 0 0 ° F . .'C o m p a ris o n o f
f e e d and p r o d u c t d i s t i l l a t i o n
a tu re
was d e t e r m i n e d by ASTM a t m o s p h e r i c
done.
o f f - g a s has n o t
RESULTS AND DISCUSSION
The o b j e c t o f t h e
PAMCO1s SoI v e n t - R e f i n e d
c o m m e rc ia l c a t a l y s t s
e x p e r i m e n t s mas t o
C o a l (SRC) t o
w e re f i r s t
c le a n
te s te d ,
c a ta ly tic a lly
d is tilla te
th e n c a t a ly s t s
co n ve rt
fu e ls .
A v a ila b le
p re p a re d here a t
M o n ta n a S t a t e U n i v e r s i t y .
L iq u id
to
700°F;
c o n v e r s i o n mas m ea su re d by d i s t i l l a t i o n
s u lfu r
o f'p r o d u c ts
c o n t e n t o f t h e p r o d u c t s mas d e t e r m i n e d by t h e
t u b e c o m b u s t i o n m e th o d ;
n itro g e n
up
q u a rtz
c o n t e n t mas d e t e r m i n e d by t h e M acro
K j e l d a h l m e th o d .
T w e n ty -e ig h t c a t a ly s t s
fiv e
c a ta ly s ts
te m p e ra tu re ,
w ere u s e d i n
re s id e n c e tim e
and h y d r o g e n - t o - o i l r a t i o
th e ,tric k le
on t h e
(in
c o n tin u o u s ru n s .
te rm s o f l i q u i d
w e re i n v e s t i g a t e d
A p p e n d ix B.
s u p p o rt,
c a ta ly s ts
h e te ro a to m re m o v a l,
in
fiv e
th irty -tw o
in
b a tc h ru n s ;
The e f f e c t s
h o u rly
of
sp a c e v e l o c i t y ) ,
th e c o n tin u o u s ru n s o f
bed r e a c t o r .
M e ta l lo a d in g ,
a v a ila b le
w ere u se d i n
s u rfa c e
te s te d
are l i s t e d
and r u n c o n d i t i o n s
A p p e n d ix C c o n t a i n s
and r u n c o n d i t i o n s
fo r
a ll
a re a ,
fo r
and p o r e v o lu m e d a t a
in
A p p e n d ix A.
each b a t c h t e s t
c o n v e rs io n s ,
C o n v e rs io n ,
a re l i s t e d
h e te ro a to m re m o v a l,
c o n tin u o u s ru n s .
P r e l i m i n a r y Runs
Feed S o l u t i o n - 'PAMCO1s S o l v e n t - R e f i n e d C o a l i s
s o lid
a t room t e m p e r a t u r e ;
Such a s o l i d
c o u ld n 't
s o lv e n t v e h ic le
o n l y 3% o f i t
be e a s i l y
mas u s e d .
w ill
pumped i n t o
b o il o f f
a d a rk,
up t o
s h in y
6 5 0 °F ( 1 3 ) .
a c o n tin u o u s r e a c t o r ,
so a
49
A s u ita b le
ERDA U n i v e r s i t y
s o lv e n t
fo r
c o a l w o rk mas s u g g e s t e d a t t h e
C o n t r a c t o r s C o n fe re n c e .
It
is
d e s c rib e d i n
1975
M a te ria ls ,
E q u ip m e n t and P r o c e d u r e s . The use o f as l i t t l e
tu re s
n e ce ssa ry.
coal o il
s o lv e n t,
To r e t a i n
th e
r a tio
b o ilin g
in
th e
o ff.
n itro g e n
SRC m i l l
s y n th e tic
d is s o lv e
coal o il
in
o f th e 7 :2
D is tilla tio n
th e
liq u id
s o lu tio n
and l i n e s
e l e c t r i c a l h e a tin g
-
L iq u id
c o n v e rs io n
was
o f th e
ta p e s to
coal s o lu tio n
showed t h a t 79% o f i t
21% o f n o n - d i s t i l l a t e s
o f th e
s y n th e tic
b e lo w 7 0 0 ° F ,
c o n v e rs io n s
fo r
d a t a was o b t a i n e d by
th e o r i g i n a l 7 :2
coal o il
but ve ry l i t t l e
th e p r o je c t
s o lu tio n .
b o ils
b e lo w
decom poses a bove 4 7 5 ° F .
s o lv e n t a lo n e
b e lo w 4 7 Q ° F ; 2% decom poses a bove 4 7 0 ° F .
s o lv e n t b o i l s
700°F,
T h is
The r e s e r v o i r , pum p, v a l v e s
D e fin itio n s
th e re m a in in g
d is tills
s o l v e n t - t o - c o a l w e ig h t
I I Q 0 C.
c o m p a r in g c a t a l y t i c a l l y - t r e a t e d p r o d u c t w i t h
475°Fj
gamma p i c o l i n e ,
s o lu tio n .
A n a ly tic a l
D is tilla tio n
of a
120°C a t
c o m p o n e n t,
a 7 :2
s o lv e n t a t
a p p a r a t u s w ere m o d i f i e d w i t h
h a n d le th e h o t
made e l e v a t e d te m p e r a ­
compound c h a r a c t e r i s t i c s
w here t h e m ost v o l a t i l e
p i c k e d as t h e f e e d s t o c k .
c o n tin u o u s
th e
as p o s s i b l e
s o l v e n t c o u l d n o t be h e a t e d p a s t
.a tm o s p h e ric p r e s s u r e ,
s ta rts
s o lv e n t
showed 98%
S in c e e s s e n t i a l l y
s o lid
SRC d i s t i l l s
w ere d e f i n e d
as f o l l o w s :
a ll
b e lo w
50
liq u id
c o n v e rs io n
L iq u id
c o n v e rs io n i s
becomes d i s t i l l a t e .
p ro d u c t,
th e
th e l i q u i d
_ % to ta l d is tilla te
^ to ta l d is tilla te
~
i n p r o d u c t _____________ i n f e e d ___________
% n o n - d i s t i l l a t e i n fe e d
th e -p e rc e n ta g e
am ount o f n o n - d i s t i l l a t e
If
of
no i n c r e a s e
c o n v e rs io n i s
c o n v e rs io n i s
ze ro .
in
c^e ^ ~
is
was 0.4 3 $ ! s u l f u r
1
in
o b ta in e d
7.
at
d is tilla te
th e
becomes IOO^o,
as f o l l o w s :
/o s u l f u r
in
in
th e
1000 p s i g ,
j
of
P ro d u ct
a liq u id
fe e d
same m a n n e r .
100 m l ;
1 0 ,0 0 0
th e
1,
h o u rly
The d i s t i l l a t i o n
are g ra p h e d w it h
d e fin e d
- /o s u l f u r
i n fe e d
com p a re d t o
;
is
C o n t i n u o u s Run -
and h y d r o g e n f l o w
F ig u re
n o te d i n
The 7 : 2 c o a l s o l u t i o n
and 0 . 9 6 5 % n i t r o g e n .
was made a t 4 5 0 ° C ,
th e p ro d u c t i s
to ta l
% s u lfu r
p ro d u c t
d e fin e d
P re lim in a ry
a ly s t,
th e
is
100/o.
P ercent d e s u lf u r iz a t io n
D e n itro g e n a tio n
If
d is tilla te
v
th a t
The f i r s t
o f N i- 4 4 0 1
S C F /b b l o i l .
d is tilla tio n
spa ce v e l o c i t y
s e rie s
n ic k e l tu n g s te n c a t ­
The d i s t i l l a t i o n
o f th e 7 :2 s o lu t io n
d i s p l a y e d on t h e
curve s o f p ro d u c t
te m p e ra tu re
c o n tin u o u s ru n
d is tilla tio n
(L U SU) o f
I
of
fe e d
g ra p h ,
was
2.
and t h e 7 : 2
s o lu tio n
v e r s u s v o lu m e p e r c e n t d i s t i l l a t e
E ig h ty -o n e
and a h a l f p e r c e n t o f t h e p r o d u c t d i s t i l l e d
The l i q u i d
c o n v e r s i o n I.
fe e d
c o lle c te d .
b e lo w 7 0 0 ° F .
.
'
--------------------- -------------------- — ------------------------------------------------------------------------------------------------------------------- ----- 1------------
51
81.5!.s ( p r o d u c t d i s t i l l a t e s ) - 79/o ( s o l u t i o n
21/o ( s o l u t i o n f e e d n o n - d i s t i l l a t e s )
Feed d i s t i l l a t e )
= 12#.
F o r P r o d u c t . 2,
re m a in e d th e
s ta te
s e ttle
same as f o r
o p e ra tio n .
to
P roduct
The ga s r a t e
a ste a d y v a lu e .
by p u m p in g s t r a i g h t
ro se r a p id ly . .
L a te r
LHSV was c h a n g e d t o f
e x a m in a tio n
The r e a c t o r
surged th e
e n tire
The r u n was h a l t e d
s o lv e n t.
The e n t i r e
1.
and a l l
o th e r c o n d itio n s
never re a c h e d s te a d y
p e rio d
and d i d n o t
and c l e a n i n g
a tte m p te d
The r e a c t o r p l u g g e d a b r u p t l y
and p r e s s u r e
s y s te m was s h u t down and a l l o w e d t o
f o u n d a h a r d c a r b o n b l o c k had s e t up i n
c o o l.
th e r e a c to r
p ip e .
S e v e r a l i m p o r t a n t . c o n c l u s i o n s c o u l d be made a b o u t t h e r u n :
1)
M o d ific a tio n
O u tle t liq u id s
re g u la to r
th e r e a c tio n
P o s s ib ly
tin u o u s re a c to r
fa r,
fo r
to
th e
and s i m p l e r
The o t h e r p o s s i b i l i t y
h ig h
and
was t h a t
and t h e
s o lu tio n
c a rb o n .
fo r
c le a n in g
and p r e p a r i n g
n e x t r u n was t o o
to
bombs w e re u s e d t h e r e a f t e r
p ro m is in g ones.
be made.
gummed up t h e v a l v e
t e m p e r a t u r e o f 450°C was t o o
Turn around tim e
a re f a s t e r
liq u id s
th e r e a c t o r .
. fe e d cra c k e d to o
2)
s y s te m had t o
and g a s e s b o t h p a s s e d t h r o u g h t h e b a c k p r e s s u r e
v a lv e .
b a c k e d up i n t o
o f th e r e a c to r
lo n g .
p re p a re , o p e ra te ,
to
th e
con­
B a t c h bombs
and c l e a n .
scre e n poor c a t a ly s t s
fro m
B a tc h
T e m p e ra tu re i n
52
: 2 F eed
P ro d u ct
1
40
Volume P e r c e n t
60
D is tille d
F ig u re ? .
P ro d u ct I
Compared t o 7 : 2 S o l u t i o n Feed
53
Bomb Runs S t u d y i n g
V a r ia b le s O th e r
bomb r u n s w ere made w h ic h t e s t e d
ru n s
a re
lis te d
in
v a ria b le s
Two bombs w ere c h a r g e d w i t h
to
o th e r th a n c a t a l y s t .
The
fir s t
page o f A p p e n d ix
of
mas i n v e s t i g a t e d .
'
The e f f e c t o f i n i t i a l
th e o th e r
E ig h t
c h r - o n o l o g i c a l o r d e r on t h e
B , B a tc h Run D a ta .
gram s o f N i- 4 4 0 1
Than C a t a l y s t Type -
c a ta ly s t,
500 p s i g .
charge p re s s u re
1 25 g r . o f h o t 7 : 2 c o a l s o l u t i o n
b u t one was p r e s s u r i z e d t o
Run t i m e
was o n e - h a l f h o u r
and 20
2100 p s i g
and
a t 415-420 °C .
T h r e e o b s e r v a t i o n s w ere made:
1)
to
D u rin g
a ru n ,
bomb p r e s s u r e s i n c r e a s e d w i t h
a p e a k , th e n d e c re a se d r e g a r d le s s o f th e
40 0 °C was t h e
■n o t e d .
T h is
t h a t 400°C. i s
lo w e s t te m p e ra tu re
te m p e ra tu re .
a t w h ic h t h e
s u g g e s ts t h a t hydrogen i s
te m p e ra tu re
d e c r e a s e was
consumed, by r e a c t i o n
a b o u t t h e minimum r e a c t i o n
and
te m p e ra tu re .
I
2)
The p r o d u c t s w ere hom ogen eous,
liq u id s
a t room t e m p e r a t u r e
th e 7 :2
a tm o s p h e ric
p re c ip ita te s
3)
and p r e s s u r e .
s o lu tio n
fr o m t h e 7 : 2
The h i g h p r e s s u r e
tio n ,
23% t o
and 35% t o
12% l i q u i d
fe e d i s
s o lu tio n
e a s y -p o u rin g
The c h a r a c t e r o f
q u ite
a t le s s
fa v o re d l i q u i d
in c re a s e d h e te ro a to m re m o v a l.
d a ta are
b la c k ,
d iffe re n t.
th a n
SRC
1 0 0 - 1 IQ 0 C.
c o n v e rs io n
and m i l d l y
H ig h v e r s u s l o w p r e s s u r e p r o d u c t
c o n v e r s i o n , . 53% t o
20% d e n i t r o g e n a t i o n .
44/a d e s u l f u r i z a ­
54
A ru n w ith
SRC and 20 g r .
no s o l v e n t ,
ju s t
SRC and c a t a l y s t , was d o n e .
p o w d e re d c a t a l y s t - w e r e
fe w d r o p s o f l i q u i d
fo r m e d ;
ru n
a p p a re n tly
a t 725 p s i g
s o lv e n t i s
3 8 .9 g r
and 4 2 0 ° C .
n eede d f o r
A
good
c a ta ly s t c o n ta c t.
The q u e s t i o n
a r o s e w h e th e r t h e homogeneous p r o d u c t s
fir s t
tw o bomb r u n s w ere room t e m p e r a t u r e
a tu re
and p r e s s u r e
e ffe c ts
The u n c a t a l y z e d
one h a l f h o u r
SRC i n t o
tu re
or c a ta ly s t
fo u rth
a s o lu tio n
th a t
because o f te m p e r­
e ffe c ts .
ru n l i s t e d
a t 4 1 5 - 4 20°C ,and 750 p s i g
s o lu tio n s
fro m th e
in
A p p e n d ix B c o n f i r m e d t h a t
i n i t i a l p re ssu re
w ill- d is s o lv e
s t a y s hom ogenous when r e d u c e d t o
room te m p e r a ­
and p r e s s u r e .
S o lu tio n -to -S R C r a t i o
te s te d
in
th re e
versu s
s o lu tio n
c h a ra c te ris tic s
more bomb r u n s w i t h o u t c a t a l y s t
and d n e - h a l f h o u r
a t 415-420 °C .
The r e s u l t s
a t 750 p s i g
a re l i s t e d
in
were
in itia l
T a b le 8.
55
T a b le 8.
S o lv e n t-to -S R C
R a tio
7 :2
S o lu tio n
C h a ra c te ris tic s
H ig h e s t P re ssu re
D u r in g Run
Homogeneous
e a s y -p o u rin g
A b o u t 1600
D a r k e r and more
v is c o u s th a n 7 :2 , b u t
s t i l l pours e a s ily
A b o u t 1600
1 :1
V e r y s t i c k y and v i s c o u s
t a r - l i k e m a te ria l
A b o u t 1600
3: 2
Much more- l i q u i d
t h e 1 :1
A b o u t 1600
3 :2 s o lv e n t-to -S R C
7 :2
liq u id
2 :1
S in c e h i g h v i s c o s i t y
a ly s t
S o l v e n t R a t i o T e s t Runs
te s ts .
s o lu tio n .
th a n
i n c r e a s e s mass d i f f u s i o n
s o l u t i o n . w a s c h o s e n as o p tim u m f o r
The 3 : 2
s o lu tio n
w ill
re s is ta n c e ,
a ll. fu tu re
th e
c a t­
be much more c o n c e n t r a t e d t h a n t h e
T h a t s h o u ld h e lp r e a c t io n s
and r e d u c e e r r o r
in
c o n v e rs io n
c a lc u la tio n s .
L e s s s e v e r e t e m p e r a t u r e s and r e s i d e n c e
enous 3 :2
775 p s i g
s o lu tio n ,
in itia l
se ve re ru n
to o ..
w ill
A 3 : 2 bomb r u n a t 365°C f o r
p re s s u re
a t 420°C f o r
tim e
y ie ld e d
a p roduct s im ila r
o n e -h a lf h o u r.
to
g iv e
fiv e
th e
a homog­
m i n u t e s and
lo n g e r ,
more
56
C a ta ly s t
S c r e e n i n g Bomb Runs -
(te m p e ra tu re , p re s s u re ,
to -S R C r a t i o )
c o n d itio n s
mere a l l
ru n tim e ,
fix e d
in
s o lv e n t typ e
th e
o f th e ru n s are l i s t e d
L iq u id
ch arge -
In itia l
H e a t-u p p e r io d -
in
th e
fir s t
or te n m i l l i l i t e r s
p a rtia lly
c a ta ly tic
o f one c a t a l y s t
one o f t h e
th a n th e r e s t .
r a tio
s e rie s .
It
T m e n ty m i l l i l i t e r s
th e g r e a te r
th a n p e l l e t s
mas
c o n c e n tra tio n o f a c tiv e
a c tiv ity
of
a n o th e r.
c o m p a r in g t h e
Many f a c t o r s
F a c to rs in flu e n c in g
a c tiv ity
in flu e n c e
h e te ro g e n e o u s
in c lu d e :
-
ty p e
-
s u p p o r t c o m p o s i t i o n and c r y s t a l l i n e
-
s u p p o rt pore
-
a c tiv e
and l o a d i n g
o f c a ta ly tic
d ia m e te r
s u rfa c e
m e ta ls
o f re a c tio n
s tru c tu re
and p o r e vo lu m e d i s t r i b u t i o n
are a
o f a g i v e n p e l l e t o r . pomder ca n a l s o
lim ita tio n
mas.
o f homogeneous pomder c a t ­
c a t a l y s t m ust be c o n s i d e r e d i n
th e
The
hom ogeneous p o m d e r s .
o f a g iv e n c a t a l y s t .
c a ta ly s ts
The s i z e
to
s o lv e n t-to -S R C
L e s s pom der c a t a l y s t
c o m p e n s a te f o r
The e n t i r e
a c tiv ity
each r u n .
m a te ria l in
bomb r u n s .
4 3 5-445 C
o f p e lle t-rty p e
u se d t o
and. s o l v e n t -
I hour
and p r e s s u r e
mere used i n
s c re e n in g
3 :2
r u n a t Io rn e r t e m p e r a t u r e
a ly s ts
and a m o u n t,
b e lo m :
CoMo - 0 4 0 1 ,
c a ta ly s ts
v a ria b le s
1 9 0 0 -2 0 0 0 p s i g
about
Run t e m p e r a t u r e The one e x c e p t i o n i s
c a ta ly s t
175 g r t o t a l ,
p re ssu re -
The r e a c t i o n
ra te .
A ll
a f f e c t p o re
th e s e p r o p e r t ie s v a ry
d iffu s io n
among t h e
th e
57
c a ta ly s ts
A p p e n d ix
te s te d ,
as l i s t e d
in
D e s c rip tio n
a c tiv itie s
va ry in
many r e s p e c t s ,
m ust be made b e tw e e n s p e c i f i c
tw e e n c a t a l y s t s
w ith
g e n e ra liz a tio n s
to
some s i m i l a r i t i e s
is
lis te d
in
are th e
iro n -c h ro m a te
c h ro n o lo g ic a lly
tw o G i r d l e r
A g r o u p i n g by m e t a l
w ere s u l f i d e d ;
iro n -c h ro m a te s ,
on CAS-3QKR s i l i c a
b e g in n in g
T a b le 9.
.M o s t o f t h e c o m m e r c i a l c a t a l y s t s
c a ta ly s ts
C o m p a r is o n s b e ­
may n o t be p o s s i b l e .
A p p e n d ix B , B a tc h Run D a ta .
c a ta ly s ts
c o m p a ris o n o f
ca n be made, b u t e x t e n s i o n o f
t e s t bomb r u n s a r e l i s t e d
s e c o n d page o f
ty p e o f t e s t e d
c a ta ly s ts .
b road c la s s e s o f c a t a l y s t s
A ll c a ta ly s t
and a l l
o f C a t a l y s t s Used,
A.
B ecause t h e c a t a l y s t s
on t h e
th e
a lu m in a ,
u n s u lfid e d
C r-0 1 0 5 i n
th e p la in
one r u n ,
th e
s u p p o r t CA5-30KH,
th e m e ta l c h lo r id e s .
T a b le 9.
B a tc h C a t a l y s t s
T e s t e d by M e t a l Type
N i-M o
---H a rs h a w H T - 100
- H arshaw HT-500
- MSU S T K -I
S u p p o rte d
- N iC l
on C e l l i t e 410
M e t a l C h l o r i d e s - N i C l ^ on CAS-30KR
- C dC lg on CAS-30KR
N i-W
- H a rsh a w N i - 4 4 0 1
- H arshaw N i - 4 3 0 3
- K e tje n
HC-5
- K e tje n
3 3 0 -E 3
M e ta l C h lo rid e
P ow ders
Co-Mo
- H arshaw Co-Mo 0401
- H arshaw Co-Mo 0603
- H a rsh a w H T-400
Cr and - H a rsh a w C r - 0 1 0 5
F e -C r
- H a rsh a w C r - 0 3 0 4
- G i r d l e r G-3A t a b l e t s
- F e -C r on CAS-30KR
O th e rs '
H arshaw W-Q1 0 1
H arshaw M o - 1 2 0 1
H arshaw N i - 3 2 1 0
Sn pow der
CAS-30KR u n l o a d e d s u p p o r t
58
The c a t a l y s t s
in
th e
fo llo w in g
are ra n k e d a c c o r d in g
ta b le .
p ro d u ct d is t r ib u t io n ,
The N i - 4 4 0 1
and o v e r a l l
w ere h i g h e r
o th e r
re s u lts .
fo r
h e te ro a to m re m o va l i s
ru n
c o n c e n tra te d
e a s ie r
fr o m t h e
d is tilla te
and d e n i t r o g e n a t i o n .
th e v e ry
u s in g th e
c a ta ly s ts
p roduct q u a lity
b a tc h c a t a l y s t s ,
tw ic e :
fir s t
s ta n d a rd 3 :2
b a tc h ru n
s o lu tio n
m ust be made u s i n g t h e lo w
As ca n be s e e n ,
th e le s s
th e
d is tilla te
d e s u lfu riz a tio n
lis te d
and a l a t e r
C o m p a r is o n w i t h
s o lv e n t r a t i o
10 l i s t s
c a ta ly s t is
u s i n g .7 :2 s o l u t i o n ,
fe e d .
T a b le
to
s u lfu r
and n i t r o g e n r e m o v a l
s o lu tio n .
lig h t
T h is in d ic a t e s
s o lv e n t f r a c t i o n
th a t
th a n fro m
t h e h e a v y SRC f r a c t i o n .
N iC lg i s
a ls o
a r e a s u p p o r t and t h e
lis te d
24% N i C l g i s
The s u p p o r t s a r e n o t e d i n
s u p p o r t N i C l g had b e t t e r
The f i v e
tw ic e :
d e ta il
in
3% CoO,
-
N i-4 3 0 3 ,
-
K e t je n 330-E 3,
-
A l C l 3 pow der
s u rfa c e
A p p e n d ix A.
h y d ro c ra c k in g
on 3M / g r , s u r f a c e
a re a s u p p o rt.
The h i g h
s u rfa c e
and d e s u l f u r i z a t i o n .
c a ta ly s ts
w ere:
15% MoO^ on a l u m i n a
- H T - 5 0 0 , 3.2% N iO ,
and
on 43M / g r .
b e s t h y d ro c ra c k in g
- H T -400,
' t h e -15^ N i C l g i s
6% N iO ,
15.5% MoD^ on a l u m i n a
19% WO^ on a l u m i n a
6.6% N iO ,
19.8% VJO3 on a l u m i n a
area
59
T a b le
BATCH CATALYSTS - RANKED-BY DISTILLATE CURVE QUALITY
P ercent
P ercent
P ercent
P ercent
P e r c e n t P e r aN a p h th a
DeS
Fuel O il
Gas O i l
cent
R e s id u e
I B P - 4 2 5 °F 4 2 5 - 6 0 0 ° F
DeN
6 00-700 °F
C a ta ly s t
-14
22
0
94
29
G i r d l e r . G-3 t a b l e t
( F e 2O , )
C r-0 3 0 4 , u n s u l.
0
8
0
92
' o
0
11
0
89
0
0
C r-0105,
0
8
0
94
0
0
0
11
0
86
6
0'
8
8
89
46
22
-1 1
25
0
86
12
•13
W-OIOI
-8
25
0
.8 3
15% N i C l 2 on 86%
s ilic a
-5 .5
19
0
86
■ 18
15
CoMo 0603
-5 .5
19
0
86
31
15
-5 .5
22
0
83
2
3
CoMo 0401
-5 .5
19
0
'8 6
28
8
N i 3210
-3 .
17
0
86
0
7
3
11
0
86 .
6
14
-8
19
11
80
65
35
0
11
8
83
22
0
3
8
■11
78
35
28
n
3
14
83
33
17
S n C l2 . ZH2O
u n s u l.
Sn pow der
C u C l2 . H2D
-5 .5
38% C d C l2 on s i l i c a
a lu m in a
Fe D - C r 0
s ilic a
C r-0105.
on
s u lfid .
'
'
K e t j e n HC-5
5 0 - 5 0 K e t j e n 3 3 0 -E 3
and CdCl
on s i l i c a
a lu m in a
,
.
CAS-30KR s i l i c a
a lu m in a
5 .5
-1 1
25
80
M o-1201
5 .5
■ 11
0
83
-5 .5
25
0
0
22
0
N i- 4 4 0 1
(lo w s o lv e n t r a t i o )
G ird le r
0
.
o -
9
a lu m in a
Z n C l 2 , p o w d e re d
STK-1
'
17
G-3A Fe^O,
po w d e r
3
0 .
18
17 '
80
37
14
78
14
.
.
19
60
(T a b le
10
~ B a tc h C a t a l y s t s c e n t 1d)
C a ta ly s t
# N a p th a
#DeN
#Gas O i l
^ R e s id u e
#DeS
3
14
78
29
6
#Fu e l O il
24# N i C l
on
s i l i c a a lu m in a
5 .5
HT-100
3
17
O
80
42
21
A l C l ^ Pomdered
0
25
O
75
31
48
11
3
5 .5
80
43
13
N i-4 3 0 3 •
8
• 14
. 78
31
20
HT-500
0
14
11
75
45
18
K e t j e n 3 3 0 -E 3
O
N i- 4 4 0 1
(h ig h s o lv e n t
ra tio )
24
4 .5
O
71
53
35
H T-400
25
O
O
75
47
23
61
The f o u r
denum o r
to p h e te ro g e n e o u s c a t a l y s t s
tu n g s te n p ro m o te d w it h
d is trib u tio n s
g e n e ra lly
o f th e
fiv e
h ig h e s t i n
fo u r p e lle t
c a ta ly s ts
b e s t, c a t a l y s t s
D is tilla tio n
a re
■The 3 : 2
55% i n
o f th e
3 :2
N a p h th a ( I B P -
e x a m p le o f t h e b o i l i n g
fo r
T h re e o f th e
th e
3 :2
s o lu tio n
fo u r
are
th e p ro d u c ts o f
F i g u r e s 8 and 9 .
f e e d h a s 64% d i s t i l l a t e s ,
p r o d u c t ha s 73% d i s t i l l a t e s .
is
ra n g e s .
. B o t h have q u i t e
fe e d c u rv e b u t b o th
c o n v e r s i o n o f 25%.
s o lu tio n
The d i s t r i b u t i o n
th o u g h c o n v e r s i o n was
g ra p h s d is p la y in g
shown i n
c u r v e s when co m p a re d t o
liq u id
v a rie d ,
The p r o d u c t
2
a r e a s o f 200 M / g r ; a l l
h a ve s u r f a c e
t h e tw o b e s t c a t a l y s t s
gave o v e r a l l
c o b a lt or n ic k e l.
th e m id d le o r lo w b o i l i n g
m ou n te d on a l u m i n a .
d iffe re n t
e ith e r
have c o m b i n a t i o n s o f m o ly b
L iq u id
s o lu tio n
4 2 5 °F ),
c o n v e r s i o n was
fe e d in
9% i n
N a p h th a r a n g e -
It
th e th re e
Gas O i l
range d i s t r i b u t i o n
t h e K e t j e n HC-5 p r o d u c t .
and t h e HT-400
b o ile d
(6 0 0 -
=■ 25%.
b o ilin g
7 0 0 ° F ) . . An
o f c o n v e rs io n i s
as f o l l o w s :
.'56%
■F u e l O i l r a n g e -
12%
G a s .O il range -
4%
72% d i s t i l l a t e s
T o ta l
O v e r a l l c o n v e r s i o n = * ^ 7 7 ^ ' = 22%
36
to liq u id s
C o n v e rs io n to
N a p h th a
C o n v e rs io n t o
Fuel O il
C o n v e rs io n t o
Gas O i l
56-55
36
1 2 -9
36
4 -0 ■
: 3% ( r o u n d e d o f f )
= 8%
=11%
-..22 %
ranges
g iv e n ..h e re ■
T e m p e ra tu re i n
62
Feed
P ro d u ct
Volume P e r c e n t D i s t i l l e d
F ig u re
8.
D i s t i l l a t i o n o f H T -400 P r o d u c t v s .
3 : 2 S o l u t i o n Feed
63
P ro d u ct
Temperati
Feed
Volume P e r c e n t
F ig u re
9.
D is tilla tio n
3 :2 S o lu tio n
D is tille d
o f HT-50D P r o d u c t v s .
Feed
64
T a b le s
11 and 12 shorn t h e
m o st s u l f u r
and n i t r o g e n re m o v a l.-
ve ry w e ll in
h e te ro a to m .re m o v a l.
h y d ro c ra c k in g
T a b le
c a ta ly s ts
fiv e
c a ta ly s ts
As a g r o u p ,
A ls o ,
are a ls o i n
th e m e ta l c h lo r id e s
n o te t h a t f o u r o f th e
a t l e a s t one o f T a b l e s
10 shows t h a t none o f t h e " b e s t "
poor h e te ro a to m re m o v e rs .
w h ic h a c c o m p l i s h e d t h e
h y d ro c ra c k in g
Good h y d r o c r a c k i n g
fiv e
best
1 1 -a n d 12.
c a ta ly s ts
seems t o
d id
w ere
c o rre la te
w ith
good h e t e r o a t o m r e m o v a l .
The h e t e r o a t o m r e m o v a l d a t a p o i n t t o
was a l s o i n d i c a t e d
h a rd e r
to
in
th e l i t e r a t u r e
rem ove t h a n s u l f u r .
g re a te r p e rc e n t re d u c tio n
in
one g e n e r a l i z a t i o n
se a rch :
n itro g e n
O n ly one c a t a l y s t ,
n itro g e n
th a n
s u lfu r
is
A lC l^ ,
th a t
c o n s is te n tly
gave a
(48% de-N v s ,
31% d e - S ) .
C o m p a r is o n s o f Some N i- W t N i- M o ,
N i-W c a t a l y s t s ( K e t j e n
s im ila r
m e ta l lo a d in g s ,
U n fo rtu n a te ly ,
o f pore
H C -5,
but
d iffe re n c e
e ffe c ts
on h i g h
t h e H T -500 i s
rem oval f o r
th e
T /8 "
th e
s ilic a te d ,
H T -400
s u p p o r t s and v a r y i n g
and j u s t
tw o d i f f e r
a lu m in a .
r
r e s u lts .
u n c e rta in .
a b o u t 3% N iO ,
and s i l i c a t e d ;
S u r p r is in g ly , ^ n itro g e n
ve ry l i t t l e .
L iq u id
have
so t h e p o s s i b i l i t y
b u t HT-IOO j s - l / l 2". d i a m e t e r
s m a lle r p a r t i c l e .
(3%-CoO,
s iz e p e l l e t ,
HT-IOO and HT-500 a r e b o t h
area s u p p o rt,
T h re e
and H arshaw N i - 4 3 0 3 )
makes g e n e r a l i z a t i o n s
The H arshaw c a t a l y s t s
16% MoO
K e tje n 330-E 3,
each was on a d i f f e r e n t
d iffu s io n
and Co-Mo C a t a l y s t s -
c o n v e rs io n i s
and s u l f u r
le s s f o r
.
15% MoO3 on a l u m i n a ,
' 2
220 M / f l r ,
and a v e r a g e
65
T a b le
11.
BEST BATCH DESULFURIZATIONS
Z n C l 2 p o w d e re d
65^
H T-400 !>% CoO,. 1 5 ^ MoO3 on a l u m i n a
47#
C u C l2 . H2O f i n e
c ry s ta ls
46#
H T-500
1 5 . 5 # MoO3 on a l u m i n a
45#
3 . 2 # N iO ,
K e t j e n 3 3 0 -E 3 6 . 6 # N iO ,
on a l u m i n a
T a b le
12.
A lC lv
p o w d e re d
Z n C l2
p o w d e re d
1 . 2 # SiO
43#
BEST BATCH DENI TROGENATIONS
48#
.
K e t j e n HC-5 6 . 5 # N iO ,
HT-400 3# CoO,
1 9 . 8 # WO3 ,
21# WO3 on a l u m i n a
15# MoO3On a l u m i n a
C u C l2 . HJD f i n e
c ry s ta ls
’
35#
28#
23#
22#
66
p o re
d ia m e te r
a lu m in a ,
s u rfa c e
100 f l ° )
166 M ^ / g r ,
is
106 f l ° ) .
to
1 /3 b e t t e r i n
te m p e ra tu re ;
and Cd)
do n o t m e l t b e lo w r e a c t i o n
a ll
c h lo rid e s
g e n a tio n
in
(48% ).
c ra c k in g
atom r e m o v a l was v e r y g o o d .
n itro g e n
and b e s t o f a l l
and s u l f u r
w ith
tio n s
a n d /o r lo w e r
fo r
d e n itro -
ave ra g e c a t a l y s t
.
u n su p p o rte d c h lo r id e s
b u t as a g r o u p t h e i r
h e te ro -
w ere b o t h among
iro n -c h ro m a te
22% o v e r a l l
te s te d ,
c o n v e rs io n ,
G ird le r
14%
f o r m o f G-3A p r o v e d i n e f f e c t i v e ,
P o re d i f f u s i o n
lim ita ­
are a p ro b a b ly caused th e p o o r r e s u l t s .
in te rm e d ia te
a re a s i l i c a - a l u m i n a im p re g n a te d w i t h
good r e s u l t s
e ith e r.
The
F e -C r d i d n o t g i v e
'
O th e r i n v e s t i g a t o r s
u n s u lfid e d
Z n , . and Al).
was t h e b e s t o f
c a ta ly s ts
and no h e t e r o a t o m r e m o v a l .
s u rfa c e
A lC l^
w ere f a i r l y
The f i r s t
B ut th e p e l l e t
lo w c o n v e r s io n
Cu,
re m o ve rs.
G-3A p o w d e r , gave e n c o u r a g i n g r e s u l t s :
and 19% d e - N .
(S n,
C opper and z i n c c h l o r i d e
Fe and F e -C r C a t a l y s t s -
d e-S ,
and t h e h i g h
s u p p o rte d c h lo r id e s ( N i
te m p e ra tu re .
good h y d r o c r a c k e r s ,
12/^ MoO^ on
h e te ro a to m re m o v a l.
and h e t e r o a t o m r e m o v a l ; t h e
fr o m p o o r t o
th e b e s t f i v e
p e lle ts ,
th e
The s u p p o r t e d c h l o r i d e s
b o th c r a c k in g
ranged
fo r
l/8 "
CoO,
The u n s u p p o r t e d c h l o r i d e s
m e l t b e lo w t h e r e a c t i o n
th e
Co-Mo 0603 (
B o th a r e
a r e a H T -400 d i d a b o u t
M e ta l C h lo rid e s -
a ll
s im ila r
a t M o n ta n a S t a t e had b e t t e r r e s u l t s
c h r o m a t e s on s u p p o r t t h a n w i t h
Two u n s u l f i d e d
Cr c a t a l y s t s
3 :2 fe e d s to c k ,
th o u g h .
d id n o t g iv e
The e f f e c t o f
e
th e
same c a t a l y s t s
good r e s u l t s
s u lfid in g
w ith
was t e s t e d
w ith
s u lfid e d .,
th e
SRC
by r u n n i n g
■
67
one o f t h e
Cr c a t a l y s t s
a g a in ,
h e te ro a to m rem oval a l l
O th e r E f f e c t s
43 M / g r , was t e s t e d
-
o n ly
s u lfid e d .
in c re a s e d w ith
The u n l o a d e d s u p p o r t CAS-30KR s i l i c a
h e lp
d e te rm in e th e
su p p o rt cracked f a i r l y
w e ll
( it
h e te ro a to m re m o v a l.
is
F uel O il range th a n th e
e ffe c t of
m idw ay i n
One i n t e r e s t i n g
s u p p o r t p r o d u c t was t h e o n l y c a t a l y s t
S o lu tio n
and
s u lfid in g .
to
lig ib le
H y d ro c ra c k in g
a lu m in a ,
s u p p o rt.
The p l a i n
t h e t a b l e ) , b u t had n e g - l
s i d e l i g h t — th e p la in
w h ic h had l e s s
d is tilla te
in
th e
F e e d s to c k .
C o n c l u s i o n s o f Bomb T e s t s ' -
B a tc h
s c r e e n i n g -of t h e c a t a l y s t s
showed s e v e r a l t h i n g s :
-
The b e s t h e t e r o g e n e o u s h y d r o c r a c k e r s w ere c o m b i n a t i o n s
o f Mo o r W p r o m o te d w i t h N i o r Co on h i g h a r e a a l u m i n a .
-
The b e s t m e t a l c h l o r i d e
and N i C l 2 .
S i n c e H T-400
g o rie s o f "b e s t"
(Co-Mo on a l u m i n a )
c a ta ly s ts ,
it
K e t j e n HC-5 ( N i- W o r a l u m i n a )
it
was n o t c h o s e n f o r
in h e r e n t w ith
was i n
was c h o s e n f o r
was c h o s e n f o r
had t h e b e s t d e n i t r o g e n a t i o n
A lC l^
c a ta ly s ts
te s tin g
o f th e
w ere A l C l , ,
Z nC l ,
each o f t h e t h r e e
c a te ­
c o n t i n u o u s mode t e s t i n g .
c o n tin u o u s t e s t i n g
s in c e
h e te ro g e n e o u s c a t a l y s t s .
because o f c a t a l y s t r e c o v e r y p ro b le m s
m e ta l c h lo r id e s ,
C o n t i n u o u s Runs
The e f f e c t s
o f te m p e ra tu re ,
hydrogen f l o w - t o - o i l r a t i o
liq u id
h o u rly
w ere i n v e s t i g a t e d ,
space v e l o c i t y ,
u s in g
th e
and
c o n tin u o u s
68
re a c to r
d e s c rib e d i n
See A p p e n d ix C,
c a ta ly s ts ,
th e M a t e r ia ls ,
C o n t i n u o u s R uns:
ru n c o n d it io n s ,
F ix e d v a r i a b l e s
-
p re ssu re
-
1000 p s i g
-
fe e d
-
3 :2
-
Amount o f
c a ta ly s t
-
te s te d
s o lu t io n fe e d ,
a t 400°C
70 m l.
mere H T-400
W on a l u m i n a ) ,
5 -2 -1
( C o -N i-M o on a l u m i n a ) .
MSU STK-7
second p a r t o f
fro m
fr o m t h e Bomb r u n s .
2 5 - 6 6 % . com p a re d t o
HC-5 mere 44 t o
61%,
th e
fo r
a ll
mas o b s e r v e d t h a t n i t r o g e n
A l l o f th e c a t a ly s t s
( CoMo on a l u m i n a ) , K e t j e n HC-5
and MSU STK
d e s c rip tio n s
c o n t i n u o u s r u n s mere b e t t e r
L iq u id
th e
th a n th e
c o n v e r s i o n s f o r H T -400 r a n g e d
bom b; l i q u i d
22% i n
c o n v e rs io n f o r
K e tje n
t h e bomb.
88%,
mas done by HC-5
(N i-W ).
mas o b t a i n e d by H T-400
(C o M o ).
is
s u lfu r
more d i f f i c u l t
th a n
t e s t e d gave a 55-60% c o n v e r s i o n t o
a t . l e a s t one s e t o f c o n d i t i o n s
O v e ra ll l i q u i d
are l i s t e d
f r o m C o n t i n u o u s Runs - .Of t h e . f o u r c a t a l y s t s
best d e s u lfu riz a tio n ,
64%,
bombs
A.
co m p a re d t o
b e st d e n itr o g e n a tio n ,
p repared in
C o m p le te c a t a l y s t
25% i n
Summary o f R e s u l t s
te s te d ,
L iq u id ,
o f th e c o n tin u o u s , r u n s .
( C o -N i-M o on a l u m i n a ) ,
A p p e n d ix
The p r o d u c t s f r o m t h e
p ro d u c ts
C o n v e r s i o n of- SRC t o
ond p r o d u c t r e s u l t s
(N i -
th e
and P r o c e d u r e S e c t i o n .
m e re :
C a ta ly s ts
in
E q u ip m e n t,
te s te d .
c o n v e rs io n te n d s t o :
The
The t r e n d
to
rem ove.
liq u id s
d u rin g
69
1) i n c r e a s e
w ith
in c re a s in g
2) be b e s t a t LHSV f r o m
3)
2
m a x im iz e a t .10,000 S C F /b b l f o r
P roduct d i s t r i b u t i o n s
LHSV,
1 to
te m p e ra tu re
va ry in
LHSV = I
no d e f i n a b l e
a nd H^ r a t i o .
and 4 4 5 ° C .
tre n d w ith
te m p e ra tu re ,
'
H e te ro a to m re m o v a l te n d s t o :
1)
in c re a s e
2)
d e c r e a s e as LHSV i n c r e a s e s
3)
m a x im iz e a b o u t
H y d ro c ra c k in g v e lo c ity ,
th re e
and H^ r a t i o
in c re a s e s
1 0 ,0 0 0 S C F /b b l f o r
The e f f e c t s
LI-ISV = I and 4 4 5 °C .
o f te m p e ra tu re ,
on h y d r o c r a c k i n g
liq u id
a re i l l u s t r a t e d
in
h o u rly
th e
space
fo llo w in g
fig u re s .
F ig u re
u s in g
as t e m p e r a t u r e
S T K -7.
s im ila r
to
th e
F ig u re
10 d i s p l a y s ' t h e
e f f e c t o f t e m p e r a t u r e on h y d r o c r a c k i n g ,
The 420°C p r o d u c t h a s l e s s
s o lu tio n
fe e d th a n i s
liq u id
c o n v e r s i o n and i s
0
t h e 445 C p r o d u c t .
11 shows t h e H T -400 p r o d u c t
d is tilla tio n s
d iffe re n t
sp a c e v e l o c i t i e s .
m a te ria l,
b u t t h e LHSV=I p r o d u c t h a s t h e m o st o v e r a l l
LHSV=3 p r o d u c t i s
e x te n d e d .
A p p e n d ix ,
m o st n a p h t h a f o r HC-5 a l s o ,
fo r
th re e
•LHSV=2 p r o d u c t h a s t h e m ost n a p h t h a r a n g e
n o t much d i f f e r e n t
From t h e
more
it
th a n th e
c o n v e rs io n .
fe e d s to c k ,
b u t somewhat
can be seen t h a t LHSV=2 g i v e s t h e
but not fo r
The
t h e o t h e r tw o c a t a l y s t s .
70
420 C
T e m p e r a tu r e i n
Feed
Volume P e r c e n t D i s t i l l e d
F ig u re
10.
E f f e c t o f T e m p e r a tu r e on
H y d r o c r a c k i n g by 5TK-7
71
700 __
600 —
T e m p e r a tu r e i n
500-
300LHSU
445 C;
.
1 0 ,0 0 0 S C r / b b l
Volume P e r c e n t D i s t i l l e d
F ig u re
11.
E f f e c t o f LHSU on
H y d r o c r a c k i n g by H T-400
72
F ig u re
12 shows t h e
by STK 5 - 2 - 1 .
5 ,0 0 0
The 1 0 ,0 0 0
S C F /b b l p r o d u c t .
e ffe c t
o f H '^ - to - o il r a t i o
on h y d r o c r a c k i n g
S C F / b b l . p r o d u c t shows im p r o v e m e n t o v e r t h e
In c re a s in g
th e r a t e
to
HC-5 and STK-7 r u n d i d n o t i m p r o v e t h e l i q u i d
1 5 ,0 0 0 S C F /b b l i n
th e
c o n v e r s i o n n o r n a p h th a
range c o n v e rs io n .
L im ite d
v e lo c ity
fo r
o th e r
STK 5 - 2 - 1
d a ta i s
th a n
I.
a v a ila b le
A p p e n d ix
LHSV,
N itro g e n
F ig u re s
and
and s u l f u r
ve rs u s te m p e ra tu re
fo r
F ig u re
V a ria tio n
17 and 18 f o r
E ig h t f ig u r e s
on s u l f u r
d a ta p l o t s
tw o d i f f e r e n t
o f e ffe c ts
F ig u re
18.
I qw H£ r a t i o s .
of
th e
The STK 5 - 2 - 1
at
e ffe c ts
of
re m o v a l.
te m p e ra tu re .
and n i t r o g e n
re m o va l
c a ta ly s ts .
in c re a s e
as L-HSV
t h e t e n d e n c y . ’ One d a t a p o i n t
ra tio
2
re m o va l d id
A p o in t
o f 7500 S C F / b b l .
and n i t r o g e n
s u lfu r
of H - to - o il
D e n p tro g e n a tio n r e s u l t s
in
d is p la y
is
d is p la y e d in
h e t e r o a t o m r e m o v a l a t LHSV=I and 4 4 5 ° C .
S u lfu r
a t a .s p a c e
in
th e tr e n d .
f o r HC-5 and STK-7 p e a k e d o r l e v e l e d
M S C F /b b l.
ra tio
and d e n i t r o g e n a t i o n
15 and 16 d i s p l a y
16 does n o t f o l l o w
ra tio
re m o v a l b o th in c r e a s e d w it h
B o th d e s u l f u r i z a t i o n
F ig u re s
of
A r e v e a ls th e b e s t o v e r a l l c o n v e rs io n
ra tio
13 and 14 d i s p l a y
de cre a se s.
e ffe c t
a t LHSV=2 and 44 5 °C came a t a
H e t e r o a t o m Rem oval te m p e ra tu re s ,
on t h e
o ff
a t H^ r a t i o s
n o t v a r y much f o r
c o n flic te d
D e s u lfu riz a tio n
o f a b o u t 10-11
STK 5 - 2 - 1 .
f o r HC-5 and S T K - 7 , as seen
r u n was made t o
1 0 ,0 0 0
F ig u re s
d e te rm in e th e
S C F /b b l was o b t a i n e d f o r
e ffe c t
of
b o th th e f i r s t
73
5000 - Z T
Feed
F-
400
Volume P e r c e n t D i s t i l l e d
F ig u re
12.
E f f e c t o f H R a t i o on
H y d r o c r a c k i n g by STK 5 - 2 - 1 .
D e s u lfu riz a tio n
74
O
£i
H T -400
STK-7
T e m p e ra tu re
Figure
13
Percent
D e s u l f urization vs.
Temperature
% D e n itro g e n a tio n
75
H I-4 0 0
STK-7
400°C
425 C
450 C
T e m p e ra tu re
Figure
14
Percent
Denit r o g e n a t i o n vs.
Temp e r a t u r e
76
O
H T-400
HC-5
D e s u lfu riz a tio n
STK-7
75
_
STK 5 - 2 - 1
L i q u i d H o u r l y Space V e l o c i t y
( V o l , Feed p e r h o u r / V o l . C a t a l y s t )
F ig u re
15.
P ercent D e s u lfu r iz a tio n
vs.
LHSV
77
100
% D e n itro g e n a tio n
75
50
_
O
h t-4 0 0
O
HC" 5
A
STK-7
x
STK 5 - 2 - 1
_
BBL
25
-
L i q u i d H o u r l y Space V e l o c i t y
( V o l . Feed p e r h o u r / V o l . C a t a l y s t )
Figure 16.
Percent
D e n i t r o g e n a t i o n vs.
LHSV
78
HC-5
STK-7
% D e s u lfu riz a tio n
STK 5 - 2 - 1
H2 t o O i l R a t i o ,
F ig u re
17.
^
" '2
P e rce n t D e s u lfu r iz a tio n
H yd ro g e n - t o - O il R a tio
vs.
79
HC-5
5TK-7
% D e n itro g e n a tio n
STK 5 - 2 - 1
H2 t o
F ig u re 18.
O il
SP F H
R a tio , ^ — 2
P e rce n t D e n itro g e n a tio n vs.
O i l R a tio
H ydrogen - t o -
80
X LHSV=I
D e s u lfu riz a tio n
$
LHSV=2
C a ta ly s t
STK 5 - 2 - 1 ;
445 C
to O il R a tio
F ig u re
19.
P e rc e n t D e s u l f u r i z a t i o n v s . H ydrogen to
O il R a tio a t d i f f e r e n t l i q u i d h o u r ly
sp a ce v e l o c i t i e s
81
LHSV=I
C a ta ly s t
STK 5 - 2 - 1 ;
4A5°C
to
Figure
20
O i l R a tio
P e r c e n t D e n i t r o g e n a t i o n v s . H y d ro g e n
to O il R a tio a t d i f f e r e n t l i q u i d
h o u r l y sp a c e v e l o c i t i e s
82
and l a s t
s a m p le s o f t h e r u n .
n it r o g e n re m o v a l,
b u t th e l a s t
S in c e t h e h i g h p o i n t
'r u n ,
it
The f i r s t
fa r
sa m p le h ad an u n u s u a l l y h i g h
sam ple c o r r e l a t e d
STK-7 was a l s o
fro m th e
w ith
a ll
fir s t
th e o th e rs .
sa m p le o f t h e
can be c o n c l u d e d t h a t t h e tw o MSU c a t a l y s t s h a v e a h i g h
a c tiv ity
w h ic h s t e a d i e d o u t l a t e r
r e m o v a l does i n d e e d p e a k a t
in
th e ru n .
1 0 ,0 0 0 S C F /b b l f o r
T h e re fo re ,
in itia l
n itro g e n
s te a d y -s ta te
c a ta ly s t
a c tiv ity .
F ig u re s
v e lo c itie s
LHSU=I o v e r
1 9 . and 20 com pare
over th e
e ffe c ts
same c a t a l y s t .
th e range o f
of
ra tio
D e s u lfu riz a tio n
is
20 shows t h a t
s im ila r
s lig h tly
fo r
n e a rly le v e l
d e n itro g e n a tio n
(See F i g u r e
lo w e r H
ra tio ,
at
d is p la y e d
at
o v e r t h e r a n g e o f H^ r a t i o s
1 9 ). .
is
b o t h LHSV=I and LHSV=2. ' The n i t r o g e n r e m o v a l p e a k s a t
L o o k in g
c a ta ly s t
tw o space
r a t i o s ; b u t a t LHSV=2', d e s u l f u r i z a t i o n
p e a k s a t 5000 S C F /b b l and d e c r e a s e s a t h i g h e r r a t i o s
F ig u re
fo r
7500,
fo r
th e h ig h e r
spa ce v e l o c i t y .
A p p e n d ix C, t h e c o n t i n u o u s r u n d a t a ,
K e t j e n HC-5
th e h ig h e s t c o n s is t e n t h e te ro a to m re m o va l over a
range o f h y d r o g e n - t o - o il r a t i o s .
HT-AOO h a s t h e h i g h e s t c o n s i s t e n t
h e t e r o a t o m r e m o v a l o v e r t h e r a n g e o f spa ce v e l o c i t i e s
LHSV=I t o
3.
CONCLUSIONS
1.
C o n v e rs io n
o b t a i n e d up t o
fro m n o n d i s t i l l a t e s
55-60% w i t h
to
d is tilla te s
c o m m e r c i a l and l a b - p r e p a r e d
ca n be
c a ta ly s ts
in
a
c o n tin u o u s r e a c t o r .
2.
The b e s t h e t e r o g e n e o u s c a t a l y s t s
te s te d in
a t i o n s o f m olybdenum o r t u n g s t e n p r o m o t e d w i t h
3.
re m o ve rs;
M e ta l c h lo r id e
a lu m in u m c h l o r i d e
.4 .
s u rfa c e
hom ogeneous c a t a l y s t s
c o b a lt or n ic k e l.
a r e good h e t e r o a t o m
was t h e b e s t c h l o r i d e
The b e s t M o -W -C o -N i c a t a l y s t s
bombs had co m b in
c a ta ly s t o v e r a ll.
t e s t e d had r e l a t i v e l y
h ig h
area.
5.
th a n s u l f u r
6.
N itro g e n
is
h a rd e r to
re m o ve f r o m s o l v e n t - r e f i n e d
coal
is .
In c re a s e d te m p e ra tu re g iv e s in c re a s e d h y d r o c r a c k in g
and
h e te ro a to m re m o v a l.
7.
L iq u id h o u rly
h y d ro c ra c k in g
8.
fr o m
I to
2 g iv e
th e b e s t
and h e t e r o a t o m r e m o v a l .
Ten t h o u s a n d S C F /b b l h y d r o g e n - t o - o i l r a t i o
h y d ro c ra c k in g
and 70 m l .
spa ce v e l o c i t i e s
and h e t e r o a t o m r e m o v a l f o r
o f c a ta ly s t.
445°C ,
g iv e s th e b e s t
LHSU = I ,
1000 p s i g ,
RECOMMENDATIONS
S h o r t Term
1.
In v e s tig a te
c o n tin u o u s r e a c t o r .
t h e n be e m p lo y e d t o
th e e f f e c t s
o f film
The p r o p e r c a t a l y s t
m in im iz e
d iffu s io n
2.
Use an e l e c t r i c
H
3.
Do c h r o m a t r o g r a p h i c
flo w
and p o r e d i f f u s i o n
s iz e
and mass f l o w
in
ra te
th e
can
lim ita tio n s .
m e te r t o
a c c u ra te ly
m o n ito r
in p u t
gas.
a llo w
a m a t e r i a l b a l a n c e on t h e
a n a ly s is o f p ro d u c t gases.
s y s te m and c o r r e l a t i o n
T h is w i l l
o f g as-m ake
ve rsu s v a r ia b le s .
4.
C o n s id e r u s in g
w o u ld e l i m i n a t e
5.
lite ra tu re
a c id ity
th e
was t h e
p r o d u c t s as r e a c t o r
fe e d .
s u rfa c e
a c id ity
reason th e
is
a c id ity
o f c a ta ly s ts
te s te d .
an i m p o r t a n t v a r i a b l e .
c h r o m a te c a t a l y s t s
Recent
P erhaps a h ig h
p re v io u s ly
te s te d
d id n o t
w o rk w e l l .
Long Term
1.
C o n tin u e t e s t i n g
2.
A fte r
• com pare v a r i o u s
film
new c o m m e r c i a l h y d r o t r e a t i n g
and p o r e
c a ta ly s t
d iffu s io n .e ffe c ts
s u p p o rt c o m p o s itio n ,
lo a d in g s .
3.
p re ssu re s
y ie ld s
fo r
That
use o f a s o l v e n t .
M e a su re t h e
in d ic a te s
SRC ' 11 l i q u i d
c a ta ly s ts .
are m in im iz e d ,
pore s iz e ,
and m e t a l
x
F i n d o p tim u m c o n v e r s i o n p r e s s u r e .
s ig n ific a n tly
h ig h e r
a g iv e n te m p e r a tu r e .
th a n
1000 p s i g
L ite ra tu re
g iv e
s u g g e s ts
in c re a s e d l i q u i d
85
4.
p a c k e d bed w i t h
re co ve ry
•liq u id s .
C o n s i d e r use o f a hom ogeneous c a t a l y s t
h ig h
te c h n iq u e s
g a s -liq u id
fo r
c o n ta c t a re a .
c a ta ly tic
in
fe e d over a
R ecent w ork has im p ro v e d
a m o u n ts o f m e t a l c h l o r i d e s
fro m c o a l
LITERATURE CITED
1.
P e rry 5 H.
V o l . 15,
" C o a l C o n v e r s i o n T e c h n o l o g y , " C h e m ic a l E n g i n e e r i n g ,
No. 15, J u l y 22 , 1974, p p . 8 8 - 1 0 2 .
2.
K l a s s , D .L .
" S y n t h e t i c C rude O i l
A u g u s t 1 975, p p . 4 4 9 - 5 1 0 .
3.
D o n a th , E .E .
" H y d r o g e n a t i o n o f C o a l and T a r , "
Chap. 22 , C h e m i s t r y
o f C o a l U t i l i z a t i o n , S u p p le m e n t a r y V olum e, H .H . L o w r y , E d . ,
New Y o r k :
J o h n W i l e y & Sons, 1963.
4.
S q u i r e s , A . M.
" R e a c t i o n P a th s i n Donor S o l v e n t C o a l L i q u e f a c t i o n , "
D e p t. Chem. E n g . , V i r g i n i a P o l y t e c h n i c I n s t i t u t e and S t a t e
U n iv e rs ity .
( F o r p r e s e n t a t i o n a t C o n f e r e n c e on C o a l G a s i f a c t i o n /
L i q u e f a c t i o n , Moscow, U . S . S . R . , O c t . 1976, s p o n s o r e d by US-USSR
T r a d e and E conom ic C o u n c i l , I n c . )
5.
O f f i c e o f F o s s i l E n e r g y , ER DA, " C o a l L i q u e f a c t i o n R e p o r t , " A p r i l - J u n e 1 975, ERDA 7 6 - 3 3 - 2 , p p . 9 - 1 3 .
6.
R h lp h M. P a r s o n s Co.
" C o a l C o n v e r s i o n and U t i l i z a t i o n - L i q u e f a c t i o n :
•S o lv e n t-R e fin e d C o a l,"
P r e p a r e d f o r ER DA, F E - 1 2 3 4 - 6 , May 1976.
S h a le and C o a l , "
"A New C h e m ic a l S t r u c t u r e
5 4 , p . 3 6 , 1952.
ChemTech, '
Q u a rte rly
7.
H i l l , G .R .,
I n d , Eng.
.8.
B a t e l l e C olum bus L a b o r a t o r i e s , " L i q u e f a c t i o n and C h e m ic a l R e f i n i n g
o f C o a l."
A B a t e l l e E n e rg y P ro g ra m R e p o r t , C o lu m b u s , O h i o ,
J u l y 1974.
9.
C .B . L y o n .
Chem. , V o l .
fro m
fo r
C o a l,"
Wadden, R . A.
" C o a l H y d r o g e n a t i o n and E n v i r o n m e n t a l H e a l t h , "
E n v i r o n m e n t a l H e a l t h P r o s p e c t i v e s , V o l . 14, A p r i l 1976, p p .
201-206 .
10.
F o s s i l E n e rg y D i v i s i o n o f M a t e r i a l s .and E x p l o r a t o r y R e s e a r c h , ER DA,
S c i e n t i f i c R e s o u r c e s R e l e v a n t t o t h e C a t a l y t i c P r o b le m s i n t h e
C o n v e rs io n o f C o a l, ' F E -2 0 1 7 - I .
P r e p a r e d by C a t a l y t i c a
A s s o c i a t e s , . I n c . , • P a lo A l t o , C a l i f o r n i a , O c t . 1 976.
11.
K o p p e n a u l , D.W. and S. E1. M anahan.
"H a z a rd o u s C h e m ic a ls fro m C oal
C o n v e rs io n P ro c e s s e s ? "
E n v i r o n m e n t a l S c ie n c e and T e c h n o l o g y ,
V o l . 10, No. 12, November 1 976, p p . 1 1 0 4 - 1 1 0 7 .
0
^
i
i
I
-
'
■
j
'
87
12.
S ta n u lo n is , 3 .3 . e t a l.
" C a t a l y s t A g in g i n a P r o c e s s o f L i q u e ­
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3,
13.
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G r e s k o v i c h , E .O .
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.1 8 .
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2028 -
6,
20.
S ta n f o r d R e se a rch I n s t i t u t e .
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88
23.
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FE -
04
25.
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C rynes , B .L .
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P ro c e s s e s f o r C o n v e rs io n o f C oal to L i q u i d F u e ls :
B a s i c and
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. May-Oune 1976.
33.
C h o u d a ry , N .,
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34.
Cox, 3 .
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35.
H i n d i n , S.G.
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Chem. P r o c e s s D es.
U p g ra d in g C o a l- D e r iv e d L i q u i d s , "
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" H y d ro c ra c k in g :
V o l . '1 4 , No. 2,
A R e v ie w ,"
1975.
In d .
" C a t a l y s t s f o r C o a l C o n v e r s i o n , ” Symposium P a p e rs From C o a l , I n s t i t u t e o f Gas T e c h n o l o g y , S e p t . 1 0 - 1 4 ,
C le a n
1973.
" C a t a l y s t D e v e lo p m e n t f o r C o a l L i q u e f a c t i o n , "
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}
89
36 .
'3 7 .
B e rg , L .
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S e p t . - N o v . 1976.
S t a n b e r g , U. I . , R . I . B a l t i s b e r g e r , K . O. K l a b u n d e , e t a l .
"Chem­
i s t r y o f L i g n i t e L i q u e f a c t i o n , ” U n i v e r s i t y o f N o r t h D a k o ta ,
ERDA R e p o r t F E - 2 2 1 1 - 3 , O u l y - S e p t . 197.6.
38 .
"C o a l L iq u e fa c tio n :
. E n g in e e rin g , J u ly
39.
Hammer, G . P . ,
3 ,9 2 8 ,1 7 6 .
40.
R a p o p o rt, I . B .
C h e m i s t r y and T e c h n o l o g y o f S y n t h e t i c L i q u i d
2nd e d . , T r a n s l a t e d f r o m R u s s i a n , S i v a n P r e s s , J e r u s a l e m ,
I s r a e l , 1962.
41.
H a r t l e y , O . , E . J . R o s i n s k i , and P .B . V e n u t o . . " D e n i t r o g e n a t i o n and
U p g r a d i n g o f H ig h N i t r o g e n C o n t a i n i n g H y d r o c a r b o n S t o c k s ' w i t h
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e t a l.
S h o o tin g
19, 1976.
fo r
B e tte r
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"H e a v y C rude C o n v e r s i o n , "
C h e m ic a l
EXXON, U .S .
P a te n t
F u e ls ,
.. G a t s i s , J . G .
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R i e v e , R.W. and H . S h a l i t .
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H y d r o c a r b o n s C o n t a i n i n g S u l f u r and N i t r o g e n C o m p o u n d s," ARCO,
U .S . P a t e n t 3 , 8 4 7 , 7 9 5 .
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P e rry, J .H .,
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N a y lo r, J .
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46.
P a r r I n s t r u m e n t Co.
I n s t r u c t i o n s F or t h e S e r i e s 4000 P r e s s u r e
R e a c t i o n A p p a r a t u s , P a r r M a n u a l No. 141.
47.
H a s k e l E n g i n e e r i n g and S u p p ly Company.
O p e r a t i n g and M a in t e n a n c e
I n s t r u c t i o n s f o r H a s k e l A i r D r i v e Gas B o o s t e r C o m p r e s s o r , BH 3 .
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..
A m e r ic a n S o c i e t y o f T e s t i n g and M a t e r i a l s .
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' T e s t f o r D i s t i l l a t i o n o f P e t r o l e u m P r o d u c t s , " 1974 A n n u a l Book
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Ed.
P e r r y 's
McGraw H i l l ,
C h e m ic a l E n g i n e e r i n g H a n d b o o k , 4 t h
1969.
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90
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P e te r s , E. D ., e t s i .
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A m e r ic a n S o c i e t y o f T e s t i n g and M a t e r i a l s , " S t a n d a r d M eth o d o f
T e s t f o r S u l f u r i n P e t r o l e u m O i l s ( Q u a r t z Tube M e t h o d ) , " 1974
A n n u a l Book o f ASTM S t a n d a r d s , P a r t 23, ASTM D e s i g n a t i o n D 1551.
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F r i t z , O . S . , and G.H* S ch e n k.
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D e s ig n a tio n E 258.
APPENDICES
• 92
APPENDIX A
DESCRIPTION OF CATALYSTS USED
BATCH RUN CATALYSTS
Harshaui N i- 4 4 0 1 E._„1/.10"
6 ^ N iO , ' 19#. WO^,
25#'. A l O ^1 5 0 # S iO ^.
H arshaw .Co-Mo 0401 T l / 8 "
3# CoO, 9# MoO on a l u m i n a ,
s i l i c a p r o m o te d 160 tn / g r ,
0 .4 0 c c /g r
H arshaw W -0 1 0 1 T 1 / 8 "
10# WOj
on
alumina
H arshaw H T - 100 E 1 / 1 2 "
3 . 8 # N iO 5 1 6 . 8 # MoO ,
^
o.37_ c c / g r
1 . 5 # s i l i c a on a l u m i n a
175 m / g r , 0 . 5 4 c c / g r
■Harshaw M o - 1 2 0 1 T 1 / 8 "
H o O 3 on
Olumina
H a rsh a w C r - 0 3 0 4 u n s u l . T 1 / 8 "
3 3# Cr 0 on s i l i c a t e d
^
m 2/ g I )
0 .36 c c / g r
a lu m in a
120 m / g r ,
0 .2 6 c c /g r
H arshaw Co-Mo 0603 T 1 / 8 "
3# CoO, 12# MoO on a l u m i n a ^
166 m / g r , 0 . 4 4 c c / g r
T i n pow der
H arshaw N i - 4 3 0 3 E 1 / 1 2 "
6# N iO ,
19# WO^ on a l u m i n a
152 m / g r ,
H arshaw N i - 3 2 1 0 T 3 / 1 6 "
3 5 # NiO on p r o p r i e t a r y
G ird le r
su p p o rt
175 m / g r ,
G-3A po w d e r
82# FBgQ;, 10# CrgOj
S n C l2 .
2H20
&
/
0 .5 4 c c / g r
0 .4 5 c c / g r
93
( D e s c rip tio n
o f C a t a l y s t s Used -
c o n t'd )
H arshaw C r - 0 1 0 5 u n s u l . I 1 / 8 "
9 / C r ^ O - , 1 . 5 / K O on a l u m i n a
67 m / g r ,
H arshaw C r - 0 1 0 5 ,
s u lfid e d
I
0 .3 4 c c /g r
l/8 "
H arshaw H T -400 E l / 8 "
3 / CoO' 1 5 / MoO^ on a l u m i n a
220 m / g r , 0 . 5 5
c c /g r
A lC l^ p o w d e r'
C u C l^ . H^O f i n e
c ry s ta ls
Z n C l^ po w d e r
1 5 / N i C l g on O o h n s - M a n s v i l l e
C e llite
410 s i l i c a
H arshaw H T-500 E 1 / 8 "
1 5 . 5 / MoO , 3 . 2 / NiO on a l u m i n a
210 m / g r ,
3 8 / C dC lg on O o h n s - M a n s v i l l e
CAS-30KR s i l i c a
l / 4"
0 .4 4 c c / g r
a lu m in a
K e t j e n HC-5
1 .5 mm ( 1 / 1 6 " )
2 1 / WO^1 6 . 5 / NiO on a l u m i n a
'
200 m / g r ,
S ilic a
A lu m in a I l / 8 "
CAS-30KR -Si.
1 3 . 5 / Fe 0 , 1 0 / Cr 0
K e tje n
-
on CAS-30KR—1 s i l i c a
410 -
a lu m in a
a lu m in a
1 . 2 / S iO - on a l u m i n a
.
o 193 m / g r , 0 . 4 3 c c / g r
8 6 / S iO g , 9 / A lg O 3 , 2/ FegO3 ,
3 m / g r , mean p o r e d i a m e t e r
0 .8 2 m ic ro n s ; 0 .5 6 c c / g r
2
“ ‘ (see n e x t page)
c c /g r
on CAS-30 KR £ .
3 3 0 -E 3 mm ( 1 / 8 " )
1 9 . 8 / WO , 6 . 6 / N iO ,
J
C e llite
0 .6 2 c c /g r
43 m2/ g r , . 0 , 6 1
s ilic a
2 4 / N iC l
—I
I/
CaO
1 /8 "
94
(D e s c rip tio n
5 0 - 5 0 m ix o f K e t j e n
on CAS-30KR
of
C a t a l y s t s Used c o n t ' d )
3 3 0 -E 3 and 30% CdCl
2
MSU STK - 1
15.8% MoO , 6.5% NiO on CAS-30KR*Ps i l i c a
G i r d l e r G - 3A T 3 / 1 6 " x 3 / 8 "
82% Fe2O3 , 10% C r 2O3
70 m ^ / g r ,
a lu m in a
0 .0 4 c c / g r
CONTINUOUS RUN CATALYSTS
Harsham N i - 4 4 0 1 E 1 / 1 0 "
6% N iO , 19% WO3 ,
Harsham H T-400 E 1 / 1 6 "
- i f CoO,
25% A l P3 , 50% S i O ^
■
15% HoO3 on o l u m i n a
^
K e t j e n H C -5-E 1 .5 ( 1 / 1 6 " )
21% WO3 , 6.5 % NiO on a l u m i n a
MSU STK - 7 E 1 / 8 "
17.1% MoO ,
1.5% N iO ,
m2/ g r ,
0 .5 5 'c c /g r
^ 2 /^ ,
o ,6 2 c c /g r
1.4% Co 0
on N o r t o n .6176— a l u m i n a
MSU STK 5 - 2 -1 E 1 / 1 6 "
23.9% MoO, .48% N iO ^ , .75% CoO^
on N o r t o n 6176—" a l u m i n a
-
CAS-30KR
-
51% S iO 2 , 46% A lg O 3 , 0.7% Fe3O3 , 0.3% CaO
43 m ^ / g r ; mean p o r e d i a m e t e r 0 . 52m i c r o n s ; 0 .6 1 c c / g r
—' N o r t o n 6176
-
9 9.85% A l
O3 , 0.-014% NaO3 , 0 .1 2 0 % S iO 3 ,
0 .0 6 5 % Fe3O3
250 m 'y ' g r , 0 . 8 - 1 . 1 c c / g r
9
APPENDIX B .
S o lv e n tto-S R C
W t. R a t i o
CATALYST
I n i t i a l ' F in a l
C o ld H2
C o ld H2
p s ig
p s ig
BATCH RUN
Run
Temp
0C
DATA
. C onver­
s io n to
L iq u id s
% deS
%deN
(V o l.% ;
7 :2
. 2100
1000
Harsham
N i- 4 4 0 1
7 :2
500
275
725
600
'420
Harsham
N i-4 4 0 1
pom dered
s o lid
SRC
o n ly
.
425
29%
415
12%
No c a t a l y s t
7 :2
750
675
417
No c a t a l y s t .
2:1
725
675
No c a t a l y s t
1:1
750
No c a t a l y s t
3 :2
No c a t a l y s t
3 :2 t
*X'
s o lid
S'.& N
35%
44%
——
—” ™
9%
7%
420
1%
0%
625
418
0%
9%
750
700
417
——
4%
14%
750
—
365
— ™ —
4%
.15%
—
•
N o te :
'
53%
■fee.
8
Tl arsham
N i- 4 4 0 1
-
S o l i d SRC i s 2.28% n i t r o g e n and 0.68% s u l f u r .
S y n t h e t i c c o a l o i l s o l v e n t i s .59% n i t r o g e n and| .36/$ s u l f u r .
a n a ly s e s l i s t e d
in
ta b le
are f o r
b o th
s o l v e n t and SRC s t i l l
+ S p e c ia l s h o r t- tim e ru n :
h e a t e d t o 3 6 5 °C , h e l d
h e ld a t ru n te m p e ra tu re f o r I ' / 2 h r . ■
fo r
5 m in u te s ,
m ix e d as t h e p r o d u c t .
quenched.
-
A ll o th e r runs
.BATC H
CATALYST
Harsham
Co-MoOA01
S o lv e n tto -S R C
W t. R a t i o
'
In itia l
C o ld H2
p s ig
F in a l
C o ld H2
■ p s ig
RUN
D flT fl-
Run
Temp
0C
C o n v e rs io n
to liq u id s
' ( v o l . %}
••
% deS
% deN
3 :2
800
400
425
13.9%
28%
8%
Harsham
W -0101
3 :2
2000
' 1600
438
16.7%
0%
9%
Ha r s h am
HT-100
3; 2
1900
1000
440
19.4%
42%
21%
Harsham
Mo-1201
3 :2
1900
1500
430
1 6 .7 %
:18%
17%
Har sham
C r-0304
u n s u lfid e d
3 :2
Harsham
CoMo-0603
3 :2
VO
Ov
1900
1700
435
11.1%
0%
0%
............
1925
1000
435
13.9%
31%
15%
■ BATCH RUN
•CATALYST
S d lv e n tto -S R C
W t. R a t i o
In itia l
C o l d Hg
p s ig
F in a l
C o ld H
p s ig
DATA
Run Temp
C o n v e rs io n
to L iq u id s
# deN
••■. .-6#
0#
31#
20#
0C
Sn pow der
3 :2
2000
1675
435
1 3 .9 #
H arshaw
N i-4 3 0 3
3 :2
2000
1100
435
2 2 .2 #
H arshaw
3 :2
20 25
1625
437
1 3 .9 #
3 :2
1950
1750
430
G ird le r
G-3A
Fe20^ pow der
3 :2
2025.
1650
437
SnCl .2 H 20
c ry s ta ls
3 :2
2000
950
H arshaw
C r - O 105
u n s u lfid e d
3 :2
2075
1900
.
# deS
•
o#-
.7 #
N i-3 2 1 0
*none
( fe e d s to c k
ru n )
* Run # 24 was t h e b a s i s
fo r c a lc u la tio n
.
0#
0#
1#
2 2 .2 #
14#
19#
425
.5 .5 #
29#
17#
435
5 .5 #
o f c o n v e rs io n y i e l d
fo r
a ll
o#-
3 :2
0#
s o lv e n t r a t i o
runs
BATCH RUN
S o lv e n tt o SRC r a t i o
CATALYST
In itia l
C o l d Hg
p s ig
F in a l
C o ld H0
p s ig
^
DATA
Run
■Temp
0C
C o n v e rs io n
1600
435
1 3 .8 #
H arshaw HT-400
3 :2
■ 2000
1200
445
25
A lC lj,
3 :2
2075
1275
450
IA
C u C l2 ; H O
fin e .c r y s ta ls
3 :2
1975
1000
440
Z n C l 2 , p o w d e re d
3 :2
1900
900
IS # N i C l
s ilic a
3 :2
20 25
' 3 :2
38fo CdCl
on ( B )
s i l i c a a lu m in a
K e t j e n H C -S ;
on
(B )
#
47#
23#
31#
48#
1 1 . 1#
46#
22#
441
1 9 .4 #
65#
35#
1500
440
1 3 .8 #
18#
15#
1950
’ 850
4 42
45#
18#
3 :2
1900
1000
443
1 3 .8 #
3 :2
20 25
1400
441
2 2 .2 #
(A )
H a rsh a w HT-500
(A ) 3 m ^ / g r ;
14#
CM
p o w d e re d
6#
VL
2000
VL
3 :2
LA
CM
H arshaw Cr-OIOS
s u lfid e d
mean p o r e d i a m e t e r
43 m ^ / g r ;
= 0 . 8 2 u ; 86% SiO , 9 # A l 2O ^,
mean p o r e d i a m e t e r = 0 . 5 2 u ;
51)o SiO j , ,
2 # Fe2O j ,
4 6 # A l 2O , ,
0 .7 #
13#
35#
1# CaO
F e 2O3 , 0 . 3 #
CaO
28#
S ilic a A lu m in a
(B)
I n i t i a l Hp
P ressure
! F i n a l Hp
P re ssu re
Run
Temp
C o n v e rs io n
#deS-"
JodeN-: :
3 :2
2000
1950
435 -
1 9 .5 #
d#
3#
1 3 . SJfi Fe 0
(B )
IOJfi C r 2O^ on
s i l i c a a lu m in a
3 :2
1950
1650
435
1 6 .6 #
2#
3J&
24jfi N i C l
on
(B )
s i l i c a a lu m in a
3 :2
1875
1225
442
.2 2 .2 #
29#
K e tje n
3 :2
2000
1050
442
1 9 .4 #
43#
13 Jfi
5 0 - 5 0 m ix o f
K e t j e n 3 3 0 -3 E
and 38jfi C d C l2 on
s i l i c a a lu m in a
3 :2
1925
1100
447
1 6 .6 #
33#
IYJfi
MSU STK-1
3 :2
1900
1450
437
1 6 .6 #
22#
OJfi
G i r d l e r G-3
Fe2O^ t a b l e t
3 :2
1800
1400
.452
■
8 .3 #
0#
OJfi
Harsham N i 4 4 0 1 ■
3 :2
1825
1175 .
442
■
1 9 .4 #
37#
14jfi
B.
3 3 0 -3 E
43 m ^ / g r ;
-
-------- .
..
mean p o r e
d ia m e te r■ = 0 .5 2 u ;
5 Ijfi S i O 2 , 4 5 # A l 2O3 , 0 . 7
.
-
Fe2O3 , 0 . 3 # CaO
•
S o lv e n t-to
Wt SRC R a t i o
CATALYST
DATA
66
BATCH RUN
APPENDIX C
CONTINUOUS RUNS:
SCF
-'BBL,.
CONVERSION OF SRC TO L IQ U ID
TEMP
( 0 C) . deS
%
deN
%
NAPTHA
IB P 425°F
LHSU
H a r sham
N i - 4401
E 1 /1 0 " *
2
1 0 ,0 0 0
450
.7
I
1 0 ,0 0 0
1 0 ,0 0 0
1 0 ,0 0 0
1 0 ,0 0 0
1 0 ,0 0 0
445
445
445
420
400
75
67
63
71
59
■
445
445
445
445
55
,
85
69
88
46
35
25
36
'
445
445
445
445
445
420
39
57
53
41
33
'36
55 '
23
21
' 9
9
0
- 42
5
3 ■ 0 '
-3
-5
Ha r sh am
•
K e tje n
HC-5
VD
c .
Ul
MSU
STK-7
E 1 /8 "
A .)
B .)
c .)
D .)
E .)
2
3
■ 1
'
.
I
V
A .)
B .)
c.)
D .)
2
1
1 0 ,0 0 0
1 0 ,0 0 0
7 ,0 0 0
1 3 ,0 0 0
A .)
B .)
c.)
D .)
E .)
F .)
1
I
1
3
2
1
7 ,0 0 0
9 ,2 0 0
1 3 ,0 0 0
1 0 ,0 0 0
■ 1 0 ,0 0 0
1 0 ,0 0 0
I
I .
N o te :
*
;
■
%
GAS O IL
600700°F
'
RESIDUE
20
14
-2
0
88
64
33
12
17
14
11
58
0
- -5
0
35
0
31
22
11
21
0
14
14
33
42
6969
75
33
. 21
28
26
0
24
17
18
39
44
55
56
19
14
- 19
14
19
11
28
53
47
'58
58
72
28
11
0.
.0
11
28 '
31
28
25
22
0
■
7 : 2 s o l v e n t - t o - SRC a t m o s p h e r i c s o l u t i o n u s e d .
A l l o t h e r s u se d a 3 : 2
r a t i o f e e d > c p r e t r e a t e d a t h i g h p r e s s u r e and t e m p e r a t u r e .
100
CATALYST
■ %
FUEL O IL
4256 0 0 °F
CATALYST
MSU
S TK -5-2-1
E 1 /1 6 "
’ LHSV
A .)
B•)
c.)
'D . )
- E .)
F .)
:G , )
H. )
I.)
1
2
I
I
2
1
2
2
I
'
'
TEMP
( 0 C)
CD -ao.
Ul
SCF
BBL
CONVFRSirNS OF SRC TO LIQUID.
-O L
CONTINUOUS RUMS:
% '
deN
%
NAPTHA
IB P 425°F
59
17
23
20
11
1.8
20
15
25
36
6
11
8
-10
-7
5
-1
13
H2
1 0 ,0 0 0
5 ,0 0 0
7 ,5 0 0
5 ,0 0 0
2 ,5 0 0
2 ,5 0 0
7 ,5 0 0
1 0 ,0 0 0
1 0 ,0 0 0
445
445 ■
445
445
445
445
445
445
. 445
63
65
57
59
59
63
51
45
37
%
FUEL OIL
4 2 5 -6 0 0 °F
22
19
21
17
22
32
24
29
33
'
%
GAS O IL
600700°F '
11
11
10
14
13
14
13
0
10
RESJ DUE
31
64
58
61
75
61
58
72
44
101
N o te :
N i - 4401 r u n u s e d 100 ml c a t a l y s t , b u t a l l o t h e r s used 70 m l .
C a t a l y s t mas d i l u t e d '5 0 -5 0 w i t h i n e r t l / 8 " s u p p o r t .
P r e s s u r e o f r u n s a p p r o x i m a t e l y 1000 p s i g .
<
192
APPENDIX D
AVERAGE PORE DIAMETER CALCULATIONS
For a ' c a t a l y s t p e l l e t
d ia m e te r
w ith pore le n g th
D L
P o re Volume =
S u rfa c e
trTT .
A re a
^
P o re Volume
S u r f a c e A re a
/
lx
nr
D
4
4
P o r e Volume
• S u r fa c e A re a
..-D
L
.
L
L and a v e r a g e p o r e
103
APPENDIX E
L IS T OF TERMS
A s p h a ltb ls -
c o a l c o n v e rs io n p r o d u c ts s o lu b le
benzene.
A s p h a lte n e -
s o lu b le
O il -
s o lu b le
S c is s ile
-
benze n e b u t n o t i n
-
p y rid in e
but not in
p e n ta n e
p e n ta n e
c a p a b le o f b e in g c u t o r
B e n e fic ia tio n
NMR -
in
in
in
p h y s ic a l c le a n in g
s p lit
to
e a s ily
s e p a ra te ro c k
and ash f r o m c o a l •
n u c le a r m a g n e tic re s o n a n c e s p e c o s tro p y
H e te ro g e n e o u s c a t a l y s t s
re a c ta n ts .
re a c ta n ts .
- c a t a l y s t s i n a d i f f e r e n t phase t h a n t h e
U s u a l l y d e n o t e s s o l i d c a t a l y s t used i n f l u i d
Homogeneous c a t a l y s t s
c a ta ly s ts
LHSV -
liq u id
It
P s ig -
h o u rly
is
pounds p e r
-
in
space v e l o c i t y .
th e
same p hase as t h e r e a c t a n t s
D e fin e d as:
V olum e l i q u i d - p e r h o u r
Volume o f a c t i v e c a t a l y s t ’
a m easure o f r e s i d e n c e t i m e .
square i n c h ,
gauge.
MONTANA STATE UNIVERSITY LIBRARIES
R378
H398
cop.2
O
O
ill11 IIIill
3 1762
4306
Henton, Lee Morgan
Catalytic hydrogena­
tion of PAMCO solventrefined coal
DATE
IS S U E D T O
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/7^''
l
H S ^9i
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