The effect of hydrogenated creosote oil as a hydrogen donor agent on upgrading of solvent refined coal
(SRC-II)
by Chia-Ren Jack Pan
A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in
Chemical Engineering
Montana State University
© Copyright by Chia-Ren Jack Pan (1983)
Abstract:
The effect of partially hydrogenated creosote oil as a hydrogen donor agent on catalytic upgrading of
SRC-II was investigated. Creosote oil is a coal-derived solvent used as a start-up solvent in the Solvent
Refined Coal process.
The hydrogenated creosote oil was added in three different ratios to SRC-II Light End Column Feed
product: 25%:75%, 50 % : 50%, 75%:25%. MSU-C-49 catalyst which was developed at Montana State
University, and two commercial catalysts, Shell NM324 and Harshaw HT-400, were evaluated in a
small scale trickle bed reactor.
The effect of high concentration of creosote oil on catalytic upgrading of SRC-II is nonbeneficial. As
the percentage of creosote oil is increased the activity in denitrogenation and desulfurization decreased.
Harshaw HT-400 is more active for denitrogenation and desulfurization than either Shell NM324 or
MSU-C-49. THE EFFECT OF HYDROGENATED CREOSOTE OIL AS
A HYDROGEN DONOR AGENT ON UPGRADING OF
SOLVENT. REFINED COAL (S R C -II) .
by
C h ia -R e n J a c k Pan
A t h e s i s submitted i n p a r t i a l f u l f i l l m e n t
o f th e r e q u i r e m e n ts f o r th e d e g re e
of
M a s te r o f S c ie n c e
in
C h e m ic a l E n g in e e r in g
MONTANA STATE UNIVERSITY
Bozem an, M ontana
March -19 83.
MAIN li b .
ii
N 3V %
P n a
Cop. S
APPROVAL
o f a t h e s i s s u b m itte d by
C h ia -R e n J a c k Pan
T h is t h e s i s h a s b e e n r e a d by e a c h member o f th e t h e s i s
c o m m itte e and h a s b e e n fo u n d to b e s a t i s f a c t o r y r e g a r d i n g
c o n t e n t , E n g li s h u s a g e , f o r m a t , c i t a t i o n s , b i b l i o g r a p h i c
s t y l e , and c o n s i s t e n c y , an d i s re a d y f o r s u b m is s io n to th e
C o lle g e o f G ra d u a te S t u d i e s .
3 H—
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C h a i r p e r s p j r f G ra d u a te C om m ittee
A pproved f o r th e M ajor D e p a rtm e n t
3
- v J.
H e a d ,'-7M ajor D e p a rtm e n t
D ate
A pproved f o r ■
Z - 2- 7 - Z 7 3
Date
Graduate Dean
iii
STATEMENT OF PERMISSION TO USE
In p re s e n tin g th is t h e s i s .i n p a r t i a l f u lf illm e n t o f
th e r e q u i r e m e n ts f o r a m a s t e r 's d e g re e a t M ontana S t a t e
U n i v e r s i t y , I a g r e e t h a t th e L i b r a r y s h a l l make i t
a v a ila b le
to b o r r o w e r s u n d e r r u l e s o f th e L i b r a r y .
B r i e f q u o t a t i o n s fro m t h i s t h e s i s a r e a ll o w a b le w i t h o u t
s p e c i a l p e r m i s s i o n , p r o v id e d t h a t a c c u r a t e a c k n o w le d g ­
m en t o f s o u r c e i s m ade.
P e r m is s io n f o r e x t e n s i v e q u o t a t i o n fro m o r r e p r o d u c ­
t i o n o f t h i s t h e s i s may b e g r a n t e d by my m a jo r p r o f e s s o r ,
i■
o r i n h i s / h e r a b s e n c e , by t h e D i r e c t o r o f L i b r a r i e s w hen,
i n th e o p i n io n o f e i t h e r ,
is fo r s c h o la rly p u rp o se s.
t h e p ro p o s e d u se o f t h e m a t e r i a l
Any c o p y in g o r u s e o f th e
m a t e r i a l i n t h i s t h e s i s f o r f i n a n c i a l g a in s h a l l n o t be
a llo 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 .
V
ACKNOWLEDGEMENTS
The a u t h o r w is h e s t o th a n k th e s t a f f o f th e C h em ical
E n g in e e r i n g D e p a rtm e n t a t M ontana S t a t e U n i v e r s i t y f o r
t h e i r h e l p an d c o n c e r n .
A s p e c i a l th a n k s g o e s t o D r.
L lo y d B e rg an d D r. F . P . M cC andless f o r t h e i r g u id a n c e an d
e n c o u ra g e m e n t w i t h t h i s r e s e a r c h .
Added th a n k s g o e s t o
Lyman F e llo w s f o r h i s a s s i s t a n c e i n m a in te n a n c e o f th e
e q u ip m e n t and T u r g u t S a h in an d Nam Kim f o r t h e i r f r i e n d l y
s u g g e s tio n s .
The a u t h o r w o u ld l i k e
to th a n k th e U n ite d S t a t e s
D e p a rtm e n t o f E n e rg y f o r th e f i n a n c i a l s u p p o r t t h a t made,
th is re se a rc h p o s s ib le .
T hanks a l s o g o e s t o th e a u t h o r 's w i f e , W ei, f o r h e r
p a t i e n c e and h e l p an d t o th e ~ a u th o r 1s p a r e n t s , Mr. an d Mrs
P a n , f o r t h e i r e n c o u ra g e m e n t.
F in a lly ,
t h e a u t h o r w o u ld l i k e
to e x te n d h i s warm
th a n k s t o J a n e C u r t i s f o r h e r m o th e rI ik e c o n c e r n .
U
vi
TABLE OF CONTENTS
<
- •- -■
Page
APPROVAL...................................................................
ii
STATEMENT OF PERMISSION TO USE........................
VITA.............................................. ........... ................................... . . --------ACKNOWLEDGEMENTS........................................
iii
iv
v
TABLE OF CONTENTS.................................... .. ; ....................................
vi
LIST OF TABLES ........................................... * .......................................
v iii
LIST OF FIGURES............................
ix
ABSTRACT..................
xi
CHAPTER I
INTRODUCTION......................................
I
CHAPTER I I
COAL CONVERSION.......... ................................. .. . ^ . i
3
C o a l L i q u e f a c t i o n ...............................................
S o l v e n t R e f in e d C o a l(S R C )................................
3
4
CHAPTER I I I USE OF HYDROGENATED CREOSOTE OIL
IN S R C -II UPGRADING...................................
CHAPTER IV
9
H i s t o r y . .................
H y d ro g en D onor S o l v e n t i n C o al
L i q u e f a c t i o n .......................................................... . . .
H y d r o p r o c e s s in g o f C o a l L i q u i d s .................
R e s e a rc h on U p g ra d in g o f S R C -II .................
C r e o s o te O i l ...............................................................
9
10
12
16
17
EXPERIMENTAL...............................................................
20
C a t a l y s t s ...................................................................
E q u ip m e n t............ ....................... ........... .............. ..
H y d r o t r e a t i n g , C r e o s o te O i l . . . ...................... ■
A n a l y s i s ..........................................................................
20
20
24
25
vii
P age
CHAPTER V
RESULTS AND CONCLUSION. ................
......
H ydro t r e a t i n g C r e o s o te O i l ............ .. . . . .
D e n i t r o g e n a t i o n .....................................................
D e s u l f u r i z a t i o n ..................................................... .. .
ASTM D i s t i l l a t i o n R e s u l t . . . ...................... .
Sum m ary
............ ......................... ................
CHAPTER VI
CONCLUSION............ .. . ------------------------. . . . . .
28
.3 0
30
31
39
40
49
BIBLIOGRAPHY .................................... V .....................■ . . . . ............... .
,51
APPENDIX
54
viii
LIST OF TABLES
T a b le
P age
I
Y ie ld s from S R C -II P r o c e s s . . . ................
II
Gas C h ro m a to g ra p h ic A n a l y s i s o f
C r e o s o te O i l . . . . ........................................................
8
18
III
C a t a l y s t P r o p e r t i e s .................................
IV
M a t e r i a l s f o r E x p e r im e n ta l R u n s......................
28
V
R e a c tio n C o n d i t i o n s .................................................
29
VI
S R C -II LECF and Two B a tc h e s o f
. C r e o s o te O i l .........................................................
,21
32
V II
Run CPC-C25...................................................................
54
V III
Run CPC-C50.....................
55
IX
Run CPC-C75........................ ................................. .. . . .
56
X
Run C PS-C 25.................................... .. . . ......................
57
XI
Run CPH-C25....................................................................
58
X II
ASTM D i s t i l l a t i o n f o r Run
CPC-C25................................................................
59
ASTM D i s t i l l a t i o n f o r Run
CPC-C50......................................
60
ASTM D i s t i l l a t i o n f o r Run
CPC-C75.............................................................................
61
ASTM D i s t i l l a t i o n f o r Run
CPS-C25.......... ...................................................................
62
ASTM D i s t i l l a t i o n f o r Run
C P H - C 2 5 .......................................................................'
63
X III
XIV
XV
XVI
ix
LIST OF FIGURES
F ig u re
1
Flow Scheme o f SR C-1..............................................
6
2
Flow Scheme o f S R C - II .......................
7
■3
4
■ .5
Flow Scheme o f S m a ll S c a le
T r ic k le - B e d R e a c to r . .........................................
22
C a t a l y s t a n d P a c k in g D i s t r i b u t i o n
i n T r ic k le - B e d R e a c t o r ................... ................ i .
26
N itr o g e n C o n te n t i n P r o d u c ts U pgraded
by MSU-C49 w ith D i f f e r e n t C o n c e n t r a t i o n
o f C r e o s o te O i l ..........................................................
.3 3
N itr o g e n C o n te n t i n P r o d u c ts U p g rad ed
by D i f f e r e n t C a t a l y s t s w ith . 25%
C r e o s o te O i l .................................
34
7
W e ig h t P e r c e n t D e n i t r o g e n a t i o n .....................
35
8
S u l f u r C o n te n t i n P r o d u c ts U pgraded
. by MSU-C49 w ith D i f f e r e n t C o n c e n t r a t i o n
o f C r e o s o te O i l . . . ................................................
36
S u l f u r c o n t e n t i n P r o d u c ts U pgraded
by D i f f e r e n t C a t a l y s t s w ith 25%
C r e o s o te O i l ......................................
37
W e ig h t P e r c e n t D e s u l f u r i z a t i o n ..........................
38
ASTM D i s t i l l a t i o n f o r CPS-C25 an d
CPH-C25....... ...........................................................
41
6
■
P age
-9
10
. 11
ASTM D i s t i l l a t i o n f o r CPC-C25........................
42
.13 /
ASTM D i s t i l l a t i o n f o r CPC-C50............... . . .
43
14
ASTM D i s t i l l a t i o n f o r CPC-C7 5
44
15
-N itro g en - C o n te n t i n D i f f e r e n t
F r a c t i o n s ................... ............................................... .. .
...........................
..............
45
X
F ig u re
16
17
18
Page
S u l f u r C o n te n t i n D i f f e r e n t
F r a c t i o n s ........................
.46
N itr o g e n C o n te n t i n F r a c t i o n s f o r
E ach R un..................................................
S u l f u r C o n te n t i n F r a c t i o n s f o r
E ach R un........................................................................
47
,
48
xi
ABSTRACT
The e f f e c t o f p a r t i a l l y h y d r o g e n a te d c r e o s o t e o i l a s
a h y d ro g e n d o n o r a g e n t on c a t a l y t i c u p g r a d in g o f SR C -II
was i n v e s t i g a t e d .
C r e o s o te o i l i s a c o a l - d e r i v e d s o l v e n t
u s e d a s a s t a r t - u p s o l v e n t i n th e S o l v e n t R e f in e d C oal
p ro ce ss.
The h y d r o g e n a te d c r e o s o t e o i l was a d d e d i n t h r e e
d i f f e r e n t r a t i o s to S R C -II L i g h t End Column F e e d p r o d u c t :
25%:75%, 50 %: 50%, 75%:25%. MSU-C-49 c a t a l y s t w h ic h was
d e v e lo p e d a t M ontana S t a t e U n i v e r s i t y , a n d two c o m m e rc ia l
c a t a l y s t s . S h e l l NM324 an d H arshaw H T -400, w ere e v a l u a t e d
i n a s m a ll s c a l e t r i c k l e b e d r e a c t o r .
The e f f e c t o f h ig h c o n c e n t r a t i o n o f c r e o s o t e o i l on
c a t a l y t i c u p g r a d in g o f S R C -II i s n o n b e n e f i c i a l ; As th e .
p e r c e n t a g e o f c r e o s o t e o i l i s i n c r e a s e d th e a c t i v i t y i n
d e n i t r o g e n a t i o n an d d e s u l f u r i z a t i o n d e c r e a s e d . H arshaw
HT-400 i s m ore a c t i v e f o r d e n i t r o g e n a t i o n a n d d e s u l f u r ­
i z a t i o n th a n e i t h e r S h e l l NM324 o r MSU-C-49.
)
I
'CHAPTER I
INTRODUCTION
The t h i r t y y e a r s o f s u c c e s s i n c o a l l i q u e f a c t i o n
te c h n o lo g y h a s d e m o n s tr a te d c o a l 's f e a s i b i l i t y a s a new
e n erg y s o u r c e .
H ow ever, no c o m m e rc ia l p l a n t h a s b e e n
c o n s t r u c t e d s i n c e th e te c h n o lo g y h a s becom e a r e a l i t y .
P o l i t i c s , e c o n o m ic s an d e n v ir o n m e n ta l c o n s i d e r a t i o n s ! h a v e 7
in flu e n c e d i t s p r o g r e s s .
The m o st e f f i c i e n t u se o f c o a l i s when i t i s b u rn e d
d ire c tly
in fu rn a c e s o r u n d er b o i l e r s .
The p ro b le m o f
c o m b u s tio n i s t h e e m is s io n o f n o x io u s g a s e s su c h a s s u l f u r
o x id e s a n d n i t r o g e n o x i d e s .
rea so n fo r i n i t i a t i n g
In d e e d ,
t h i s c o n c e rn was one
th e s h i f t from c o a l t o o i l f o r
e l e c t r i c a l pow er g e n e r a t i o n .
L i q u i f y i n g c o a l h a s b e e n p ro v e d to b e t h e m o st
e f f i c i e n t w a y (I)
to p r o v id e l i q u i d f u e l from c o a l .
H ow ever, l i q u i f i e d c o a l h a s to o h ig h a s u l f u r a n d n i t r o g e n
c o n t e n t t o b e a c c e p t e d e i t h e r by t h e EPA(2 ,3 )
c o n v e n t i o n a l p e tr o c h e m i c a l r e f i n i n g p r o c e s s e s .
o r in
The
p e tr o le u m r e f i n i n g i n d u s t r i e s do n o t a c c e p t l i q u i f i e d c o a l
b e c a u s e o f e q u ip m e n t and p o l l u t i o n p ro b le m s .
ta in e d in
N itr o g e n co n ­
th e f e e d s t o c k f o r F l u i d C a t a l y t i c C racking(F C C )
w o u ld b e a m a jo r s o u r c e o f p o l l u t i o n an d e q u ip m e n t dam age.
2
H y d ro g en b l i s t e r i n g i s an e x am p le o f th e e x t e n s i v e damage
'
■
C
p o s s i b l e i n e q u ip m e n t.
A n o th e r i m p o r t a n t r e a s o n f o r th e
u p g r a d in g o f c o a l l i q u i d s i s
t h a t h ig h n i t r o g e n an d s u l f u r
c o n t e n t i n o r g a n i c com pounds c a u s e u n d e s i r a b l e p o i s o n i n g
o f th e a c i d i c f u n c t i o n s o f c a t a l y s t s i n r e f i n i n g p r o c e s s e s
(5 ).
P o is o n in g s h o r t e n s c a t a l y s t l i f e
c o s t o f i n v e s tm e n t .
and i n c r e a s e s ..th e
From e co n o m ic c o n s i d e r a t i o n s , p r i c e
d e te r m in e s th e f e a s i b i l i t y o f s u b s t i t u t i n g c o a l l i q u i d f o r
p e tr o l e u m .
The u p g r a d in g o f c o a l l i q u i d s becam e a n e c e s ­
s a r y p r o c e d u r e i f th e l i q u i d s a r e to be u s e d a s . s u b s t i t u t e s
f o r p e tr o le u m .
The p u r p o s e o f t h i s r e s e a r c h i s t o i n v e s t i g a t e th e
e f f e c t o f d i f f e r e n t c a t a l y s t s on th e u p g r a d in g o f S o l v e n t
R e f in e d C o a l (S R C -II) by t h e a d d i t i o n o f h y d r o g e n a te d
c re o s o te o i l .
a g e n t.
The c r e o s o t e o i l a c t s a s a h y d ro g e n d o n o r
3
CHAPTER I I
GOAL CONVERSION
C o a l h a s b e e n u s e d i n many d i f f e r e n t w ays f o r more
th a n a c e n t u r y .
I n th e b e g in n i n g i t was u s e d p r i m a r i l y
f o r h e a t by c o m b u s tio n .
D i r e c t c o m b u s tio n i s t h e m ost
s tr a ig h tf o r w a r d and c o n v e n ie n t u se o f c o a l.
C oal g a s i f i ­
c a t i o n was i n t r o d u c e d a s a s u b s t i t u t e f o r n a t u r a l g a s .
H ow ever, t h e e n e r g y s u p p ly a n d t h e r e s o u r c e s t r u c t u r e h a s
c h a n g e d o v e r th e y e a r s .
I t was n o t u n t i l W orld War I I
when p e o p le n e e d e d much m ore e n e r g y .
p e tr o le u m s h o r t a g e ,
re so u rc e .
B e c a u se o f th e
c o a l a g a in becam e an i m p o r t a n t e n e rg y
I t was d u r in g W orld War I I
t h a t t h e non­
p e tr o le u m p r o d u c in g c o u n t r i e s w e re f o r c e d to d e v e lo p a
s u b s titu te
f o r p e tr o le u m .
H ow ever, c o n su m ers c u r r e n t l y u se
a b o u t 75% o f t h e i r p e tr o le u m p r o d u c t s i n th e fo rm o f d i s ­
t i l l a t e s (6) .
The enorm ous c o n su m p tio n o f d i s t i l l a t e s
in
t r a n s p o r t a t i o n a n d h e a t i n g f u e l h a s becom e a m a jo r r e a s o n
to th e l i q u i f y c o a l .
C o al L i q u e f a c t i o n
C o a l i s c o n v e r t e d to a l i q u i d p r o d u c t th r o u g h e i t h e r
d ir e c t o r in d ir e c t liq u e fa c tio n
liq u e fa c tio n is
te c h n iq u e s .
t h e 'm o s t d e v e lo p e d .
F irs t,
In d ire c t
co al is g a s i­
4
f i e d to p ro d u c e a m ix tu r e o f h y d ro g e n a n d c a rb o n m onoxide
w h ich i s
th e n co m b in ed by c a t a l y s t s
p o u n d s.
C u rre n tly ,
to fo rm l i q u i d com­
th e O hly eom m erO ial p r o c e s s . i s th e
P i s h e r - T r o p s c h b e in g u s e d i n S o u th A f r i c a i n c o n j u n c t i o n
w i t h K o p p e r s - T o tz e k , T e x a c o , W in k le r - L u r g i a n d S h e l l K o p p ers g a s i f i e r s .
Two d i f f e r e n t p r o c e s s e s o f d i r e c t l i q u e f a c t i o n a r e
c a t a l y t i c h y d r o g e n a t io n a n d th e u s e o f a d o n o r s o l v e n t .
The l a t t e r was c h a r a c t e r i z e d a s t h e S o l v e n t R e f in e d C oal
(SRC) p r o c e s s d e v e lo p e d by P i t t s b u r g and Midway C o a l Co.
a n d t h e Exxon D onor S o lv e n t(E D S ) p r o c e s s .
B o th p r o c e s s e s
p ro d u c e l i q u i f i e d g o a l by s o l v e n t e x t r a c t i o n .
D i r e c t c a t a l y t i c h y d r o g e n a tio n e s s e n t i a l l y r e d u c e s
m o le c u la r w e ig h t a n d i n c r e a s e s t h e H/C r a t i o o f th e p a r e n t
c o a l m o le c u le to a r a t i o
c ru d e .
s i m i l a r to t h a t o f a p e tr o le u m
The p r o c e s s u s e d c a t a l y s t s c o m p r is in g c o b a l t and
m olybdenum o x id e on a lu m in a o r m o lte n ZnCl2 ( S ) .
The
S y n t h o i l a n d H -c o a l p r o c e s s e s a r e e x a m p le s o f d i r e c t
c a t a l y t i c h y d r o g e n a t io n .
S o l v e n t R e fin e d C o a l (SRC)
I n 1974, P i t t s b u r g & Midway C o a l M in in g Company owned
by th e G u lf O i l Company was a w a rd e d a c o n t r a c t by th e
D e p a rtm e n t o f Energy(DOE)
f o r th e SRC-I p i l o t p l a n t s t a r t ­
up o p e r a t i o n . . F i g u r e I show s th e flo w schem e o f th e SRC-I
p ro c e ss.
SRC-I was d e s ig n e d t o p ro d u c e low a s h an d low
5
s u l f u r s o l i d b o i l e r f u e l (7)
r e q u i r e m e n t.
to m e e t t h e s u l f u r e m is s io n
The p u l v e r i z e d c o a l a n d a n th r a n c e n e o i l was
i n t r o d u c e d i n t o a s l u r r y ta n k a n d pumped t o t h e s l u r r y
p r e h e a t e r , w h ere s l u r r y w as p r e h e a t e d to ab o v e 800°F a t
100 a tm .
The p r e h e a t e d s l u r r y was f e d to a d i s s o l v e r and
th e s o l v e n t i n th e s l u r r y fro m t h e d i s s o l v e r was r e c o v e r e d
a s a r e c y c l e s tr e a m w h ich w e n t b a c k to th e s l u r r y t a n k .
The S R C -II mode was c o n n e c te d t o SRC-I i n 1 9 7 7 ( 8 ) .
2 show s t h e S R C -II flo w sc h e m e .
S R C -II i s
F ig u r e
The f i n a l p r o d u c t in
l i q u i d a t room t e m p e r a t u r e .
c o n s i d e r a b l y d i f f e r e n t fro m S R C -I.
T h is m akes SR C -II
The o v e r a l l y i e l d arid
h y d ro g e n c o n su m p tio n o f th e S R C -II p r o c e s s a r e g iv e n i n
T a b le I .
The f e e d f o r t h i s r e s e a r c h i s L ig h t End Column
F eed (L E C F ), a l i g h t l i q u i d from t h e v a p o r - l i q u i d
s e p a r a t o r s o f th e S R C -II p r o c e s s .
H Y D RO G EN
• HYDROCARBON GAS
COAL
LIQUID fUCL TO SO U D lflC A TtO N
F ig u r e I . Flow Scheme o f SRC-I P r o c e s s .
CAS K tC O V tW Y
DEA
FRESH HVOfiOOEM
I MATHTHA
COM PRESSOR
I t TOOWM
MtOM PRESSURE
KECVCLE
COHCENSATE
SEPARATION
FRACTIONATlOM
v essel
H YOROCEN
QUENCH
COAL
INTERMEDIATE
V-MSll
FLASH VESSEL
WATER QUENCH
VACUUM
VACUUM B O TTO M S
R f C Y C L t SLURRY
F ig u r e 2 . Flow Scheme o f S R C -II P r o c e s s
8
T a b le I
Y ie ld s from S R C -II p r o c e s s
wt%
M o is tu re -fre e
C o a l C harge
Math a n e
E th a n e
P ro p a n e
I s o - B u ta n e
n -B u ta n e
Ct- - I S S 0 C N ap h th a
19 3 -316°C M id d le D i s t i l l a t e
3 1 6 -4 82°C Heavy D i s t i l l a t e
482 C + R e sid u e
P y r i d i n e - I n s o l u b I e O rg a n ic M a t e r i a l
(IOM)
Ash
R e s id u a l S
C arbon M onoxide
C arbon D io x id e
H y d ro g en S u l f i d e
Ammonia
W ater
T o ta l
H y d ro g en C on su m p tio n
5 .8
4 .4
4 .1
0.2
2.0
10.2
1 7 .9
7 .9
2 4 .0
4 .6
12.0
1.1
0.1
1.0
2 .5
0 .4
6.2
1 0 4 .4
4 .4
9
CHAPTER I I I
USE OF HYDROGENATED CREOSOTE OIL IN S R C -II UPGRADING
H is to ry
B e c a u se o f th e l a r g e am ount o f p o ly a ro m a t i c c o n t e n t ,
c r e o s o t e o i l , a c o a l - d e r i v e d s o l v e n t o n c e w id e ly u s e d f o r
wood p r o t e c t i o n , becam e a f a v o r i t e i n th e s t a r t - u p o f th e
SRC p r o c e s s .
S e v e r a l s t u d i e s h a v e i n v e s t i g a t e d th e u se o f
c r e o s o t e o i l a s a h y d ro g e n d o n o r s o l v e n t i n t h e l i q u e ­
fa c tio n o f c o a l.
I t w as n o t a n a t t r a c t i v e a g e n t i n th e
u p g r a d in g o f l i q u i f i e d c o a l u n t i l G iv en s e t a l . ( 8) an d
P o t t s e t a l . (9) i n t r o d u c e d c r e o s o t e o i l i n 1978 a s a
s o l v e n t i n a s tu d y o f d e r i v i n g l i q u i d f u e l s fro m SRC-I
'
p r o d u c t a n d i n th e e v a l u a t i o n o f c o m m e rc ia l c a t a l y s t s .
I n 1982 S t i e g e l e t a l . ( 1 0 )
u s e d c r e o s o t e o i l f o r th e
s c r e e n i n g o f u p g r a d in g c a t a l y s t s f o r S R C -I.
I t i s r e a s o n a b l e t o u s e h y d r o g e n a te d c r e o s o t e o i l i n
th e u p g r a d in g o f SRC-I b e c a u s e i t i s a s o l i d p r o d u c t and
n e e d s to b e d i s s o l v e d b e f o r e i t c a n b e h a n d le d .
H ydrogen­
a t e d c r e o s o t e o i l c a n a c t a s a h y d ro g e n d o n o r s o l v e n t i n
th e u p g r a d in g .
10
The b a s i c c o n c e p t, i n u s i n g h y d r o g e n a te d c r e o s o t e o i l
i n SRC-I u p g r a d in g i s s im p ly an a p p l i c a t i o n o f i t s
h y d ro g e n -tra n s fe r c a p a c ity .
H ow ever, s i n c e S R C -II en d
p r o d u c t s a r e l i q u i d s , th e i n t r o d u c t i o n o f h y d r o g e n a te d
c r e o s o t e o i l i n u p g r a d in g i s b e in g s t u d i e d b e c a u s e o f th e
a n tic ip a tio n of i t s
s y n e rg is tic -h y d ro g e n donor e f f e c t .
H ydrogen D onor S o l v e n t i n C o a l L i q u e f a c t i o n
The e s s e n c e o f c o a l p r o c e s s i n g to l i q u i d f u e l s i s
to i n c r e a s e th e H/C r a t i o o f th e c o a l ( ^ 0 . 8 )
m o to r f u e l ( = 2 . 0 ) .
to t h a t o f
T h is i s a c c o m p lis h e d w ith a s p e c i f i c
s o l v e n t i n a h y d r o g e n - g a s a tm o s p h e r e .
A lth o u g h t h e m echanism o f how a s o l v e n t h e l p s i n
i n c r e a s i n g th e H/C r a t i o o f c o a l i s n o t c o m p le te ly u n d e r­
s t o o d , i t i s w e l l a c c e p t e d t h a t th e e f f i c i e n c y o f c e r t a i n
h y d ro g e n -ric h s o lv e n ts i s a fu n c tio n o f t h e i r a b i l i t y
d o n a te h y d ro g e n ato m s to c o a l a n d c o a l p r o d u c t s .
A
commonly s u g g e s te d r o u t e i n v o l v i n g f r e e r a d i c a l s an d
h y d ro g e n t r a n s f e r i s : ( 11)
c o a l - c o a l ----- - 2 c o a l ©
coal©
h y d ro g e n
donor
■®-coal© H
to
11
I
I n 1 9 8 1 , D e r b y s h ir e e t a l . (13) f u r t h e r p r o p o s e d a
" s y n e r g i s t i c e f f e c t " b e tw e e n p y r e n e - t e t r a l i n m ix t u r e s an d
m o le c u la r h y d ro g e n by w h ic h c o a l c o n v e r s i o n w as e n h a n c e d .
I t . c a n b e e x p l a i n e d by f o l l o w i n g r e a c t i o n s :
t e t r a l i n + c o a l ---- n a p h th a le n e + coalH
t e t r a l i n + p y re n e ---- n a p h th le n e + d ih y d r o p y r e ne
p y re n e +
---- ®»» d ih y d r o p y r e n e
d ih y d r o p y re n e + c o a l — *»- p y re n e + coalH
T h e re i s a r e d u c t i o n i n th e h y d ro g e n t r a n f e r r e d from
te tra lin ,
a n d h y d r o g e n a t io n o f c o a l by p y re n e i s e n h a n c e d
by h y d ro g e n a n d p y r e n e .
A c tu a lly ,
th e u s u a l c r i t e r i o n f o r s o l v e n t s e l e c t i o n
i s th e s o l v e n t ’ s h y d r o g e n - d o n a tio n a b i l i t y .
H y d ro g e n a te d
s o l v e n t s h a v e b e e n shown by F u r lo n g a t a l .( 1 4 )
to b e b e t t e r
s o l v e n t s i n c o a l c o n v e r s io n th a n th e o r i g i n a l u n h y d ro ­
g e n a te d m a t e r i a l .
D a v ie s an d o t h e r s (15) a l s o show ed t h a t
e x t r a c t i o n e f f i c i e n c i e s o f h y d r o g e n a te d a n th r a c e n e o i l s
a r e c o n s i s t e n t l y h i g h e r o v e r th e e n t i r e b o i l i n g ra n g e th a n
th e o r i g i n a l a n th r a c e n e o i l , p re s u m a b ly due t o th e
p r e s e n c e o f p o l y c y c l i c h y d r o a r o m a tic com pounds.
T hese
com pounds a r e known to b e r e a c t i v e s o l v e n t s and e f f e c t i v e
d o n o rs o f h y d ro g e n t o c o a l f r a g m e n ts .
M e an w h ile , i t i s
w o rth n o t i n g t h a t th e u h h y d ro g e n a te d a n th r a c e n e o i l h a v e
a h i g h e r s o l v e n t pow er th a n w o u ld b e e x p e c te d fro m t h e
12
e x t r a c t i o n e f f i c i e n c i e s o f i t s m ain co m p o n en ts su c h a s
n a p h t h a l e n e , a n t h r a c e n e , p h e n a n th r e n e a n d d i b e n z o f u r a n ( 1 5 ) .
H y d r o p r o c e s s in g o f C o a l L iq u id s
T h is r e s e a r c h i s c o n c e rn e d w i t h t h e h y d r o p r o c e s s in g
o f c o a l l i q u i d s w ith s p e c i a l em p h ases on d e n i t r o g e n a t i o n
a n d d e s u l f u r i z a t i o n a s w e l l a s th e p r o d u c t i o n o f a g r e a t e r
f r a c tio n o f l i g h t p ro d u c ts .
I n c o n v e n t i o n a l p e tr o l e u m r e f i n i n g i n d u s t r i e s
d e n i t r o g e n a t i o n i s g r e a t l y o v e rsh a d o w e d by d e s u l f u r i z a t i o n ,
b e c a u s e c ru d e o i l g e n e r a l l y c o n t a i n s l i t t l e
o r no n i t r o g e n .
H ow ever, th e h ig h c o n t e n t o f n i t r o g e n i n c o a l p r o d u c t s c a n
n o t be ig n o re d .
S in c e th e h y d r o t r e a t i n g c a t a l y s t s
d e v e lo p e d f o r p e tr o le u m r e f i n i n g i n d u s t r i e s show l i t t l e
d e n i t r o g e n a t i o n a c t i v i t y , a s e p a r a t e d e v e lo p m e n t o f
c a ta ly s ts fo r h y d ro tre a tin g o f c o a l liq u id s i s needed.
M e ta ls su c h a s Mo, Co, N i, a n d W h a v e b e e n p ro v e n to be
w o r k a b le .
U n lik e d e s u l f u r i z a t i o n ,
d e n i t r o g e n a t i o n r e q u i r e s th e
s a t u r a t i o n o f t h e a r o m a tic r i n g p r i o r to t h e c le a v a g e o f
th e c a r b o n - n i t r o g e n b o n d .
T h e r e f o r e , h y d ro g e n c o n su m p tio n
i s u s u a l l y h ig h f o r f e e d s t o c k s w ith- h ig h c o n c e n t r a t i o n s o f
n i t r o g e n b e c a u s e o f th e s a t u r a t i o n o f a r o m a tic r i n g s .
13
M ost o f th e s t u d i e s on d e n i t r o g e n a t i o n m echanism
used
a s p e c i f i e d n i t r o g e n com pound i n s t e a d o f th e c o a l
liq u id .
G a te s e t a l . (16) p r o p o s e d a m echanism f o r t h e
h y d ro d e n itr o g e n a tio n o f q u in o lin e a s fo llo w s :
Pr
T h re e m in o r h y d r o c a r b o n s
14
The p r o p o s e d m e c h a n is m f o r h y d r o d e s u l f u r i z a t i o n o f
d i b e n z o t h i o p h e n e (DBT)
is
as fo llo w s:
CnD
C o al i s
f i r s t c le a v e d i n t o r a d i c a l f r a g m e n ts by th e
s o l v e n t u n d e r h ig h te m p e r a tu r e an d p r e s s u r e ,
th e n th e
h y d ro g e n d o n o r s o l v e n t g iv e s up a h y d ro g e n r a d i c a l to th e
c o a l f r a g m e n t p e rm a n e n tly r e d u c i n g th e c o a l m o le c u la r s i z e .
In th is o p tio n ,
th e s o l v e n t i s a h y d r o g e n - t r a n s f e r a g e n t
w h ich d o n a te s h y d ro g e n s to m a s s iv e c o a l m o le c u le s .
H ow ever,
t h e r e i s a n o th e r i m p o r t a n t r o l e w h e re in t h e
s o l v e n t a i d s i n th e r e d i s t r i b u t i o n o f h y d ro g e n , b u t w h e re in
no n e t t r a n s f e r o f H ydrogen o c c u r s .
t i n g u i s h i t from "h y d ro g e n t r a n s f e r " ,
I n o r d e r to d i s ­
i t i s c a l l e d " h y d ro ­
g en s h u t t l i n g " w h ic h i s shown a s f o l l o w s : ( 12)
15
+ S o lv e n t•
+ S o lv e n t-H
H-C •
* 0 i s a n y p a r t o f c o a l m o le c u l e .
B e rg a n d M c C a n d le ss(17) h a v e b e e n i n v e s t i g a t i n g th e
u p g r a d in g o f c o a l l i q u i d s s i n c e th e 1 9 7 0 's .
T h e ir r e s u l t s
show t h a t p o re s i z e a n d th e am ount o f m e ta l l o a d i n g o f th e
c a t a l y s t a r e some o f th e m o st i m p o r t a n t f a c t o r s i n
d e te r m in in g th e e f f e c t i v e n e s s o f a c a t a l y s t .
N e v e rth e le s s ,
h y d ro g e n c o n su m p tio n i s n o t a n e g l i g i b l e f a c t o r i n th e
c o n s i d e r a t i o n o f th e e c o n o m ic s o f c o a l - l i q u i d u p g r a d in g .
16
From u n d e r s t a n d i n g th e m ech an ism s f o r h y d r o t r e a t i n g
in c o a l liq u e f a c tio n ,
i t i s r e a s o n a b l e to e x p e c t t h a t
h y d r o g e n a te d c r e o s o t e o i l m ig h t b e u s e d i n u p g r a d in g o f
c o a l l i q u i d an d g iv e some im p ro v e m e n t i n th e a c t i v i t y o f
h y d ro tre a tin g .
R e s e a rc h on U p g ra d in g o f SR C -II
Many v a r i a b l e s i n f l u e n c e th e u p g ra d in g o f S R C -II,
in c lu d in g te m p e ra tu re , p r e s s u r e , c a t a l y s t ,
l i q u i d h o u rly
s p a c e v e l o c i t y (LHSV), a n d h y d ro g e n flo w r a t e .
C a ta ly tic
e f f e c t i v e n e s s i s i n f l u e n c e d fry p o r e d ia m e te r d i s t r i b u t i o n ,
s u r f a c e , a r e a , m e ta l l o a d i n g , c a t a l y s t d e a c t i v a t i o n , a n d
th e p r e s e n c e o f a p ro m o to r o r i n h i b i t o r .
S e v e r a l d i f f e r e n t c o m m e rc ia l c a t a l y s t s , new c a t a l y s t s
w ith v a r i o u s m e t a l s , m e t a l - l o a d i n g am ounts a n d p o re s i z e
d i s t r i b u t i o n w ere a l l i n v e s t i g a t e d by Y e h ( I S ) .
The s tu d y
show ed t h a t a c o m b in a tio n o f 4% CoO, 8% MoO^, 1% NiO, 8%
WOg b a s e d on N a l c o - 7 8 -6 0 0 8 c - 1 /3 2 " was th e m o st e f f e c t i v e
i n h y d r o d e n i t r o g e n a t i o n o f S R C -II.
same c a ta ly s t(M S U -C -4 9 )
B h a t i a (19) u s e d th e
i n h i s r e s e a r c h an d f u r t h e r show ed
t h a t a t th e o p e r a t i n g c o n d i t i o n o f 425°C te m p e r a tu r e and
-I
a LHSV o f I . 2 5 h r , th e w e ig h t p e r c e n t d e n i t r o g e n a t i o n i s
a b o u t 57.2% an d w e ig h t p e r c e n t d e s u l f u r i z a t i o n i s a b o u t
88.3% .
17
R e s u l t s o f a c o n c u r r e n t i n v e s t i g a t i o n by S a h in (2 0 )
w ere u t i l i z e d i n t h i s r e s e a r c h i n th e c o m p a r is io n o f
re s u lts .
In S a h i n 1s r e s e a r c h , H arshaw HT-400 g av e th e ;
b e s t p e rfo rm a n c e i n u p g r a d in g S R C -II VFF(Vacuum F la s h
F eed) .•
The s tu d y show ed 77% d e n i t r o g e n a t i o n a n d 65%
d e s u l f u r i z a t i o n u s i n g th e H arshaw HT-400 c a t a l y s t w i t h o u t,
w a te r a d d i t i o n .
C r e o s o te O il
I n t h i s r e s e a r c h H o p p ers c r e o s o t e o i l , a c o a l - d e r i v e d
s o l v e n t u s e d a s a s t a r t - u p s o l v e n t i n SRC p r o c e s s , was
i n t r o d u c e d a s a h y d ro g e n d o n o r a g e n t .
H o p p ers t a r c r e o s o t e
o i l i s c o m p ris e d p r i m a r i l y o f tw o , t h r e e an d f o u r r i n g
p o l y n u c l e a r a r o m a ti c c o m p o n e n ts , an d i t s h y d ro g e n c o n t e n t ■
i s lo w e r th a n f o r c o n v e n t i o n a l r e c y c l e s o l v e n t s .
H ow ever,
when u s e d a s s o l v e n t i n th e SRC p r o c e s s th e h y d ro g e n d o n o r
c a p a c i t y o f c r e o s o t e o i l was im p ro v e d by h y d r o t r e a t i n g ( 2I ) .
The c r e o s o t e o i l was a n a ly z e d by A l l i e d C h e m ica l Co.
(22) a s shown i n T a b le I I .
B e c a u se i t i s a s o l i d - l i q u i d
m i x t u r e , i t s v i s c o s i t y a t 200° f i s a b o u t 6 c e n t i p o s e ( 8) ,
w h ic h c a u s e s h a n d l i n g p ro b le m s t h a t w ere ov erco m e by th e
m o d i f i c a t i o n o f th e f e e d s y s te m w i t h h e a t i n g t a p e s an d
c o ils .
18
*
T a b le i i .
Gas C h ro m a to g ra p h ic A n a ly s is o f C r r o s o t e O il
Compound________________
Wt%
N itr o g e n Compounds
B e n z o n itrile
o -E th y la n ilin e
Q u in o lin e
I s o q u in o lin e
2 - M e th y ! q u in o lin e
I n d o le
I-N a p th o n itrile
2 -N a p h th o n it r i l e
0 .1 2
0 .0 3
0 .3 7
0 .3 0
0 .4 2
0 .2 1
0 .1 9
0 .1 4
A c r id in e
C a rb a z o le
2 -M eth y I c a r b a z o l e
S u l f u r Compounds
0 .1 9
2 .2
1 .7
T h ia n a p h th e n e
D ip h e n y le n e s u l f i d e
Oxygen Compounds
0 .0 8
0 .5 2
Coum arone
D ib e n z o fu ra n
3-M eth y l d ip h e n y I e n e o x id e
0 .1 0
6 .7
1 .7
I , 2 -B e n z o d ip h e n y le n e o x id e
0 .9 6
0 .1 2
Phenol
o -C re so l
p -C reso l
m -C re s o l
4 -In d a n o l
0 .0 5
0 .3 7
0 .1 6
0 .5 5
* G uin , J . A. e t a l . , I n d . E ng. Chem. P r o c e s s D e s.
D e v ., V o l. 17, No. 2, 1978.
19
T a b le I I .
(C o n tin u e d )
____________Compound____________________ Wt%
H y d ro c a rb o n s
p - Cymene
In d a n
N a p h th a le n e
2 - M e th y !n a p h th a le n e
0.02
0 .1 1
5 .1
1 .3
1 - M e th y ln a p h th a le n e
0 .3 8
D ip h e n y l
I , 6- D im e th y ! n a p h th a le n e
0 .4 9
0 .3 9
2 , 3 - D im e th y ! n a p h th a le n e
0 .1 9
A c e n a p h th e n e
F lu o r e n e
6 .0
1 0 .3
9 , IO -D ih y d ro a n th ra c e n e
2 - M e th y Iflu o r e n e
P h e n a n th re n e
2 .4
0 .8 5
1 8 .6
A n th ra c e n e
3 - M ethyl p h e n a n th r e n e
4 , 5-Me th y le n e p h e n a n th r e n e
4 .3
0 .9 8
2 .5
2 - M e th y !a n th r a c e n e
9 - M e th y !a n th r a c e n e
0 .2 4
1 .2
F lu o r a n th e n e
5 .5
P y re n e
2 .6
U n i d e n t i f i e d com pounds
in d i s t i l l a t e
7 .5 6
T o ta l d i s t i l l a t e
8 8 .1 8
20
CHAPTER IV
EXPERIMENTAL
C a ta ly s ts
Two c o m m e rc ia l c a t a l y s t s
( S h e l l NM324 a n d H arshaw HT-
400) a n d MSU-C-49 w h ic h h a d b e e n d e v e lo p e d by Y eh (18) w ere
a p p lie d in th is re s e a rc h .
The p r o p e r t i e s o f t h e s e
c a t a l y s t s a r e shown i n T a b le I I I .
A l l c a t a l y s t s w ere p r e s u l f u r i z e d w ith a 10% h y d ro g e n
s u l f i d e i n h y d ro g e n m ix tu r e f o r 10 h o u r s i n o r d e r to
p r e v e n t t h e r e d u c t i o n o f c a t a l y s t a c t i v i t y by h ig h te m p e r­
a t u r e h y d r o g e n a tio n (23) .
E q u ip m e n t
A s m a ll-s c a le ,
t r i c k l e - b e d r e a c t o r a s show en i n F ig u r e
3 was u s e d t h r o u g h o u t t h i s r e s e a r c h .
The t r i c k l e - b e d
r e a c t o r i s 40 in c h e s lo n g a n d made o f I" ID , s c h e d u le 80
in c o n e l p ip e .
A t th e to p o f r e a c t o r a c r o s s was w e ld e d to th e
r e a c t o r a n d f i t t e d w ith a 3 6 - in c h lo n g s t a i n l e s s s t e e l tu b e
in to
th e r e a c t o r to s e r v e a s a th e rm o w e ll.
The o t h e r two
o p e n in g s w ere f o r S R C -II f e e d an d th e h y d ro g e n i n l e t .
21
T a b le I I I . C a t a l y s t P r o p e r t i e s
MSU-C-49 S h e l l NM324
H arshaw HT-400
Type
E x tr u d e d
E x tru d e d
E x tru d e d
S iz e
1 /3 2 "
1 /1 6 "
1 /3 2 "
B ulk D e n s ity ( g /c c )
P o re V olum e(m l/gram )
2
S u r f a c e A r e a (m /g ram )
0 .8 4
0 .8 5 5
0 .8 0 1
0 .3 9 6
0 .5
2 1 4 .6
18 8
220
A v e rag e P o re D ia m e te r 1 5 6 .5
(A°)
98
HO
M e ta l C on ten t(w t% )
NiO
1.0
2.72
MoOg
8.0
1 3 .1 6
CoO
4 .0
WO3
8.0
1 5 .0
3 .0
N ote : C a t a l y s t s u p p o r t o f MSU-C-49 i s N a lc o - 7 8-6 00 SC
Legend:
REACTOR
FR I: Flow Rate R e c o r d er/In d icator
PUMP
SEPARATOR
ABSORBER
—
—
T R I : Te mp. R e c o r d e r /
Ind icator
In d ic a to r
to
vent
C.W, o u t
to vent
f ! I
Sample
Sam ple
,
Continuous Scheme
Batch Scheme
*
C o n tin u o u s Scheme i s U sed f o r E x p e r im e n ta l Runs
** B a tc h Scheme i s U sed f o r H y d r o t r e a t i n g C r e o s o te O i l
F i g u r e 3 . Flow Scheme o f S m a ll S c a le T r i c k l e - B e d R e a c t o r .
23
A t t h e b o t to m o f t h e r e a c t o r was a t h r e a d e d c a p f i t t e d
w i t h an o u t l e t f o r p r o d u c t r e l e a s e a n d / o r l o a d i n g and u n ­
lo a d in g o f th e c a t a l y s t .
The r e a c t o r was h e a t e d by a n e l e c t r i c w i n d i n g w hich
was w ra p p e d a r o u n d a 6- i n c h O.D. alum inum b l o c k s u r r o u n d e d
by i n s u l a t e d m a t e r i a l .
The b l o c k had a I - i n c h b o r e h o l e
fo r th e r e a c t o r .
T e m p e r a tu r e was m e a s u r e d by two c h ro m e 1 - a lu m e I
th e r m o c o u p l e s w h ic h w e re c o n n e c t e d t o d i g i t a l th e r m o c o u p le
'
re a d o u ts.
'
'
The t h e r m o c o u p l e s w e re l o c a t e d i n t h e p e r h e a t
and r e a c t i o n s e c t i o n s .
L i q u i d f e e d was pumped t h r o u g h a 1 / 8 - i n c h s t a i n l e s s
s t e e l t u b e by a m e t e r i n g pump.
c re o so te o i l ,
In h y d r o tr e a tin g o f
t h e f e e d s y s te m was h e a t e d by w r a p p in g
e l e c t r i c t a p e s o r c o i l s a r o u n d t h e t u b e s t o r e d u c e ’t h e h i g h
v i s c o s i t y o f th e c re o s o te o i l .
G aseous p h a s e p r o d u c t was c o n d e n s e d by a d o u b l e - p i p e
ty p e c o n d e n se r and c o l l e c t e d a f t e r a g a s - l i q u i d s e p a r a t o r
e i t h e r c o n t i n u o u s l y o r by b a t c h .
The l a t t e r was u s e d i n
h y d r o tr e a tin g o f c re o s o te o i l because of i t s h ig h v i s c o s i ­
t y and h i g h b o i l i n g p o i n t .
I n t h i s c a s e , l i q u i d was
a l l o w e d t p be c o l l e c t e d i n a c a t c h p o t f i r s t .
W henever t h e
l i q u i d p r o d u c t was rem o v e d , t h e v a l v e b e tw e e n t h e s e p a r a t o r
an d t h e c a t c h p o t was c l o s e d and t h e c a t c h p o t was
d e p r e s s u r iz e d th ro u g h a v e n t.
A fte r th e l i q u i d p ro d u c t
was d r a i n e d fro m t h e b o t t o m , t h e c a t c h p o t was r e p r e s s u r i z e d
24
w i t h n i t r o g e n a n d t h e v a l v e was r e o p e n e d .
H y d r o tr e a tin g C re o so te O il
The h y d r o g e n t o c a r b o n r a t i o o f c r e o s o t e o i l c an be
i n c r e a s e d by h y d r o t r e a t i n g ,
i t c a n t h e n be u s e d a s a
s o l v e n t i n t h e SRC p r o c e s s .
H y d ro tre a tin g in c r e a s e d th e
h y d r o g e n c o n t e n t a b o u t 1% fro m 6.1% to 7.5% .
The h y d r o -
t r e a t i n g c o n d i t i o n s ' w e re s u g g e s t e d by W r i g h t e t a l . (21)
i n 1975 a s shown i n T a b le V.
!
To i n c r e a s e p u m p a b i l i t y o f c r e o s o t e o i l i n t h e
e x i s t i n g e q u ip m e n t ,
tfre LHSV was i n c r e a s e d t o 1 .0 c . c . /
c .c . of c a ta ly s t/h r,
an d t h e h y d r o t r e a t i n g was r e p e a t e d
u n d e r t h e same c o n d i t i o n s u n t i l t h e p r o d u c t was l i q u i d .
T h e o re tic a lly ,
t h e f e e d f lo w r a t e c an b e i n c r e a s e d
by i n c r e a s i n g t h e volum e o f c a t a l y s t i n s t e a d o f i n c r e a s i n g
t h e LHSV.
H ow ever, t h e c a p a c i t y o f t h e r e a c t o r r e s t r i c t s
u s a g e t o no more t h a n 100ml o f c a t a l y s t , h e n c e ,
t h e LHSV
was i n c r e a s e d .
The c a t a l y s t and i n e r t p a c k i n g d i s t r i b u t i o n i n t h e
r e a c t o r i s shown i n F i g u r e 4.
A n a ly sis
The n i t r o g e n and s u l f u r c o n t e n t o f c r e o s o t e o i l a r e
s i m i l a r t o t h a t o f S R C - I I , a n d t h i s makes i t d i f f i c u l t
to d i f f e r e n t i a t e
t h e c o n t r i b u t i o n o f S R C -II a n d c r e o s o t e
o i l in th e m ix tu r e .
T h e r e f o r e , i t was a ssu m e d t h a t
25
c a t a l y s t s p r o d u c e ' t h e same d e g r e e o f h y d r o t r e a t i n g on SR C -II
a n d c r e o s o t e o i l . ". The a n a l y s i s o f t h e p r o d u c t s ' for- s u l f u r
a n d n i t r o g e n c o n t e n t was b a s e d , on o v e r a l l p r o d u c t s i n l i e u
o f s p e c i f y i n g i t f o r S R C -II o r c r e o s o t e o i l .
■ S u l f u r c o n t e n t was a n a l y z e d an d r e p o r t e d t o 0.03%
a c c u r a c y u s i n g a q u a r t z tu b e c o m b u s tio n m ethod w h ic h was
d e v e l o p e d by S h e l l D e v e lo p m e n t C o . ( 2 4 ) , an d w e i g h t p e r c e n t
d e s u l f u r i z a t i o n was c a l c u l a t e d b y 'a s s u m i n g ' n o - w e i g h t c h a n g e
b e tw e e n f e e d a n d p r o d u c t .
The m a t e r i a l b a l a n c e e q u a t i o n f o r s u l f u r i n t h i s
p r o c e s s i s shown a s f o l l o w s :
Ws ° Cs f * (1™X) +
Cc f * (1" X) = Cp
A f te r a rra n g e m e n t, i t becom es:
I-X
Ws - C s f + (I-W s ) - C c f
X=Iw S - c S f ' 4"
- Cc f
26
=BxN—
S e c t i o n A:
175 m l. o f 1 / 4 '
S e c tio n B:
25 m l. o f 1 /8
D e n sto n e i n e r t .
D e n sto n e i n e r t .
S e c t i o n C:
60 m l. o f C a t a l y s t
60 m l. o f 1 /8 D e n sto n e i n e r t .
Il
S e c t i o n D:
A b o u t 80 m l. o f 1 /8
D en sto n e
in e rt.
F i g u r e 4.
C a t a l y s t a n d P a c k in g D i s t r i b u t i o n i n
T ric k le -B e d R e a c to r.
27
L i k e w i s e , w e i g h t p e r c e n t d e n i t r o g e n a t i o n was d e t e r ­
m ined by an im p ro v e d K j e l d a h l M e th o d (25) an d f o l l o w e d th e
e q u a tio n :
C
P
Y = 1•Cs f
( 1—Wg)
ci f
ANSI /A S TM D86-77 s t a n d a r d d i s t i l l a t i o n was a p p l i e d
i n t h e d e t e r m i n a t i o n o f t h e e x t e n t o f c r a c k i n g (26) .
.
28
CHAPTER V
RESULTS AND DISCUSSION
/
The f i r s t t h r e e r u n s u s i n g MSU-C-49 w e re c o n d u c t e d a t
t h r e e d i f f e r e n t r a t i o s o f . c r e o s o t e o i l to S R C - I I , a n d t h e
l a s t two r u n s u s e d S h e l l NM324 a n d H arshaw H T - 4 0 0 - c a t a l y s t s ,
k e e p i n g t h e c r e o s o t e o i l t o S R C -II r a t i o a t 25%:75%.
The
o t h e r c o n d i t i o n s o f a l l r u n s w e re k e p t c o n s t a n t and a r e
shown i n T a b le IV and T a b le V.
T a b le IV . M a t e r i a l s f o r E x p e r i m e n t a l Runs
C re o so te O il
S R C -II .
Run No.
C a ta ly s t
CPC-C25
• MSU-C-49
' 25%:75% '
CPC-C50
: MSU-C-49
50%:50%
CPC-C75
MSU-C-49
75%:25% .
CPS-C25
S h e l l NM324
25%:75%
CPH-C25
H arshaw HT-400
25%:75%
29
7
T a b le V.
R e a c tio n C o n d itio n s
U p g r a d in g o f S R C -II
T e m p e r a tu r e (0C) , ( F)
2
P r e s s u r e (-Kg/m ) , ( p s i g )
L i q u i d H o u rly S p a c e V e l o c i t y
( c .c . S R C -II/c .c . c a ta ly s t/h r )
H ydrogen Flow R a te
( S C F / b b i: o f SR C -II)
R un n in g T im e (h r)
4 2 5 /( 7 9 7 )
7 .OSxlO5, ( 1 , 0 0 0 )
1 .2 5
10,000
60 (=0=4,500ml
S R C -II)
H y d ro g e n atin g C re o so te O il
T e m p e r a tu r e (0C ), (0F)
2
P r e s s u r e (Kg/m ■) , ( p s i g )
L i q u i d H o u r ly S pa c e V e l o c i t y
(c .c . c re o so te o i l / c . c .
c a ta ly st/h r)
4 1 5 ,( 7 8 0 )
1 .0 5 x l0 6 ,(1 ,5 0 0 )
1.0
H ydrogen Flow R a te
(S C F /b b l. o f c r e o s o te o i l )
10,000
C a ta ly s t
S h e l l NM324
30
Raw d a t a f o r n i t r o g e n and s u l f u r a n a l y s e s a n d ASTM
d i s t i l l a t i o n s a r e shown i n A p p e n d i x .' The d a t a i s p l o t t e d
i n F i g u r e 5 t o F i g u r e 18.
ASTM d i s t i l l a t i o n
E v e ry p r o d u c t was s e p a r a t e d by
i n t o t h r e e f r a c t i o n s w hich r a n g e d from
up t o 4 0 0 °F , 400°F-----7 0 0 °F , a n d a b o v e 7 0 0 ° F .
E ach f r a c t i o n
was a n a l y z e d f o r n i t r o g e n an d s u l f u r c o n t e n t .
H y d r o tr e a tin g C re o so te O il
F irst,
t h e K o p p e rs c r e o s o t e o i l was h y d r o g e n a t e d
to i n c r e a s e i t s h y drogen c o n t e n t .
I n t h i s r e s e a r c h two
b a t c h e s o f h y d r o g e n a t e d c r e o s o t e o i l w ere made a t t h e same
c o n d i t i o n s w i t h t h e same c a t a l y s t s .
R e s u l t s sh o w in g th e
c o n s i s t e n c y b e tw e e n t h e s e two b a t c h e s a r e i n ‘T a b le V j .
A c tu a lly ,
t h e s e two p r o d u c t s c an b e com bined i n t o o n e .
How ever, f o r c o m p a r i s i o n ,
t h e r e s u l t s a r e shown s e p a r a t e l y .
D e n itro g e n a tio n
F i g u r e s 5 - 7 show t h e n i t r o g e n c o n t e n t i n t h e p r o d u c t s
and th e w e ig h t p e r c e n t' d e n itr o g e n a tio n .
F ig u r e . 5 a n d
F ig u re 5 a re p l o t s f o r n itr o g e n c o n te n t v s . th ro u g h p u t
o f S R C -II.
E x c e p t f o r t h e CPH-C25 r u n w h ich i s o b v i o u s l y
lo w , t h e n i t r o g e n c o n t e n t i n t h e p r o d u c t s i s a b o u t 0.35% .
The CPC-C25, CPS-C25 arid CPH-C25 r u n s h a v e a h i g h e r
n itr o g e n c o n te n t in th e f e e d s to c k b e ca u se o f th e h ig h
c o n te n t in S R C -II.
H ow ever, r e f e r r i n g t o F i g u r e 7,
t h e e x t e n t o f n i t r o g e n r e m o v a l shows some v a r i a t i o n .
31
I n CPH-C25 r u n ,
CPC-C25.
t h e r e i s a h i g h e r d e n i t r o g e n a t i o n th a n , i n
T h is f a c t c a n be e x p l a i n e d by t h e h i g h m o ly b d a te
c o n c e n t r a t i o n i n t h e c a t a l y s t w h ic h i s shown i n T a b le I I I .
The same c a t a l y s t u s e d by S a h i n i n h i s r e s e a r c h r e v e a l e d
t h e c o n c l u s i o n t h a t H arshaw HT-400 c a t a l y s t h a s a h i g h e r
a c t i v i t y i n d e n i t r o g e n a t i o n t h a n t h e MSU c a t a l y s t .
F i g u r e 7 shows t h e same t e n d e n c y o f d e n i t r o g e n a t i o n
w ith th ro u g h p u t f o r d i f f e r e n t c a t a l y s t s .
e a c h r u n shows a lo w e r a c t i v i t y
N e v e rth e le ss,
t h a n when i n v e s t i g a t e d by
p r e v i o u s c o w o r k e r s w i t h no c r e o s o t e o i l a d d e d .
The lo w e r
a c t i v i t y o f d e n itr o g e n a tio n in t h i s re s e a rc h o b v io u sly
shows t h a t t h e e f f e c t o f a d d in g c r e o s o t e o i l i n 1 : 3 ,
a n d 3 :1 r a t i o s
t o S R C -II i s n o t b e n e f i c i a l .
1 :1
.
D e su lfu riz a tio n
I n t h e same m anner a s t h e d e n i t r o g e n a t i o n r e s u l t s
shown a b o v e , t h e s u l f u r c o n t e n t an d w e i g h t p e r c e n t d e s u l ­
f u r i z a t i o n i n e a c h p r o d u c t a r e p l o t t e d i n F i g u r e s 8 ,9 a n d
10.
In -g en eral, d e s u l f u r i z a t i o n i s e a s i e r to a c h ie v e f o r
c o a l l iq u i d s th an d e n itr o g e n a tio n .
The t h r e e t e s t r u n s show o n l y s l i g h t v a r i a t i o n i n
d e su lfu riz a tio n a c tiv ity .
r e p o r te d i n th e l i t e r a t u r e ,
Compared t o 90% d e s u l f u r i z a t i o n
th e a c t i v i t y f o r th e s e ru n s has
b e e n r e d u c e d t o 60%. L ik e d e n i t r o g e n a t i o n , F i g u r e 10 shows
t h a t d e s u lf u riz a tio n d ecreases as p e rc e n t o f c re o so te o i l
in th e fe e d i n c r e a s e s .
32
T a b le V I.
SR C -II LECF an d Two B a tc h e s o f H ydrogena t e d
C re o so te O il
SR C -II
LECF
H y d r o g e n a te d C r e o s o t e O i l
B a tc h I
B a tc h 2
N i t r o g e n C onten t(w t% )
0 .6 3
0 .3 5
0 .3 9
S u l f u r C onten t(w t% )
0 .6 7
0 .3 2
0 .3 0
D e n s i t y (g/cm ^)
0 .9 8 3
1 .0 5
1 .0 5
ASTM D i s t i l l a t i o n
IB P (0F)
122
205
210
5%
217
490
495
10%
288
575
580
20%
381
645
650
30%
446
690
695
40%
488
———
*
700
4 3%
—
700
50%
541
60%
577
70%
611
80%
660
87%
700
R e s id u e and l o s s
( v o l . %)
13
57
60
33
C re o so te O il
N i t r o g e n C o n t e n t (wt%)
O CPC-C25
© CPC-C50
• CPC-C75
1,800
Figure 5.
2 ,7 0 0
3 ,6 0 0
S R C -II T h ro u g h p u t (ml)
4 ,5 0 0
Nitrogen content in products upgraded
by MSU-C49 with different concentrations
of creosote oil.
34
1.0
N i t r o g e n C o n t e n t (wt%)
0. 8
O
■
CPC-C25
CPS-C25
A
CPH-C25
C a ta I y s t
MSU -C -49
S h e l l NM324
H arshaw HT-400
0.6
0 .4
O
O
A
Gl
O
a
0.2
0.0
0
900
Figure 6.
1 ,8 0 0
2 ,7 0 0
3 ,6 0 0
S R C -II T h r o u g h p u t (ml)
4 ,5 0 0
Nitrogen content in products upgraded
by different catalysts with 25%
creosote oil.
35
C re o so te
O CPC-C25
C a ta ly s t
MSU-C-49
#
■
CPC-C75
CPS-C25
MSU -C -4 9
MSU-C-49
S h e l l NM324
A
CPH-C25
H arshaw HT-400
@ CPC-C50
F ig u re 7.
S R C -II T h ro u g h p u t (ml)
W e ig h t p e r c e n t d e n i t r o g e n a t i o n .
36
C re o so te O il
S u l f u r C o n t e n t (wt%)
O
@
•
O
CPC-C25
CPC-C50
CPC-C75
•©
1,800
Figure 8.
3 ,6 0 0
2 ,7 0 0
S R C -II T h ro u g h p u t (ml)
4 ,5 0 0
Sulfur content in products upgraded
by MSU-C49 with different concentra­
tion of creosote oil.
37
A CPH-C25
H arshaw HT-400
S u l f u r C o n t e n t (wt%)
O CPC-C25
■ CPS-C25
C a ta ly s t
MSU-C-49
S h e l l NM324
1,800
2 ,7 0 0
3,6 0 0
4 ,5 0 0
S R C -II T h r o u g h p u t (ml)
Figure 9.
Sulfur content in products upgraded
by different catalysts with 25%
creosote oil.
38
C re o so te C a t a l y s t
O CPC-C25
MSU -C-4 9
MSXJ-C-4 9
#
CPC-C75
MSU-C-49
CPS-C25
NM324
CPH-C25
HT-400
A
1,800
2 ,7 0 0
3 ,6 0 0
S R C -II T h ro u g h p u t (ml)
4 ,5 0 0
F i g u r e l o . W e ig h t p e r c e n t d e s u l f u r i z a t i o n .
39
The d a t a p r e s e n t e d i n F i g u r e 10 shows t h a t t h e Harshaw
HT-4Q0 c a t a l y s t h a s h i g h e r d e s u l f u r i z a t i o n a c t i v i t y th a n
S h e l l NM324 o r MSU-C-49.
ASTM D i s t i l l a t i o n R e s u l t
H y d r o t r e a t i n g S R C -II l i q u i f i e d c o a l n o t o n l y r e d u c e d
t h e n i t r o g e n a n d s u l f u r c o n t e n t , b u t a l s o i n c r e a s e d th e
q u a n t i t y o f t h e lo w e r b o i l i n g p o i n t f r a c t i o n .
For
c o m p a r a t i v e c o n v e n i e n c e , we p l o t t e d t h e ASTM d i s t i l l a t i o n
d a t a f o r e a c h r u n i n d i v i d u a l l y i n F i g u r e 11 t o F i g u r e 14.
Runs o f CPS-C25 a n d CPH-C25 u s e d t h e same r a t i o o f h y d r o ­
g e n a t e d c r e o s o t e o i l t o S R C -II i n t h e f e e d — I t o 3.
The i n c r e a s e d s h i f t fro m a h i g h e r p r o d u c t b o i l i n g p o i n t
r a n g e t o a lo w e r one w i t h t h e H arshaw c a t a l y s t , r u n CPH- .
C25, t h a n w i t h t h e S h e l l c a t a l y s t ,
r u n CPS-C25, ' i s con­
s i s t e n t w ith th e f a c t t h a t b e t t e r d e n i t r o g e n a ti o n and
d e s u l f u r i z a t i o n was o b t a i n e d w i t h H arshaw HT-400 i n t h i s
research .
F or th e t h r e e d i f f e r e n t m ix i n g - r a t i o r u n s , th e
d i s t i l l a t i o n c u r v e s i n F i g u r e 13 an d F i g u r e 14 show o n l y a
t i n y e f f e c t i n i n c r e a s i n g t h e lo w e r b o i l i n g p o i n t f r a c t i o n
o f u p g r a d e d S R C -II f o r CPH-C75 a n d CPC-C50 r u n s .
The ASTM d i s t i l l a t i o n s r e v e a l t h e f a c t t h a t ' I t ' i s
n o t b e n e f i c i a l f o r a h i g h p e r c e n t a g e o f c r e o s o t e o i l t o be
added in h y d ro p ro c e ss in g S R C -II.
40
F i g u r e 15 a n d F i g u r e 16 show t h e n i t r o g e n a n d s u l f u r
c o n t e n t i n e a c h p r o d u c t f r a c t i o n v s . p e r c e n t a g e o f a d d ed
c r e o s o t e o i l a f t e r t r e a t m e n t u s i n g MSU-C49 c a t a l y s t .
The
medium b o i l i n g f r a c t i o n h a s a s l i g h t l y h i g h e r n i t r o g e n
c o n te n t f o r each o f th e th re e d i f f e r e n t b l e n d i n g - r a t i o
runs.
I t r e v e a l s t h a t t h e e f f e c t o f c r e o s o t e o i l on
d e n i t r o g e n a t i o n i s d i f f e r e n t fro m t h a t o f d e s u l f u r i z a t i o n .
F i g u r e 17 a n d 18 show t h e d i s t r i b u t i o n o f n i t r o g e n
and s u l f u r in th e p ro d u c ts o f d i s t i l l a t i o n
f o r th e d i f f e r ­
en t ru n s.
Summary
I n sum m ary, t h e n e g a t i v e e f f e c t o f h y d r o g e n a t e d
c r e o s o t e o i l on u p g r a d i n g S R C -II l i q u i f i e d c o a l i s o b v io u s
f o r b l e n d s o f 25%:75%; 50%:50%; a n d 75%:25%.
T h is f a c t c a n
be e x p l a i n e d by t h e c o m p e t i t i o n b e tw e e n t h e c r e o s o t e o i l
an d S R C -II m o l e c u l e s b e i n g a d s o r b e d on t h e a c t i v e s i t e s o f
c a ta ly st.
The l e s s c r e o s o t e o i l a d d e d , t h e l e s s compe­
t i t i o n comes fro m c r e o s o t e o i l f o r t h e a c t i v e s i t e s an d t h e
more m o l e c u l e s o f S R C -II t h a t w i l l b e a d s o r b e d by t h e c a t a ­
ly st.
A h i g h e r a c t i v i t y i n u p g r a d i n g SR C -II i s o b t a i n e d
when l e s s c r e o s o t e o i l i s a d d e d , a n d t h e e f f e c t o f c r e o s o t e
o i l is n o t b e n e fic ia l a t th is p o in t.
41
700
600
500
-P
c
400
CU
□
Cn
▲
C
-H
1—1
-H
O
« 300
CPS-C25
CPH-C25
Feed
2 00
100
I
5 10
I
40
I
60
F r a c t i o n (vol.% )
F i g u r e 11. ASTM d i s t i l l a t i o n
CPH-C25.
L
80
100
f o r CPS-C25 and
42
700l
600 —
B o i l i n g p o i n t (0F)
500 -
400
O
□
CPC-C25
F eed
300
200
r~
±
10 0
0
5 10
20
40
I
I
60
80
F r a c t i o n (vol.% )
Figure 12. ASTM distillation for CPC-C25.
100
43
•h 400
@ CPC-C50
B F eed
n 30 0
5 10
F ra c tio n
(vol.% )
F i g u r e 13. ASTM d i s t i l l a t i o n
f o r CPC-C50.
44
700 -
600 —
B o ilin g P oint
( F)
500 -
CPC-C75
400
Feed
300
200
10 0 *
0
L
' 1
5 10
I
20
I
40
60
F r a c t i o n (vol.% )
80
Figure 14. ASTM distillation for CPC-C75.
100
45
ASTM F r a c t i o n s
up t o 400 F
N i t r o g e n C o n t e n t (wt%)
400 F
70 0 F
a b o v e 700 F
C r e o s o t e O i l C o n c e n t r a t i o n (v o l.% )
F i g u r e 15. N i t r o g e n c o n t e n t i n
d iffe re n t fra c tio n s .
46
ASTM F r a c t i o n s
S u l f u r C o n t e n t (wt%)
up t o 400 F
400 F
700 F
above 700 F
0
25
50
75
100
C r e o s o t e O i l C o n c e n t r a t i o n (vol.% )
F i g u r e 16. S u l f u r c o n t e n t i n
d iffe re n t fra c tio n s.
47
N i t r o g e n C o n t e n t (wt%)
O
C P C -C 2 5
C P S -C 2 S
A
O
400
CPC-CSO
T e m p e r a tu r e Range ( F)
F ig u re 17. N itro g e n C o n te n t in F r a c t i o n s
f o r Each Run.
48
S u l f u r C o n t e n t (wt%)
O
C P C -C 2 5
O
CPC-CSO
e
0 .4
cpc- c 7s
-
T e m p e r a tu r e Range (°F)
F ig u re 18. S u lf u r C o n te n t in F r a c tio n s f o r
E ac h Run.
49
CHAPTER VI
CONCLUSION
1.
The e f f e c t o f h y d r o g e n a t e d c r e o s o t e o i l a s a h y d r o g e n
d o n o r a g e n t on u p g r a d i n g o f S R C -II i s n o t b e n e c i f i a l .
2.
The e x t e n t o f h y d r o d e n i t r o g e n a t i o n and. h y d r o d e s u l ­
f u r i z a t i o n o f S R C -II w i t h h y d r o g e n a t e d c r e o s o t e o i l
v a r i e s w ith th e p e rc e n ta g e o f th e b le n d in g r a t i o .
The
more h y d r o g e n a t e d c r e o s o t e o i l a d d e d , t h e lo w e r t h e
e x te n t of d e n itro g e n a tio n .
3.
ASTM d i s t i l l a t i o n
i s an in d e x o f e x t e n t o f h y d r o t r e a t ­
in g th e c o a l l i q u i d .
The more h y d r o g e n a t e d c r e o s o t e
o i l added, th e le s s lo w -b o ilin g p o i n t f r a c t i o n o b ta in e d
4.
H arshaw HT-400 c a t a l y s t h a d t h e m o s t s i g n i f i c a n t e f f e c t
on h y d r o t r e a t i n g SR C -II c o a l l i q u i d s o f t h e c a t a l y s t s
stu d ie d .
50
NOMENCLATURE
:
S u lfu r c o n te n t o f c re o so te o i l in feed
(w t f r a c t i o n )
N i t r o g e n c o n t e n t o f c r e o s o t e o i l i n f e e d (w t f r a c t i o n )
S u l f u r c o n t e n t o f S R C -II i n f e e d (w t f r a c t i o n )
N i t r o g e n c o n t e n t o f S R C -II i n f e e d (w t f r a c t i o n )
S u l f u r c o n t e n t i n p r o d u c t (wt f r a c t i o n )
N i t r o g e n c o n t e n t i n p r o d u c t (w t f r a c t i o n )
C o n c e n t r a t i o n o f S R C -II (wt. f r a c t i o n )
W e ig h t f r a c t i o n r e m o v a l o f s u l f u r
W e ig h t f r a c t i o n r e m o v a l o f n i t r o g e n
51
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P o t t s , J . D . e t a l . , "C om m ercial S c a l e E xp an d ed Bed
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10.
S t i e g e l , G.J'. ; T i s c h e r , R . E . ; P o l i n s k i 7 L .M ..
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T e c h n o lo g y C e n t e r DOE/PETC/TR-8217 (1982) .
11.
P u l l e n , J . R . " S o l v e n t E x t r a c t i o n o f C o a l" IEA C oal
R e s e a r c h R e p o r t No. IC T IS /T R 16, Nov. 1981.
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L a r s e n , J.W . ;■ Sams, T .L . " F a c i l e I n t e r n a l H ydrogen
* R e a r r a n g e m e n t i n C o a l s " , F u e l , V o l . 6 0 , M arch , 1981
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13.
176,. Exxon R e s e a r c h and
D e r b y s h i r e , F . J . ; V a r g h e s e , P . ; W h i t e h u r s t , D.D.
" I n t e r a c t i o n s B etw een S o l v e n t C om ponents, M o l e c u l a r
H ydrogen a n d M i n e r a l M a t t e r D u r in g C oal L i q u e f a c t i o n " ,
A m erican C h e m ic a l S o c i e t y , D i v i s i o n o f F u e l C h e m i s t r y ,
52
P re p rin ts ;
2 6 (1 );
84-9 3 (19 81) .
14.
F u r l o n g , L . E . ; E f f r o n , E . ; V e rn o n , L .W .; W il s o n , E .L .
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P r o g r e s s ; 7 2 ( 8 ) ; 6 9-75 ( 1 9 7 6 ) .
15.
D a v i e s , G. O.; D e r b y s h i r e , F . J . ; P r i c e , R. "An . I n v e s t i ­
g a t i o n o f C o a l S o l u b i l i t y i n A n th r a c e n e O i l s " J o u r n a l
o f t h e I n s t i t u t e o f F u e l ; 50 ( 4 0 4 ) ; 121-126 S e p . 1 9 7 7 .
16.
G a t e s , B .C .; K a t z e r , J . R . ; O l s o n , J . H . ; Kwart , H .;
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DOE R e p o r t No. F E - 2 0 2 8 - 1 1 , 1978.
17.
B e r g , L . ; a n d M c C a n d le s s , F . P . " C a t a l y t i c H ydro­
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No. F E -2 0 3 4 - 1 1 , 1 9 7 8 .
18.
Y eh, A .- G . " U p g r a d in g S o l v e n t R e f i n e d C o a l by
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19.
B lia tija , H .; "The D e t e r m i n a t i o n o f Optimvim T h r o u g h - P u t
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C o a l 11M .S. T h e s i s , M ontana S t a t e U n i v e r s i t y , 1 9 8 1 .
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S a h i n , T . ; " U p g r a d in g o f S o l v e n t R e f i n e d C o a l (SR C -II)
L i q u i d s by C a t a l y t i c H y d r o t r e a t i n g and t h e E f f e c t o f
W ater o r C a t a l y s t A c t i v i t y "
M .S. T h e s i s , M ontana
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W r i g h t , C.H ..; P a s t o r , G. R.;' P e r r u s s e l , R .E . ERDA
R e p o r t No. F E -4 9 6 -T 4 , S e p . 1975.
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G uin , J . A . ; T a r r e r , A .R .; P r a t h e r ; J .W .; J o h n s o n ,,
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H y d r o g e n a t i o n , D e s u l f u r i z a t i o n , and S o l v e n t Ex­
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K o b y l i n s k i , T.- P . and T a y l o r , B . W., . U .S . P a t e n t
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24.
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P e t r o l e u m O i l s ( Q u a r tz Tube M ethod)"., 19 74 A nnual
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D1551. ■
. ,
53
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O r g a n ic M a t e r i a l by M o d if ie d K j e l d a h l M e th o d " , 1974
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26.
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P e t r o l e u m P r o d u c t s " , 1977 A n n u a l Book o f ASTM
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54
APPENDIX
T a b l e V I I . Run CPC- C25
C a t a l y s t : MSU-C-49
C r e o s o t e O i l / SRC-■II: 25% : 75%
A n a ly sis:
*
Sam ple No.
N itro g en
(wt%)
S u lfu r
0 .2 9
0 .2 0
2
0 .3 3
0 .1 6
3
0 .3 7
0 .2 1
4
0 .3 9
0.26
5
0.33
0 .1 9
6
0.36
0 .2 1
7
0.33
0 .2 1
8
0.33
0 .2 0
9
0.33
0 .2 1
10
0.25
Avg.
0.34
0 .2 1
Feed
0.54
0.58
37. 04
6 3. 7 9
Wt% Removal
*
O
• to
m
I
Sample was taken every 6 hours.
(wt%)
55
Table VIII. Run CPC-C50
C a t a l y s t : MSU-C-49
C r e o s o t e O i l / SRC- I I :
50%:50%
A nalysis:
*
Sample No.
N i t r o g e n (wt%)
Sulfur
i
0.37
0.16
2
0.35
0 .2 1
3
0. 33
0.17
4
0.24
0.17
5
0.31
0.14
6
0.33
0 .2 1
7
0.39
0.19
8
0.30
0 .2 1
9
0.35
0.18
10.
0.38
0 .2 0
Avg.
0.335
0.184
Feed
0.49
0.49
31.63
62.36
Wt% Removal
*
Sample was taken every 6 hours
(wt%)
56
Table IX. Run CPC-C75
C a t a l y s t : MSU-C-49
C r e o s o t e O i l / S R C - I I : 75%:25%
A nalysis:
Sample No*_______ N i t r o g e n
(wt%)__________ S u l f u r (wt%)
I
0.28
0.08
2
0.31
0 .2 0
3
0.30
0 .2 1
4
0. 31
0.25
5
0. 33
0.23
6
0.32
0 .2 0
7
0.31
0.26
8
0.36
0.14
9
0.31
0.19
10
0 . 36
0.14
Avq.
0.319
0.19
Feed
0.42
0.40
24.05
52.50
Wt% Removal
* Sample was t a k e n e v e r y 6 h o u r s .
57
Table X.
Run CPS-C25
C atalyst:
S h e l l NM324
C r e o s o t e O i l / S R C - I I : 25%:75%
A nalysis:
Sample Not________ N i t r o g e n
(wt%)__________ S u l f u r
I
0.33
0.17
2
0.34
0.17
3
0.39
0 .2 2
4
0.33
0 .2 1
5
0.37
0.30
Avg.
0.352
0.214
Feed
0.55
0.58
36 .00
6 3.1 0
Wt% Removal
* Sample was taken every 12 hours.
(wt%)
58
Table XI. Run CPH-C25
C a t a l y s t : Ha rshaw HT-400
C r e o s o t e O i l / S R C - I I : 25%:75%
A nalysis:
Sample No._________N i t r o g e n
(wt%)__________ S u l f u r
I
0.23
0.15
2
0.23
0.14
3
0.27
0.23
4
0.26
0.23
5
0 .2 2
0 .2 1
Avg.
0.242
0.192
Feed
0.55
0.58
5 6 .0 0
66.90
Wt% Removal
*
Sample was taken every 12 hours.
(wt%)
59
Table X I I . ASTM Distillation for Run CPC-C25
T e m p e r a tu r e
F raction
( uF)
Product
Feed
IBP
170
2 30
5%
265
375
10%
310
405
20%
385
440
30%
425
465
40%
460
488
50%
490
512
60%
520
545
70%
560
600
80%
625
695
84%
—
700
89%
700
—
11%
16%
F ractions
N (wt%) S (wt%)
N (wt%) S (wt%)
-----400°F
0.187
0.209
0.488
0.618
400 °F— 700°F
0.391
0.204
0 .6 1 5
0.566
700 °F-----
0.39 7
0.208
0.557
0.582
Residue &
Loss
60
T a b l e X I I I . ASTM D i s t i l l a t i o n f o r Run CPC-C50
T em perature
Product
F raction
(0 F)
Feed
IBP
175
16 7
5%
285
32 7
10%
350
400
20%
440
450
30%
495
485
40%
543
527
50%
600
580
60%
662
655
65%
—
700
70%
700
— — —
30%
35%
F ractions
N (wt%) S (wt%)
N (wt%) S (wt%)
---- 400°F
0.255
0.170
0.458
0.647
400 °F— 700°F
0.400
0.15 7
0 . 5 30
0.496
700°F-----
0.299
0.195
0.428
0.392
Residue &
L o ss
61
T a b l e XIV. ASTK D i s t i l l a t i o n f o r Run. CPC- C75
Tem perature
Product
F raction
(0 F)
Feed
IBP
175
175
5%
330
360
10%
425
443
20%
510
505
30%
582
578
40%
650
643
50%
696
694
53%
700
—
5 7%
— — —
700
4 7%
43%
F ractios
N (wt%) S (wt%)
N (wt%) S (wt%)
-----400°F
0.327
0 .2 1 0
0.351
0.518
400°F--700°F
0.370
0 .2 0 1
0.438
0.354
7 00°F-----
0. 326
0.226
0.404
0.456
Residue &
Loss
62
T a b le XV. ASTM D i s t i l l a t i o n
f o r Run CPS-C25
_____ T e m p e r a tu r e
P rodu ct
F r a c tio n
( 0 F)
F eed
IBP
172
177
5%
271
310
10%
318
380
20%
390
4 30
30%
432
458
40%
463
485
50%
495
515
60%
528
550
70%
575
620
79%
—
700
80%
683
—
85%
700
— — —
15%
21%
N (wt%) S (wt%)
N (wt%) S (wt%)
-----400°F
0.178
0.243
0 .4 6 6
0.396
4 0 0 ° F — 700°F
0.412
0.242
0.767
0.586
700OF---
0.420
0.234
0.478
0.418
Residue &
Loss
F ractions
63
f o r Run CPH- C25
T a b l e XVI. ASTM D i s t i l l a t i o n
Tem perature
Product
Fraction
(0F)
Feed
IBP
175
177
5%
250
310
10%
295
380
20%
365
430
30%
417
458
40%
455
485
50%
487
515
60%
525
550
70%
578
620
79%
—
700
80%
683
---—
86%
700
—
14%
21%
Residue &
L o ss
F ractions
N (wt%) S (wt%)
N (wt%) S (wt%)
-----400°F
0.059
0.280
0.466
0.396
400 °F — 700°F
0.295
0.160
0.767
0.586
0.100
0.478
0.418
700OF--
0.357
RU
WAfN I IBv
N378
Pl92
Pan, Ghia-Ren Jack
cop.2
The e ff e c t of
hydrogenated Creosote
Oil as a hydrogen . . .
I S S U E D TO
DATE
A/518
f 11 AL