Hydrocracking and Hydrotreating

Hydrocracking and Hydrotreating
J o h n W. W a r d , EDITOR
Union Oil Co. of California
Shai A. Q a d e r , EDITOR
Burns and Roe Industrial Service Corp.

Publication Date: June 1, 1975 | doi: 10.1021/bk-1975-0020.fw001
A symposium sponsored by
the Division of Petroleum
Chemistry, Inc. at the
169th Meeting of the
American Chemical Society,
Philadelphia, Penn.,
April 9, 1975
ACS SYMPOSIUM SERIES 20
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1975
American Chemical Society
1155 16th St., N.W.

Washington, D.C. 20036
In Hydrocracking and Hydrotreating; Ward, J., el al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1975.
TP 690.4 .H9 Copy 1
Hydrocracking and
hydrotreating
Library of Congress Œ Data

Hydrocracking and hydrotreating.
(ACS symposium series; 20 ISSN 0097-6156)
Includes bibliographical references and index.
1. Cracking process—Congresses. 2. Petroleum—Re-
fining—Congresses. 3. Hydrogénation—Congresses.
I. Ward, John William, 1937- II. Qader, S. A.
III. American Chemical Society. Division of Petroleum
Chemistry. IV. Series: American Chemical Society. ACS
symposium series; 20.
TP 690.4.H9 665'.533 75-33727
ISBN 0-8412-0303-2 ACSMC8 20 1-168
Copyright © 1975
All Rights Reserved
PRINTED IN THE UNITED STATES OF AMERICA

Library
1155 16th
In Hydrocracking and St.. N.W. Ward, J., el al.;
Hydrotreating;
Washington,
ACS Symposium Series; D.C. 20036
American Chemical Society: Washington, DC, 1975.
ACS Symposium Series
Robert F. Gould, Series Editor

FOREWORD
The ACS S Y M P O S I U M S E R I E S was founded in 1974 to provide
a medium for publishing symposia quickly in book form. The

format of the S E R I E S parallels that of the continuing A D V A N C E S
I N C H E M I S T R Y S E R I E S except that in order to save time the
papers are not typeset but are reproduced as they are sub-
mitted by the authors in camera-ready form. As a further
means of saving time, the papers are not edited or reviewed
except by the symposium chairman, who becomes editor of
the book. Papers published in the ACS S Y M P O S I U M S E R I E S
are original contributions not published elsewhere in whole or
major part and include reports of research as well as reviews
since symposia may embrace both types of presentation.

PREFACE
'"phe efficient upgrading of energy resources to desirable products is an

important national goal. This volume contains a series of papers
concerned with the hydroprocessing of petroleum stocks, shale oil, and
coal. Subjects covered range from catalyst structure to product proper-
ties. The hydroprocessing routes discussed offer excellent means of
selectively producing the desired fuels and the means of reducing poten-
Publication Date: June 1, 1975 | doi: 10.1021/bk-1975-0020.pr001
tial polluting contaminants from fuels and their precursors.
Union Oil Co. of California JOHN W. WARD

Brea, Calif.
Burns and Roe Industrial Services Corp. SHAI A. QADER
Paramus, N.J.
September 4, 1975
vii

1
T h e Influence o f C h a i n Length in H y d r o c r a c k i n g
and Hydroisomerization o f n-Alkanes
JENS WEITKAMP
Engler-Bunte-Institute, Division of Gas, Oil, and Coal, University of Karlsruhe,
D-75 Karlsruhe, West Germany
Publication Date: June 1, 1975 | doi: 10.1021/bk-1975-0020.ch001
Since 1960 catalytic hydrocracking has received considerable

importance in petroleum refining where it is used mainly for the
production of gasoline, jet fuel, middle distillates and lubricants.
Its outstanding advantages are flexibility as well as high quality
of the products. In the course of its commercial growth the
chemistry of hydrocracking over various types of bifunctional
catalysts has been scrutinized with model hydrocarbons, most
commonly with alkanes. Several reviews on this subject are now
available (1-3) showing that the product distributions are marked-
ly influenced by the relative strength of hydrogenation activity
versus acidity of the catalyst.
A unique type of hydrocracking associated with an utmost
degree of product flexibility may be attained with bifunctional
catalysts of both high acidity and especially high hydrogenation
activity which have been counterbalanced carefully. The term
"ideal" hydrocracking has been introduced (2) to characterize the
reactions of n-alkanes with hydrogen on such catalysts. Typical
features of ideal hydrocracking of long chain alkanes include:
1. low reaction temperatures
2. the possibility of high selectivities for isomerization
3. the possibility of pure primary cracking
all being in contrast to catalytic cracking over monofunctional
catalysts. Actually, both reactions may be looked upon as pure
mechanisms of cracking with many intermediate mechanisms
between them. Such a concept has been shown to be fruitful for
classifying the numerous types of product distributions obser-
vable in hydrocracking of pure compounds over bifunctional
catalysts with a hydrogénation activity ranging from very weak to
very strong (2, 3). The validity of this concept for hydrocracking
real feedstocks has also been confirmed, e. g., by Coonradt and
Garwood (4) or by Sullivan and Meyer (5).
1
2 HYDROCRACKING AND HYDROTREATING
O t h e r p u r e m e c h a n i s m s of c r a c k i n g a r e t h e r m a l c r a c k i n g and
hydrogenolysis over metals. V e r y detailed investigations on p l a -
t i n u m c a t a l y z e d h y d r o g e n o l y s i s of v a r i o u s a l k a n e s , e. g . , the
i s o m e r i c h e x a n e s , have b e e n p u b l i s h e d r e c e n t l y (6-8).
I d e a l h y d r o c r a c k i n g and h y d r o i s o m e r i z a t i o n of n - d o d e c a n e
f u r n i s h e d m u c h i n s i g h t into the p r i m a r y r e a r r a n g e m e n t and
c l e a v a g e r e a c t i o n s of a l k y l c a r b e n i u m i o n s (9). T h e s y s t e m s e e m s
to be s t r o n g l y g o v e r n e d b y c o m p e t i t i v e c h e m i s o r p t i o n at the a c i d i c
s i t e s and, to a l e s s e r d e g r e e , at the h y d r o g e n a t i v e s i t e s (10). It
i s the i n t e n t i o n o f the p r e s e n t p a p e r to extend t h e s e data that
s e e m to be of p r i n c i p l e s i g n i f i c a n c e f o r the c h e m i s t r y of c a t a l y -
t i c c o n v e r s i o n of h y d r o c a r b o n s , to the l o w e r m o l e c u l a r weight
n - a l k a n e s . In l i t e r a t u r e o n h y d r o c r a c k i n g s o m e r e s u l t s have
b e e n r e p o r t e d c o n c e r n i n g r e a c t i v i t i e s of and p r o d u c t d i s t r i b u -
t i o n s f r o m n - a l k a n e s of d i f f e r e n t c h a i n l e n g t h (11, 12). H o w e v e r ,
as a c o n s e q u e n c e of the c a t a l y s t s u s e d , h y d r o c r a c k i n g i n t h e s e
cases was far f r o m being i d e a l .
Experimental
T h e e x p e r i m e n t s w e r e c a r r i e d out i n a s m a l l flow type f i x e d

b e d r e a c t o r w h i c h has been d e s c r i b e d i n a r e c e n t p u b l i c a t i o n (9)
a l o n g w i t h the m e t h o d s of a n a l y s i s by c a p i l l a r y g a s - l i q u i d c h r o -
m a t o g r a p h y . R e s u l t s a r e r e p o r t e d that w e r e g a i n e d w i t h a l l p u r e
n - a l k a n e s r a n g i n g f r o m n - h e x a n e to n - d o d e c a n e . F e e d h y d r o c a r -
bons w e r e d e l i v e r e d f r o m F l u k a , B u c h s , S w i t z e r l a n d (purum).
P u r i t y e x c e e d e d 99. 5 wt. - % i n any c a s e . T h e P t / C a - Y - z e o l i t e
c a t a l y s t (0. 5 wt. - % P t , S K 200, U n i o n C a r b i d e , L i n d e D i v i s i o n ;
3
v o l u m e of c a t a l y s t b e d : 2 c m ; p a r t i c l e s i z e : 0. 2 - 0 . 3 m m )
w a s c a l c i n e d i n a d r i e d s t r e a m of N and a c t i v a t e d i n a d r i e d
2
s t r e a m of at a t m o s p h e r i c p r e s s u r e p r i o r to u s e . T h e m a s s
of d r y c a t a l y s t was 1. 0 g. T h e t o t a l p r e s s u r e and m o l a r r a t i o
h y d r o g e n : n - a l k a n e w e r e kept c o n s t a n t at 39 b a r and 1 7 : 1 ,
r e s p e c t i v e l y , w h e r e a s the r e a c t i o n t e m p e r a t u r e s and s p a c e v e l o -
cities were varied.
C o n v e r s i o n o f n - A l k a n e s , H y d r o i s o m e r i z a t i o n and H y d r o c r a c k i n g
It was found that h y d r o i s o m e r i z a t i o n and h y d r o c r a c k i n g of

n - d o d e c a n e o v e r the P t / C a - Y - z e o l i t e r e q u i r e l o w r e a c t i o n t e m -
p e r a t u r e s , a t y p i c a l v a l u e b e i n g 275 °C (9). T h i s t e m p e r a t u r e was
c h o s e n i n the p r e s e n t w o r k to i n v e s t i g a t e the i n f l u e n c e of c h a i n
l e n g t h o n the r e a c t i v i t y of the n - a l k a n e s . In F i g u r e 1 the d e g r e e
of o v e r a l l c o n v e r s i o n has b e e n p l o t t e d v e r s u s the s u p e r f i c i a l

1. WEiTKAMP Influence of Chain Length 3
h o l d i n g t i m e . A s e x p e c t e d r e a c t i v i t y of the h y d r o c a r b o n s i n c r e a s e s
with i n c r e a s i n g chain length. F o r a quantitative c o m p a r i s o n appro
x i m a t e v a l u e s of the i n i t i a l r e a c t i o n r a t e s m a y be d e r i v e d f r o m
the i n i t i a l s l o p e s i n F i g u r e 1 u s i n g the equation
1 dX
- ra 100 m ,
d(ysL)
a
In T a b l e I t h e s e v a l u e s a r e r e p o r t e d , t h o s e f o r n-nonane and
n - u n d e c a n e b e i n g l e s s a c c u r a t e on account of the r e l a t i v e l y h i g h
d e g r e e s of c o n v e r s i o n even at l o w h o l d i n g t i m e s . F r o m n - h e x a n e
to n - u n d e c a n e a t e n f o l d i n c r e a s e i n the i n i t i a l r e a c t i o n r a t e i s
observed.
T a b l e I. Influence of c h a i n l e n g t h o n i n i t i a l r e a c t i o n r a t e s
(T = 275 °C)
^2 ( r ) ["raole n - a l k a n e l
Feed " a Ig catalyst · h J
n C H
0.13
" 6 14
n H
0. 38
-S 16
n C H 0. 53
- 8 18
n C H 1.1
- 9 20
n C H 1. 3
- ll 24
H y d r o g e n a t i v e c o n v e r s i o n of n - a l k a n e s on the P t / C a - Y - z e p l i t e
r e s u l t s i n two p r i n c i p l e r e a c t i o n s , h y d r o i s o m e r i z a t i o n o r h y d r o
c r a c k i n g , the r e l a t i v e i m p o r t a n c e of e a c h d e p e n d i n g o n the r e a c
t i o n c o n d i t i o n s . A t l o w s e v e r i t i e s and c o r r e s p o n d i n g l y l o w d e g r e e s
of o v e r a l l c o n v e r s i o n h y d r o i s o m e r i z a t i o n p r e d o m i n a t e s . W i t h
η - o c t a n e at 275 ° C , f o r e x a m p l e , the r a t e of h y d r o i s o m e r i z a t i o n
i s h a r d l y affected b y h y d r o c r a c k i n g at l o w h o l d i n g t i m e s ( F i g u r e 2).
A t h i g h h o l d i n g t i m e s , h o w e v e r , w h e r e the d e g r e e of h y d r o i s o m e
r i z a t i o n c o n v e r s i o n goes t h r o u g h a m a x i m u m the r a t e of h y d r o
c r a c k i n g i n c r e a s e s . It m i g h t be s u g g e s t e d f r o m the shape of the
c u r v e s i n F i g u r e 2 that h y d r o i s o m e r i z a t i o n and h y d r o c r a c k i n g
are reactions in series.
A w i d e r i n s i g h t into the i n f l u e n c e of c h a i n l e n g t h o n r e a c t i v i
t i e s o f n - a l k a n e s m a y be g a i n e d by p l o t t i n g the d e g r e e s of h y d r o -

20 40 60 80 100
SUPERFICIAL HOLDING TIME [s]
Figure 1. Hydroisomerization and hydrocracking of n-alkanes with different

chain length (T - 275°C)

1. W E I T K A M P Influence of Chain Length 5
i s o m e r i z a t i o n c o n v e r s i o n and h y d r o c r a c k i n g c o n v e r s i o n v e r s u s
r e a c t i o n t e m p e r a t u r e (cf. F i g u r e s 3 and 4, r e s p e c t i v e l y ) . S i m i l a r
c u r v e s a r e o b s e r v e d f o r a l l n - a l k a n e s u s e d . It w i l l be noted that
lower reaction temperatures are required for hydroisomerization
than f o r h y d r o c r a c k i n g . T h e d e g r e e s of h y d r o i s o m e r i z a t i o n c o n -
v e r s i o n , h o w e v e r , a r e p a s s i n g t h r o u g h a m a x i m u m w h i c h i s due
to the c o n s u m p t i o n of b r a n c h e d i s o m e r s b y h y d r o c r a c k i n g . W i t h
d e c r e a s i n g c h a i n l e n g t h the p o s i t i o n of the m a x i m a s h i f t s t o w a r d s
higher reaction temperatures reflecting decreasing reactivities.
It s h o u l d be m e n t i o n e d that v e r y h i g h m a x i m u m v a l u e s e x c e e d i n g
60 % a r e a t t a i n a b l e e v e n f o r l o n g c h a i n n - a l k a n e s l i k e n - d e c a n e .
T h i s r e s u l t has to be a t t r i b u t e d to the h i g h h y d r o g é n a t i o n a c t i v i t y
of the P t / C a - Y - z e o l i t e and i s i n c o n t r a s t to h y d r o c r a c k i n g o v e r
c a t a l y s t s of l o w h y d r o g é n a t i o n a c t i v i t y (9, 11,12) o r c a t a l y t i c
c r a c k i n g (13), w h e r e l i t t l e o r no i s o m e r i z a t i o n of the feed t a k e s

p l a c e . W i t h d e c r e a s i n g c h a i n l e n g t h the height of the m a x i m a
i n c r e a s e s , indicating a d e c r e a s i n g tendency for cleavage. A n
a c t i v a t i o n e n e r g y of 45 k c a l / m o l e i s c a l c u l a t e d f o r the h y d r o i s o -
m e r i z a t i o n of, e. g . , n - d e c a n e .
A n e v e n m o r e m a r k e d i n f l u e n c e of c h a i n l e n g t h e x i s t s f o r
the h y d r o c r a c k i n g r e a c t i o n ( F i g u r e 4). T h e d e g r e e s of h y d r o -
c r a c k i n g c o n v e r s i o n r a p i d l y i n c r e a s e w i t h t e m p e r a t u r e i n the
c a s e of n - d e c a n e , n - n o n a n e and η - o c t a n e . W i t h t h e s e h y d r o c a r
b o n s h y d r o c r a c k i n g i s c o m p l e t e at c a . 300 - 320 ° C . In s h a r p
c o n t r a s t to t h i s the d e g r e e of h y d r o c r a c k i n g c o n v e r s i o n i n c r e a s e s
v e r y s l o w l y w i t h r e a c t i o n t e m p e r a t u r e i n the c a s e of n - h e x a n e ,
whereas a somewhat intermediate behaviour is o b s e r v e d for
η - h e p t a n e . It w i l l be s h o w n l a t e r i n c o n n e c t i o n w i t h p r o d u c t
d i s t r i b u t i o n s that o n the P t / C a - Y - z e o l i t e h y d r o c r a c k i n g of h e x a n e
p r o c e e d s v i a a d i f f e r e n t m e c h a n i s m as c o m p a r e d w i t h i d e a l h y d r o
c r a c k i n g of the l o n g e r c h a i n h o m o l o g u e s .
F r o m a p r a c t i c a l viewpoint catalysts with high h y d r o g é n a t i o n
a c t i v i t y l i k e the P t / C a - Y - z e o l i t e p r o v i d e a h i g h d e g r e e of p r o d u c t
f l e x i b i l i t y . L o n g c h a i n feed h y d r o c a r b o n s i n the b o i l i n g r a n g e o f
k e r o s e n e m a y be i s o m e r i z e d w i t h e x c e l l e n t y i e l d s w h i c h i s of
i n t e r e s t f o r p o u r p o i n t l o w e r i n g . If, o n the o t h e r h a n d , c o m p l e t e
h y d r o c r a c k i n g i s d e s i r e d , t h i s m a y be a c h i e v e d s i m p l y b y a p p l i c a -
tion of somewhat higher r e a c t i o n t e m p e r a t u r e s .
In P ' i g u r e 5 the g e n e r a l l y a c c e p t e d r e a c t i o n path (14) f o r h y d r o -
i s o m e r i z a t i o n of n - a l k a n e s has b e e n r e p r e s e n t e d a l o n g w i t h d i f f e -
r e n t p o s s i b i l i t i e s f o r the c r a c k i n g s t e p . T h e n - a l k a n e m o l e c u l e s
a r e a d s o r b e d at a d e h y d r o g e n a t i o n / h y d r o g e n a t i o n s i t e w h e r e
n - a l k e n e s a r e f o r m e d . A f t e r d e s o r p t i o n and d i f f u s i o n to an a c i d i c
s i t e c h e m i s o r p t i o n y i e l d s s e c o n d a r y c a r b e n i u m i o n s that r e a r r a n g e

6 HYDROCRACKING A N D HYDROTREATING
240 260 280 300 320 340

TEMPERATURE [ C]
e
Figure 3. Influence of reaction temperature on hydroisomerization conversion

3 1
of n-alkanes with different chain length (F = 12 · 10~ mole · h' )
a
TEMPERATURE [ Cj
e
Figure 4. Influence of reaction temperature on hydrocracking conversion of

3 1
n-alkanes with different chain length (F = 12 · 10~ mole · h' )
a

into t e r t i a r y c a r b e n i u m i o n s w i t h a b r a n c h e d c a r b o n s k e l e t o n . D e -
s o r p t i o n of i - a l k e n e s and h y d r o g é n a t i o n at a m e t a l l i c s i t e f i n a l l y
y i e l d s i - a l k a n e s . A l l s t e p s of the o v e r a l l h y d r o i s o m e r i z a t i o n r e a c -
tion are r e v e r s i b l e .
F o u r p r i n c i p l e c r a c k i n g r e a c t i o n s , a l l of t h e m b e i n g i r r e v e r -
s i b l e , have to be t a k e n into account: h y d r o g e n o l y s i s of the
n - a l k a n e feed; / 3 - s c i s s i o n of s t r a i g h t c h a i n c a r b e n i u m i o n s ;
β - s c i s s i o n of b r a n c h e d c a r b e n i u m i o n s ; h y d r o g e n o l y s i s of
i - a l k a n e s f o r m e d b y h y d r o i s o m e r i z a t i o n . It w i l l be s h o w n that
the t h i r d step (full a r r o w i n F i g u r e 5) r e p r e s e n t s the m a i n r e a c
t i o n path of i d e a l h y d r o c r a c k i n g . C a r b e n i u m i o n s w i t h a b r a n c h e d
c a r b o n s k e l e t o n then p l a y the r o l e of k e y i n t e r m e d i a t e s i n that
t h e y m a y e i t h e r d e s o r b o r c l e a v e thus d e t e r m i n i n g the d i r e c t i o n
of the o v e r a l l r e a c t i o n .
W h i l e the r a t e of c l e a v a g e i s g i v e n b y t e m p e r a t u r e , a c i d i t y
of the c a t a l y s t and c o n c e n t r a t i o n of i - a l k y l c a t i o n s , the r a t e of
d e s o r p t i o n i s a s s u m e d to be enhanced b y the s t e a d y s t a t e c o n c e n
t r a t i o n s of n - a l k e n e s , i . e . , a h i g h d e h y d r o g e n a t i o n a c t i v i t y of
the c a t a l y s t f a v o r s h y d r o i s o m e r i z a t i o n . T h i s i s the concept of
competitive chemisorption which in ideal bifunctional catalysis
k e e p s the r e s i d e n c e t i m e s of the a l k y l c a r b e n i u m i o n s l o w .
H e n c e , p r i m a r y p r o d u c t s m a y be o b t a i n e d w h i c h i s not the c a s e
in catalytic c r a c k i n g over monofunctional catalysts where f o r m a
t i o n of c a r b e n i u m i o n s o c c u r s b y h y d r i d e a b s t r a c t i o n f r o m the
n-alkane r a t h e r than v i a n - a l k e n e s .
A c c o r d i n g to F i g u r e 5 a s e r i e s of e l e m e n t a r y r e a c t i o n s a r e
i n v o l v e d i n h y d r o i s o m e r i z a t i o n and h y d r o c r a c k i n g o f n - a l k a n e s .
A t the t i m e b e i n g , the r a t e c o n t r o l l i n g step of the o v e r a l l r e a c t i o n
i s unknown b e c a u s e of the l a c k of a d e t a i l e d k i n e t i c a n a l y s i s of the
s y s t e m . P o s s i b l e i n t e r p r e t a t i o n s of the i n f l u e n c e of c h a i n l e n g t h
upon r e a c t i v i t y a r e s p e c u l a t i v e . M a x i m u m c o n c e n t r a t i o n s of n -
alkenes, l i m i t e d by thermodynamics, increase with i n c r e a s i n g
c h a i n l e n g t h of the feed. T h e s a m e w i l l be t r u e f o r r a t e s of a d s o r p
t i o n b o t h of the feed and the o l e f i n i c i n t e r m e d i a t e s . R a t e s of s u r
face r e a c t i o n s too m a y depend on the c h a i n l e n g t h of the c h e m i -
s o r b e d s p e c i e s . T h e c h e m i s t r y of i d e a l h y d r o c r a c k i n g w i l l be
d i s c u s s e d i n t e r m s of d e t a i l e d p r o d u c t d i s t r i b u t i o n s , p r o v i d i n g
i n s i g h t into the p r i m a r y p r o d u c t s of b i f u n c t i o n a l c a t a l y s i s .
Hydroisomerization
L i t e r a t u r e o n h y d r o i s o m e r i z a t i o n of l o n g c h a i n a l k a n e s > C^
i s v e r y l i m i t e d (2, 9 , 1 5 , 1 6 ) due to both a n a l y t i c a l d i f f i c u l t i e s and
the fact that h y d r o c r a c k i n g p r e d o m i n a t e s u n l e s s the b i f u n c t i o n a l

c a t a l y s t has b e e n s u i t a b l y s e l e c t e d . In F i g u r e 6 the c o m p o s i t i o n
of the o c t a n e and undecane f r a c t i o n have b e e n p l o t t e d v e r s u s h o l
d i n g t i m e at a r e a c t i o n t e m p e r a t u r e of 275 ° C . T h e f o l l o w i n g
g e n e r a l f e a t u r e s of h y d r o i s o m e r i z a t i o n m a y be r e c o g n i z e d : M o n o -
branched i s o m e r s are p r i m a r y products from which multiple
branched i s o m e r s are formed in a consecutive reaction. The
c h a i n l e n g t h o f the feed has a m a r k e d i n f l u e n c e both on r a t e of
h y d r o i s o m e r i z a t i o n and the amount of m u l t i p l e b r a n c h e d i s o m e r s ,
which increases considerably with i n c r e a s i n g chain length. Q u a l i
t a t i v e l y , t h i s i s i n a g r e e m e n t w i t h t h e r m o d y n a m i c s and m a y be
a t t r i b u t e d to the n u m b e r of m u l t i p l e b r a n c h e d i s o m e r s w h i c h
r a p i d l y grows with increasing chain length.
A m o r e d e t a i l e d p i c t u r e of h y d r o i s o m e r i z a t i o n of n - o c t a n e
and n - n o n a n e i s g i v e n i n T a b l e II i n w h i c h p r o d u c t d i s t r i b u t i o n s
a r e l i s t e d f o r d i f f e r e n t d e g r e e s of c o n v e r s i o n a l o n g w i t h t h e r m o
d y n a m i c e q u i l i b r i u m v a l u e s . T h e l a t t e r have b e e n c a l c u l a t e d
f r o m G i b b s f r e e e n e r g y data a v a i l a b l e i n l i t e r a t u r e (17) the a c c u r a
c y of w h i c h , h o w e v e r , i s not k n o w n . F r o m T a b l e II the f o l l o w i n g
c o n c l u s i o n s m a y be d r a w n :
H y d r o i s o m e r i z a t i o n proceeds towards thermodynamic equili
b r i u m w h i c h i s a p p r o x i m a t e l y r e a c h e d b e t w e e n the n o r m a l , m o n o -
b r a n c h e d and d i - b r a n c h e d s t r u c t u r e s at h i g h d e g r e e s of o v e r a l l
conversion. H y d r o c r a c k i n g , however, i s severe under these
c o n d i t i o n s . It i s evident f r o m T a b l e II that m o n o m e t h y l i s o m e r s
a r e p r i m a r y p r o d u c t s ; the s a m e i s a p p a r e n t l y t r u e f o r m o n o e t h y l
i s o m e r s a l t h o u g h due to t h e r m o d y n a m i c r e a s o n s l o w e r c o n c e n t r a
tions are obtained. D i m e t h y l i s o m e r s including those containing
a q u a r t e r n a r y c a r b o n a t o m a r e f o r m e d as s e c o n d a r y p r o d u c t s .
H o w e v e r , t r i m e t h y l i s o m e r s a r e f o r m e d v e r y s l o w l y so that t h e i r
c o n c e n t r a t i o n s do not r e a c h e q u i l i b r i u m v a l u e s . It f o l l o w s f r o m
t h i s that the n u m b e r of r a m i f i c a t i o n s i s d e c i d i n g as to w h e t h e r a
branched i s o m e r is a p r i m a r y , secondary or t e r t i a r y product i n
h y d r o i s o m e r i z a t i o n of η - o c t a n e and n - n o n a n e .
T h o u g h m o n o m e t h y l i s o m e r s , as a w h o l e , a r e p r i m a r y p r o
d u c t s , the r a t e s of f o r m a t i o n of i n d i v i d u a l m e m b e r s m a y d i f f e r
s u b s t a n t i a l l y f r o m e a c h o t h e r . F u r t h e r m o r e t h e y depend o n the
d e g r e e of c o n v e r s i o n . W i t h , e. g . , n - d e c a n e ( T a b l e III) at l o w
d e g r e e s of c o n v e r s i o n r e l a t i v e r a t e s of f o r m a t i o n f o r 2 - m e t h y l -
nonane : 3 - m e t h y l n o n a n e : 4 - m e t h y l n o n a n e : 5 - m e t h y l n o n a n e
a r e 1 : 2 : 2 : 1 and shift to 2 : 2 : 2 : 1 at h i g h d e g r e e s of c o n
version.
T h e l a t t e r r e p r e s e n t the t h e r m o d y n a m i c e q u i l i b r i u m d i s t r i b u
t i o n w h i c h m a y e a s i l y be u n d e r s t o o d i n t e r m s of s t a t i s t i c s : L e t m
r e p r e s e n t the c a r b o n n u m b e r of the n - a l k a n e feed. If i t i s e v e n

1. WEiTKAMP Influence of Chain Length
HYDROGENOLYSIS
n-ALKANE — CRACKED PRODUCTS

-21 1 /?-SCISSION
n-ALKENES SEC. n-ALKYL CATIONS — f * C R A C K E D PRODUCTS
REARRANGEMENT 1 /Î-SCISSION
7
/
- H ®
i-ALKENES TERT. i-ALKYL CATIONS CRACKED PRODUCTS
ι
• 2H1"Î" HYDROGENOLYSIS
i-ALKANES CRACKED PRODUCTS
Figure 5. Reaction scheme for hydroisomerization of n-alkanes on bifunctional cata-

lysts and possible modes of cleavage
FEED: n-OCTANE F E E D : n-UNDECANE
SUPERFICIAL HOLDING TIME [s] SUPERFICIAL HOLDING TIME [s]
Figure 6. Course of hydroisomerization of η-octane and n-undecane (T — 275°C)

Table II. Mole-% of Isomers Formed in Hydroisomerization of «-Octane and w-Nonane
F E E D n- O C T A N E n-NONANE
τ [ c]
e
275 275 310 275 275 300 327
F -ΙΟ"
a
3
[mole h" ]
1
1 7 3 13 43 7 12 Thermo
dynamic
X ,so ['/·] 29.6 67.0 26.5 25.8 67.1 24.3
Equili
Xcr W <1 15.6 69.0 <1 9.3 72.6 brium (a)
n-Octane 69.5 20.3 14.0 13.8
2-Methylheptane 9.1 19.0 19.7 14.3
3-Methylheptane 11 .4 22.3 23.3 17.3

4-Methylheptane 4.5 8.5 8.7 5.7
3-Ethylhexane 1 .5 2.8 2.8 8.0
2,3-Dimethylhexane 0.7 4.1 4.6 2.7
2,4-Dimethylhexane 1 .3 8.0 9.2 9.8
2-Methyl-3-ethylpentane 0.1 0.5 0.7 1.1
2,2- Dimethylhexane 0.5 4.3 4.6 5.0
3,3- Dimethylhexane 0.4 3.2 3.7 4.6
Trimethylpentanes - 0.2 0.2 5.4
n-Nonane 74.1 25.9 11.1 6.5

2-Methyloctane 5.7 13.7 15.0 9.4
3-Methyloctane 7.8 15.8 16.7 9.9
4-Methyloctane 6.7 13.2 13.5 9.9
3-Ethylheptane 1.4 2.8 3.2 2.6
4-Ethylheptane (b) 1.4 4.0 5.2 5.0
2,3-Dimethylheptane 0.3 2.6 3.8 3.2
2,4-Dimethylheptane 0.4 3.5 5.1 7.9
2,5*3,5-Dimethylheptane 0.9 8.6 11.3 10.9
2,6 *4,4- Dimethylheptane 0.4 4.0 6.0 6.4
2,2- Dimethylheptane 0.3 2.3 3.2 5.5
3,3- Dimethylheptane 0.3 1.9 2.7 5.3
Others (c) 0.3 1.7 3.2 17.5
(a) Thermodynamic equilibrium calculated from ref. (Γ7)

(b) Including 3,4-dimethylheptane
(c) Mainly trimethylhexanes

(e. g . , m = 10) t h e n the m a i n c h a i n i n the m o n o m e t h y l i s o m e r s

c o n t a i n s an odd c a r b o n n u m b e r ( m - 1 = 9). In t h i s c a s e a s i n g l e
c a r b o n a t o m e x i s t s f o r c e n t e r b r a n c h i n g (5~ methylnonane) where
as two c a r b o n a t o m s a r e a v a i l a b l e f o r b r a n c h i n g i n any o t h e r p o s i
tion.
T h e l o w i n i t i a l r a t e of f o r m a t i o n f o r 2 - m e t h y l n o n a n e amoun
t i n g to one h a l f as c o m p a r e d to that of 3 - m e t h y l n o n a n e o r 4-
m e t h y l n o n a n e r e v e a l s a r e m a r k a b l e k i n e t i c f e a t u r e of h y d r o i s o
m e r i z a t i o n of l o n g c h a i n n - a l k a n e s . It i s not o b s e r v e d i n h y d r o
i s o m e r i z a t i o n of n o r m a l a l k a n e s c o n t a i n i n g a r e l a t i v e l y s h o r t
c h a i n , e. g . , n - h e x a n e as r e p o r t e d b y B o l t o n and L a n e w a l a (18).
M o r e d a t a a r e r e q u i r e d f o r a d e t a i l e d u n d e r s t a n d i n g of the i s o
m e r i z a t i o n of l o n g c h a i n p a r a f f i n s . P o s s i b l y , h o w e v e r , the s e l e c -
t i v i t i e s found w i t h n - d e c a n e at l o w d e g r e e s of c o n v e r s i o n r e f l e c t
the r e a r r a n g e m e n t c h e m i s t r y of l o n g c h a i n a l k y l c a r b e n i u m i o n s .
T a b l e III. H y d r o i s o m e r i z a t i o n of n - d e c a n e . C o m p o s i t i o n of
m o n o m e t h y l i s o m e r s (mole-%)
3 1
( F = 12 · 1 0 " m o l e decane · h " )
τ °c j 224 250 274 300
x "[% ] 2. 3 19 76 99. 8
2 - Methylnonane 17. 2 21. 7 27. 8 28. 5
3 - Methylnonane 34. 3 32. 3 31. 8 31. 2
4 - Methylnonane 31. 2 30. 1 26. 7 26. 8
5 - Methylnonane 17. 3 15. 9 13. 7 13. 5
C a r b o n N u m b e r D i s t r i b u t i o n of C r a c k e d P r o d u c t s
S e l e c t i v i t i e s of h y d r o c r a c k i n g n - a l k a n e s n - C + ^ with
m
even and odd c a r b o n n u m b e r s o n the P t / C a - Y - z e o ï i t e r e s h o w n
i n F i g u r e s 7 and 8, r e s p e c t i v e l y . R u n s have b e e n s e l e c t e d w i t h a
m e d i u m d e g r e e of c r a c k i n g c o n v e r s i o n r a n g i n g f r o m 40 to 73 %.
In e a c h c a s e the c u r v e s a r e s y m m e t r i c a l i n d i c a t i n g p u r e p r i m a r y
a r e
c r a c k i n g . M e t h a n e and ethane as w e l l as C - i and C _ 2 m m
v i r t u a l l y absent. P r o d u c t d i s t r i b u t i o n s l i k e this a r e t y p i c a l for

ideal hydrocracking.
H i g h h y d r o g e n a t i o n / d e h y d r o g e n a t i o n a c t i v i t y of the b i f u n c -
t i o n a l catalyst i s a p r e r e q u i s i t e for p u r e p r i m a r y c r a c k i n g of long
c h a i n n - a l k a n e s (4, 19). T h u s it i s the s a m e type of c a t a l y s t that

FEED Τ F -103 eXCR

Pc] [mole-h-1] [%]
• n-CeHje 310 13 69
• n-CioH22 285 12 40
• n-C H 6 285
12 2
12 56
3 4 5 6 7 8 9 10 11
CARBON NUMBER OF C R A C K E D PRODUCTS
Figure 7. Hydrocracking of n-alkanes with an even carbon number. Distribu

tion of the cracked products.
FEED Τ
Fa-10 3
XCR
PC] [moleh" ] ['/·]
1
ο n-CyHi6 330 13 53
• n-CgH20 300 12 73
• n-CnH24 275 8 46
3 4 5 6 7 8 9 10
C A R B O N NUMBER OF C R A C K E D PRODUCTS
Figure 8. Hydrocracking of n-alkanes with an odd carbon number. Distribu

tion of the cracked products.

m a k e s p o s s i b l e both h i g h d e g r e e s of h y d r o i s o m e r i z a t i o n c o n v e r
s i o n and p u r e p r i m a r y c r a c k i n g . T h e m e c h a n i s t i c p a t h w a y of
i d e a l h y d r o c r a c k i n g v i a a l k e n e s and c a r b e n i u m i o n s i s r e p r e s e n
ted i n F i g u r e 5 by a full a r r o w . The c r a c k e d products formed by
β - s c i s s i o n of the l o n g c h a i n c a r b e n i u m i o n s m a y s u f f e r two
d i f f e r e n t i a t e s : R a p i d d e s o r p t i o n of b o t h p r i m a r y f r a g m e n t s
f r o m the a c i d i c s i t e s f o l l o w e d by h y d r o g é n a t i o n of the o l e f i n i c
i n t e r m e d i a t e s at the m e t a l l i c s i t e s . S u c h a p u r e p r i m a r y c r a c k i n g
w i l l r e s u l t i n s y m m e t r i c a l p r o d u c t d i s t r i b u t i o n s . If, o n the o t h e r
h a n d , d e s o r p t i o n of one of the p r i m a r y f r a g m e n t s f r o m the a c i d i c
s i t e ( u s u a l l y the one w i t h the h i g h e r m o l e c u l a r weight) i s s l o w ,
s e c o n d a r y c r a c k i n g m a y o c c u r . T h u s r e l a t i v e r a t e s of d e s o r p t i o n
and β - s c i s s i o n a r e d e c i s i v e as to w h e t h e r o r not p u r e p r i m a r y
c r a c k i n g m a y be a c h i e v e d . T h e s t e a d y s t a t e c o n c e n t r a t i o n of l o n g
c h a i n a l k e n e s i n f l u e n c e s the r a t e of d e s o r p t i o n of the p r i m a r y
f r a g m e n t s ( c o m p e t i t i v e c h e m i s o r p t i o n ) but not the r a t e of the s u r
f a c e r e a c t i o n , i . e . , β - s c i s s i o n . T h e c o n c e n t r a t i o n of l o n g c h a i n
a l k e n e s , i n t u r n , depends on the d e h y d r o g e n a t i o n a c t i v i t y of the
bifunctional catalyst.
T h i s p i c t u r e e x p l a i n s the g r e a t d i f f e r e n c e s i n p r o d u c t d i s t r i
b u t i o n s of i d e a l h y d r o c r a c k i n g and c a t a l y t i c c r a c k i n g . F u r t h e r
m o r e , i t i s i n a g r e e m e n t w i t h the o b s e r v a t i o n that c a r b o n n u m b e r
d i s t r i b u t i o n s a r e s i m i l a r i n i d e a l h y d r o c r a c k i n g of n - a l k a n e s and
i n c a t a l y t i c c r a c k i n g of n - a l k e n e s w i t h the s a m e c a r b o n n u m b e r
(19).
A c c o r d i n g to the r o l e of c o m p e t i t i v e c h e m i s o r p t i o n p u r e
p r i m a r y c r a c k i n g of n - a l k a n e s as s h o w n i n F i g u r e s 7 and 8 f o r
m e d i u m d e g r e e s of c r a c k i n g c o n v e r s i o n m a y no l o n g e r be e x p e c
t e d u n d e r s e v e r e r e a c t i o n c o n d i t i o n s w h e n the feed h y d r o c a r b o n
i s e n t i r e l y c o n s u m e d . A c t u a l l y , i t has b e e n s h o w n (9, 20) that o n
the P t / C a - Y - z e o l i t e s e c o n d a r y c r a c k i n g of n - d o d e c a n e ( m = 12)
o r n - d e c a n e (m = 10) s t a r t s i f s e v e r i t i e s e x c e e d t h o s e that a r e
n e c e s s a r y f o r a 100 % d e g r e e of c r a c k i n g c o n v e r s i o n . T h e s a m e ,
h o w e v e r , i s not t r u e i f n - a l k a n e s w i t h l o w e r c h a i n l e n g t h ( m £ 9)
a r e u s e d . T h i s m a y be a t t r i b u t e d to the l o w r a t e s of h y d r o c r a c k i n g
of a l l f r a g m e n t s f r o m p r i m a r y i o n i c c r a c k i n g (< 6) r e g a r d l e s s of
w h e t h e r c o m p e t i t i v e c h e m i s o r p t i o n i s e f f e c t i v e o r not (cf. F i g u r e
4 f o r h e x a n e ) . C h e c k s f o r i d e a l i t y of a g i v e n h y d r o c r a c k i n g
s y s t e m , t h e r e f o r e , s h o u l d be c a r r i e d out w i t h an a l k a n e feed of
at l e a s t 10 c a r b o n a t o m s .
I d e a l h y d r o c r a c k i n g of a l k a n e s r e q u i r e s a m i n i m u m of s e v e n
c a r b o n atoms. T h i s m a y be d e r i v e d f r o m F i g u r e 9 i n w h i c h
d i s t r i b u t i o n s o f the c r a c k e d p r o d u c t s a r e c o m p a r e d that w e r e
g a i n e d w i t h n - h e x a n e (left hand side) and t h r e e of i t s h i g h e r h o m o -

l o g u e s ( r i g h t hand side) at s i m i l a r d e g r e e s of c r a c k i n g c o n v e r s i o n .
H y d r o c r a c k i n g of n - h e x a n e r e q u i r e s a m u c h h i g h e r r e a c t i o n t e m
p e r a t u r e and y i e l d s m e t h a n e and ethane i n c o n s i d e r a b l e c o n c e n
t r a t i o n s . A b s t r a c t i o n of m e t h a n e i s f a v o r e d o v e r that of ethane.
T h e s e f i n d i n g s m a y not be u n d e r s t o o d i n t e r m s o f c a r b e n i u m i o n
c l e a v a g e . R a t h e r , they a r e i n q u a l i t a t i v e a g r e e m e n t w i t h the
r e s u l t s , that h a v e been r e p o r t e d f o r h y d r o g e n o l y s i s of the i s o m e
r i c hexanes catalyzed by p l a t i n u m on v a r i o u s supports (6-8). F r o m
a l l data of the p r e s e n t w o r k i n c l u d i n g r e l a t i v e r e a c t i v i t i e s and
d i s t r i b u t i o n of i s o m e r s a m o n g the c r a c k e d p r o d u c t s the f o l l o w i n g
c o n c l u s i o n s c o n c e r n i n g the m e c h a n i s m of h y d r o g e n a t i v e c o n v e r
s i o n of n - h e x a n e o v e r the P t / C a - Y - z e o l i t e a r e d r a w n : H y d r o
i s o m e r i z a t i o n p r o c e e d s v i a the g e n e r a l l y v a l i d m e c h a n i s m out
l i n e d i n F i g u r e 5. T h e m e c h a n i s m o f c l e a v a g e , on the o t h e r hand,
d i f f e r s s u b s t a n t i a l l y f r o m the one w h i c h i s v a l i d f o r the h i g h e r

h o m o l o g u e s . It i s m a i n l y h y d r o g e n o l y t i c s t a r t i n g f r o m both the
n - h e x a n e feed and i - h e x a n e s f o r m e d b y h y d r o i s o m e r i z a t i o n . B e
s i d e s , a s m a l l c o n t r i b u t i o n of i o n i c c l e a v a g e of a s e c o n d a r y
n - h e x y l c a t i o n , v i z . the m e t h y l - n - b u t y l c a r b e n i u m i o n , β - s c i s s i o n
of w h i c h y i e l d s C + C ^ , m a y not be t o t a l l y r u l e d out.
In F i g u r e 8 the f o r m a t i o n o f m e t h a n e and ethane was s h o w n
to a c c o m p a n y i d e a l h y d r o c r a c k i n g of η - h e p t a n e to s o m e v e r y
s m a l l extent. It i s s o m e w h a t enhanced at l o w d e g r e e s of c r a c k i n g
c o n v e r s i o n , w h i c h m a y be s e e n f r o m the r i g h t hand s i d e of
F i g u r e 9. U n d e r t h e s e c o n d i t i o n s s u p e r i m p o s i t i o n of the m e t h a n e
and ethane a b s t r a c t i n g m e c h a n i s m , v i z . h y d r o g e n o l y s i s , m a y be
d e t e c t e d e v e n f o r η - o c t a n e and n - n o n a n e .
P r o b a b i l i t y of O v e r a l l C r a c k i n g R e a c t i o n s
A c c o r d i n g to the r e a c t i o n s c h e m e s h o w n i n F i g u r e 5 both
h y d r o i s o m e r i z a t i o n and h y d r o c r a c k i n g of the n - a l k a n e s (except
n-hexane) p r o c e e d v i a b r a n c h e d a l k y l c a r b e n i u m i o n s . In the
r a n g e of m e d i u m d e g r e e s of c o n v e r s i o n (40 % < , X <, 90 %) both
r e a c t i o n s m a y be i n v e s t i g a t e d s i m u l t a n e o u s l y . A r e l a t i o n s h i p
b e t w e e n the p r o d u c t s of both t y p e s of r e a c t i o n w i l l be d i s c u s s e d
i n the p r e s e n t s e c t i o n .
F o r t h i s p u r p o s e s e l e c t i v i t i e s of h y d r o c r a c k i n g of the n -
a l k a n e s a r e e x p r e s s e d i n t e r m s of p r o b a b i l i t i e s of o v e r a l l c r a c k i n g
r e a c t i o n s . T h e l a t t e r a r e c a l c u l a t e d f r o m the c a r b o n n u m b e r
d i s t r i b u t i o n s of the c r a c k e d p r o d u c t s ( n ç . = n u m b e r of m o l e s of
cracked products with carbon number i , f r o m F i g u r e s 7, 8 o r 9).
E x a m p l e s f o r the m o d e of c a l c u l a t i o n a r e r e p r e s e n t e d i n the
following scheme which is v a l i d for pure p r i m a r y c r a c k i n g .

Overall Cracking Reaction P r o b a b i l i t y (%)
V
C + C (=
c
icT -* 3 7
C + C
(=n r )
c
i o "-> 4 n
^6
6
S
c C + C n r 12
i o --> 5 5
c C + C (=n )
u - -^ 3 8 " S
n
c
u - ->c 4 + c 7 (=n„ )
"°* S
c
n- (=n )
" S p
°6
T h e v a l u e s defined i n t h i s m a n n e r do not r e p r e s e n t any p r o

b a b i l i t y f o r r u p t u r e of d e f i n i t e c a r b o n - c a r b o n bonds i n the feed
m o l e c u l e . T h i s t e r m i s m e a n i n g l e s s i f r e a r r a n g e m e n t of the
c a r b o n s k e l e t o n p r e c e d e s the c r a c k i n g s t e p . R a t h e r , the v a l u e s
i n d i c a t e the p r o b a b i l i t y of an n - a l k a n e f o r b e i n g h y d r o c r a c k e d
a c c o r d i n g to the o v e r a l l c r a c k i n g r e a c t i o n i n q u e s t i o n . T h e s e
p r o b a b i l i t i e s a r e u s e f u l f o r a c o m p a r i s o n w i t h the r e l a t i v e
c o n c e n t r a t i o n s of the p r o d u c t s f o r m e d b y h y d r o i s o m e r i z a t i o n
(cf. T a b l e I V ) .
The mechanistic background for such a c o m p a r i s o n i s i l l u s t r a
t e d i n F i g u r e 10 w h i c h r e p r e s e n t s i n m o r e d e t a i l the pathway o f
h y d r o i s o m e r i z a t i o n and h y d r o c r a c k i n g of two n - a l k a n e s . B r a n c h e d
c a r b e n i u m i o n s a r e f o r m e d v i a n - a l k e n e s and l i n e a r c a r b e n i u m
ions. Then, either desorption o r β - s c i s s i o n m a y occur i n
p a r a l l e l r e a c t i o n s . D e s o r p t i o n ( f o l l o w e d b y h y d r o g é n a t i o n ) of a
g i v e n c a r b e n i u m i o n y i e l d s an i s o - a l k a n e w i t h the s a m e c a r b o n
s k e l e t o n , β - s c i s s i o n , o n the o t h e r h a n d , y i e l d s f r a g m e n t s of
definite carbon numbers ( β - s c i s s i o n s which would y i e l d C^ o r
are excluded). Thus a c o m p a r i s o n between r e l a t i v e concentrations
of the i s o - a l k a n e s and r e l a t i v e p r o b a b i l i t i e s o f the c r a c k i n g r e a c
t i o n s m a y be i n f o r m a t i v e s i n c e both s e t s of data a r e d e t e r m i n a b l e
independently f r o m each other.
Such a c o m p a r i s o n i s made i n T a b l e I V for a l l n-alkanes with
a c h a i n l e n g t h r a n g i n g f r o m 8 to 12 c a r b o n a t o m s . S u m s h a v e b e e n
f o r m e d w h e n e v e r n e c e s s a r y , i . e . , i f the s a m e set of c a r b o n
n u m b e r s i s f o r m e d b y β - s c i s s i o n of different c a r b e n i u m i o n s , o r ,
i f d i f f e r e n t s e t s of c a r b o n n u m b e r s m a y be f o r m e d b y β - s c i s s i o n

Figure 9. Hydrocracking of n-hexane and different n-alkanes at low degrees of conver-

sion. Distribution of the cracked products.
FEED INTERMEDIATES PRODUCTS
2- METHYLHEXANE
-2 M * H ® NORMAL
n-HEPTANE « n-HEPTENES HEPTYL- i=? C *C
4 3
CATIONS 3- METHYLHEXANE
2- METHYLNONANE
c *c
4 6
3- METHYLNONANE
-2H NORMAL
n-DECANE n-DECENES C *C
DECYL- 5 5
CATIONS A-METHYLNONANE
c *c
6 4
5-METHYLNONANE |
C *C
3 7
Figure 10. Reaction scheme for hydroisomerization and hydrocracking of n-alkanes

Table IV. Hydroisomerization and Hydrocracking of w-Alkanes. Comparison Between

Relative Concentrations of Iso-alkanes and Probabilities of Overall
3 1
Cracking Reactions (F = 12 · 10" mole • h" )-
a
Feed Reaction Reaction Temperature [ C] e
265 275 285 300 310

3-Methylheptane 54.8 54.2
44.0 43.0
n-Octane
2-Methylheptane 45.2 45.8
55.0 56.5
4-Methyloctane 31.2 29.9 26.7

c *c
3 6
21.4 21.7 21.5
n-Nonane 2- Methyloctane 1
68.8 70.1 73.3
3- Methyloctane J
75.9 77.5 77.9
C 5
5-Methylnonane 14.3 13.7 13.4 13.4

C * C
3 7 14.5 13.5 13.0 13.4
2-Methylnonane1
n-Decane 4-Methylnonanej 53.3 54.5 54.7 54.8
C 6 53.3 54.5 54.6 54.7
3-Methylnonane 32.4 31.8 31.9 31.8
C * c
5 5
31.1 32.0 32.1 31.4
2-Methyldecane1
48.2
5-Methyldecane j
C *C ι
3 8
51.3
n-Undecane C^C 7 j
3- Methyldecane1
4- Methyldecanej 51.8
c *c 5 6 48.5
3-Methylundecanel
5-MethylundecaneJ 49.0 47.6 46.9
C *C Λ
48.7 47.8 47.5
3 9
C *C 5 J7
n-Dodecane
2-Methylundecanel
29.1 31.2 32.7
6-MethylundecaneJ
<V C 29.68 30.5 31.2
4-Methylundecane 21.9 21.2 20.4

Cf>*C 6
21.7 21.7 21.3

of a p a r t i c u l a r c a r b e n i u m i o n (e. g . , β - s c i s s i o n o f both the

3 - m e t h y l d e c y l c a t i o n and the 4 - m e t h y l d e c y l c a t i o n y i e l d s C + C^;
+
β - s c i s s i o n of the 5 - m e t h y l d e c y l c a t i o n m a y y i e l d e i t h e r
C or C + C ) .
g 4 ?
A good a g r e e m e n t b e t w e e n b o t h s e t s of data i s found f o r the

l o n g c h a i n n - a l k a n e s , e s p e c i a l l y f o r decane and dodecane. In
p a r t i c u l a r , the g r e a t d i f f e r e n c e s i n p r o b a b i l i t i e s of o v e r a l l
c r a c k i n g r e a c t i o n s f r o m t h e s e n - a l k a n e s a r e r e f l e c t e d b y the
r e l a t i v e c o n c e n t r a t i o n s of the m o n o m e t h y l c o m p o u n d s f o r m e d by
h y d r o i s o m e r i z a t i o n . A s a w h o l e , the r e s u l t s s h o w n i n T a b l e I V
f o r n - d e c a n e , n - u n d e c a n e and n - d o d e c a n e a r e c o n s i s t e n t w i t h
a b r a n c h i n g s t e p o c c u r i n g p r i o r to the c r a c k i n g step (cf. F i g u r e
10). F o r n - n o n a n e the a g r e e m e n t b e t w e e n both s e t s of d a t a i s
only qualitative whereas p r i n c i p l e deviations are observed for
η - o c t a n e . P o s s i b l e interpretations include differences i n rate

c o n s t a n t s of i s o m e r i c c a r b e n i u m i o n s e i t h e r f o r β - s c i s s i o n o r
d e s o r p t i o n , o r s u p e r i m p o s i t i o n of a d i f f e r e n t m o d e of c r a c k i n g ,
the extent and s e l e c t i v i t y of w h i c h a r e u n k n o w n .
W h i l e t h e r e i s v e r y l i t t l e doubt that c l e a v a g e i n i d e a l h y d r o
c r a c k i n g of n - a l k a n e s s t a r t s f r o m b r a n c h e d c a r b e n i u m i o n s the
e x a c t m o d e of β - s c i s s i o n m a y not be d e r i v e d u n a m b i g u o u s l y .
T h r e e a l t e r n a t i v e s a r e r e p r e s e n t e d i n F i g u r e 11 w h i c h a l l p r o
v i d e β - s c i s s i o n of c a r b e n i u m i o n s w i t h a s i n g l e r a m i f i c a t i o n .
A d d i t i o n a l m o d e s of c l e a v a g e s t a r t i n g f r o m m u l t i p l e b r a n c h e d c a r
b e n i u m i o n s m i g h t be c o n s i d e r e d as e m p h a s i z e d b y P o u t s m a (22).
β - S c i s s i o n a s s h o w n b y m o d e N o . 1 r e s u l t s i n the f o r m a t i o n
of a p r i m a r y c a t i o n w h i c h w o u l d s t a b i l i z e i n a r a p i d h y d r i d e s h i f t .
T h e o c c u r e n c e of the p r i m a r y c a t i o n m a y be a v o i d e d b y a s s u m i n g
(mode N o . 2) the s t a b i l i z i n g h y d r i d e shift to be concerted
r a t h e r t h a n i n s e r i e s w i t h β - s c i s s i o n . In p r i n c i p l e , then, m o d e
N o . 1 and 2 a r e s i m i l a r . A t h i r d m o d e of c l e a v a g e w h i c h has b e e n
t a k e n into c o n s i d e r a t i o n (2) s t a r t s f r o m s e c o n d a r y c a r b e n i u m i o n s
b e a r i n g the c h a r g e at c a r b o n a t o m 3 w i t h r e s p e c t to the t e r t i a r y
c a r b o n a t o m . A c o n c e r t e d h y d r i d e shift a g a i n a v o i d s the i n t e r -
m e d i a c y of a p r i m a r y c a r b e n i u m i o n . A l t h o u g h the e q u i l i b r i u m
c o n c e n t r a t i o n o f the s e c o n d a r y c a t i o n s r e q u i r e d f o r r o u t e N o . 3
w i l l be v e r y l o w , this mode of β - s c i s s i o n i s e n e r g e t i c a l l y
attractive since a secondary — > tertiary reaction is involved.
S t a r t i n g f r o m the c a r b o n s k e l e t o n of 2 - m e t h y l n o n a n e the
c a r b o n n u m b e r s of the f r a g m e n t s a r e + C g , i r r e s p e c t i v e of
the e x a c t m o d e of β - s c i s s i o n . T h u s e a c h r e a c t i o n shown i n
F i g u r e 11 f i t s the o v e r a l l c r a c k i n g r e a c t i o n C — > C + C and
1 Q 4 g
h e n c e , any of the above m o d e s of c l e a v a g e m i g h t s t a n d f o r the

c r a c k i n g r e a c t i o n s i n d i c a t e d i n F i g u r e 10. H o w e v e r , m o d e s

N o . 2 and 3 s e e m to be m o r e a p p r o p r i a t e to e x p l a i n the f i n d i n g
that n - h e x a n e i s e x c l u d e d f r o m i d e a l h y d r o c r a c k i n g .
D e g r e e of B r a n c h i n g i n the C r a c k e d P r o d u c t s
F u r t h e r i n s i g h t into the c h e m i s t r y of h y d r o c r a c k i n g m a y be
g a i n e d b y e x a m i n a t i o n of the i s o m e r d i s t r i b u t i o n a m o n g the
c r a c k e d p r o d u c t s . A n y m o d e of β - s c i s s i o n shown i n F i g u r e 11
p r e d i c t s b o t h b r a n c h e d and u n b r a n c h e d f r a g m e n t s to be p r i m a r y
p r o d u c t s of c l e a v a g e , w i t h a content o f b r a n c h e d i s o m e r s a m o u n
t i n g to c a . 50 %. A c t u a l l y , h i g h e r v a l u e s a r e found i n i d e a l
h y d r o c r a c k i n g i n d i c a t i n g the c o n t r i b u t i o n of β - s c i s s i o n of m u l
tiple branched c a r b e n i u m ions o r some secondary i s o m e r i z a t i o n ,
i . e . , r e a r r a n g e m e n t r e a c t i o n s f o l l o w i n g the c r a c k i n g s t e p . H o w
e v e r , the d e g r e e s of b r a n c h i n g i n i d e a l h y d r o c r a c k i n g a r e l o w e r
t h a n t h o s e e n c o u n t e r e d i n h y d r o c r a c k i n g o v e r c a t a l y s t s of l o w
d e h y d r o g e n a t i o n a c t i v i t y (12) and t h e y a r e m u c h l o w e r as c o m p a r e d
w i t h c a t a l y t i c c r a c k i n g o v e r m o n o f u n c t i o n a l c a t a l y s t s (13, 19).
T h i s i s c o n s i s t e n t w i t h a m o s t effective r o l e of c o m p e t i t i v e c h e
m i s o r p t i o n i n i d e a l h y d r o c r a c k i n g w h i c h m i n i m i z e s the amount
of s e c o n d a r y i s o m e r i z a t i o n .
T h e i n f l u e n c e of c h a i n l e n g t h of the feed o n the d e g r e e of
b r a n c h i n g of the c r a c k e d p r o d u c t s w i l l be d i s c u s s e d f i r s t l y f o r a
m e d i u m d e g r e e of c o n v e r s i o n . F o r t h i s p u r p o s e e x p e r i m e n t a l
data h a v e b e e n i n t e r p o l a t e d to a 50 % d e g r e e of c r a c k i n g c o n v e r
s i o n . In F i g u r e 12 the content of b r a n c h e d i s o m e r s i n the a l k a n e
f r a c t i o n s f o r m e d b y i o n i c h y d r o c r a c k i n g has b e e n p l o t t e d v e r s u s
c h a i n l e n g t h o f the f e e d .
R o u g h l y , t h e content of b r a n c h e d i s o m e r s i n a g i v e n f r a c t i o n
of the c r a c k e d p r o d u c t s (e. g . , i - b u t a n e i n the C ^ - f r a c t i o n ) i s
independent of the c h a i n l e n g t h of the feed. T h i s i s no l o n g e r t r u e ,
h o w e v e r , i f the c a r b o n n u m b e r f r a c t i o n i n q u e s t i o n i s f o r m e d b y
s p l i t t i n g of C g . R a t h e r , i t m a y be s e e n f r o m F i g u r e 12 that, i f
n-C H2m m + 2 r e p r e s e n t s the f e e d , the content of b r a n c h e d i s o
m e r s i s e x t r a o r d i n a r i l y h i g h i n the f r a c t i o n C p H 2 p +2 (ρ na-3).
=
T h i s r e s u l t i s i n a g r e e m e n t w i t h any m o d e of β-scission
r e p r e s e n t e d i n F i g u r e 11, s i n c e a C g - f r a g m e n t f o r m e d m a y not
c o n t a i n the o r i g i n a l r a m i f i c a t i o n . T h i s i s i l l u s t r a t e d i n m o r e
d e t a i l i n F i g u r e 13 w h i c h r e p r e s e n t s the p r i m a r y p r o d u c t s e x
p e c t e d f o r β - s c i s s i o n a c c o r d i n g to m o d e N o . 2 and 3. C r a c k i n g
of C ^ Q h a s b e e n c h o s e n as an e x a m p l e and a g a i n , c l e a v a g e of
m u l t i p l e branched c a r b e n i u m ions has been omitted.
It m a y be r e c o g n i z e d by s u m m i n g up the p r o d u c t s that b o t h
n o r m a l and b r a n c h e d s t r u c t u r e s a r e p r e d i c t e d i n the C - , C -
4 5

7 8 9 10 11
CARBON NUMBER OF F E E D
Figure 12. Hydrocracking of n-alkanes (Xcr = 50%). Influence of chain length

of the feed on content of branched isomers in the cracked products.

and C - f r a c t i o n s . B o t h m o d e s of c l e a v a g e , h o w e v e r , p r e d i c t a
b r a n c h e d s k e l e t o n o n l y f o r the C ^ - f r a c t i o n . T h u s , the content of
b r a n c h e d i s o m e r s i n the f r a c t i o n r e s u l t i n g b y a b s t r a c t i o n of
s h o u l d be 100 %. A c t u a l l y , t h i s v a l u e i s a p p r o x i m a t e d , the s m a l l
d e v i a t i o n of c a . 10 % b e i n g due to e i t h e r s e c o n d a r y i s o m e r i z a t i o n
of the b r a n c h e d f r a g m e n t s i n d i r e c t i o n to u n b r a n c h e d s t r u c t u r e s
o r to s o m e s m a l l c o n t r i b u t i o n of a n o n - b r a n c h i n g m e c h a n i s m .
G e n e r a l l y , the d e g r e e of b r a n c h i n g i n an a l k a n e f r a c t i o n
CpH 2 2 f o r m e d b y h y d r o c r a c k i n g of an n - a l k a n e feed
+
n-C Tï m + 2 2 m
a t a
50 % d e g r e e of c r a c k i n g c o n v e r s i o n depends
on the v a l u e of ρ as c o m p a r e d w i t h m . It f o l l o w s f r o m T a b l e V
m a v e
that the a l k a n e f r a c t i o n s C p H g p ^ d i v i d e d into t h r e e
+ 2
g r o u p s a c c o r d i n g to t h e i r d e g r e e of b r a n c h i n g .
3<p<m-3 T h e content of b r a n c h e d i s o m e r s depends

m a i n l y o n p . It i n c r e a s e s w i t h i n c r e a s i n g p,
h o w e v e r , as a good a p p r o x i m a t i o n , i t i s not
dependent on m .
ρ = m-3 D e g r e e s of b r a n c h i n g are e x t r a o r d i n a r i l y
high.
m-3<p<m R e p r e s e n t s the f r a c t i o n s f o r m e d b y a b s t r a c
t i o n of and C^. C o n t e n t s of b r a n c h e d
i s o m e r s a r e l o w e r as c o m p a r e d w i t h o t h e r
f r a c t i o n s . T h e y a r e h i g h e r f o r ρ = m - 1 than
f o r ρ = m - 2 . It i s r e c a l l e d h o w e v e r , that both
f r a c t i o n s o c c u r at v e r y l o w c o n c e n t r a t i o n s
except w h e n n - h e x a n e i s the f e e d . T h u s the
d e g r e e of b r a n c h i n g i n t h e s e f r a c t i o n s i s of
i n t e r e s t o n l y f o r the m e c h a n i s m of a b s t r a c
t i o n of m e t h a n e and ethane r a t h e r t h a n f o r
product quality.
H y d r o g e n o l y s i s has b e e n c o n c l u d e d i n a p r e c e e d i n g s e c t i o n
a n
to be m a i n l y r e s p o n s i b l e f o r the f o r m a t i o n of C ^ + C _ i d m
Cg + C _ . B r a n c h i n g i n the f r a c t i o n s ρ = m - 1 and ρ = m - 2 ,
m 2
t h e n , m a y be due to h y d r o i s o m e r i z a t i o n of e i t h e r the feed o r the

c r a c k e d p r o d u c t s a c c o r d i n g to the r e a c t i o n s e q u e n c e s :
n C H + C Ο Γ
- m 2m + 2 > ^ m ^ m + 2^ > + 2 l S
n C H ( C o r C + n C H
- m 2m + 2 ^ 1 2 " p 2p + 2 " > ^ p ^ P + 2

MODE 2 MODE 3
i-C, n-C6 i-C 4 n-C 6
i-C 5 n-C 5 i-C 5 n-C 5
i-C 6 n-C 4 -C 6 n-C 4

i-C 7 c 3 i-C 7 C 3
Figure 13. Primary products in β-scission of mono-branched decyl cations
Table V. Hydrocracking of «-Alkanes ( X = 50%). Classification of cr
Cracked Products According to the Degree of Branching.
FEED MOLE-% OF BRANCHED ISOMERS C p H p * 2 2
n
" m
C
H2m*2 C^ 10
H C
5 12 H C
6 U H C
7 16
H C
8 18
H C
9 20
H
n-HEXANE * ( }
41.0 56.5
n-HEPTANE 87.5 56 71
n-OCTANE 63.5 91.5 62 76
n-NONANE 63.7 75.8 91.0 71 79
n-DECANE 65.7 73.0 78.0 91.0 73
n-UNDECANE 67.3 75.7 78.1 83.1 92.0
n-DODECANE 65.6 74.1 78.0 82.8 X85.5 9 2

^
^CR = 7 7.

T h e h i g h e r c o n t e n t s of b r a n c h e d i s o m e r s found i n the f r a c t i o n
ρ = m - 1 as c o m p a r e d to the f r a c t i o n ρ = m - 2 a r e b e s t e x p l a i n e d
b y the s e c o n d r o u t e : S e c o n d a r y h y d r o i s o m e r i z a t i o n of
n-CpHgp + g i s e x p e c t e d to be f a s t e r f o r ρ = m - 1 due to both
h i g h e r r e a c t i v i t y (cf. F i g u r e 3) and c o m p e t i t i v e c h e m i s o r p t i o n .
T h e d e g r e e of b r a n c h i n g i n the c r a c k e d p r o d u c t s has b e e n
d i s c u s s e d , so f a r , f o r a m e d i u m d e g r e e of c r a c k i n g c o n v e r s i o n .
In F i g u r e 14 h y d r o c r a c k i n g of η - h e p t a n e and η - o c t a n e h a v e b e e n
s e l e c t e d to d e m o n s t r a t e the i n f l u e n c e of the r e a c t i o n t e m p e r a t u r e
and, h e n c e , of the d e g r e e of c r a c k i n g c o n v e r s i o n . A g a i n , a c l a s s i
f i c a t i o n of the c a r b o n n u m b e r f r a c t i o n s i s u s e f u l :
C H a n c C H f r o m
m-3<p<m ( 5 12 * 6 14 η-heptane or C g H 1 4
and CryH^g f r o m η - o c t a n e ) T h e d e g r e e of
c r a c k i n g c o n v e r s i o n has a p r o n o u n c e d i n f l u e n
c e o n the content of b r a n c h e d i s o m e r s i n t h e s e
f r a c t i o n s . T h e s h a p e of the c u r v e s i s s i m i l a r
to the one that i s o b s e r v e d f o r h y d r o i s o m e r i
z a t i o n of the feed (cf. d a s h e d l i n e f o r heptane).
T h i s i n f l u e n c e of the d e g r e e of c o n v e r s i o n i s
i n a g r e e m e n t w i t h the h y d r o g e n o l y t i c m e
c h a n i s m o u t l i n e d above.
ρ = m-3 (C H 4 1 Qfrom η-heptane or C H from 5 1 2
η-octane) T h e d e g r e e of b r a n c h i n g i n t h e s e
f r a c t i o n s p a s s e s t h r o u g h a m a x i m u m at
m e d i u m d e g r e e s of c o n v e r s i o n . T h e d e c r e a s e
at h i g h s e v e r i t i e s i n d i c a t e s an i s o m e r i z a t i o n
reaction i - C H p 2 > n-C H
p + 2 R + 2
w h i c h , due to c o m p e t i t i v e c h e m i s o r p t i o n , i s
i n h i b i t e d as l o n g as the s y s t e m c o n t a i n s h i g h
s o
c o n c e n t r a t i o n s of n o r m a l - o r i ~ C H . m 2 m + 2
T h e l o w e r contents of b r a n c h e d i s o m e r s
found at l o w d e g r e e s of c o n v e r s i o n i n d i c a t e
the c o n t r i b u t i o n of a d i f f e r e n t type of c r a c k i n g
m e c h a n i s m which yields unbranched frag
m e n t s . I n p r i n c i p l e , t h i s m i g h t be a s p e c i a l
m o d e of β - s c i s s i o n o r , m o r e l i k e l y , h y d r o
g e n o l y s i s of the u n b r a n c h e d feed. T h e l a t t e r
i s i n a g r e e m e n t w i t h the s h i f t s i n c a r b o n
n u m b e r d i s t r i b u t i o n s e n c o u n t e r e d at l o w
d e g r e e s of c r a c k i n g c o n v e r s i o n (cf. F i g u r e 9).
3<p^m-3 ( C ^ H ^ Q from η-octane) T h e s e a r e the m o s t
important fractions i n ideal hydrocracking.
It f o l l o w s f r o m F i g u r e 14, that the content

Figure 14. Hydrocracking of η-heptane and τι-octane. Influence of reaction temperature

and degree of cracking conversion on content of branched isomers.

of b r a n c h e d i s o m e r s depends o n l y s l i g h t l y on
the d e g r e e of c r a c k i n g c o n v e r s i o n . T h i s has
b e e n s h o w n i n r e c e n t p u b l i c a t i o n s (2, 9, 21)
to be g e n e r a l l y v a l i d f o r the f r a c t i o n s i n
question. A d d i t i o n a l informations concer-
n i n g d i s t r i b u t i o n s of i n d i v i d u a l i s o m e r s ,
e. g . , a k i n e t i c p r e f e r e n c e of 2 - m e t h y l i s o -
m e r s a m o n g the c r a c k e d p r o d u c t s o r the
o c c u r r e n c e of e q u i l i b r i u m c o n c e n t r a t i o n s of
q u a r t e r n a r y s t r u c t u r e s at h i g h s e v e r i t i e s ,
have been d i s c u s s e d there.
Conclusions
L o w t e m p e r a t u r e h y d r o c r a c k i n g of n - a l k a n e s o v e r s u i t a b l y
selected bifunctional catalysts with a high h y d r o g é n a t i o n / d e h y d r o -
g e n a t i o n a c t i v i t y m a y be c o n s i d e r e d to be a p u r e t y p e of c r a c k i n g
r e a c t i o n the p r o d u c t s of w h i c h d i f f e r s u b s t a n t i a l l y f r o m t h o s e
obtained i n catalytic c r a c k i n g , hydrogenolysis o r t h e r m a l c r a c k i n g .
It i s a c c o m p a n i e d b y h y d r o i s o m e r i z a t i o n and the d i s t r i b u t i o n of
the c r a c k e d p r o d u c t s i s that of a p u r e p r i m a r y c r a c k i n g . P r o b a -
b i l i t i e s of o v e r a l l c r a c k i n g r e a c t i o n s , as w e l l as b r a n c h i n g of the
c r a c k e d p r o d u c t s , i n d i c a t e a r e a r r a n g e m e n t step p r i o r to the
c r a c k i n g step. C o m p e t i t i v e c h e m i s o r p t i o n p l a y s a n i m p o r t a n t r o l e
b y e n h a n c i n g the r a t e s of d e s o r p t i o n o f c a r b e n i u m i o n s . T h u s
i n i d e a l h y d r o c r a c k i n g p r i m a r y p r o d u c t s of i o n i c r e a r r a n g e m e n t
and c r a c k i n g r e a c t i o n s a r e o b t a i n a b l e .
T h e c h a i n l e n g t h of n - a l k a n e s h a s a m a r k e d i n f l u e n c e on
r e a c t i v i t i e s f o r h y d r o i s o m e r i z a t i o n , and e s p e c i a l l y f o r h y d r o -
c r a c k i n g . T o a v e r y s m a l l extent a m e t h a n e and ethane a b s t r a c -
t i n g m e c h a n i s m , p r o b a b l y h y d r o g e n o l y s i s as p r e d i c t e d i n a b a s i c
w o r k o n b i f u n c t i o n a l c a t a l y s i s (14), i s found to be s u p e r i m p o s e d
when l o w e r c a r b o n n u m b e r feeds ( C ^ , C g , Cg) a r e u s e d . n - H e x a n e
i s e x c l u d e d f r o m i d e a l h y d r o c r a c k i n g . O n the P t / C a - Y - z e o l i t e
c a t a l y s t it i s c r a c k e d v i a a m e c h a n i s m that i s m a i n l y h y d r o g e n o -
lytic.
F r o m a p r a c t i c a l v i e w p o i n t i d e a l h y d r o c r a c k i n g o f f e r s an
u t m o s t d e g r e e of p r o d u c t f l e x i b i l i t y . H o w e v e r , as a c o n s e q u e n c e
of the c a t a l y s t s r e q u i r e d c o n t e n t s of p o i s o n s i n the feed m a t e r i a l s
s u c h as s u l f u r and n i t r o g e n c o m p o u n d s a r e s t r o n g l y l i m i t e d .
Acknowledgement
T h e a u t h o r i s i n d e b t e d to P r o f . K . H e d d e n who g e n e r o u s l y
s u p p o r t e d t h i s i n v e s t i g a t i o n . I w o u l d a l s o l i k e to thank

M r s . H . Schlifkowitz and M r . G . Walter for their excellent ex

perimental work.
Symbols Used
-1
Feed rate of n-alkane [mole
m Carbon number of n-alkane feed
m cat Mass of catalyst [gj
η. Number of moles of cracked products with

carbon number i £ moles per 100 moles
n-alkane cracked J
Carbon number of alkanes formed by
hydrocracking
Reaction rate of n-alkanes ί mole η alkane j
[ g catalyst. h J
Τ Reaction temperature [ ° c ]
Χ Degree of overall conversion
Χ Degree of hydrocracking conversion \%~\
cr
c
Degree of hydroisomerization conversion [%j
Χ.ISO
Literature Cited
(1) Langlois, G . E., and Sullivan, R. F., Preprints, Div. Petr.

C h e m . , A . C . S. (1969), 14 (1), D - 1 8 .
(2) P i c h l e r , Η., Schulz, Η., Reitemeyer, Η. Ο., and Weit
kamp, J., Erdöl, K o h l e - E r d g a s - P e t r o c h e m . (1972), 25,
494.
(3) Hedden, Κ., and Weitkamp, J., Chemie-Ing.-Techn. (1975),
47, 505.
(4) Coonradt, H . L., and Garwood, W. Ε., Preprints, Div.
Petr. C h e m . , A . C . S. (1967), 12 (4), B-47.
(5) Sullivan, R. F., and Meyer, J Α., Preprints, Div. Petr.
C h e m . , A . C . S. (1975), 20, 508.
(6) Anderson, J . R., Advances in Catalysis, (1973), 23, 1.
(7) Matsumoto, Η . , Saito, Υ., and Yoneda, Υ., J . Catal.
(1970), 19, 101.

1. WEITKAMP Influence of Chain Length 27
(8) Matsumoto, Η., Saito, Υ., and Yoneda, Υ., J. Catal.

(1971), 22, 182.
(9) Schulz, Η., and Weitkamp, J., Ind. E n g . C h e m . , P r o d .
Res. Develop. (1972), 11, 46.
(10) Weitkamp, J., and Schulz, Η., J. C a t a l . , (1973), 29, 361.
(11) F l i n n , R. A., L a r s o n , D . A., and Beuther, Η., Ind. E n g .
C h e m . , (1960), 52, 153.
(12) Archibald, R. C., Greensfelder, B . S., Holzman, G., and
Rowe, D. H., Ind. Eng. Chem.(1960), 52, 745.
(13) Plank, C . J., Sibbett, D. J., and Smith, R. Β., Ind. Eng.
Chem. (1957), 49, 742.
(14) Weisz, P . Β., Advances in Catalysis (1962), 13, 137.

(15) Orkin, Β . A., Ind. Eng. Chem. P r o d . Res. Develop. (1969),
8, 155.
(16) Ciapetta, F . G., and Hunter, J. Β., Ind. E n g . Chem. (1953),
45, 155.
(17) Stull, D . R., Westrum, E. F., Jr., and Sinke, G . C.,
"The Chemical Thermodynamics of Organic Compounds",
John Wiley and Sons, Inc., New York, 1969.
(18) Bolton, A . P., and Lanewala, Μ. A., J. Catal. (1970), 18,1.
(19) Coonradt, H . L., and Garwood, W. Ε., Ind. Eng. Chem.
P r o c e s s Des. Develop. (1964), 3, 38.
(20) Weitkamp, J., and Hedden, Κ . , Chemie-Ing. - T e c h n .
(1975), 47, 537.
(21) Schulz, Η., and Weitkamp, J., Preprints, Div. Petr.
C h e m . , A . C. S. (1972), 17 (4), G-84.
(22) Rabo, J. A., "Zeolites Chemistry and Catalysis", A . C . S.

Chemical Monograph Series, Chapter on "Mechanistic
Considerations of Hydrocarbon Transformation Catalyzed
by Zeolites", by M . L. Poutsma, in print.

2
Catalyst Effects on Yields and Product Properties

in Hydrocracking
R. F. SULLIVAN and J. A. MEYER

Chevron Research Co., Richmond, Calif. 94802
The flexibility o f h y d r o c r a c k i n g as a p r o c e s s f o r
refining p e t r o l e u m has r e s u l t e d in its phenomenal
growth d u r i n g the p a s t 15 y e a r s . F e e d s t o c k s t h a t can
be c o n v e r t e d t o lower boiling o r more d e s i r a b l e p r o d -
u c t s range from r e s i d u a t o n a p h t h a s . Products i n c l u d e
such w i d e l y d i v e r s e m a t e r i a l s as g a s o l i n e , kerosene,
middle distillates, lubricating oils, fuel oils, and
various chemicals ( 1 , 2 ) .
Commercial h y d r o c r a c k i n g is c a r r i e d out in a
single s t a g e o r in two o r more s t a g e s in s e r i e s .
Numerous h y d r o c r a c k i n g c a t a l y s t s have been d e v e l o p e d ;
and the more r e c e n t o f t h e s e have e x c e p t i o n a l l y long
lives, even at s e v e r e o p e r a t i n g c o n d i t i o n s . The c h o i c e
of the c a t a l y s t and o f the particular p r o c e s s i n g scheme
will depend on many f a c t o r s such as feed p r o p e r t i e s ,
p r o p e r t i e s o f the d e s i r e d p r o d u c t s , s i z e o f the h y d r o -
cracking unit, availability of other processing facili-
ties, and v a r i o u s o t h e r economic c o n s i d e r a t i o n s .
In t h i s p a p e r , we will examine s e v e r a l h y d r o -
cracking catalysts of varying acidities and
hydrogenation-dehydrogenation activities and show dif-
ferences in p r o d u c t distributions and p r o d u c t p r o p e r -
ties o b t a i n e d from two r e p r e s e n t a t i v e domestic
f e e d s t o c k s in the second s t a g e o f a t w o - s t a g e h y d r o -
cracking process. I n such a p r o c e s s , the f e e d t o the
second s t a g e has been h y d r o f i n e d in the first stage i n
o r d e r t o remove most o f the i m p u r i t i e s such as n i t r o g e n
and s u l f u r .
In particular, we will emphasize (1) total liquid
yield, i n c l u d i n g pentanes and all o f the h i g h e r boiling
p r o d u c t , and (2) octane number o f the l i g h t p r o d u c t
c o n s i s t i n g m a i n l y o f m o l e c u l e s w i t h carbon numbers o f 5
and 6, r e f e r r e d t o as C - l 8 0 ° F p r o d u c t .
5 H i g h C5+
28
2. SULLIVAN A N D M E Y E R Catalyst Effects 29
l i q u i d y i e l d s are d e s i r a b l e i n s i t u a t i o n s i n which
butanes and propane are i n o v e r s u p p l y o r o f l o w e r v a l u e
than the l i q u i d products. A h i g h o c t a n e number i n t h e
C5-l80°F product i s p a r t i c u l a r l y d e s i r a b l e because i t
i s more d i f f i c u l t t o u p g r a d e t h i s l o w b o i l i n g f r a c t i o n
t h a n t h e h i g h e r b o i l i n g n a p h t h a s , w h i c h c a n be u p g r a d e d
r e l a t i v e l y e a s i l y by c a t a l y t i c r e f o r m i n g .
Background
Most h y d r o c r a c k i n g c a t a l y s t s o f c o m m e r c i a l i n t e r -
est are dual f u n c t i o n a l i n nature, c o n s i s t i n g o f both
a h y d r o g e n a t i o n - d e h y d r o g e n a t i o n component and an a c i d i c
support. The r e a c t i o n s c a t a l y z e d b y t h e i n d i v i d u a l
components a r e q u i t e d i f f e r e n t . In specific catalysts,
t h e r e l a t i v e s t r e n g t h s o f t h e two components can be
varied. The r e a c t i o n s o c c u r r i n g and t h e p r o d u c t s

formed depend c r i t i c a l l y upon t h e b a l a n c e between t h e s e
two c o m p o n e n t s .
The a c i d f u n c t i o n o f t h e c a t a l y s t i s s u p p l i e d b y
the support. Among t h e s u p p o r t s m e n t i o n e d i n t h e
l i t e r a t u r e are s i l i c a - a l u m i n a , s i l i c a - z i r c o n i a , s i l i c a -
magnesia, alumina-boria, s i l i c a - t i t a n i a , a c i d - t r e a t e d
c l a y s , a c i d i c m e t a l p h o s p h a t e s , a l u m i n a , and o t h e r
such s o l i d a c i d s . The a c i d i c p r o p e r t i e s o f t h e s e
amorphous c a t a l y s t s c a n be f u r t h e r a c t i v a t e d by t h e
a d d i t i o n o f s m a l l p r o p o r t i o n s o f a c i d i c h a l i d e s s u c h as
HF, B F , S i F i t , and t h e l i k e (3.).
3 Z e o l i t e s s u c h as t h e
f a u j a s i t e s and m o r d e n i t e s a r e a l s o i m p o r t a n t s u p p o r t s
for hydrocracking c a t a l y s t s (2).
The h y d r o g e n a t i o n - d e h y d r o g e n a t i o n c o m p o n e n t i s a
m e t a l s u c h as c o b a l t , n i c k e l , t u n g s t e n , v a n a d i u m ,
molybdenum, p l a t i n u m . o r p a l l a d i u m , o r a c o m b i n a t i o n o f
metals. The n o n - n o b l e m e t a l s a r e u s u a l l y p r e s u l f i d e d
a l t h o u g h i t has been s u g g e s t e d t h a t the a c t u a l h y d r o -
g é n a t i o n a c t i v i t y f o r the s u l f i d e d c a t a l y s t s e x i s t s
i n t r a n s i t o r y m e t a l l i c r e g i o n s on t h e s e c a t a l y s t s (h).
The s u l f i d e d m e t a l s a r e g e n e r a l l y r e p o r t e d t o b e l e s s
a c t i v e f o r h y d r o g é n a t i o n than the noble metal
c a t a l y s t s (5.).
The r e l a t i o n s h i p b e t w e e n t h e t w o c a t a l y t i c c o m -
ponents i s q u i t e complex. I n t e r a c t i o n s between the
s u p p o r t and t h e h y d r o g é n a t i o n component c a n a l t e r t h i s
relationship. F o r e x a m p l e , L a r s o n et- a l . (6) s h o w e d
t h a t , w i t h p l a t i n u m on s i l i c a - a l u m i n a , a s e l e c t i v e
a d s o r p t i o n o f p l a t i n u m by a c i d s i t e s c a u s e s a r e d u c t i o n
in catalyst acidity. S i m i l a r l y , n i c k e l reacts w i t h the
a c i d s i t e s on s i l i c a - a l u m i n a f o r m i n g n i c k e l s a l t s o f
the s i l i c a - a l u m i n a a c i d s i t e s . I t has been s u g g e s t e d
(7) t h a t one o f t h e e f f e c t s o f s u l f i d i n g a n i c k e l o n

s i l i c a - a l u m i n a c a t a l y s t i s that hydrogen s u l f i d e r e a c t s
w i t h t h e s e s a l t s and r e g e n e r a t e s t h e o r i g i n a l s t r o n g
a c i d s i t e s of the s i l i c a - a l u m i n a .
I n t h e r e a c t i o n s o f t h e many c o m p o n e n t m i x t u r e s
t h a t make up m o s t c o m m e r c i a l f e e d s t o c k s , t h e r e l a t i o n -
s h i p b e t w e e n t h e t w o c a t a l y t i c c o m p o n e n t s may be f u r -
t h e r a l t e r e d by p r e f e r e n t i a l a d s o r p t i o n o f c e r t a i n
h y d r o c a r b o n r e a c t a n t s o n c a t a l y t i c s i t e s ( £0 . For
example, p o l y c y c l i c a r o m a t i c s have a h i g h l y v a r i a b l e
e f f e c t d e p e n d e n t o n t h e t y p e a n d amount a s w e l l a s
c a t a l y s t and r e a c t i o n c o n d i t i o n s . Catalyst poisons
s u c h a s s u l f u r , n i t r o g e n , a n d o x y g e n may a f f e c t either
or b o t h c a t a l y s t components ( £ ) .
The l i t e r a t u r e o n t h e h y d r o c r a c k i n g o f v a r i o u s
hydrocarbons i s summarized i n s e v e r a l r e v i e w a r t i c l e s
(5310*11) and mechanisms o f h y d r o c a r b o n r e a c t i o n s
presented. B e u t h e r a n d L a r s o n (h) a n d C o o n r a d t a n d
c o w o r k e r s (9312,1331*0 compare t h e r e a c t i o n s o f n o b l e
m e t a l c a t a l y s t s and the n o n - n o b l e m e t a l s u l f i d e s .
C a t a l y s t s w i t h h i g h h y d r o g é n a t i o n a c t i v i t y s u c h as t h e
noble metal c a t a l y s t s are reported to favor the forma-
t i o n o f h i g h e r b o i l i n g p r o d u c t s and minimum l i g h t
hydrocarbon production. C a t a l y s t s w i t h low h y d r o g é n a -
t i o n a c t i v i t y r e l a t i v e to a c i d i t y y i e l d product with a
higher r a t i o of branched paraffins to normal p a r a f f i n s
and l e s s s a t u r a t i o n o f a r o m a t i c s . With the latter
c a t a l y s t s , t h e naphtha p r o d u c t has a h i g h e r octane
number.
S c h u t z a n d W e i t k a m p (15.) show p r o d u c t d i s t r i b u -
t i o n s f o r t h e h y d r o c r a c k i n g o f dodecane on s e v e r a l
n o b l e m e t a l s on z e o l i t e c a t a l y s t s . Product d i s t r i b u -
t i o n s are i n general s i m i l a r to those d i s t r i b u t i o n s
p r e v i o u s l y r e p o r t e d f o r n o b l e m e t a l s on amorphous
supports. T h e s e r e s u l t s show n o m a j o r u n e x p e c t e d
e f f e c t o f t h e z e o l i t i c s u p p o r t ; d i f f e r e n c e s among t h e
c a t a l y s t s t e s t e d a r e r e l a t e d t o changes i n h y d r o g é n a -
t i o n a b i l i t y or a c i d i t y .
In o r d e r t o o b t a i n q u a n t i t a t i v e measurements o f
h y d r o g é n a t i o n a c t i v i t y and a c i d i t y , v a r i o u s schemes
are employed. F o r e x a m p l e , m e t a l s u r f a c e a r e a has
been r e l a t e d t o h y d r o g é n a t i o n a c t i v i t y and the a d s o r p -
t i o n o f b a s e s s u c h a s p y r i d i n e a n d ammonia h a v e b e e n
c o r r e l a t e d w i t h a c i d i t y (6). Some a u t h o r s h a v e u s e d
c e r t a i n k e y r e a c t i o n s i n v o l v i n g p u r e compounds a s a n
i n d i c a t i o n o f c a t a l y t i c p r o p e r t i e s (16). Each o f these
methods i s u s e f u l ; h o w e v e r , b e c a u s e o f t h e complex
interdependence of the c a t a l y t i c functions of the
h y d r o c r a c k i n g c a t a l y s t s and changes i n t h e s e f u n c t i o n s
w i t h c a t a l y s t a g i n g , r e s u l t s f r o m e a c h method must be
interpreted with caution.

C o o n r a d t a n d c o w o r k e r s (13_) u s e a n e m p i r i c a l
h y d r o g é n a t i o n a c t i v i t y i n d e x b a s e d on t h e a r o m a t i o -
naphthene r a t i o i n the hydrocracked p r o d u c t . This
a p p r o a c h does n o t p r o v i d e an i n d e p e n d e n t measure o f
catalytic properties. However, i t has t h e a d v a n t a g e
t h a t a c t i v i t i e s are measured under a c t u a l h y d r o c r a c k i n g
c o n d i t i o n s ; and changes i n c a t a l y t i c p r o p e r t i e s w i t h
c a t a l y t i c a g i n g can be o b s e r v e d .
Most d i r e c t comparisons a v a i l a b l e i n the l i t e r a -
t u r e among c a t a l y s t s o f v a r y i n g h y d r o g e n a t i o n - t o -
a c i d i t y r a t i o s are f o r s i n g l e pass p r o c e s s i n g . Because
o f t h e d i f f e r e n t r e a c t i v i t i e s o f t h e components o f com-
m e r c i a l feed m i x t u r e s , the s p e c i f i c molecules that
r e a c t i n a s i n g l e pass w i l l depend s t r o n g l y upon t h e
t o t a l conversion. I n o t h e r w o r d s , t h e most s t r o n g l y
adsorbed s p e c i e s w i l l r e a c t p r e f e r e n t i a l l y ; and the
r e s u l t i n g product d i s t r i b u t i o n w i l l r e f l e c t the proper-

t i e s of these reacting molecules. As t h e c o n v e r s i o n
i n c r e a s e s , the p r o p e r t i e s of the r e a c t i n g molecules
and t h e r e f o r e the p r o d u c t w i l l change. A l s o , i f two
c a t a l y s t s w i t h d i f f e r e n t p r o p e r t i e s are compared at
constant conversion, the p a r t i c u l a r species that react
i n t h e p r e s e n c e o f one c a t a l y s t w i l l n o t n e c e s s a r i l y b e
t h e same s p e c i e s t h a t r e a c t p r e f e r e n t i a l l y u s i n g t h e
other.
I n t h i s p a p e r we c o m p a r e b e h a v i o r o f c a t a l y s t s i n
extinction recycle hydrocracking. In such a p r o c e s s i n g
scheme, a l l o f the feed i s u l t i m a t e l y c o n v e r t e d t o
product b o i l i n g below a c e r t a i n p r e d e f i n e d temperature.
The r e a c t i o n p a t h s o f i n d i v i d u a l f e e d c o m p o n e n t s may
d i f f e r from c a t a l y s t t o c a t a l y s t . Product d i s t r i b u -
t i o n s and p r o p e r t i e s a r e examined t o d e t e r m i n e the
g e n e r a l e f f e c t s o f changes i n c a t a l y t i c p r o p e r t i e s .
Experimental
Equipment. A l l o f the c a t a l y s t s were t e s t e d i n

continuous flow, fixed-bed p i l o t plants equipped for
b o t h l i q u i d and gas r e c y c l e o p e r a t i o n and c o n t i n u o u s
d i s t i l l a t i o n of products. Hydrocarbons b o i l i n g above
t h e d e s i r e d p r o d u c t end p o i n t were r e c y c l e d t o e x t i n c -
t i o n , t h a t i s , t o 100$ c o n v e r s i o n o f f r e s h f e e d . The
p r o d u c t was c o o l e d a n d p a s s e d i n t o a h i g h p r e s s u r e
phase s e p a r a t o r . H e r e , h y d r o g e n - r i c h r e c y c l e g a s was
f l a s h e d from the h y d r o c a r b o n p r o d u c t and r e c y c l e d back
to the r e a c t o r i n l e t . E l e c t r o l y t i c h y d r o g e n make-up
was a d d e d o n demand t o m a i n t a i n c o n s t a n t s y s t e m
pressure.
The l i q u i d f r o m t h e h i g h p r e s s u r e s e p a r a t o r was
d e p r e s s u r e d and f l a s h e d at a t m o s p h e r i c p r e s s u r e . The

l i q u i d h y d r o c a r b o n p h a s e was f e d t o t h e f i r s t o f t w o
c o n t i n u o u s d i s t i l l a t i o n columns f o r the p r o d u c t f r a c -
tionation. In the f i r s t column, the m a t e r i a l b o i l i n g
a b o v e t h e d e s i r e d r e c y c l e c u t p o i n t was s e p a r a t e d f r o m
the lower b o i l i n g product. The o v e r h e a d f r o m t h i s
c o l u m n was c o m b i n e d w i t h t h e g a s e o u s p r o d u c t f r o m t h e
low p r e s s u r e f l a s h and f e d t o the second column i n
w h i c h t h e p e n t a n e s and l i g h t e r gases were s e p a r a t e d
from the l i q u i d p r o d u c t . The g a s e o u s p r o d u c t f r o m
t h i s d e p e n t a n i z e r was m e t e r e d a n d a n a l y z e d b y g a s
chromatography.
L i q u i d p r o d u c t was d i s t i l l e d b a t c h w i s e f o r
d e t e r m i n a t i o n o f l i q u i d y i e l d s and p r o d u c t p r o p e r t i e s .
In the batch d i s t i l l a t i o n , the f i r s t l i q u i d product
c u t was made a t l 8 0 ° F ( t r u e b o i l i n g p o i n t ) . Isopentane
and n - p e n t a n e were added back t o t h i s d i s t i l l a t i o n c u t
i n t h e amount m e a s u r e d i n t h e g a s e o u s p r o d u c t . The
r e s u l t i n g b l e n d , m a i n l y c o n s i s t i n g o f components w i t h
c a r b o n numbers o f 5 a n d 6, i s r e f e r r e d t o as M
C5-l80°F
product."
The b o i l i n g r a n g e s o f t h e d i s t i l l a t i o n c u t s
(shown as " t r u e b o i l i n g p o i n t " t e m p e r a t u r e r a n g e s ) were
c h o s e n a r b i t r a r i l y a n d do n o t r e p r e s e n t o p t i m u m o r
maximum p o t e n t i a l y i e l d s o f s p e c i f i c p r o d u c t s . In the
e x a m p l e s g i v e n , t h e amount o f j e t f u e l o r n a p h t h a
c o u l d be a l t e r e d b y c h a n g i n g t h e b o i l i n g r a n g e s ,
d e p e n d i n g on t h e d e s i r e d p r o d u c t p r o p e r t i e s . Simi-
l a r l y , t h e r e c y c l e c u t p o i n t c o u l d be v a r i e d t o m a x i -
mize i n d i v i d u a l products.
A l l o f t h e p i l o t p l a n t t e s t s w e r e made a t 60
l i q u i d volume p e r c e n t p e r pass c o n v e r s i o n below the
r e c y c l e cut p o i n t . T e m p e r a t u r e s were a d j u s t e d as
necessary to maintain t h i s conversion. Total pressure
and r e c y c l e gas r a t e were h e l d c o n s t a n t f o r a l l o f t h e
runs w i t h a g i v e n feed.
Feeds. P r o p e r t i e s o f two h y d r o f i n e d t e s t f e e d s
are given i n Table I . The C a l i f o r n i a g a s o i l b l e n d
was u s e d i n t e s t s s i m u l a t i n g a h y d r o c r a c k i n g u n i t p r o -
d u c i n g b o t h naphthas and j e t f u e l , the M i d - C o n t i n e n t
blend i n t e s t s r e p r e s e n t i n g a u n i t producing naphtha
as t h e major p r o d u c t .
Catalysts. Seven e x p e r i m e n t a l c a t a l y s t s were

p r e p a r e d w i t h v a r y i n g h y d r o g é n a t i o n a c t i v i t y and
a c i d i t y t o t e s t t h e e f f e c t s o f t h e s e p r o p e r t i e s on
product d i s t r i b u t i o n s . A l l o f the c a t a l y s t s were
reasonably s t a b l e at t e s t c o n d i t i o n s .
In the f o l l o w i n g t a b l e , the c a t a l y s t s are l i s t e d
i n order of decreasing ratios of hydrogénation

TABLE I
FEED PROPERTIES
Hydrotreated Hydrotreated
California Mid-Continent
Gas O i l B l e n d Gas O i l B l e n d
G r a v i t y , °API 33.9 33-3

Aniline Point, °F 192.7 177.6
S u l f u r , ppm 1 9
T o t a l N i t r o g e n , ppm 0.1 0.2
Mass S p e c t r o m e t r i c
Type A n a l y s i s , LV %
Paraffins 31.3 19.4

Naphthenes 56.3 63-9
Aromatics 12.4 16.6
ASTM D 1160
Distillation, °P
St/5 553/589 325/441

10/30 595/617 515/616
50 646 666
70/90 684/732 705/762
95/EP 763/859 802/826

a c t i v i t y to acid a c t i v i t y . N o m i n a l l y , C a t a l y s t A has
the highest h y d r o g é n a t i o n a c t i v i t y r e l a t i v e to i t s
a c i d i t y ; C a t a l y s t G has t h e l o w e s t h y d r o g é n a t i o n
a c t i v i t y r e l a t i v e to i t s a c i d i t y . The a s s i g n m e n t i s
b a s e d on a v a r i e t y o f l a b o r a t o r y t e s t s . As i n d i c a t e d
p r e v i o u s l y , a l l such t e s t s are not completely unambi-
g u o u s ; t h e r e f o r e , t h e a s s i g n m e n t may be r e g a r d e d as
somewhat a r b i t r a r y .
Experimental Catalysts
Catalyst Metals
Identi- Hydrogénation Content,
fication Component Wt % Support M a t e r i a l
A Pd 0.5 A c t i v a t e d Clay
(Low A c i d i t y )
Β Pd 1.0 Amorphous Silica-

Alumina
C Pd 0.2 Amorphous Silica-

Alumina
D Pd 0.5 Activated Clay

(Moderate Acidity)
Ε Pd 0.5 Faujasite
Ρ Pd 0.5 Amorphous S i l i c a -
Alumina (Activated)
G Sulfided Ni 10.0 Amorphous Silica-

Alumina
Results With C a l i f o r n i a Gas O i l
Product D i s t r i b u t i o n s . A l l o f the t e s t s w i t h
C a l i f o r n i a g a s o i l w e r e made a t a r e c y c l e c u t p o i n t o f
550°F, a r b i t r a r i l y c h o s e n and n o t n e c e s s a r i l y an
optimum c u t p o i n t f o r o p e r a t i o n w i t h any o f t h e
catalysts.
T a b l e I I compares p r o d u c t d i s t r i b u t i o n s f o r
c a t a l y s t s near to the extremes o f h y d r o g e n a t i o n - t o -
acidity ratios studied. Catalyst Β gives a higher
y i e l d o f l i q u i d p r o d u c t i n c l u d i n g the pentanes and a l l
h i g h e r b o i l i n g m a t e r i a l ( r e f e r r e d t o as "C5-550°F

SULLIVAN A N D M E Y E R Catalyst Effects
TABLE I I
YIELDS AND PRODUCT PROPERTIES FROM

HYDROCRACKING OF CALIFORNIA GAS O I L
60% PER PASS CONVERSION BELOW 550°F
Catalyst
T e m p e r a t u r e , °F ΤΪ(Γ
Wt % LV % Wt % LV %
No L o s s P r o d u c t Y i e l d s
( B a s e d on F r e s h F e e d )
Methane 0.01 0.01
Ethane 0.02 0.04
Propane 1.0 1.5
Isobutane 3.8 5.8 6.3 9.6
n-Butane 1.1 1.6 1.8 2.6
C -180°F 10.1 13.2
5 15.5 20.2
180-280°F 21.6 25.0 25.6 29.5
280-300°F 4.9 5.5 6.4 7.2
300-550°F 59.2 63-9 44.8 48.2
Total C -550°F
5 95.8 107.6 92.3 I 105.1
Chemical Hydrogen 950 1000
C o n s u m p t i o n , SCF/B
Product Properties
C -180°F
5 Product
O c t a n e Number 81.5 85.0
F - l Clear
l80-280°F Product
O c t a n e Number 58.7 63.4
F - l Clear
Paraffins 47.5 42.6
Naphthenes 52.5 55.5
Aromatics 0.0 1.9
280-300°F Product
Paraffins 44.0 40.1
2.4
Aromatics
300-550°F Product
Paraffins 42.6 41.5
Aromatics 0.2 2.5
ASTM D 86 D i s t . Op
St/5 334/350 333/349

10/30 358/381 355/375
50 408 398
70/90 444/486 436/488
95/EP 500/531 503/528

product"). A l s o , t h i s c a t a l y s t p r o d u c e s more m a t e r i a l
b o i l i n g above 280°F, a r b i t r a r i l y r e f e r r e d t o as j e t
fuel. The p r o d u c t i s m o r e c o m p l e t e l y h y d r o g e n a t e d t h a n
t h a t f o r C a t a l y s t G . C a t a l y s t G , on t h e o t h e r h a n d ,
p r o d u c e s more n a p h t h a , more p r o p a n e a n d b u t a n e , a n d
h i g h e r octane numbers.
The g e n e r a l t r e n d s shown b y t h e s e p r o d u c t d i s t r i
b u t i o n s are i n b a s i c agreement w i t h the l i t e r a t u r e
results discussed e a r l i e r .
C -l80°F Product.
5 T a b l e I I I shows t h e c o m p l e t e
d i s t r i b u t i o n o f hydrocarbons from r e p r e s e n t a t i v e
s a m p l e s o f C s - l 8 0 F p r o d u c t as d e t e r m i n e d by gas
o
c h r o m a t o g r a p h y f o r t h e same t w o c a t a l y s t s . Both
p r o d u c t s a m p l e s c o n t a i n a b o u t 90% p a r a f f i n s a n d 10$
cycloparaffins. The C 5 - l 8 0 ° F p r o d u c t f r o m C a t a l y s t G
c o n t a i n s a t r a c e o f b e n z e n e (0.2%); t h a t f r o m C a t a l y s t
Β c o n t a i n s no d e t e c t a b l e a r o m a t i c c o m p o u n d . The s m a l l
d i f f e r e n c e i n t h e t o t a l c y c l o p a r a f f i n s c o n t e n t shown
i n Table I I I i s p r o b a b l y not s i g n i f i c a n t .
The C - l 8 0 ° F p r o d u c t c o n s i s t s m a i n l y o f C5 a n d C6
5
p a r a f f i n s ; t h e r e f o r e , i t i s p r i m a r i l y t h e s e components
t h a t d e t e r m i n e t h e o c t a n e number.
With a l l o f the c a t a l y s t s i n t h i s study, the r a t i o
o f i s o p e n t a n e t o n o r m a l p e n t a n e v a r i e s d i r e c t l y as t h e
r a t i o o f isohexanes to n-hexane. (In t h i s paper, the
b r a n c h e d Ce p a r a f f i n s a r e c o l l e c t i v e l y r e f e r r e d t o a s
isohexanes.) T h e r e f o r e , the i s o / n o r m a l r a t i o o f the
p a r a f f i n s o f e i t h e r c a r b o n number c a n b e c o r r e l a t e d
w i t h o c t a n e number f o r C s - l 8 0 F p r o d u c t o f a g i v e n
o
c y c l o p a r a f f i n c o n t e n t a n d s e r v e as a c o n v e n i e n t i n d i
c a t i o n o f c a t a l y s t performance.
I n t h e s p e c i f i c example shown i n T a b l e I I I , t h e
difference i n r a t i o s of i s o p a r a f f i n s to normal paraf
f i n s i n t h e C - l 8 0 ° F p r o d u c t from t h e two c a t a l y s t s
5
r e s u l t s i n a f o u r o c t a n e number d i f f e r e n c e .
F i g u r e 1 shows t h e e f f e c t o f t e m p e r a t u r e o n
isohexane/n-hexane r a t i o for Catalysts A - G , i n c l u s i v e .
M o s t o f t h e c a t a l y s t s show a s l i g h t d e c r e a s e i n i s o - t o -
normal r a t i o w i t h i n c r e a s i n g temperature. The r a t i o s
f o r t h e g r o u p o f c a t a l y s t s t e s t e d r a n g e f r o m 20/1 t o
3/1. The l a t t e r r a t i o i s a p p r o x i m a t e l y t h e e q u i l i b r i u m
r a t i o f o r s i n g l y b r a n c h e d C6 p a r a f f i n s t o n o r m a l
hexane.
F i g u r e 2 i s a comparison showing the e f f e c t o f
t e m p e r a t u r e on i s o p e n t a n e / n - p e n t a n e r a t i o s . The
r e l a t i o n s h i p i s q u i t e s i m i l a r t o t h a t shown f o r t h e
hexanes.

TABLE III
D I S T R I B U T I O N OP C - l 8 0 ° F PRODUCT PROM
5
HYDROCRACKING OP C A L I F O R N I A GAS O I L
Catalyst 1 Β G
Average C a t a l y s t
Temperature, °F 598 610
Product, LV % o f C -l80°F
5
Butanes 0.4 0.3

Isopentane 41.0 44.1
n-Pentane 9.5 2.8

2.2- Dimethylbutane 0.2 0.04
2.3- Dimethylbutane 2.5 3.2
2- M e t h y l p e n t a n e 17.3 19.3
3- M e t h y l p e n t a n e 9.3 11.4
n-Hexane 6.3 2.2
Isoheptanes 3.7 4.5
n-Heptane 0.1 0.02
Total Paraffins 90.3 87.8
Cyclopentane 0.5 0.4

Methylcyclopentane 7.1 9.4
Cyclohexane 0.6 0.4
Dlmethylcyclopentanes, 1.3 1.5
Ethylcyclopentane
Methylcyclohexane 0.1 0.3
Total Cycloparaffins 9.6 12.0
Benzene - 0.2
Total Aromatics - 0.2
Octane No., F - l Clear 81.1 85.0
Isopentane/n-Pentane 4.3 16.4
Isohexanes/n-Hexane 4.6 15.5

HYDROCRACKING AND HYDROTREATING
20 Γ-
600 630
Average Catalyst Temperature, °F
Figure 1. Effect of temperature on isohexanes/n-hexane hydrocracking

of California gas oil
|Τ0 40
201
550 600 650 700
Average C a t a l y s t T e m p e r a t u r e , °F
Figure 2. Effect of temperature on isopentane/n-pentane hydrocrack

ing of California gas oil

2. SULLIVAN AND MEYER Catalyst Effects 39
W i t h b o t h pentanes and hexanes, the iso-to-normal
r a t i o s appear to vary i n v e r s e l y w i t h the hydrogenation-
to-acidity ratios.
Butanes. The b u t a n e s a r e t h e p r i n c i p a l l o w
b o i l i n g p r o d u c t s ; a n d , as i n d i c a t e d e a r l i e r , c a t a l y s t s
w i t h a low r a t i o o f h y d r o g é n a t i o n a b i l i t y to a c i d i t y
p r o d u c e more b u t a n e t h a n do t h o s e w i t h r e l a t i v e l y h i g h
hydrogénation activity. However, the d i f f e r e n c e s i n
i s o b u t a n e / n - b u t a n e r a t i o s among c a t a l y s t s o f w i d e l y
d i f f e r e n t h y d r o g e n a t i o n - t o - a c i d i t y r a t i o s are small.
F i g u r e 3 shows t h e e f f e c t o f t e m p e r a t u r e on i s o b u t a n e /
η - b u t a n e r a t i o f o r C a t a l y s t s A , B , F , and G , r e p r e
s e n t i n g extremes o f h y d r o g e n a t i o n / a c i d i t y r a t i o s . The
isobutane/n-butane r a t i o with Catalyst G i s s l i g h t l y
h i g h e r than t h a t f o r the other c a t a l y s t s at the lower
temperatures. However, at h i g h e r temperatures, the

r a t i o s from a l l o f the c a t a l y s t s are e s s e n t i a l l y the
same.
T h i s r e s u l t i n d i c a t e s t h a t t h e r e i s no d i r e c t
r e l a t i o n s h i p between i s o / n o r m a l r a t i o s f o r the butanes
w i t h those f o r the pentanes and hexanes. The f o l l o w i n g
hypothesis i s suggested to e x p l a i n t h i s r e s u l t .
An i m p o r t a n t r e a c t i o n o c c u r s i n h y d r o c r a c k i n g
w h i c h p r o d u c e s i s o b u t a n e more s e l e c t i v e l y f r o m c y c l o -
p a r a f f i n s t h a n from a r o m a t i c compounds. This reaction
has b e e n r e f e r r e d t o as t h e p a r i n g r e a c t i o n . I t was
s h o w n b y E g a n e t a l . (17) t h a t c y c l o p a r a f f i n s w i t h
c a r b o n n u m b e r s o f 10 o r m o r e r e a c t v e r y s e l e c t i v e l y t o
give isobutane plus lower molecular weight c y c l o
paraf fins. A l k y l aromatics with side chains of three
o r more c a r b o n s c r a c k m a i n l y b y d é a l k y l a t i o n , w i t h
much l e s s i s o m e r i z a t i o n o f t h e a l k y l g r o u p (18.)·
Therefore, i f the aromatics i n the feed are hydro-
g e n a t e d p r i o r t o c r a c k i n g , as w o u l d be e x p e c t e d w i t h a
catalyst of high hydrogénation a c t i v i t y , a high
isobutane/n-butane r a t i o i s favored. With a catalyst
o f l o w e r h y d r o g é n a t i o n a c t i v i t y , c r a c k i n g w o u l d be
expected to occur to a greater extent before hydro-
génation. Therefore, a lower isobutane/n-butane ratio
w o u l d be e x p e c t e d .
H o w e v e r , b u t a n e s a r e p r o d u c e d by c r a c k i n g r e a c -
t i o n s other than the p a r i n g r e a c t i o n . In reactions
s u c h a s p a r a f f i n c r a c k i n g , t h e same f a c t o r s t h a t f a v o r
a h i g h i s o p e n t a n e / n - p e n t a n e r a t i o and a h i g h
i s o p e n t a n e / n - p e n t a n e r a t i o and a h i g h i s o h e x a n e s /
n-hexanes r a t i o ( i . e . , h i g h a c i d i t y ) w i l l f a v o r a h i g h
isobutane/n-butane ratio.
T h e r e f o r e , we h a v e t w o e f f e c t s o n i s o b u t a n e /
η - b u t a n e r a t i o t h a t tend to o f f s e t each o t h e r . The
r e s u l t , w i t h t h e C a l i f o r n i a gas o i l , i s t h a t t h e r e i s

40 HYDROCRACKING A N D H Y D R O T R E A T I N G
l i t t l e e f f e c t o f c h a n g i n g a c i d i t y and h y d r o g é n a t i o n
a c t i v i t y on t h e i s o b u t a n e / n - b u t a n e ratio.
This r e l a t i o n s h i p w i l l vary w i t h the aromatic con-
t e n t of the feedstock. With a highly aromatic feed,
t h e c a t a l y s t w i t h t h e h i g h e r h y d r o g é n a t i o n a c t i v i t y may
give a higher isobutane/n-butane r a t i o , although with
the pentanes and hexanes the e f f e c t i s r e v e r s e d .
T o t a l L i q u i d (C5+) Y i e l d . Product molecules w i t h

c a r b o n numbers o f f i v e a n d h i g h e r c a n be c o m b i n e d i n a
f r a c t i o n r e f e r r e d t o as "C5+" l i q u i d p r o d u c t . This
f r a c t i o n i n c l u d e s the pentanes and a l l o f the p r o d u c t
b o i l i n g below the r e c y c l e cut p o i n t . The e x a m p l e s i n
T a b l e I I show t h a t t h e m o r e a c i d i c c a t a l y s t p r o d u c e s
l e s s p r o d u c t i n t h e C 5 + f r a c t i o n , more b u t a n e s a n d
p r o p a n e , and l e s s p r o d u c t i n the j e t f u e l b o i l i n g range
t h a n does t h e c a t a l y s t w i t h h i g h e r h y d r o g é n a t i o n
activity.
F i g u r e 4 shows t h a t t h e t o t a l C5+ y i e l d c a n be
r e l a t e d to the r a t i o of the isohexanes/n-hexane. No
r e s u l t s a r e i n c l u d e d f o r C a t a l y s t A a s no a n a l y s e s w e r e
a v a i l a b l e i n t h i s temperature range.
W i t h i n t h i s r e a s o n a b l y narrow temperature span
and w i t h p r e s s u r e and gas r a t e c o n s t a n t , t h e r e s u l t s
correlate quite well. The same g e n e r a l f a c t o r s w h i c h
contribute to a high t o t a l l i q u i d y i e l d also result i n
a l o w e r i s o - t o - n o r m a l r a t i o and v i c e v e r s a .
I t s h o u l d be e m p h a s i z e d t h a t i n a c t u a l p r a c t i c e i t
i s t h e maximum f i n i s h e d p r o d u c t r a t h e r t h a n t h e q u a n -
t i t y o f C5+ h y d r o c r a c k a t e t h a t i s t h e most c r i t i c a l
y i e l d a f f e c t i n g economic e v a l u a t i o n s o f h y d r o c r a c k i n g
catalysts. A p o r t i o n o f the hydrocracked naphtha i s
u s u a l l y c a t a l y t i c a l l y reformed to produce h i g h octane
gasoline. K i t t r e l l , S c o t t , and L a n g l o i s (19) p r e s e n t e d
and i n t e r p r e t e d r e s u l t s showing t h e optimum r e l a t i o n -
s h i p between h y d r o c r a c k i n g and r e f o r m i n g . Such a
r e l a t i o n s h i p c a n be u s e d i n c o n j u n c t i o n w i t h r e s u l t s
of the type d e s c r i b e d here to evaluate s p e c i f i c hydro-
cracking catalysts.
Jet Y i e l d . F i g u r e 5 shows t h e r e l a t i o n s h i p
b e t w e e n t h e y i e l d o f j e t ( a r b i t r a r i l y d e f i n e d as t h e
p r o d u c t b o i l i n g between 2 8 0 ° F and 5 5 0 ° F ) and the i s o -
to-normal r a t i o f o r the hexanes. Although there i s
more v a r i a t i o n h e r e t h a n shown f o r t h e t o t a l l i q u i d
y i e l d , t h i s e m p i r i c a l r e l a t i o n s h i p i s r e a s o n a b l y good
f o r most o f t h e c a t a l y s t s .
Preferential Poisoning of Catalytic Sites. In

order t o show t h a t y i e l d s a n d C s - 1 8 0 ° F o c t a n e n u m b e r s

• Catalyst A
• Catalyst Β
• Catalyst F
Ο Catalyst G
600 650 700

Figure 3. Effect of temperature on isobutane/n-butane hydrocracking

of California gas oil
% —
ο
95 —
94 —
T3 93
-a- LJa>
OJ
• Catalyst Β
Έ " 92 A Catalyst C
>- -c
•σ » 91 • Catalyst D
^ Catalyst Ε
cr 90 — • Catalyst F
I
— Ο Catalyst G
+ 89
Ο Rft I
10 15 20
I sohexanes/n-Hexane
Figure 4. Relationship between liquid yield and isohexanes/n-hexane at 590^615°F

hydrocracking of California gas oil

a r e d i r e c t l y r e l a t e d t o t h e hydrogénation t o a c i d i t y
r a t i o , s e v e r a l experiments were made w i t h C a t a l y s t C i n
which c a t a l y t i c s i t e s were p r e f e r e n t i a l l y p o i s o n e d .
N i t r o g e n (as q u i n o l i n e ) was used as a p o i s o n f o r a c i d
s i t e s ; s u l f u r (as d i m e t h y l d i s u l f i d e ) was used t o p o i s o n
the m e t a l hydrogénation s i t e s . Admittedly, either
p o i s o n may i n f l u e n c e b o t h s e t s o f c a t a l y t i c s i t e s some-
what; however, i t i s r e a s o n a b l e t o assume t h e s e s e c o n -
dary e f f e c t s would be r e l a t i v e l y minor.
T a b l e IV shows t h e r e s u l t s . When t h e a c i d i t y i s
p r e f e r e n t i a l l y p o i s o n e d by e q u i l i b r a t i n g t h e c a t a l y s t
w i t h a f e e d c o n t a i n i n g 8 ppm o f n i t r o g e n , t h e f o l l o w i n g
e f f e c t s are noted: (1) T o t a l l i q u i d y i e l d i n c r e a s e s by
about 1 wt %\ (2) t h e j e t f u e l i n c r e a s e s by 6 LV %\
(3) t h e C5-l80°P octane number d e c r e a s e s by two
numbers.
When t h e hydrogénation a c t i v i t y i s p r e f e r e n t i a l l y
p o i s o n e d by o p e r a t i n g w i t h 100 ppm o f s u l f u r i n t h e
f e e d , (1) t h e t o t a l l i q u i d y i e l d d e c r e a s e s by about 2%;
(2) t h e j e t f u e l d e c r e a s e s by 6-755; (3) t h e octane
o
number o f t h e C s - l 8 0 F p r o d u c t i n c r e a s e s by more than
t h r e e numbers.
C a t a l y s t Aging E f f e c t s . The y i e l d s f o r most o f

the c a t a l y s t s remain r e l a t i v e l y s t a b l e w i t h c a t a l y s t
aging. I n c o n s t a n t c o n v e r s i o n runs such as t h e s e , t h e
c a t a l y s t temperature i s i n c r e a s e d t o m a i n t a i n c o n v e r -
s i o n ; and y i e l d s t a b i l i t y can be shown by a p l o t o f
y i e l d v e r s u s average c a t a l y s t t e m p e r a t u r e . Figure 6
shows r e s u l t s f o r two amorphous c a t a l y s t s .
F i g u r e 7 shows t h e R e l a t i o n s h i p between C 5 + l i q u i d
y i e l d and isohexanes/n-hexane r a t i o i n t h e temperature
range 640-660°F. The r e l a t i o n s h i p i s s t i l l good f o r
most o f t h e c a t a l y s t s ; t h e average C 5 + y i e l d a t a g i v e n
isohexanes/n-hexane r a t i o i s perhaps 0.5% lower t h a n
t h a t shown i n F i g u r e 4 f o r t h e temperature range
590-6l5°F.
A n o t a b l e e x c e p t i o n t o t h e r e l a t i o n s h i p shown i n
Figure 7 i s C a t a l y s t Ε with a f a u j a s i t e support. In
t h e temperature span between 640°F and 660°F, t h e t o t a l
l i q u i d y i e l d decreases r a p i d l y without s i g n i f i c a n t
change i n t h e isohexanes/n-hexane ratio.
F i g u r e 8 shows t h e r e l a t i o n s h i p s between tempera
t u r e , C 5 + y i e l d , and j e t y i e l d f o r C a t a l y s t E. C 5 +
y i e l d i s r e l a t i v e l y s t a b l e t o 640°F; however, a s h i f t
i n p r o d u c t d i s t r i b u t i o n from j e t f u e l t o naphtha o c c u r s
between 6l0°F and 640°F.
Above 660°F ( o f f s c a l e i n t h e p l o t s i n F i g u r e s 7
and 8 ) , t h e C 5 + and j e t f u e l y i e l d c o n t i n u e t o d e c r e a s e
rapidly. At 677°F t h e C + l i q u i d y i e l d i s 80.4 wt %;
5
the 280-550°F j e t y i e l d i s 15.1 LV %.

TABLE IV
PRODUCT FROM CATALYST C

WITH CALIFORNIA GAS OIL -
EFFECTS OF SULFUR AND NITROGEN
C -180°F
5
Catalyst c+
5
280°F+ Octane,
Tempera- Isohexanes/ Yield, Yield, F-l
t u r e , °F n-Hexane Wt % LV % Clear
Before A d d i t i o n of 609 4.9 94.3 65.3 81.0

S u l f u r or N i t r o g e n 640 4.7 95.2 64.7 80.0
8 ppm N i t r o g e n Added 650 3.0 95.8 71.0 78.0

to Feed ( C a t a l y s t
Equilibrated)
100 ppm S u l f u r Added 620 12.7 92.7 58.3 84.2

to Feed ( A f t e r 170
Volumes of Feed
Containing Sulfur)

HYDROCRACKING A N D H Y D R O T R E A T I N G
100 r-
Catalyst Β Λ
95
Catalyst G
ΤΤΟ
90
85 JL
550 600 650 700

+
Figure 6. Effect of temperature on C liquid yield hydrocracking of Cali
5
fornia gas oil
644°F^ ι *641°F
*645°F
/
• Catalyst A
Î9°F • Catalyst Β
90h
A Catalyst C
$L Catalyst C + 8 ppm Ν in Feed
I * Catalyst Ε
• Catalyst F
652°F* Ο Catalyst G
Numbers by points for Catalyst Ε indicate temperatures.
l_ I I
5 10 15
I sohexanes/n-Hexane
+
Figure 7. Relationship between C yield and isohexanes/n-hexane 640^-660°F
5


The y i e l d s h i f t s f o r t h e s e f a u j a s i t e - c o n t a i n i n g
c a t a l y s t s a r e a c c o m p a n i e d by a b u i l d u p o f h i g h b o i l i n g
m a t e r i a l (650°F+) i n the l i q u i d r e c y c l e stream.
The s h a p e s e l e c t i v e p r o p e r t i e s o f t h e a g e d f a u j a -
s i t e c a t a l y s t appear to a f f e c t the product d i s t r i b u -
tion. Composition o f the r e c y c l e stream i n d i c a t e s the
r a t e o f r e a c t i o n o f the higher b o i l i n g molecules i s
very low. Because h i g h m o l e c u l a r weight molecules d i d
c r a c k more r e a d i l y i n t h e e a r l y p a r t o f t h e r u n , t h i s
r e s u l t suggests that deposits o f carbonaceous m a t e r i a l
("coke") cause p a r t i a l p l u g g i n g o f the c a t a l y s t p o r e s .
T h e r e f o r e , the l a r g e r m o l e c u l e s have l i m i t e d access t o
catalytic sites. The h i g h r a t e o f c o k i n g i n a n a r r o w
t e m p e r a t u r e r a n g e may b e r e l a t e d t o t h e h y d r o g e n a t i o n -
d e h y d r o g e n a t i o n e q u i l i b r i a o f c e r t a i n p o l y c y c l i c com-
pounds w h i c h , i f d e h y d r o g e n a t e d , a r e w e l l known c o k e
precursors.
The r a t e o f c a t a l y s t d e a c t i v a t i o n , a s m e a s u r e d b y
the temperature increase r e q u i r e d to m a i n t a i n conver-
s i o n , does n o t i n c r e a s e a p p r e c i a b l y d u r i n g t h e p e r i o d
that the y i e l d s h i f t occurs. The c a t a l y s t r e m a i n s
a c t i v e f o r the c r a c k i n g o f r e l a t i v e l y low b o i l i n g
molecules. However, the low y i e l d o f p r o d u c t i n the
j e t b o i l i n g range i n d i c a t e s t h a t , at the c o n v e r s i o n
l e v e l s u s e d , much i n i t i a l p r o d u c t f r o m t h e j e t b o i l i n g
range i s f u r t h e r c r a c k e d t o naphtha and l i g h t g a s e s .
The s e c o n d a r y c r a c k i n g o f p r o d u c t i n t h e j e t r a n g e may
be t h e r e s u l t o f s e v e r a l f a c t o r s : ( 1 ) The r a t e s o f
d i f f u s i o n o f j e t p r o d u c t o u t o f t h e c a t a l y s t may b e
s l o w due t o t h e p a r t i a l p o r e p l u g g i n g . The l o n g e r
r e s i d e n c e t i m e o f t h e j e t p r o d u c t p e r m i t s much s e c o n -
dary c r a c k i n g . (2) P a r t i a l p o r e p l u g g i n g does n o t
a l l o w a s many o f t h e h i g h e r b o i l i n g r e a c t a n t m o l e c u l e s
to reach the c a t a l y t i c s i t e s . Therefore, there i s
l e s s c o m p e t i t i o n f o r c a t a l y t i c s i t e s ; and the apparent
r a t e o f r e a c t i o n o f m o l e c u l e s i n t h e j e t r a n g e may
increase.
The c a t a l y s t a g i n g e f f e c t s s h o w n b y t h i s f a u j a -
s i t e c o n t a i n i n g c a t a l y s t a p p e a r t o be a g e n e r a l
phenomenon; s i m i l a r e f f e c t s have been o b s e r v e d i n o u r
l a b o r a t o r i e s w i t h o t h e r f e e d s t o c k s and o t h e r z e o l i t e -
containing catalysts. Other examples have been
reported i n the patent l i t e r a t u r e (20).
T h i s c a t a l y s t a g i n g p r o p e r t y does n o t n e c e s s a r i l y
make s u c h a c a t a l y s t u n a t t r a c t i v e . R a t h e r , i t may
l i m i t the temperature span i n which a d e s i r e d product
d i s t r i b u t i o n c a n be o b t a i n e d . W i t h most amorphous
c a t a l y s t s , a run i s u s u a l l y terminated at the p o i n t at
which c a t a l y s t a c t i v i t y and s t a b i l i t y are sufficiently
l o w t h a t c o n t i n u a t i o n o f t h e r u n i s no l o n g e r

attractive. With c e r t a i n z e o l i t e - c o n t a i n i n g catalysts,

the product d i s t r i b u t i o n may b e t h e l i m i t i n g factor.
Results With
Mid-Continent Gas O i l
C a t a l y s t C and C a t a l y s t G were compared f o r t h e

h y d r o c r a c k i n g o f t h e M i d - C o n t i n e n t gas o i l a t 4 0 0 ° F
r e c y c l e c u t p o i n t w i t h n a p h t h a as t h e m a j o r p r o d u c t .
Table I l i s t s the p r o p e r t i e s o f the h y d r o f i n e d
f e e d ; T a b l e V shows y i e l d s a n d p r o d u c t p r o p e r t i e s a t
comparable c o n d i t i o n s , and T a b l e V I g i v e s d e t a i l e d
chromatographic analyses of representative Cs-l80°F
products.
The t r e n d s a r e g e n e r a l l y t h e same a s t h o s e a t t h e
h i g h e r c u t p o i n t w i t h C a l i f o r n i a g a s o i l . The c a t a l y s t
w i t h the higher r a t i o of h y d r o g é n a t i o n a c t i v i t y to
a c i d i t y , C a t a l y s t C , p r o d u c e s more C 5 + n a p h t h a ; t h e
more h i g h l y a c i d i c c a t a l y s t , C a t a l y s t G , y i e l d s p r o d u c t
w i t h a h i g h e r octane number.
Conclusions
Most d u a l f u n c t i o n a l h y d r o c r a c k i n g c a t a l y s t s
e x h i b i t an i n v e r s e r e l a t i o n s h i p between C5+ l i q u i d and
t h e P - l c l e a r o c t a n e number o f t h e C 5 - C 6 p r o d u c t .
P r e f e r e n t i a l p o i s o n i n g o f e i t h e r the a c i d s i t e s or the
hydrogenation-dehydrogenation c a t a l y t i c sites indicates
t h a t b o t h the y i e l d s and octanes are r e l a t e d t o the
r a t i o o f h y d r o g é n a t i o n t o a c i d i t y p r o v i d e d by t h e c a t a -
lyst. A h i g h r a t i o favors h i g h l i q u i d y i e l d s ; a low
r a t i o favors h i g h octane product.
Some m o d e s t c h a n g e s i n t h e r e l a t i o n s h i p b e t w e e n
C5+ y i e l d a n d l i g h t n a p h t h a o c t a n e number o c c u r as
c a t a l y s t temperature i s i n c r e a s e d . Also, with certain
aged c a t a l y s t s s u c h as t h o s e c o n t a i n i n g f a u j a s i t e ,
changes i n c a t a l y s t geometry b r o u g h t about by p o r e
p l u g g i n g due t o c a r b o n a c e o u s d e p o s i t s may c a u s e s u b -
s t a n t i a l d e v i a t i o n s from t h i s r e l a t i o n s h i p .
Acknowledgment
The a u t h o r s w i s h t o t h a n k M e s s r s . G . E . Langlois
and C. J . Egan f o r t h e i r h e l p f u l s u g g e s t i o n s during
the course of t h i s work.
Abstract
Yields and product properties in hydrocracking are
influenced by the relationship between catalyst acidity
and the hydrogenation-dehydrogenation activity of the

TABLE V
Y I E L D S AND PRODUCT PROPERTIES FROM

HYDROCRACKING OF MID-CONTINENT GAS O I L
60% PER PASS CONVERSION BELOW 4 0 0 ° F
Catalyst C G
Average C a t a l y s t Temp., °F 6:!4 632
Wt % L V % Wt % L V %
No L o s s P r o d u c t Yields
( B a s e d on F r e s h Feed)
Methane 0.02 0.03
Ethane 0 . 04 0.09
Propane 1.7 2.4
Isobutane 7.5 11.4 9-5 14.4

n-Butane 2.1 3-1 2.9 4.2
C -l80°F
5 19.1 2 4 . 8 21.3 27.7
180-280°F 33-6 39-0 3 3 . 2 38.2
280-400°F 38.1 4 1 . 9 32.9 35.9
Total C -400°F
5 90.8 105.7 87.4 101.8
Chemical Hydrogen 1220 1245
Consumption, SCF/B
Product Properties
C -180°F
5
Octane N o . , F - l C l e a r 81.1 85.7

l80-400°F
Octane N o . , F - l C l e a r 45.3 55.2
Paraffins 40.5 37.8
Aromatics 0.5 6.1
ASTM D 86
Distillation, °F
St/5 220/236 214/228
10/30 242/264 235/255
50 288 279
70/90 318/356 309/350
95/EP 368/408 365/407

TABLE V I
D I S T R I B U T I O N OF C - l 8 0 ° F PRODUCT FROM
5
HYDROCRACKING OF MID-CONTINENT GAS O I L
Catalyst C G
Average C a t a l y s t
Temperature, °F 627 642
Product, LV % o f C - l 8 0 ° F
5
Butanes 0.8 0.2

Isopentane 36.6 44.6
n-Pentane 8.7 3.5

2 . 2 - DimethyIbutane 0.3 0.1
2.3- DlmethyIbutane 2.9 3.8
2- Methylpentane 16.9 19.5
3- M e t h y l p e n t a n e 10.1 11.2
n-Hexane 6.6 1.8
Isoheptanes 4.5 3.6
Total Paraffins 87.4 88.3
Cyclopentane 0.5 0.5

MethyIcyclopentane 9.1 8.4
Cyclohexane 0.9 0.7
Dlmethylcyclopentanes, 1.7 1.5
Ethylcyclopentane
MethyIcy clohexane 0.4 0.2
Total Cycloparaffins 12.6 11.3
Benzene - 0.3
Total Aromatics - 0.3
Octane No., F - l Clear 81.3 85-7
Isopentane/n-Pentane 4.2 12.7
Isohexanes/n-Hexane 4.6 19.2

dual functional catalysts employed. Hydrocracking

catalysts can be tailored to meet specific refining
objectives. In this paper both amorphous and crys
talline catalysts of varying acidity and hydrogenation
activity are examined at constant process conditions
for (1) producing both jet fuel and gasoline and
(2) producing gasoline as the major product. In
general, as the hydrogenation activity of the catalyst
is increased relative to its acidity, total liquid
product (C5+) yield increases; and the octane number of
the light naphtha (C5-C6) decreases. The reverse is
also true. If either the acidity or hydrogenation
activity is preferentially poisoned, the change is
reflected in the yields and the C5-C6 octane number.
Literature Cited
1. Scott, J . W., and Kittrell, J. R., Ind. Eng.

Chem. (1969), 61, 18.
2. Baral, W. J., and Huffman, H. C., World
Petroleum Congress, Preprint PD 12 (1), (1971).
3. Hansford, R. C., U.S. Patent 3,499,835 (March 10,
1970).
4. Beuther, Η., and Larson, O. Α., Ind. Eng. Chem.
Proc. Design Dev. (1965), 4, 177.
5. Voorhies, Α., and Smith, W. Μ., Chapter in
"Advances in Petroleum Chemistry and Refining,"
Vol 8, ρ 1693 Interscience Publishers, New York
(1964).
6. Larson, O. Α., MacIver, D. S., Tobin, H. H., and
Plinn, R. Α., Ind. Eng. Chem. Proc. Design Dev.
(1962), 1, 300.
7. Langlois, G. E., Sullivan, R. F., and Egan, C. J.,
J. Phys. Chem. (1966), 70, 3666.
8. Doane, E. P., Preprints, Div. Petroleum Chem.,
(1967), ACS 12, (4), B-139.
9. Coonradt, H. L., and Garwood, W. E., Ind. Eng.
Chem. Proc. Design Dev. (1964), 3, 38.
10. Langlois, G. E., and Sullivan, R. F., Advances in
Chemistry Series No. 97, "Refining Petroleum for
Chemicals," Chapter 3, p 38, ACS (1970).
11. Beuther, H., McKinley, J. Β., and Flinn, R. Α.,
Preprints, Div. Petroleum Chem., (1961), ACS 6,
(3), A-75.
12. Coonradt, H. L., Ciapetta, F. G., Garwood, W. Ε.,
Leaman, W. Κ., and Maile, J. N., Ind. Eng. Chem.
(1961), 53, 727.
13. Coonradt, H. L., Leaman, W. Κ., Maile, J. Ν.,
Preprints, Div. Petroleum Chem., (1964), ACS 9,
(1), 59.

2. SULLIVAN AND MEYER Catalyst Effects 51
14. Coonradt, H. L., and Garwood, W. Ε . , Preprints,
D i v . P e t r o l e u m Chem., ( 1 9 6 7 ) , ACS 12 (4), B - 4 7 .
15. S c h u l z , H., and Weitkamp, J., I n d . Eng. Chem.
Prod. Res. Develop., ( 1 9 7 2 ) , 11 ( 1 ) , 46.
16. Myers, C. G., Garwood, W. Ε . , Rope, B. W.,
W a d l i n g e r , R. L., and Hawthorne, W. P., J. Chem.
Eng. Data ( 1 9 6 2 ) , 7 , 257.
17. Egan, C. J., L a n g l o i s , G. Ε . , and White, R. J.,
J . Am. Chem. Soc., ( 1 9 6 2 ) , 84, 1204.
18. S u l l i v a n , R. F., Egan, C. J., and L a n g l o i s , G. E . ,
J . C a t a l y s i s ( 1 9 6 4 ) , 3 , 183.
19. Kittrell, J . R., L a n g l o i s , G. E . , and S c o t t ,
J . W., Hydrocarbon P r o c e s s ( 1 9 6 9 ) , 48, (5), 116.
20. Hanson, F. V., and Snyder, P. W., U.S. P a t e n t
3 , 5 2 3 , 8 8 7 (August 1 1 , 1 9 7 0 ) .

3
Raflinate Hydrocracking with Palladium-Nickel-
Containing Synthetic Mica-Montmorillonite Catalysts
a
JOSEPH P. GIANNETTI and DONALD C. FISHER
Gulf Research and Development Co., P. O. Drawer 2038, Pittsburgh, Penn. 15230
The demand for liquefied petroleum gas (LPG; consisting of

propanes and butanes) is projected to increase rapidly in future
years.(1) World consumption is dominated by the United States and
Japan. Processing of natural gas accounts for the bulk of domes-
tic LPG; however, natural gas production has leveled off forcing
the LPG industry to examine other feedstock sources. Japan must
look to other countries for future LPG supplies due to environ-
mental and space limitations. An allied problem, especially in
the United States, is the continuing need for isobutane to pro-
duce valuable alkylates for the gasoline pool.
A recent publication(2) disclosed the use of a palladium—
impregnated, nickel-exchanged synthetic mica-montmorillonite
catalyst (Pd-Ni-SMM), a 2:1 layer lattice aluminosilicate clay,
for the hydrocracking and hydroisomerization of various hydro-
carbons including a raffinate fraction to predominately propane
and butanes. The results showed that these SMM based catalysts
exhibited hydrocracking and hydroisomerization activities greater
than could be obtained with Pd-rare earth-zeolite or Pd-H—
mordenite. It had earlier been shown that SMM had greater
cracking activity than silica-alumina but less than Y zeolite. (_3)
The greater activity for cracking over the silica-alumina may be
due to the increased lability of the hydrogen atoms in SMM.(4)
Our study was undertaken specifically to investigate the
processing of a typical raffinate to produce either high yields
of LPG or isobutane as well as to determine the octane improve-
ment in the fraction due to hydroisomerization. A 0.7 wt %
Pd-15 wt % Ni-SMM catalyst was used for all the experimentation.
Experimental
A l l u n i t s are expressed i n both the customary u n i t s as w e l l

as the "SI" I n t e r n a t i o n a l System of U n i t s . The "SI" designated i s
shown f i r s t followed by the customary u n i t s i n p a r e n t h e s i s .
(a) Present Address - Alcoa Research L a b o r a t o r i e s ,

New Kensington, PA 15068
52

3. GiANNETTi A N D FISHER Raffinate Hydrocracking 53
Materials. The r a f f i n a t e used i n t h i s study was obtained

from a commercial Gulf O i l Corporation r e f i n i n g run and used as
received. The composition of t h i s r a f f i n a t e i s shown i n Table I .
The 15 wt % Ni-exchanged SMM c a t a l y s t s were obtained from
the Baroid D i v i s i o n of NL I n d u s t r i e s . The carbon d i s u l f i d e was
obtained from F i s h e r S c i e n t i f i c while the palladium tetramine-
d i n i t r a t e reagent (36.5 wt % palladium) was purchased from
Matthey Bishop C o r p o r a t i o n . Hydrogen s u l f i d e was obtained from
the Matheson Gas Company. A l l the chemical reagents were used
as r e c e i v e d . Hydrogen, supplied by the A i r Reduction Company,
was deoxygenated and d r i e d over Linde 13X molecular s i e v e s .
C a t a l y s t P r e p a r a t i o n and Processing Procedure. The 15 wt %

Ni-SMM c a t a l y s t was impregnated with the palladium tetramine-
d i n i t r a t e reagent by the i n c i p i e n t wetness technique to r e s u l t
i n the i n c o r p o r a t i o n of 0.7 wt % p a l l a d i u m . Since the 15 wt %
nickel-exchanged SMM c a t a l y s t was obtained from the Baroid

D i v i s i o n of NL I n d u s t r i e s , no exact d e t a i l e d synthesis was ob
t a i n e d ; however, a t y p i c a l synthesis from our l a b o r a t o r i e s has
been d e t a i l e d . ( 2 ) A l l c a t a l y s t s were e i t h e r reduced or s u l f i d e d
3
p r i o r to use. Approximately 50 cm of c a t a l y s t d i l u t e d w i t h
3
50 cm quartz was used for each r u n . The r e d u c t i o n c o n s i s t e d of
- 3
1) t r e a t i n g the c a t a l y s t with 3.5 χ 1 0 kmol H2/hr (2.9 SCF
H2/hr) at atmospheric pressure while heating to 538°C (1000 F) at
a r a t e of 6 5 . 6 ° C / h r ( 1 5 0 ° F / h r ) , 2) h o l d i n g at 5 3 8 ° C ( 1 0 0 0 ° F ) with
the hydrogen flow f o r 1 hour, and 3) c o o l i n g to room temperature
with a small n i t r o g e n flow. The s u l f i d i n g c o n s i s t e d of 1)
heating the c a t a l y s t to 3 1 6 ° C ( 6 0 0 ° F ) i n n i t r o g e n , 2) s u l f i d i n g
3
for 3 hours at 3 1 6 ° C ( 6 0 0 ° F ) with 3.6 χ 10" kmol/hr (3 SCF/hr)
of a 92% H2-8% H2S gas mix, and 3) c o o l i n g i n n i t r o g e n to room
temperature. The Ni-SMM c a t a l y s t s received contained e i t h e r
about 1 wt % or 0.6 wt % f l u o r i d e . Some i n i t i a l processing com
parisons d i d not show one to be s i g n i f i c a n t l y d i f f e r e n t from the
other. Thus, no separation of the runs by f l u o r i d e l e v e l ap
peared necessary.
Processing runs were conducted i n a fixed-bed automated u n i t
employing a 2.54 cm (1-inch) ID r e a c t o r i n r o u n d - t h e - c l o c k
U
operations. Operating c o n d i t i o n s were 316" to 399 C (600" to
7 5 0 ° F ) , 7,000 k i l o p a s c a l s : kPa (1,000 l b / s q i n gauge: p s i g ) , 1.2
3
to 2 l i q u i d hourly space v e l o c i t y (LHSV) defined as cm of hydro
3
carbon feed per cm of c a t a l y s t per hour, and 5 hydrogen-to-
hydrocarbon mole r a t i o (to c a l c u l a t e t h i s r a t i o , the feed was
assumed to have a molecular weight of 92). Temperatures were
measured by thermocouples extending through the c a t a l y s t bed.
S u l f u r , i n the form of carbon d i s u l f i d e , was added to the
r a f f i n a t e to give the d e s i r e d s u l f u r l e v e l . The l i q u i d feed was
combined with hydrogen, preheated, and passed downflow through
the c a t a l y s t . The e f f l u e n t from the reactor entered a high
pressure separator where a hydrogen-rich gas sample was taken.
The hydrocarbon product from the separator flowed i n t o a

Table I
RAFFINATE ANALYSIS
Component Wt %
Isopentane 0.2
n-Pentane 0.2
Hexane Isomers 19.8

n-Hexane 14.6
Methylcyclopentane 4.6
Cyclohexane 0.4
Benzene 1-0
Heptane Isomers 31.5

n-Heptane 9.7
Dimethylcyclopentane 0.5
Cg and Heavier 17.5

3. GiANNETTi A N D FISHER Raffinate Hydrocracking 55
s t a b i l i z e r where a C4 and l i g h t e r gaseous product and a C5 and
heavier l i q u i d product were taken. The gaseous products were
metered and sampled, while the l i q u i d product was c o l l e c t e d ,
weighed, and sampled.
Analyses. Hydrocarbon analyses for the gaseous products

were made using a 1200 Varian gas chromatograph with a 30.5 m
(100 f t ) support coated open tubular squalene c a p i l l a r y and a
21-104 Consolidated Electrodynamics Corp. mass spectrometer.
T h i s combination a n a l y s i s was necessary i n order to a c c u r a t e l y
determine both the hydrogen and hydrocarbon content of the gas
as w e l l as a d e n s i t y . The l i q u i d samples only r e q u i r e d analyses
by the c a p i l l a r y column gas chromatograph.
Micro Research octane numbers were obtained using the s t a n -
dard CFR (Cooperative F u e l Research) knock r a t i n g u n i t .
Results and D i s c u s s i o n
Previous r e s u l t s ( 2 ) had shown that a Pd-Ni-SMM c a t a l y s t was

e f f e c t i v e f o r hydrocracking hexane as w e l l as a r a f f i n a t e feed.
Conclusions showed that t h i s c a t a l y s t system when c o n t a i n i n g two
n i c k e l atoms per u n i t c e l l (15 wt % n i c k e l ) was approximately
15 times more a c t i v e than a P d - r a r e earth-Y z e o l i t e c a t a l y s t and
1.2 times more a c t i v e than Pd-H-mordenite. T h i s same c a t a l y s t
system (0.7 wt % Pd-15 wt % Ni-SMM) was chosen for our r a f f i n a t e
processing s t u d i e s .
Comparison of S u l f u r - C o n t a i n i n g and S u l f u r - F r e e Systems.

Our i n i t i a l experimentation was designed to show the e f f e c t s of
a scheme c o n t a i n i n g l a r g e amounts of s u l f u r as opposed to a
completely s u l f u r - f r e e system. This experimentation was p e r -
formed with a s u l f i d e d 0.7 wt % Pd-15 wt % Ni-SMM c a t a l y s t
(hereafter r e f e r r e d to Pd-Ni-SMM c a t a l y s t ) using a r a f f i n a t e
feed c o n t a i n i n g 1500 ppm s u l f u r and a hydrogen reduced Pd-Ni-SMM
c a t a l y s t with a s u l f u r - f r e e feed. The LPG y i e l d s are presented
i n F i g u r e 1 with the average product component d i s t r i b u t i o n s at
3 7 1 ° C ( 7 0 0 ° F ) presented i n Table I I . These r e s u l t s showed that
the s u l f u r - c o n t a i n i n g system was more a c t i v e f o r hydrocracking
but experienced aging e s p e c i a l l y at the elevated temperatures.
The isobutane y i e l d was constant i n both systems r e s u l t i n g i n
s i g n i f i c a n t l y higher 1 0 4 / ^ 4 and ÎC4/LPG volume r a t i o s i n the
s u l f u r - f r e e system. Although converting more of the feed, the
s u l f u r - c o n t a i n i n g system produced s i g n i f i c a n t l y l e s s C^ + C2
than the s u l f u r - f r e e system.
Various Methods of I n c o r p o r a t i n g S u l f u r . The g e n e r a l l y

poorer r e s u l t s f o r LPG from the s u l f u r - f r e e system i n d i c a t e d that
s u l f u r should be incorporated at l e a s t somewhere i n the p r o -
c e s s i n g system. To determine whether best r e s u l t s are obtained
with s u l f i d i n g o n l y , s u l f u r feed a d d i t i o n o n l y , or b o t h , a s e r i e s

1 1 1 I —ι r - •••
399 ° C
100
(750°F)
3*
\ -
g 90
·-· 0
371 ° C
( 7 0 0 ° F)
Ο ° ΟΟ-ο °
•
343 ° C
( 6 5 0 ° F)
ο ι ι
ι I I I
0 100 200 300
HOURS PROCESSING
Figure 1. Effect of sulfur in Pd-Ni-SMM raffinate

hydrocracking. 7000 kPa (1000 psig), 2 LHSV, 5
ra
hydrogen-to-hydrocarbon mole ratio. Feed—O* ff^~
note; Φ, raffinate + 1500 ppm sulfur. Catalyst—O,
reduced 0.7 wt % — 15 wt % Ni-SMM; · , sulfided
0.7 wt% -15wt% Nir-SMM.
Table I I
EFFECT OF SULFUR IN Pd-Ni-SMM RAFFINATE HYDROCRACKING

Average Product D i s t r i b u t i o n s at 371°C ( 7 0 0 ° F ) ,
7,000 kPa (1,000 p s i g ) , 2 LHSV, 5 Hydrogen-to-
Hydrocarbon Mole Ratio
Vol % Y i e l d Based on Feed
Sulfur Sulfur
Component Containing Free
Methane + Ethane (Wt %) 3.2 4.7

Propane 46.8 37.5
Isobutane 28.4 28.5
n-Butane 18.9 11.7
C5 and Heavier 27.0 37.2
C3/C4 Ratio 1.0 0.93

iC^/nC^ Ratio 1.5 2.4
i C / L P G Ratio
4 0.30 0.37

3. GIANNETTI A N D FISHER Raffinate Hydrocracking 57
of c a t a l y s t s was treated and t e s t e d . The r e s u l t s are presented

i n Table I I I . The f i r s t two runs (A and B) have already been
discussed (Figure 1, Table II) and show the e f f e c t of a s u l f u r -
f r e e system and a s u l f i d e d c a t a l y s t along w i t h s u l f u r doping of
the feed. Run C shows that a reduced c a t a l y s t with s u l f u r i n the
feed ( i n - s i t u s u l f i d i n g ) was g e n e r a l l y comparable to a s u l f i d e d
c a t a l y s t with the feed s u l f u r (Run Β with compensation made f o r
aging). F i n a l l y , a s u l f i d e d c a t a l y s t (Run D) with no feed s u l f u r ,
while a c t i v e , produced high C3 and C i + C2 y i e l d s . I t appears
from t h i s that whether the c a t a l y s t was reduced or s u l f i d e d had
l i t t l e e f f e c t on product d i s t r i b u t i o n i f s u l f u r was present i n
the feed.
E f f e c t of Feed S u l f u r L e v e l on S u l f i d e d C a t a l y s t s . The im

portance of s u l f u r i n the feed l e d to examining v a r y i n g s u l f u r
levels. P r i o r to t h i s i n v e s t i g a t i o n , a l l s u l f u r doping was at
the 1500 ppm l e v e l . During t h i s i n v e s t i g a t i o n an extended run

was made i n which the s u l f u r i n the feed was incorporated at
0 ppm, 75 ppm, 200 ppm, and f i n a l l y 500 ppm. The r e s u l t s are
presented i n Figures 2, 3, and 4. Looking f i r s t at F i g u r e 2,
i t can be seen that the e n t i r e product d i s t r i b u t i o n remained
constant at a high 108 v o l % LPG l e v e l through the 200 ppm
doping. When the s u l f u r l e v e l increased to 500 ppm, however,
pronounced aging began. This aging was accompanied by a de
crease i n C 3 , n C 4 , and C^ + C2 y i e l d s , and an increase i n 1C4
and C5+ y i e l d s . A c t u a l l y , i f one assumes that i C 4 i s the most
v a l u a b l e hydrocracked product, the d i s t r i b u t i o n became more
favorable as the c a t a l y s t aged. This i s more d r a m a t i c a l l y shown
i n F i g u r e 3 where v a r i o u s product r a t i o s are presented. The
increase i n 1C4 accompanied by decreases i n the nC4 and C3 y i e l d s
brought about a more favorable C 3 / C 4 , i C 4 / n C 4 and 1C4/LPG r a t i o s .
T h i s i n d i c a t e s that the LPG composition can probably be a l t e r e d
with processing s e v e r i t y . Thus i f one wished to produce maximum
per pass C 3 , high processing s e v e r i t y should be employed while
i f 1C4 y i e l d i s to be maximized, a lower processing s e v e r i t y
would be i n o r d e r .
No mention has yet been made of the C 5 m a t e r i a l . +
Since the
feed was e s s e n t i a l l y C 6 , the C 5 s were formed from h y d r o c r a c k i n g ;
+
f
however, they have been included i n with the C 6 m a t e r i a l s i n c e +
they would not normally be separated out but would e i t h e r be

r e c y c l e d with the C 6 for f u r t h e r h y d r o c r a c k i n g , o r , i n a once-
+
through o p e r a t i o n , be perhaps added with the C 6 to the g a s o l i n e

+
pool. One t h i n g that occurred to both the C 5 s formed and tof
the remaining C 6 s was that there was a high r a t i o of the branched

?
isomers to t h e i r normal c o u n t e r p a r t s . These r e s u l t s are i n

keeping with those of Swift and Black(_2) who showed that Pd-Ni-SMM
c a t a l y s t s are very e f f e c t i v e f o r h y d r o i s o m e r i z a t i o n . F i g u r e 4
d e t a i l s the i C 5 / n C 5 and i C 5 / n C 6 r a t i o s . The i C 5 / n C 5 r a t i o was
r e l a t i v e l y constant at about 2.4 i n the product while the
iCfc/nCfc r a t i o increased from a feed l e v e l of 1.4 to between

Table I I I §5
EFFECT OF VARIOUS MEANS OF INCORPORATING SULFUR ON HYDROCRACKING

Conditions — 371°C (700°F), 7,000 kPa (1,000 p s i g ) , 2 LHSV
5 Hydrogen-to-Hydrocarbon Mole Ratio
Catalyst — 0.7 Wt % Pd-15 Wt % Ni-SMM
Wt % Y i e l d Volume % Y i e l d
+
C a t a l y s t Treatment Ci + C 2 Ç3 1C4 nC/, T o t a l LPG c 5
(A) Reduction (1,000 F ) , No S u l f u r 4.7 37.5 28.5 11.7 77.7 37.2
(B) S u l f i d i n g (600 F ) , 1500 ppm S u l f u r 3.2 46.8 28.4 18.9 94.1 27.0
(2.6) U ) (53) (33) (20) (106) (18)
(C) Reduction (1,000 F ) , 1500 ppm S u l f u r 2.2 51.2 31.8 16.8 99.8 22.9
(D) S u l f i d i n g (600 F ) , No S u l f u r 5.2 63.0 26.8 18.0 107.8 14.1

ο
(a) Numbers i n parenthesis estimated at i n i t i a l throughputs p r i o r to aging. >

GiANNETTi A N D FISHER Raffinate Hydrocracking
^•·· ·,·-··· I * * " · " " · - - · & , VOL ?{|
i n J 0 AO-o-o-o 4 i C V O L
*
Ο-οΌθΌ-ΟΟ-Ο-Ο-αο-0-Ο-ΟΟ __ C D 5
+
VOL%
n C VOL%_|
4
Cj + CgWT%
J
ο
>
105
ι ' ' * \
0 PPM S I 75 PPM S I 200 PPM SI 500 PPM S ^
200 300 400 700

HOURS PROCESSING
Figure 2. Effect of sulfur level in product yields from hydro

cracking. 371°C (700°F), 7,000 kPa (1000 psig), 2 LHSV,
5 hydrogen-to-hydrocarbon mole ratio. 0.7 wt % Pd — 15
wt % Ni-SMM, sulfided.
O 0.4 ' π -ι—- π Γ -

<
Œ
0.3
_j Ω 0(
Ο ^0-ΟΌΟΌ-Ό-Ό ^°0- - ^
> 0.2 0
' ' I
I I
0.1
1.6
2 1.4
<
Œ
1.2 ι ' \
_J 1
Ο 0 PPM S 75 PPM S |200 PPM S Q ^ 500 PPM S
Ο ! I ! ÔOô
ϋ" 0.8
100 200 300 400 500 600 700
HOURS PROCESSING
Figure 3. Effect of sulfur level in product ratios from

hydrocracking. 37ΓC (700°F), 7000 kPa (1000 psig),
2 LHSV, 5 hydrogen-to-hydrocarbon mole ratio. 0.7
wt% Pd — 15 wt % Nir-SMM, sulfided.

3 and 5 i n the product. The maximum iC6/nC6 r a t i o occurred when

the s u l f u r l e v e l was at 75 ppm and 200 ppm s u l f u r . An increase
i n the C5"*" octane number most l i k e l y d i d occur. A d d i t i o n a l i n
+
formation on t h i s C 5 upgrading i s presented l a t e r i n conjunction
with the production of maximum isobutane y i e l d s .
E f f e c t of Feed S u l f u r L e v e l on a Reduced C a t a l y s t . I t has

been shown i n Table I I I that g e n e r a l l y comparable r e s u l t s were
obtained with a sulfur-doped feed and e i t h e r a reduced or s u l
fided catalyst. To see i f the reduced c a t a l y s t had the same
response to s u l f u r l e v e l as the s u l f i d e d c a t a l y s t shown i n
Figure 2, a run was performed with a 200 ppm and 500 ppm s u l f u r
level. Results are presented i n F i g u r e 5 where comparisons are
made to the s u l f i d e d c a t a l y s t . Since the reduced c a t a l y s t was
not run at 0 and 75 ppm s u l f u r , the data are l i n e d up at the
comparable s u l f u r l e v e l s but not throughputs. The reduced
c a t a l y s t followed the same p a t t e r n as the s u l f i d e d c a t a l y s t , i.e.,

no n o t i c e a b l e aging at 200 ppm but aging at 500 ppm. Expectedly,
the reduced c a t a l y s t became s u l f i d e d during the i n i t i a l p r o
c e s s i n g stages. The i n d i c a t i o n that the s u l f i d e d c a t a l y s t was
more a c t i v e should not be considered s i g n i f i c a n t since a 3 to 4
v o l % d i f f e r e n c e i n LPG y i e l d could e a s i l y be due to s l i g h t
f l u c t u a t i o n s i n the processing c o n d i t i o n s .
Isobutane P r o d u c t i o n . The importance of isobutane domes

t i c a l l y prompted experimentation aimed at maximizing the i s o -
butane y i e l d . I n d i c a t i o n s had been obtained from Figures 2 and 3
and discussed p r e v i o u s l y that as the c a t a l y s t aged, isobutane
y i e l d s increased (at the expense of propane). I t appeared l i k e l y
that processing at l e s s severe c o n d i t i o n s would be b e n e f i c i a l
towards i n c r e a s i n g isobutane y i e l d s .
Several runs i n the 3 1 8 ° - 3 2 9 ° C ( 6 0 5 ° - 6 2 5 ° F ) , 1.2-2 LHSV
range were performed. Results as presented i n Figures 6 and 7,
show that high y i e l d s of isobutane, as high as 50 v o l %, can be
obtained. In comparing the r e s u l t s from Figure 6 with F i g u r e 2
from the more severe c o n d i t i o n s f o r LPG maximization, the i n
creased y i e l d of isobutane was p r i m a r i l y at the expense of
propane with η - b u t a n e y i e l d s being v i r t u a l l y i d e n t i c a l at the
two c o n d i t i o n s . I t i s p o s s i b l e that other sets of c o n d i t i o n s ,
for example, 307°C (585 F) and 1 LHSV would produce even higher
LPG y i e l d s .
In t h i s processing to maximize isobutane y i e l d s , a s i g n i f i
cant amount of normally l i q u i d product remained ( e . g . 40 v o l %
f !
based on f e e d ) . The i s o - t o - n o r m a l r a t i o s from the C 5 s and C 6 s
are presented i n F i g u r e 8. The same type r e l a t i o n s h i p as p r e
v i o u s l y shown i n F i g u r e 4 for LPG maximization r e s u l t e d , e . g . ,
a high iC5/nC5 r a t i o and a iCfc/nCô r a t i o of 4-5 as compared to
1.4 f o r the feed. The r e s u l t s i n d i c a t e d that t h i s total
f r a c t i o n should have a s i g n i f i c a n t l y higher octane number than
+ 4
the C 6 feed. This was indeed the case as the product C^ " RON,

GiANNETTi A N D F I S H E R Raffinate Hydrocracking
1 1 I ι I I I ι
0 PPM S 1 75 Ρ RM S 200 PPM S 500 PPM S
1 ' i C c / n C e , FEED= 1.4

5.0
l° 1
-°°o o°
1
o
4.0
° ο ϋ
ο
ο I
%
3.0
Ο ι
i :t -
• · ι'· · · · · ·
A · ·
2.0 -
r · ·
1
'C MC
5 S
0 100
ι
200
I
300
I 400
ι 500 600 700
ι 1 1 1
HOURS PROCESSING
Figure 4. Effect of sulfur level on isomer distribu

tions. 371°C (700°F), 7000 kPa (1000 psig), 2 LHSV,
5 hydrogen-to-hydrocarbon mole ratio. 0.7 wt % Pd
— 15wt% Nir-SMM, sulfided.
I· · Ο
0 PPM S 75 PPM S j 200 PPM S , 500 PPM S Ο
25 100 200 300
300 400 500 600
HOURS PROCESSING
Figure 5. Effect of sulfur level and catalyst treatment on LPG

yields from hydrocracking. 371°C (700°F), 7000 kPa (1000 psig),
2 LHSV, 5 hydrogen-to-hydrocarbon mole ratio. O, reduced 0.7 wt
% Pd- 15wt% Ni-SMM; m, sulfided 0.7 wt % Pd - 15 wt %
Ni-SMM.

50h
o—O—v.
• •"
40
O
>
o—o-
329 °C ( 6 2 5 ° F), 329 °C ( 6 2 5 ° F), 318 ° C ( 6 0 5 ° F),

2 LHSV
·
1.2 LHSV 1.2 LHSV
g 20 9
9
• C
3 O i C
4 3 n C
4 • C
5 +
C^C =
2 ~
0.8 to 1.2 WT % T H R O U G H O U T
50 100 150 200 250 300 350 400

HOURS PROCESSING
Figure 6. Product distribution in hydrocracking for maximum iso-

butane yields. 7,000 kPa (1,000 psig), 5 hydrogen-to-hydrocarbon
mole ratio, 200 ppm sulfur in feed. 0.7 wt % Pd — 15 wt %
Ni-SMM, sulfided.
329 °C ( 6 2 5 ° F ) , 329 °C (625 ° F ) , 318 °C (605 ° F ) .

2 LHSV 1.2 LHSV 1.2 LHSV
150 200 250 300 350 400
HOURS PROCESSING
Figure 7. Product ratios in hydrocracking for maxi-

mum isobutane yields. 7,000 kPa (1,000 psig), 5 hy-
drogen-to-hydrocarbon mole ratio, 200 ppm sulfur in
feed. 0.7 wt % Pd — 15 wt % Nir-SMM, sulfided.

GIANNETTT A N D FISHER Raffinate Hydrocracking
329 ° C (625 ° F ) , 329 °C (625 ° F ) , 318 ° C (605 ° F ) ,

2 LHSV 1.2 L H S V 1.2 LHSV
τ τ- —ι 1 1 r—
5.0 iCg/nCg, F E E D = 1.4

Ο — Ο
Ο
Ο Ο
Ο
O ~°
4.0
3.0 iC /nC 5 5
•
• •
• é
2.0
1 I 1 1_
• ·
0 50 100 150 200 250 300 350 400
HOURS PROCESSING
Figure 8. Isomer distributions in products from

hydrocracking for maximum isobutane yields. 7,000
kPa (1,000 psig), 5 hydrogen-to-hydrocarbon mole
ratio, 200 ppm sulfur in feed. 0.7 wt % Pd — 15
wt % Ni-SMM, sulfided.

+
clear, was about 80 while the C6 feed was only 54. Thus, a
significant upgrading of the normally liquid portion of the +
product over the feed was obtained. This C5 fraction could
have application as a blending component to the gasoline pool.
By process manipulations, it would be possible to alter the
+
isobutane-C5 yield octane to meet specified needs.
Acknowledgement
The authors would like to express their appreciation to
Dr. Sun W. Chun of Gulf Research & Development Company for his
interest and timely suggestions.
Abstract
High yields of LPG or isobutane and octane improvement of
the C5+ fraction can be simultaneously obtained by hydrocracking

raffinate over a palladium-impregnated, nickel-substituted
synthetic mica-montmorillonite catalyst (0.7 wt % Pd-15 wt %
Ni-SMM). A critical sulfur level of about 100 to 200 ppm in the
feed is essential to combine the features of desired product
yields and good aging characteristics. Processing conditions
ranged from 316° to 339°C (600° to 750°F), 7,000 kilopascals
(1,000 psig), 1.2 to 2.0 LHSV and 5 hydrogen-to-hydrocarbon mole
ratio with the lower temperatures allowing the high isobutane
yields and the higher temperatures maximizing the total LPG
yields. No significant aging was observed over 20 days pro-
cessing as the sulfur level in the feed was increased to 200 ppm.
Literature Cited
(1) Muse, T. P., Hydrocarbon Proc., (1974), 53, 5, 85.
(2) Swift, H.E., and Black, E.R., Ind. Eng. Chem., Product Res.
Develop., (1974), 13, 106.
(3) NL Industries, Baroid Division Brochure Introducing
Barasym SMM.
(4) Hattori, H., Milliron, D. C., and Hightower, J. W., Division
of Petroleum Chemists Inc., Preprints, 165th National
Meeting of the American Chemical Society, Dallas, Texas,
(April, 1973), Vol 18, pp 33-51.

4
Hydrocracking Condensed-Ring Aromatics
Over Nonacidic Catalysts
WEN-LUNG W U and HENRY W. HAYNES, JR.

Department of Chemical Engineering, University of Mississippi, University, Miss.
38677
In recent years as the shortage o f domestic petroleum has

become e v i d e n t , the l i q u e f a c t i o n o f c o a l has r e c e i v e d serious
a t t e n t i o n as an a l t e r n a t i v e source o f clean liquid f u e l s . Re-
search e f f o r t s have g e n e r a l l y concentrated upon e i t h e r o f two
objectives: E a r l i e r i n v e s t i g a t i o n s were d i r e c t e d toward the
production o f a "synthetic crude" from c o a l . This m a t e r i a l could
then be processed i n a (more or l e s s ) conventional petroleum r e -
f i n e r y to yield a wide range o f products from g a s o l i n e to heavy
fuel oils. More recent e f f o r t s have concentrated upon c o a l
l i q u e f a c t i o n as a means o f producing a "solvent r e f i n e d c o a l " ,
i.e. a product low i n s u l f u r content and s u i t a b l e f o r use as a
f u e l to an electric power p l a n t . The p r i n c i p a l f a c t o r which d i s -
t i n g u i s h e s between the s y n t h e t i c crude and solvent r e f i n e d c o a l
processes i s the amount of hydrogen added during the l i q u e f a c t i o n
and subsequent processing s t e p s . A s y n t h e t i c crude must contain
somewhere i n the neighborhood o f 11-14% hydrogen if it i s t o be
processed by conventional petroleum r e f i n e r y techniques. On the
other hand s u b s t a n t i a l d e s u l f u r i z a t i o n can be accomplished i f
hydrogen i s added to the c o a l t o the extent of only one or two
per cent t o produce a product c o n t a i n i n g 6-7% hydrogen. The
hydrogen generating cost i s of course a major f a c t o r i n the
economics of a s y n t h e t i c f u e l s p l a n t .
In p r i n c i p l e it i s p o s s i b l e to produce g a s o l i n e and s i m i l a r
products from c o a l without consuming huge q u a n t i t i e s o f hydrogen.
To illustrate, we can compare the H/C atom r a t i o s f o r a h i g h
v o l a t i v e bituminous c o a l (0.8) with those f o r benzene ( 1 . 0 0 ) ,
toluene ( 1 . 1 4 ) , and mostly p a r a f f i n i c , petroleum d e r i v e d g a s o l i n e s
(2.0). O b v i o u s l y , the more aromatic the r e f i n e d p r o d u c t , the l e s s
is the hydrogen consumption i n the o v e r a l l processing sequence.
The problem i s that petroleum c a t a l y t i c c r a c k i n g and hydrocracking
processes r e q u i r e that the feedstocks be h i g h l y saturated p r i o r
to, or during c r a c k i n g . More specifically, if one attempts to
hydrocrack a multicondensed r i n g aromatic s p e c i e s , the tendency
is to s u c c e s s i v e l y hydrogenate and split o f f t e r m i n a l end r i n g s
to produce u l t i m a t e l y a s i n g l e aromatic molecule and s u b s t a n t i a l
65

q u a n t i t i e s o f C and l i g h t e r gases ( 1 , 16, 17, 22).

4 This i s t r u e
even though h y d r o g é n a t i o n at i n n e r r i n g l o c a t i o n s i s favored
kinetically (18).
The commerical c r a c k i n g o f petroleum hydrocarbons i s almost
u n i v e r s a l l y executed over c a t a l y s t s having an a c i d i c component.
For many years amorphous s i l i c a - a l u m i n a based c a t a l y s t s were the
mainstay of the i n d u s t r y . In more recent years c r a c k i n g activ-
ities have been enhanced by orders o f magnitude by i n c o r p o r a t i n g
c r y s t a l l i n e s i l i c a - a l u m i n a s or molecular sieves ( m u l t i v a l e n t
and hydrogen forms) i n t o the c a t a l y s t composition. While a c i d i c
c a t a l y s t s are by f a r the most a c t i v e c r a c k i n g c a t a l y s t s a v a i l a b l e ,
they are not s e l e c t i v e towards c r a c k i n g at i n n e r r i n g s of p a r -
tially s a t u r a t e d condensed-ring aromatics of the type present i n
c o a l l i q u i d s . As we discuss below, there are suggestions i n the
l i t e r a t u r e that n o n a c i d i c c a t a l y s t s , or c a t a l y s t s o f low a c i d i t y
might o f f e r advantages i n terms o f selectivity. The c r a c k i n g
r e a c t i o n s that take place over such c a t a l y s t s would presumably

take place by free r a d i c a l mechanisms — s i m i l a r to the s i t u a t i o n
encountered i n thermal c r a c k i n g .
A study o f the thermal hydrogenolysis of phenanthrene at 80
atm and temperatures o f 4 7 5 ° C and 4 9 5 ° C was r e c e n t l y r e p o r t e d by
Penninger and Slotboom (11). The main hydrogénation products
were 1,2,3,4-tetrahydrophenanthrene and 9,10-dihydrophenanthrene.
At the higher temperature c r a c k i n g products appeared. The
p r i n c i p a l products were, i n decreasing order o f abundance, 2-
ethylnaphthalene, e t h y l b i p h e n y l , 2-methylnaphthalene, naphthalene,
b i p h e n y l and diphenylethane. S e v e r a l r e a c t i o n paths were sug-
guested by t h e i r d a t a . The presence o f s i z e a b l e q u a n t i t i e s o f
e t h y l b i p h e n y l and b i p h e n y l was explained by a mechanism i n v o l v i n g
the r i n g opening of dihydrophenanthrene between the 10 and 11
carbon atoms. Thus we see here f o r the first time evidence o f
hydrocracking the phenanthrene molecule at the c e n t r a l r i n g .
Still, the major r e a c t i o n path i n v o l v e d cleavage o f end r i n g s .
It can be argued, somewhat n a i v e l y perhaps, that the main
obstacle t o hydrocracking 9,10-dihydrophenanthrene and s i m i l a r
molecules, i s the 12,13- or "biphenyl" like bond. I t i s noted
that b i p h e n y l itself was observed t o be i n e r t to c a t a l y t i c c r a c k -
ing over an a c i d i c , s i l i c a - a l u m i n a c r a c k i n g c a t a l y s t ( 8_). On the
other hand the hydrogenolysis o f b i p h e n y l takes place thermally
at temperatures i n the neighborhood of 1 3 0 0 ° F (10). Gardner and
Hutchinson found t h a t low surface a r e a , low acidity, metal oxide
c a t a l y s t s were e f f e c t i v e i n hydrocracking polyphenyls i n c l u d i n g
biphenyl (7). A c i d i c c r a c k i n g c a t a l y s t s produced much lower con-
versions and s u b s t a n t i a l y i e l d s of coke. These observations were
a major f a c t o r i n our s e l e c t i o n o f a chromia-alumina c a t a l y s t f o r
this investigation. Chromia-alumina has demonstrated an ability
t o c a t a l y z e many free r a d i c a l r e a c t i o n s .
Chromia-Alumina C a t a l y s t s . Chromia-alumina c a t a l y s t s are

most notable f o r c a t a l y z i n g the dehydrogenation and dehydro-

4. wu A N D H A Y N E S Condensed-Ring Aromatics 67
c y c l i z a t i o n r e a c t i o n s o f hydrocarbons and the p o l y m e r i z a t i o n o f

o l e f i n i c hydrocarbons. R e l a t i v e t o metal dehydrogenation
c a t a l y s t s such as F e , N i , and Co, chromium oxide and chromia-
alumina c a t a l y s t s possess l i t t l e a c t i v i t y f o r a c t i v a t i n g the
the carbon-carbon bond ( 1 4 ) . Chromia-alumina i s remarkably
i n s e n s i t i v e t o poisons which might be present i n the s t a r t i n g
m a t e r i a l , though water vapor does act as a temporary poison (19).
Chromium oxide by i t s e l f i s a h i g h l y a c t i v e c a t a l y s t , but
t h i s a c t i v i t y i s not r e t a i n e d on prolonged use or upon regener
a t i o n by o x i d a t i o n . T h i s decay i s due to conversion t o c r y s t a l
l i n e C r 0 g which has been shown to be i n a c t i v e (20).
2 But i f
the chromium oxide i s deposited on alumina, i t r e t a i n s i t s
o r i g i n a l high a c t i v i t y through regeneration at quite high tem
peratures ( 9 ) . The alumina has an a d d i t i o n a l e f f e c t i n that i t
+
s t a b i l i z e s the chromium against r e d u c t i o n below the C r ^ s t a t e
i n hydrogen atmospheres at temperatures as high as 500°C (21).
F i n a l l y the alumina may or may n o t , depending upon the method o f

p r e p a r a t i o n , introduce an a c i d i c f u n c t i o n i n t o the c h a r a c t e r i s t i c s
of the c a t a l y s t . For example, Pines and C s i c s e r y (13) observed
that chromia-alumina c a t a l y s t s composed o f alumina obtained by
h y d r o l y s i s of aluminum isopropoxide and alumina prepared from
potassium aluminate behaved quite d i f f e r e n t l y i n the dehydro
genation and d e h y d r o c y c l i z a t i o n o f C 5 and Cg hydrocarbons. The
former c a t a l y s t , designated c a t a l y s t A , produced extensive
s k e l e t a l i s o m e r i z a t i o n ; whereas, the l a t t e r , designated c a t a l y s t
B , produced o l e f i n s with e s s e n t i a l l y the same s k e l e t a l arrange
ment as the s t a r t i n g p a r a f f i n s . Catalyst A yielded large
q u a n t i t i e s of aromatics — benzene, toluene and xylene — from
n-pentane. Formation o f these products could be e x p l a i n e d by an
a c i d c a t a l y z e d p o l y m e r i z a t i o n followed by i s o m e r i z a t i o n and β -
s c i s s i o n t o form propylene and isobutylene fragments which could
then undergo an aromatization r e a c t i o n . C a t a l y s t Β produced
only n e g l i g i b l e q u a n t i t i e s o f aromatics.
Pines and h i s co-workers are r e s p o n s i b l e f o r a great body
o f l i t e r a t u r e e l u d i c a t i n g the mechanisms o f hydrocarbon r e a c t i o n s
over chromia alumina. [For number t h i r t y - e i g h t i n the s e r i e s see
reference ( 1 2 ) ] . In g e n e r a l i t i s observed that r e a c t i o n s over
the "nonacidic" chromia-alumina Β can be explained by f r e e r a d i c a l
mechanisms. In a study o f the dehydroeraeking o f Cg-Cg p a r a f f i n s
C s i c s e r y and Pines made s e v e r a l i n t e r e s t i n g observations (3):
Cracking occurred most predominantly between s u b s t i t u t e d carbons,
with l i t t l e c r a c k i n g of normal p a r a f f i n s t a k i n g p l a c e . This
suggests a homolytic s p l i t t i n g of the molecule i n t o free r a d i c a l s
since the s t a b i l i t y o f free r a d i c a l s increases with s u b s t i t u t i o n .
Cracking was very much i n h i b i t e d i f n e i t h e r o f the fragments
could form an o l e f i n . A comparison was made between the
cracking o f 3-ethylhexane and 3-ethylhexenes. With the p a r a f f i n ,
c r a c k i n g occurred almost e x c l u s i v e l y between primary and t e r
t i a r y carbon atoms. With o l e f i n s , c r a c k i n g took place β t o the
double bond suggesting a mechanism i n v o l v i n g the a l l y l free
radical.

The major products obtained from the dehydrogenation o f n -

butylbenzene over chromia-alumina were 1-phenylbutenes (_2).
This r e a c t i o n was accompanied by s u b s t a n t i a l hydrogenolysis o f
the side chain t o produce ethylbenzene (or styrene) and ethylene
(or ethane). D e a l k y l a t i o n was a r e l a t i v e l y minor r e a c t i o n .
The product d i s t r i b u t i o n again suggests that free r a d i c a l i n t e r -
mediates were i n v o l v e d . A review o f the p h y s i c a l - c h e m i c a l
p r o p e r t i e s o f chromia-alumina was presented by Poole and
Mclver (15).
Experimental
The experimental p o r t i o n o f t h i s i n v e s t i g a t i o n was conducted

i n the steady-flow m i c r o r e a c t o r i l l u s t r a t e d i n F i g u r e 1. The
r e a c t o r c o n s i s t e d of a tube o f 1/2 i n c h heavy w a l l (0.083 i n c h )
type 316 s t a i n l e s s steel heated by a M a r s h a l l t u b u l a r f u r n a c e ,
model 1016. L i q u i d phenanthrene was metered i n t o the r e a c t o r by

a p r e c i s i o n Ruska p r o p o r t i o n i n g pump, model 2252-BI, with a
heated b a r r e l . Various discharge r a t e s from 2 c c / h r t o 240 c c / h r
could be obtained by s e l e c t i n g the proper choice o f gear r a t i o s .
The hydrogen flowrate was monitored by a flow meter constructed
of a 34 i n c h length o f 0.009 inch I . D . c a p i l l a r y tubing and a
Barton model 200 d i f f e r e n t i a l pressure c e l l . The c a p i l l a r y
pressure and r e a c t o r pressure were c o n t r o l l e d r e s p e c t i v e l y by a
Tescom pressure r e g u l a t o r , model 26-1023-002 and a Tescom back
pressure r e g u l a t o r model 26-1723-24. Flow r a t e s were c o n t r o l -
l e d with a Hoke m i l l i - m i t e needle v a l v e . The high pressure
accumulator was constructed o f 3/4 i n c h schedule 80 s t a i n l e s s
s t e e l pipe with a Grayloc c l o s u r e .
High p u r i t y hydrogen (99.995% according to m a n u f a c t u r e r ^
s p e c i f i c a t i o n s ) was s u p p l i e d by the Matheson Gas Products Com-
pany i n 3500 p s i g c y l i n d e r s . Phenanthrene, 98+% p u r i t y , melting
point 9 9 - 1 0 1 ° C , was purchased from the A l d r i c h Chemical Company.
The chromia-alumina c a t a l y s t , designated CR-0103-T,was s u p p l i e d
by the Harshaw Chemical Company i n the form of 1/8 inch t a b l e t s .
According to the manufacturer, the c a t a l y s t contains 12% C r 0 2 3
on a c t i v a t e d alumina, the surface area i s 63 m^/gm, and the

pore volume i s 0.35 cc/gm.
Approximately f i v e grams of f u l l s i z e c a t a l y s t p a r t i c l e s
were charged to the r e a c t o r . A preheat zone o f g l a s s beads was
s i t u a t e d above the c a t a l y s t bed. Thermocouples were i n s t a l l e d t o
a depth o f 1/2 inch i n t o both ends o f the c a t a l y s t bed. With a
f r e s h c a t a l y s t i n s t a l l e d , the system was pressured with hydrogen
and t e s t e d f o r l e a k s . Hydrogen flow was s t a r t e d and the tem-
perature r a i s e d slowly ( 1 6 0 ° F / h r maximum) to a temperature o f
500°F. At t h i s p o i n t the l i q u i d feed pump was switched on. The
furnace temperature was g r a d u a l l y brought up t o r e a c t i o n c o n d i -
t i o n s by r a i s i n g the temperature at a r a t e not to exceed 1 6 0 ° F / h r .
P r i o r t o beginning a y i e l d p e r i o d , a p e r i o d o f time s u f f i c i e n t
f o r three displacements o f the r e a c t o r was allowed t o insure

steady-state operation. The y i e l d p e r i o d was begun my momen-

t a r i l y c u t t i n g o f f the feed pump, depressuring and d r a i n i n g the
high pressure accumulator, and p r e s s u r i n g the accumulator with
pure hydrogen (through a l i n e not i n d i c a t e d on the s i m p l i f i e d
schematic). The e x i t i n g l i n e was d i r e c t e d through a low p r e s -
sure accumulator ( i n dry i c e - a c e t o n e ) , a wet t e s t meter and a
polyethylene gas bag. At the t e r m i n a t i o n of the y i e l d p e r i o d the
high pressure accumulator was depressured through the wet t e s t
meter and l i q u i d d r a i n e d . The l i q u i d product was capped and
stored i n a f r e e z e r . The contents o f the gas bag were analyzed
immediately. When i t became necessary t o place the u n i t on
over n i g h t hold the feed pump was switched o f f and the r e a c t o r
temperature lowered to 5 0 0 ° F . Hydrogen flow was maintained f o r
the d u r a t i o n o f the h o l d p e r i o d .
Both the l i q u i d and gas products were analyzed by gas chroma-
tography. The column f o r the l i q u i d a n a l y s i s was 20% Apiezon L
on 60-80 mesh Chromosorb P. The column measured 1/4 i n c h by 7

feet. The gas a n a l y s i s u t i l i z e d a 1/4 i n c h by 10 foot column o f
60-80 mesh Chromosorb 102. Temperature programming was r e q u i r e d
i n both analyses. I d e n t i f i c a t i o n o f the GC peaks was based on
r e t e n t i o n time o f pure compounds when these were a v a i l a b l e . In
a d d i t i o n , two o f the samples were analyzed by combined gas c h r o -
matography -mas s spectrometry. By comparing the observed mass
spectrometer fragmentation patterns with t a b u l a t e d patterns i t
was p o s s i b l e t o i d e n t i f y v i r t u a l l y every component i n the p r o -
duct. Further d e t a i l s are a v a i l a b l e i n the theses by Wu (23)
and E a r l y ( 4 ) .
Results
Sixteen y i e l d periods were s u c c e s s f u l l y completed at the

c o n d i t i o n s summarized i n Table I . Product y i e l d s are t a b u l a t e d
i n Table I I . These y i e l d s have been adjusted t o force a 100%
carbon m a t e r i a l balance.
While i t was beyond the scope o f t h i s i n v e s t i g a t i o n t o
evaluate c a t a l y s t d e a c t i v a t i o n k i n e t i c s , i t was deemed necessary
to maintain a r e c o r d o f any d e c l i n e s i n c a t a l y s t a c t i v i t y . The
s e l e c t e d "Base Conditions" o f operation — 8 0 0 ° F , 2000 p s i g ,
1.0 gm/hr/gm — were repeated p e r i o d i c a l l y f o r t h i s purpose. Two
measures o f c a t a l y s t a c t i v i t y , phenanthrene conversion and con-
v e r s i o n t o C ] ^ , are p l o t t e d versus hours on c a t a l y s t i n Figure 2.
While both i n d i c a t o r s r e v e a l that c a t a l y s t d e a c t i v a t i o n i s s i g -
n i f i c a n t , the c a t a l y s t does remain a c t i v e a f t e r 90 hours on
stream. No a n a l y s i s o f the spent c a t a l y s t was undertaken; how-
e v e r , i t was s u r p r i s i n g l y observed that the c a t a l y s t s t i l l
r e t a i n e d i t s o r i g i n a l green c o l o r at the run t e r m i n a t i o n . Evi-
dently carbon d e p o s i t i o n was not extensive despite the high
temperatures employed. The hydrogen p a r t i a l pressures e x p e r i -
enced by the c a t a l y s t are much higher than those experienced i n
the u s u a l a p p l i c a t i o n s o f chromia-alumina, and the extent to

TABLE I
PRODUCT YIELDS
R U N WLW02. H Y D R O C R A C K I N G O F P H E N A N T H R E N E O V E R 5.017 G M S H A R S H A W CR-0103-T
Yield period no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Yield period length, hrs. 3.00 3.00 6.00 1.00 1.50 3.00 3.00 3.00 3.00 3.00 3.00 2.75 4.00 1.00 1.00 3.00
Temperature, °F 756 805 805 810 805 800 806 803 854 806 898 949 999 1002 1009 803
Pressure, psig 2000 2000 2000 2000 2000 2000 2500 3000 3000 2000 3000 2800 2800 2800 2600 2000
High press, accumulator
temp., °F 250 230 235 255 295 314 275 285 228 210 110 90 88 100 462 260
Liquid feed rate, cc/hr 5.1 5.1 2.5 16.3 8.6 5.2 5.1 5.2 5.0 4.9 4.9 5.1 5.0 16.9 30.7 5.0
Liquid space velocity.
gm/hr/gm 1.04 1.04 0.51 3.29 1.74 1.05 1.03 1.05 1.02 1.00 0.99 1.03 1.02 3.42 6.21 1.01
Space time (gm/hr/gm)" 0.97 0.96 1.95 0.30 0.57 0.96 0.97 0.95 0.98 1.00 1.01 0.97 0.99 0.30 0.16 0.99
Approx. Η t r e a t rate.
2
L(STP)/hr 6.7 6.7 4.4 14.3 8.9 6.7 6.7 8.9 8.9 6.7 8.9 8.9 8.9 24.0 21.0 6.7
L(STP)/gm 1.29 1.29 1.73 0.86 1.02 1.28 1.30 1.70 1.75 1.34 1.79 1.72 1.75 1.40 0.67 1.33
Exit gas rate, L(STP)/hr 15.1 10.7 4.7 24.9 16.9 6.0 10.6 12.8 16.9 9.2 11.9 20.7 9.6 37.7 25.4 11.7
Cum. hrs. on catalyst 4.5 10.0 20.5 24.5 27.8 32.5 38.8 45.8 51.8 58.2 64.7 69.8 76.4 79.9 81.9 86.8
Cum. gms oil/gm catalyst 4.6 10.1 16.3 21.0 28.6 33.8 40.2 47.2 53.3 59.6 65.7 70.8 78.3 85.3 95.8 103.3
Liq. mat'l balance, wt % 84.3 103.8 103.0 99.6 104.5 90.6 99.0 106.7 104.1 84.9 85.0 83.2 75.2 46.3 97.2 100.8
Carbon mat'l bal., wt % 83.1 102.4 101.4 98.6 103.2 89.3 97.5 105.2 106.4 84.1 83.1 99.1 107.8 87.6 113.4 99.4
C O R R E C T E D Y I E L D S B A S E D ON LIQUID F E E D
Feed conversion, mole % 60.1 74.0 86.2 50.2 57.5 69.5 81.1 78.8 87.6 63.5 86.1 83.7 88.2 82.4 49.1 62.2
Conversion to C14" mole % 2.7 4.9 7.2 3.2 3.2 2.8 3.8 3.6 15.5 2.5 26.3 50.7 74.4 69.6 30.1 4.1

Hydrogen consumption.
L(STP)/gm 0.17 0.27 0.36 0.14 0.16 0.24 0.31 0.29 0.43 0.22 0.38 0.59 0.85 1.04 0.38 0.18
wt% 1.5 2.4 3.2 1.3 1.5 2.1 2.8 2.6 3.8 2.0 3.4 5.3 7.7 9.4 3.4 1.7
Gas yield iC^-C^), wt % 0.07 1 1 1.6 0.22 0.17 0.6 1.3 1.2 6.0 0.94 1.1 21.3 37.9 56.5 17.7 0.30
+
Liq. yield ( C ) , wt % g 101.4 101.3 101.6 101.1 101.3 101.5 101.5 101.4 97.8 101.0 102.3 84.0 69.7 52.9 85.7 101.4

Cg-Cg yield, mole % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.1 8.9 22.9 7.0 0.46 0.0
C -C
g yield, m o i e %
1 2 3.4 5.1 7.3 3.9 3.8 2.9 3.4 3.3 13.2 2.1 30.4 37.8 42.3 24.3 19.3 4.9
ο
v î e , d m o , e % 97.3 95.1 92.8 96.8 96.8 97.2 96.2 96.4 84.5 97.5 73.7 49.3 25.6 30.4 69.9 95.9
^13 14 '
T A B L E II PRODUCT YIELDS
C O R R E C T E D PRODUCT Y I E L D S BASED ON LIQUID F E E D , M O L E RUN WLW02, H Y D R O C R A C K I N G OF P H E N A N T H R E N E O V E R 5.017 GMS HARSHAW CR-0103-T
Y I E L D PERIOD NO. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
C 1H4 Methane 0.00 0.04 0.03 0.00 0.04 0.36 0.39 0.04 3.12 0.06 0.08 8.10 64.83 88.85 19.92 0.00
C2H6 Ethane 0.43 2.26 1.27 0.69 0.53 0.91 1.25 1.51 5.46 1.65 1.69 17.72 70.05 99.98 29.47 0.66
C3H8 Propane 0.00 0.61 0.98 0.02 0.04 0.34 0.61 0.52 5.72 0.57 0.65 21.14 48.25 71.56 25.18 0.00
C4H10 Isobutane 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.28 2.18 0.50 0.00
C4H10 Butane 0.00 1.61 3.54 0.30 0.21 1.15 2.65 2.44 10.35 1.59 2.07 37.86 24.30 40.53 13.87 0.57
C5H12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.17 0.00 0.00 0.00
C5H12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.88 0.54 0.10 0.00 0.00
C5H10 Cyclopentane 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.33 0.56 0.15 0.00 0.00
C6H14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.28 0.30 0.08 0.00 0.00
C6H14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.42 0.65 0.00 0.00 0.00
C6H 6 Benzene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.58 1.68 7.06 2.45 0.00 0.00
C7H16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.36 0.45 0.49 0.32 0.00 0.00
C7H16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.24 0.36 0.93 0.25 0.00 0.00
C7H 8 Toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.69 2.33 7.05 2.18 0.00 0.00
C 7H16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.37 0.29 0.00 0.00 0.00
C8H10 Ε thy I benzene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.25 1.55 3.77 1.37 0.00 0.00
C8H10 Xylenes 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.23 0.55 0.12 0.46 0.00
C8H10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.29 0.00 0.00 0.00
C8H18 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.27 0.00 0.00 0.00
C9H12 Alky I benzenes 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.40 0.10 0.00 0.00
C9H12 Alkylbenzenes 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.36 0.58 0.30 0.00 0.00
C10H14 Alkyl benzenes 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.27 0.59 0.32 0.00 0.00
C10H14 N-Buty I benzene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.58 0.00 2.42 4.83 5.38 2.03 0.89 0.00
C10H18 Decalin (Trans) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.17 2.56 3.66 1.52 0.95 0.00
C11H16 Methylbutylbenzenes 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.91 1.54 1.10 0.68 0.00 0.00
C10H12 Tetralin 0.87 1.33 2.05 1.11 0.92 1.13 1.03 0.93 3.48 0.49 10.08 11.88 10.02 4.77 3.08 0.97
C10H 8 Naphthalene 0.60 0.75 0.62 0.80 0.58 0.46 0.25 0.47 1.02 0.33 2.93 6.23 12.25 8,03 6.22 1.20
C10H12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.62 0.00 0.39 1.19 0.95 0.55 0.00 0.00
C11H14 6-Methyltetralin 0.00 0.00 0.42 0.00 0.00 0.00 0.00 0.00 0.90 0.00 1.47 1.39 1.15 0.86 0.63 0.00
C11H10 2-Methylnaphthalene 0.62 1.00 0.86 0.57 0.54 0.80 0.73 0.72 1.08 0.38 1.04 2.20 2.65 2.37 2.89 1.03
C12H16 6-Ethyltetralin 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.34 0.00 0.50 0.74 0.50 0.31 0.26 0.00
C12H10 Biphenyl 0.70 1.08 1.41 0.66 0.91 0.56 0.65 0.66 2.05 0.00 3.93 1.54 0.99 0.52 0.64 0.91
C12H12 2-Ethylnaphthalene 0.59 0.95 0.72 0.77 0.87

0.00 0.31 0.27 1.28 0.00 2.49 1.46 1.44 1.47 3.16 0.82
C12H20 0.00 0.00 0.64 0.00 0.00 0.00 0.25 0.27 0.96 0.48 1.56 0.82 0.48 0.42 0.60 0.00
C12H24 0.00 0.00 0.57 0.00 0.00 0.00 0.21 0.00 0.89 0.42 1.52 0.75 0.20 0.07 0.00 0.00
C14H20 6-N-Butyltetralin 2.21 9.91 20.16 3.23 3.70 9.68 12.89 10.34 22.94 5.67 22.45 8.38 2.56 1.61 1.39 3.96
C14H15 2-N-Butylnaphthalene 1.50 4.57 5.76 2.53 2.70 4.10 3.71 3.83 6.52 3.83 10.38 7.43 3.23 3.64 4.28 3.68
C14H12 2.30 4.05 4.20 1.96 2.31 3.36 4.47 4.39 3.63 2.65 1.94 1.42 1.01 0.93 1.89 2.66
C14H12 2.30 4.31 5.21 2.07 2.67 4.20 5.64 5.19 4.38 2.87 2.05 1.42 0.78 0.54 1.02 2.99

C14H14 2-Ethylbiphenyl 0.00 0.53 0.43 0.00 0.69 0.62 0.26 0.23 0.61 0.23 0.65 1.00 0.52 0.65 1.02 0.31
C14H12 Dihydrophenanthrene 18.59 9.28 7.10 12.98 14.11 11.05 9.42 11.75 6.66 12.36 5.47 4.00 2.08 2.61 5.08 13.97
C14H18 Octahy drophenanth rene 12.79 17.96 20.53 7.78 9.56 14.10 23.29 22.85 15.04 14.19 6.35 2.55 0.99 0.35 0.21 12.11
C14H14 Tetrahydrophenanthrene 17.73 18.45 15.65 16.40 18.60 19.61 17.61 16.63 12.30 19.25 10.57 6.74 2.62 2.45 4.12 18.42
C14H10 Phenanthrene 39.86 26.02 13.78 49.81 42.49 30.50 18.91 21.17 12.39 36.48 13.89 16.32 11.85 17.63 50.87 37.82
TOTALS 101.11 104.70 105.93 101.70 101.47 102.90 104.54 104.21 122.31 103.50 112.75 180.70 299.58 364.86 178.61 102.06
DPC PG
PR
Hydrogen t f~\
Supply I KJ~
Proportioning
Pump
7 \ Vent, W T M , or
" G a s Bag
,4 ,< ,</,<,*,< H e a t e d Lines

CO Cutoff Valve
MV Metering Valve
PR Pressure Regulator
BPR Back Pressure Regulator
PG Pressure Gauge
C Capillary
DPC Differential Pressure Call
Low Pressure
Accumulator
Figure 1. Simplified flow diagram of steady-state microreactor
Figure 2. Deactivation of chromia-alumina catalyst

which t h i s may have damaged the c a t a l y s t , e . g . by r e d u c t i o n o f

chromium o x i d e , i s not known.
Y i e l d s o f the various h y d r o g é n a t i o n products o f phenanthrene
are presented i n F i g u r e 3 and Table I I . No perhydrophenanthrene
was detected i n any o f the p r o d u c t s . This i s c o n s i s t e n t with the
observation that h y d r o g é n a t i o n o f the l a s t r i n g o f a p o l y c o n -
densed r i n g aromatic proceeds with considerable d i f f i c u l t y as
compared with the i n i t i a l h y d r o g é n a t i o n steps (18). It i s
f r e q u e n t l y supposed that the h y d r o g é n a t i o n o f p o l y n u c l e a r a r o -
matics takes place r i n g - b y - r i n g i n a s e r i e s f a s h i o n . While con-
f i r m a t i o n o f t h i s behavior would r e q u i r e more p r e c i s e data at
lower conversions than are a v a i l a b l e h e r e , i t i s apparent that
tetrahydrophenanthrene appears almost simultaneously with d i -
hydrophenanthrene suggesting that the i n i t i a l h y d r o g é n a t i o n s
might take place i n a p a r a l l e l manner.
I t i s o f i n t e r e s t to compare the observed h y d r o g é n a t i o n
product r a t i o s with e q u i l i b r i u m v a l u e s . E q u i l i b r i u m constants

were c a l c u l a t e d using equations a v a i l a b l e i n the l i t e r a t u r e
(5,6). A hydrogen mole f r a c t i o n o f u n i t y was assumed f o r c a l -
c u l a t i o n o f the e q u i l i b r i u m product r a t i o s , a reasonable assump-
t i o n when the hydrogen t r e a t r a t e g r e a t l y exceeds the r a t e o f
hydrogen consumption. Otherwise the extent o f h y d r o g é n a t i o n at
e q u i l i b r i u m w i l l be somewhat l e s s than these c a l c u l a t i o n s would
indicate. The c a l c u l a t e d r e s u l t s are compared with the observed
r a t i o s i n Tables I I I and I V . At 8 0 0 ° F and 2000 p s i g only the
phenanthrene-dihydrophenanthrene e q u i l i b r i u m appears t o be e s t a b -
1
l i s h e d at the l a r g e s t space time i n v e s t i g a t e d , 1.9 (gm/hr/gm)" .
At the more severe c o n d i t i o n s 1 0 0 0 ° F and 2800 p s i g , the r a t e s are
more r a p i d and the degree o f h y d r o g é n a t i o n i s l e s s under e q u i l i -
brium c o n d i t i o n s . A l l the h y d r o g é n a t i o n products o f phenan-
t h r e n e , with the exception o f perhydrophenanthrene, approach
t h e i r e q u i l i b r i u m values at l a r g e space t i m e s . The same i s t r u e
of the n a p h t h a l e n e - t e t r a l i n - ( t r a n s ) d e c a l i n e q u i l i b r i a .
Inspection o f Figures 4- and 5 r e v e a l s that the c r a c k i n g
r e a c t i o n s at 8 0 0 ° F are l i m i t e d t o α - r i n g opening o f a saturated
terminal r i n g . At higher temperatures d e a l k y l a t i o n r e a c t i o n s
become s i g n i f i c a n t . The predominant r e a c t i o n at the lower
temperatures was h y d r o g é n a t i o n t o sym-octahydrophenanthrene
followed by r i n g opening t o 6 - n - b u t y l t e t r a l i n and d e a l k y l a t i o n to
tetralin. At the higher temperatures naphthalenes were present
i n greater abundance, presumably because o f the s h i f t i n thermo-
dynamic e q u i l i b r i u m towards the more unsaturated s p e c i e s . The
y i e l d s of n-butylnaphthalene and naphthalene are comparable t o
the y e i l d s of n - b u t y l t e t r a l i n and t e t r a l i n r e s p e c t i v e l y at 950-
1000°F. Considerable q u a n t i t i e s o f n-butylbenzene (Table I I )
were observed i n the products suggesting a mechanism i n v o l v i n g
α - r i n g opening of t e t r a l i n . D e a l k y l a t i o n o f the side chain was
not as clean as had been observed with the b u t y l s u b s t i t u t e d two
ring species. Toluene and benzene were formed i n approximately
equal amounts with smaller amounts o f ethylbenzene. Some xylenes

TABLE I I I
COMPARISON OF EQUILIBRIUM AND OBSERVED HYDROGENATION

PRODUCT RATIOS ( T = 8 0 0 ° F P=2000 p s i g )
YP4 YP5 YP6 YP2 YP3 Equili-

brium
Space Time Hr 9 0.30 0.57 0.96 0.96 1.95

C H /C H
0.26 0.33 0.36 0.36 0.52 0.55
14 12 14 10
C H /C H 0.33 0.44 0.64 0.71 1.14 2.5

14 14 14 10
C l i + H (sym)/C
1 8 1 1 + H 1 0 0.16 0.22 0.46 0.69 1.49 6.1
C 1 4 H 2 ] + (L.B.P.)/C 1 4 H 8 0 0 0 0 0 40
C H / C H
1.39 1.60 2.5 1.9 3.3 12.7
10 12 10 8
C 1 0 H 1 8 (cis)/C 1 0 H 8 0 0 0 0 0 24
C 1 0 H 1 8 (trans)/C 1 0 H 8 0 0 0 0 0 118

wu A N D H A Y N E S Condensed-Ring Aromatics
TABLE IV
COMPARISON OF EQUILIBRIUM AND OBSERVED HYDROGENATION

PRODUCT RATIOS ( T = 1 0 0 0 ° F P=2800 p s i g )
YP 15 YP 14 YP 13 Equili-
brium
Space Time, Hr 0.16 0.29 0.98

C H /C H
0.10 0.15 0.18 0.25
14 12 14 10
C H /C H
0.081 0.14 0.22 0.29
14 14 14 10
C H (sym)/C
1 4 l 8 1 1 + H 1 0 0.004 0.02 0.084 0.084
C H (L.B.P.)/C H
W M U 1 0
0 0 0 0.018
C H /C H
0.50 0.60 0.82 1.53
10 12 10 8
C 1 0 H l 8 (cis)/C 1 0 H 8 0 0 0 0.10
C H ( t r a n s ) / C H
0.15 0.19 0.30 0.37
10 18 10 8

HYDROCRACKING A N D HYDROTREATING
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
SPACE TIME, (gm/hr/gm)"
Figure 3. Hydrogénation reactions (2000 psig, 800°F nominal)
( 3 0 0 0 p s i g , 1.0 gm/hr/gm NOMINAL)
Figure 4. Effect of temperature on product distri-

bution (3000 psig, 1.0 gm/hr/gm nominal)

were a l s o p r e s e n t . Cracking w i t h i n the side chain of a l k y l

benzenes i s i n d i c a t i v e o f a free r a d i c a l c r a c k i n g mechanism and
i n agreement with the chromia-alumina c a t a l y z e d n-butylbenzene
d e h y d r ο c r a c k i n g r e s u l t s r e p o r t e d by C s i c s e r y ( 2 ) .
As shown i n Figure 5 b i p h e n y l and 2 - e t h y l M p h e n y l were
observed i n the r e a c t i o n products i n s i g n i f i c a n t q u a n t i t i e s .
Thus a r i n g opening o f dihydrophenanthrene between the 10 and 11
carbons i s l i k e l y t a k i n g p l a c e . This same mechanism, i t i s
r e c a l l e d , was p o s t u l a t e d by Penninger and Slotboom to e x p l a i n
the thermal h y d r o p y r o l y s i s o f phenanthrene. As shown i n Figure
5, the y i e l d o f b i p h e n y l at 2800 p s i g , 1.0 gm/hr/gm goes through
a maximum o f approximately 4% at about 9 0 0 ° F . At these same
conditions the y i e l d s of t e t r a l i n and naphthalene were 10% and
3% (Figure 4) r e s p e c t i v e l y . The decrease i n b i p h e n y l y i e l d at
temperatures above 9 0 0 ° F can be explained by c r a c k i n g to produce
benzene, or by the lower e q u i l i b r i u m concentration o f d i h y d r o
phenanthrene .
The product y i e l d s by carbon number are p l o t t e d in Figure 6.
At a l l except the most severe conditions s t u d i e d , t h e major com
ponent i n the gas phase was η - b u t a n e . This observation i s con
s i s t e n t with the α - r i n g opening and d e a l k y l a t i o n mechanism
proposed f o r t e t r a - a n d octa-hydrophenanthrene c r a c k i n g . At the
most severe conditions ethane was present i n the greatest
quantities. This can be explained by side chain cracking o f n -
butylbenzene according t o the R i c e - K o s s i a k o f f mechanism or by
secondary r e a c t i o n s o f the n-butane.
Conclusions
Three r e a c t i o n paths were i d e n t i f i e d during the hydrocrack

ing o f phenanthrene over chromia-alumina. These are summarized
i n Figure 7. The major r e a c t i o n paths proceeded through s a t u
r a t i o n and cleavage of t e r m i n a l end r i n g s as evidence by the
presence o f n - b u t y l t e t r a l i n and n-butylbenzene intermediates and
the l a r g e q u a n t i t i e s o f η - b u t a n e i n the p r o d u c t s . However the
presence o f b i p h e n y l and 2 - e t h y l b i p h e n y l i n s i g n i f i c a n t quan
t i t i e s i n d i c a t e s that a r e l a t i v e l y minor r e a c t i o n path i n v o l v e d
cracking at the saturated middle r i n g . Because o f the impor
tance o f t h i s l a t t e r r e a c t i o n , i t appears that f u r t h e r s t u d i e s
i n v o l v i n g n o n a c i d i c c a t a l y s t s are warranted.
Acknowle dgment s
The f i n a n c i a l support f o r t h i s i n v e s t i g a t i o n was provided

by the N a t i o n a l Science Foundation under grant GI-36597X. The
a s s i s t a n c e o f a number of i n d i v i d u a l s i s g r a t e f u l l y acknowledged:
Dr. Stephen B i l l e t s f o r conducting the GC-Mass Spec a n a l y s e s ,
Mr. W. F . E a r l y f o r a i d i n g i n the i n t e r p r e t a t i o n o f the mass-
spec d a t a , and Mr. K. Chandrasekhar f o r h i s a s s i s t a n c e i n the
c o n s t r u c t i o n and operation of the equipment. The authors would

Figure 5. Effect of temperature on product distri-

bution (3000 psig, 1.0 gm/hr/gm nominal)

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
CARBON NUMBER
Figure 6. Product distribution by carbon number (3000 psig,

1.0 gm/hr/gm nominal)

also like to express their appreciation to the Harshaw Chemical

Company for providing the catalyst.
ABSTRACT
This paper reports the results of an investigation of the

reactions of phenanthrene over a commerical chromia-alumina
catalyst. Chromia-alumina was selected because of i t s demon-
strated a b i l i t y to catalyze free radical reactions. Three major
reactions paths were identified. The f i r s t involved hydro-
g e n a t i o n to sym-octahydrophenanthrene, α - r i n g opening of a
terminal ring and dealkylation to produce t e t r a l i n . The
t e t r a l i n reacted further by a similar pattern to produce alkyl
benzenes. The second reaction path was identical to the f i r s t
except that the initial α-ring opening occurred with tetra-
hydrophenanthrene. A t h i r d , relatively minor reaction path

involved saturation of the center r i n g , α-ring opening to produce
'
2-ethylbiphenyl, dealkylation and cracking at the 1,1 -position
to produce benzene.
LITERATURE CITED
(1) Catalytic Hydrotreating of Coal Derived Liquids, Project

Seacoke Phase II Final Report, Prepared for Office of Coal
Research by Arco Chemical Co., Contract No. 14-01-0001-473,
Dec., 1966.
(2) Csicsery, S. M . , J. Catalysis, (1968), 9, 416.
(3) Csicsery, S. Μ., and Pines, H., J. Catalysis, (1962), 1,
329.
(4) Early, W. F., M.S. Thesis, University of Mississippi, 1975.
(5) Frye, C. G., J. Chem. Eng. Data, (1962), 7, 592.
(6) Frye, C. G., and Weitkamp, A. W., J. Chem. Eng. Data, (1969),
14, 372.
(7) Gardner, L. E., and Hutchinson, W. Μ., Ind. Eng. Chem.,
Prod. Res. Dev., (1964), 3, 28.
(8) Greensfelder, B. S., et al., Ind. Eng. Chem., (1945), 37,
1168.
(9) G r i f f i t h , R. H., Adv. Catalysis, (1948), 1, 103.
(10) Haynes, H. W., Jr., unpublished data, 1970.
(11) Penninger, M. L., and Slotboom, H. W., Erdol und Kohle,
Erdgas, Petrochemie, (1973), 26, 445.
(12) Pines, H., and Abramovici, M., J. Org. Chem., (1969), 34,
70.
(13) Pines H., and Csicsery, M . , J. Amer. Chem. Soc., (1962),
84, 292.
(14) Pines, H., and Goetschel, C. T., J. Org. Chem., (1965),
30, 3530.
(15) Poole, C. P., and MacIver, D. S., Adv. Catalysis, (1967),
17, 223.

4. wu AND HAYNES Condensed-Ring Aromatics 81
(16) Qader, S. Α . , et al., ACS Div. Fuel Chem. Preprints,(1973),

18 (4), 127.
(17) Qader, S. Α . , et al., PREPRINTS, Div. Petrol. Chem., ACS,
(1973), 18 (1), 60.
(18) Smith, Η. Α . , "The Catalytic Hydrogenation of Aromatic
Compounds", Catalysis, V o l . V, (P. H. Emmett, e d . ) , 175
(1957).
(19) Thomas, C. L., "Catalytic Processes and Proven Catalysts",
Academic Press, New York, 1970.
(20) Turkevich, J., et al., J . Amer. Chem. Soc., (1941), 63, 1129.
(21) Voltz, S. E., and Weller, S. W., J. Amer. Chem. Soc., (1954)
76, 4701.
(22) Wiser, W. H., et al., Ind. Eng. Chem., Proc. Res. Dev.,
(1970), 9, 350.
(23) Wu, Wen-lung, M.S. Thesis, University of Mississippi, 1974.

5
Conversion of Complex Aromatic Structures to
Alkylbenzenes
SHAIK A. QADER
Burns and Roe Industrial Services Corp., Paramus, N.J. 07652
DAVID B. McOMBER
University of Utah, Salt Lake City, Utah 84112
A l k y l b e n z e n e s (BTX) a r e m a i n l y made from p e t -

roleum and c o a l i n the U n i t e d S t a t e s . Petroleum
refineries produce about 95% o f BTX and the r e s t comes
from coal. C o a l based BTX i s o b t a i n e d as a b y - p r o d u c t
from h i g h temperature c a r b o n i z a t i o n o f c o a l employed
f o r the p r o d u c t i o n o f metallurgical coke. Carbonization
p r o c e s s yields o n l y 2-3 g a l l o n s o f BTX p e r t o n o f c o a l .
BTX can be produced i n l a r g e r q u a n t i t i e s by h y d r o -
genation and h y d r o c r a c k i n g o f c o a l ( 1 , 2 ) . The o r g a n i c
matter o f c o a l i s m a i n l y a r o m a t i c i n n a t u r e and it
c o n s i s t s o f c l u s t e r s o f each 3 t o 4 benzene r i n g s on
an a v e r a g e , i n t e r - c o n n e c t e d b y aliphatic linkages.
The clusters c o n t a i n m a i n l y a r o m a t i c r i n g s w i t h some
h y d r o a r o m a t i c and n a p h t h e n i c s t r u c t u r e s (3). Con-
v e r s i o n of c o a l to s i n g l e r i n g aromatics involves
r e l e a s e o f c l u s t e r s from complex o r g a n i c m a t t e r w i t h
subsequent c o n v e r s i o n o f the clusters to f i n i s h e d
products. T h e r e f o r e , p r o d u c t i o n o f a l k y l b e n z e n e s from
c o a l i s due t o the o c c u r r e n c e o f hydrogenation and
h y d r o c r a c k i n g r e a c t i o n s o f c o a l and p o l y n u c l e a r a r o -
m a t i c s t r u c t u r e s r e l e a s e d from coal. An u n d e r s t a n d i n g
o f the hydrogenation and h y d r o c r a c k i n g r e a c t i o n s o f
coal, c o a l oil and p o l y n u c l e a r a r o m a t i c h y d r o c a r b o n s
will, t h e r e f o r e , l e a d t o the u n d e r s t a n d i n g o f the
p r o d u c t i o n o f a l k y l b e n z e n e s from coal. In this inves-
tigation, c o a l , c o a l oil, a n t h r a c e n e and phenanthrene
were h y d r o c r a c k e d over different catalysts i n batch
systems. Product distributions, reaction kinetics and
catalyst e f f e c t s were s t u d i e d .
82

5. QADER A N D M C O M B E R Complex Aromatic Structures 83
E x p e r imenta1
H y d r o c r a c k i n g o f c o a l , c o a l o i l , a n t h r a c e n e and
phenanthrene was c a r r i e d out i n b a t c h s t i r r e d tank
r e a c t o r s ( F i g u r e s 1 and 2) i n t h e temperature range
450 - 540 c under p r e s s u r e s up t o 3500 p s i . R e a c t o r
c o m b i n a t i o n shown i n F i g u r e 2 was used f o r t h e h y d r o -
cracking of coal. H y d r o c r a c k i n g experiments o f
a n t h r a c e n e , phenanthrene and c o a l o i l were conducted
i n t h e same manner as d e s c r i b e d e a r l i e r ( 4 ) . In case
of c o a l , hydrogen was p r e h e a t e d i n r e a c t o r (_1) and
p a s s e d i n t o r e a c t o r (2) c o n t a i n i n g c o a l . No s t i r r i n g
was done d u r i n g c o a l h y d r o c r a c k i n g e x p e r i m e n t s .
A b i t u m i n o u s c o a l from Utah (Table I) was used
i n t h i s work. The c o a l o i l (Table I I ) used was

o b t a i n e d from a b i t u m i n o u s c o a l b y hydrogénation u s i n g
z i n c c h l o r i d e as the c a t a l y s t i n a s e m i - c o n t i n u o u s
r e a c t o r system. A n t h r a c e n e , phenanthrene, WS~ and
NIS used were pure grade c h e m i c a l s o f o v e r 99% p u r i t y .
H-zeolon was a s y n t h e t i c mordenite c r a c k i n g c a t a l y s t
and was s u p p l i e d by Norton C h e m i c a l Company. NIS-H-
z e o l o n was p r e p a r e d b y s p r a y i n g n i c k e l on H-zeolon
w i t h a subsequent s u l f i d i n g o p e r a t i o n . NIS-WS -SiC> - 2
Al 0 c a t a l y s t used was a commercial h y d r o c r a c k i n g

catalyst. A n a l y s e s o f r e a c t a n t s and p r o d u c t s were
done by s t a n d a r d methods.
R e s u l t s and D i s c u s s i o n
H y d r o c r a c k i n g o f a n t h r a c e n e and phenanthrene was

done b y u s i n g two d i f f e r e n t t y p e s o f d u a l - f u n c t i o n a l
c a t a l y s t s , impregnated and p h y s i c a l m i x t u r e s . Data
g i v e n i n T a b l e s I I I and IV i n d i c a t e d t h a t t h e g r o s s
h y d r o c r a c k i n g p a t t e r n o f b o t h hydrocarbons remained
almost same i r r e s p e c t i v e o f t h e n a t u r e o f c a t a l y s t
used. Both impregnated and p h y s i c a l l y mixed c a t a l y s t s
y i e l d e d almost s i m i l a r l i q u i d and gaseous p r o d u c t s
i n d i c a t i n g t h a t h y d r o c r a c k i n g r e a c t i o n mechanisms
remained same i n b o t h c a s e s under t h e e x p e r i m e n t a l
c o n d i t i o n s used i n t h i s work. However, t h e r e were
s l i g h t differences i n actual conversions obtained with
impregnated and p h y s i c a l l y mixed c a t a l y s t c o m b i n a t i o n s .
Product d i s t r i b u t i o n d a t a i n d i c a t e d t h a t h y d r o c r a c k i n g
o f a n t h r a c e n e and phenanthrene proceeded t h r o u g h t h e

X
11
10. Slurry Pump

1. Heating Jacket
15
2. Thermowell ||| 8. Gas Sampling Line
3. Magnetic Drive Assembly ^ 9. Pressure Gage
4. Cooling Coil 10. Sample Injector
5. Stirrer ^ II. Temperature Recorder
6. Liner 10 12. Hydrogen Tank
7. Thermowell, Temperature 13. Stirrer Controller
Indicator 14. Motor
15. Temperature Controller
Figure 1. Batch stirred tank reactor
H2 Coal
1 2
Figure 2. Hydrocracking of coal. 1 and
2: Batch stirred tank reactor.

5. QADER A N D M C O M B E R Complex Aromatic Structures
TABLE I
PROPERTIES OF COAL
Proximate (dry) Wt, %

V o l a t i l e Matter 42.4
Ash 6.9
F i x e d Carbon 50.7
U l t i m a t e (dry)
Carbon 76.42
Hydrogen 5.45
Oxygen 8.65
Sulfur 0.96
Nitrogen 1.62
TABLE I I
PROPERTIES OF COAL OIL
G r a v i t y °API : 12.0
B o i l i n g Range, c : 200-350
S u l f u r , wt. % : 0.82
N i t r o g e n , wt. % : 0.94
Oxygen, wt. % : 3.82
H/c (atomic) : 0.83

TABLE I I I
Anthracene Hydrocracking
Temperature, °c : 475
P r e s s u r e , p s i : 3000
R e a c t i o n Time, mts. : 20
R e a c t a n t / c a t a l y s t , wt. : 1.0
Products, % NIS-H-Zeolon NIS-H-Zeolon NIS-WS2-Si0 -Al 0 2 2 3 N I S - W S - S i O · AI9O3

2 ?
(Impregnated) (Physical Mixture) (Impregnated) (Physical Mixture)
Anthracene and
Higher 54.5 55.1 51.2 52.8
Dihydro Anthracene 4.8 5.2 4.4 4.7
Tetrahydro Anthracene 15.1 15.3 16.9 16.8
Octahydro Anthracene 2.1 2.5 1.8 1.2
Hydro A n t h r a c e n e Isomer
c
( 14) 1.7 1.4 1.9 2.3
Hydro A n t h r a c e n e Isomer
(C13) 2.8 3.0 5.1 5.6
Naphthalene, Tetralin,
Indanes 8.5 8.6 9.8 8.2

Benzene and Alkyl-
benzenes 10.5 8.9 8.9 8.4
Butanes 0.8 0.3 1.9 1.7

Propane 11.5 10.5 10.7 9.6
Ethane 17.3 13.0 28.3 24.7
Methane 21.5 22.7 19.1 18.5

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en ε
nthrene
Η Η
hrene
hrene
53 ~
rd •Ρ 4J
β -s
Φ β eu Φ β —
β eu β β rd ^ rd ro Φ Ό
Φ U ,β 0 ω Φ β fH β rH β β
μ eu (u Ο n (DU Φυ Φ rd
'p , β H ^ rH
•Ρ CT» 0 >i4J Ό -Ρ eu rd si φ 10 φ Φ
•Ρ Φ Φ
β -H >Λ β u ,β Φ β β β
υ rd A Ό rd rd Λ rd Ο Φ Ο Φ •Ρ β φ β rd β rd
β U C rd β u g , β rd Ν rd rd ,β
Ό CU Ό >t
,C 4J φ •Ρ Φ M 0
Ό e Ό Ο ftTJ β •Ρ ft
Ο ,β •Ρ
ο Λ β •H Φ A U ,β >i W rd β Φ U •Ρ Φ
Pi rd Q EH Λ Ο m H Κ H 53 Η m PQ CU Η

o c c u r r e n c e o f hydrogénation, i s o m e r i z a t i o n and h y d r o -
c r a c k i n g r e a c t i o n s as a l s o shown p r e v i o u s l y by Qader
e t a l (4-6). However, t h e r e were some d i f f e r e n c e s
i n t h e c o n v e r s i o n s and n a t u r e o f p r o d u c t s o b t a i n e d
from NIS-H-zeolon and N I S - W S - S i 0 - A l C >2 2 2 3 combinations
from b o t h anthracene and phenanthrene.
Product d i s t r i b u t i o n d a t a (Table V) o b t a i n e d i n
t h e h y d r o c r a c k i n g o f c o a l , c o a l o i l , a n t h r a c e n e and
phenanthrene over a p h y s i c a l l y mixed NIS-H-zeolon
c a t a l y s t i n d i c a t e d s i m i l a r i t i e s and d i f f e r e n c e s
between the p r o d u c t s o f c o a l and c o a l o i l on the one
hand and a n t h r a c e n e and phenanthrene on t h e o t h e r hand.
There were d i f f e r e n c e s i n the c o n v e r s i o n s which v a r i e d
i n the o r d e r c o a l > a n t h r a c e n e > p h e n a n t h r e n e >· c o a l o i l .
The y i e l d o f a l k y l b e n z e n e s a l s o v a r i e d i n the o r d e r
a n t h r a c e n e > p h e n a n t h r e n e > c o a l o i l > c o a l under t h e
c o n d i t i o n s used. The a l k y l b e n z e n e s and C -C^ h y d r o -
carbon p r o d u c t s from a n t h r a c e n e were s i m i l a r t o t h e
p r o d u c t s o f phenanthrene. The most predominant com-
ponent o f a l k y l b e n z e n e s was t o l u e n e and x y l e n e s were
produced i n v e r y s m a l l q u a n t i t i e s . Methane was t h e
most and butanes the l e a s t predominant components o f
t h e gaseous p r o d u c t . The p r o d u c t s o f c o a l and c o a l
o i l were a l s o found t o be s i m i l a r . The most p r e d o m i -
nant components o f a l k y l b e n z e n e s and gaseous p r o d u c t
were benzene and propane r e s p e c t i v e l y . The d a t a a l s o
i n d i c a t e d d i s t i n c t d i f f e r e n c e s between p r o d u c t s o f
c o a l o r i g i n and pure a r o m a t i c h y d r o c a r b o n s . The a l k y l -
benzene p r o d u c t s o f c o a l and c o a l o i l c o n t a i n e d more
benzene and x y l e n e s and l e s s t o l u e n e , e t h y l b e n z e n e and
h i g h e r benzenes when compared t o the p r o d u c t s from
a n t h r a c e n e and phenanthrene. The gaseous p r o d u c t s o f
c o a l and c o a l o i l c o n t a i n e d more propane and butanes
and l e s s methane and ethane when compared t o t h e
p r o d u c t s o f a n t h r a c e n e and phenanthrene. The d i f f e r -
ences i n the h y d r o c r a c k e d p r o d u c t s were o b v i o u s l y due
t o t h e d i f f e r e n c e s i n the n a t u r e o f r e a c t a n t s . Coal
and c o a l o i l c o n t a i n h y d r o a r o m a t i c , n a p h t h e n i c ,
h e t e r o c y c l i c and a l i p h a t i c s t r u c t u r e s , i n a d d i t i o n t o
polynuclear aromatic s t r u c t u r e s . H y d r o c r a c k i n g under
s e v e r e c o n d i t i o n s y i e l d e d more BTX as shown i n T a b l e
VI. The y i e l d s o f BTX o b t a i n e d from c o a l , c o a l o i l ,
a n t h r a c e n e and phenanthrene were r e s p e c t i v e l y 18.5,
25.5, 36.0, and 32.5 p e r c e n t . Benzene was the most

TABLE V
NATURE OF HYDROCRACKED PRODUCTS fO
C a t a l y s t : H - z e o l o n (10) + W S 2
T e m p e r a t u r e , ° c : 500
P r e s s u r e , p s i : 3000
R e a c t i o n T i m e , m t s . : 0 + 20 η
Reactant/catalyst, (wt) : 1.0 ο
Coal Coal O i l Anthracene Phenanthrene

Ο
Conversion, wt. % 61.0 45.0 58.0 49.0 ο
A l k y l b e n z e n e s , wt.% 2.6 3.5 8.4 4.4 1
Composition o f Benzenes,
vol. % S"
Benzene 45.9 40.2 17. 20.
Toluene 20.2 17.5 46, 44.
Ethylbenzene 10.2 8.7 15. 13, 3
Xylenes 16.3 14.3 1, 1,
P r o p y l and Butylbenzenes 7.4 19.3 19. 20, 3
Composition of Gas, V o l . % a
Methane 12.4 13.2 42.6 46.4

Ethane 24.6 26.1 35.4 28.4
Propane 35.9 45.3 20.6 21.9
Butanes 27.1 15.4 1.4 3.3

95
CD
TABLE VI
BTX PRODUCTION FROM DIFFERENT FEEDSTOCKS
Coal Coal O i l Anthracene Phenanthrene
Temperature, c 540 520 520 520

Pressure, p s i 3500 3000 3000 3000
R e a c t i o n Time, mts 30 30 30 30
C o n v e r s i o n , wt. % 82 71 79 73
BTX y i e l d , wt. % 18.5 25.5 36.0 32.5
BTX A n a l y s i s , v o l . %
Benzene 49.5 48.4 21.5 24.8
Toluene 22.4 20.8 54.6 51.3
Ethylbenzene 9.5 10.2 19.1 18.8
Xylenes 18.6 20.6 4.8 5.1

predominant component o f c o a l and c o a l o i l p r o d u c t s ,
whereas anthracene and phenanthrene p r o d u c t s c o n t a i n e d
more t o l u e n e .
Kinetics
H y d r o c r a c k i n g c o n v e r s i o n d a t a were e v a l u a t e d b y
a s i m p l e f i r s t o r d e r r a t e e q u a t i o n ( i ) where "x" i s
f r a c t i o n a l c o n v e r s i o n o f r e a c t a n t and Q i s a c o n s t a n t .
The d a t a were found t o be c o m p a t i b l e w i t h e q u a t i o n ( i )
as shown i n F i g u r e s 3 - 6 .
L n ( l - x ) = -KT + Q ( i )
F i r s t o r d e r r a t e c o n s t a n t s (Table V I I ) v a r i e d i n t h e
order c o a l >anthracene> ghenanthrene>coal o i l i n the
temperature range o f 450 - 500 c under a p r e s s u r e o f
3000 p s i . The a r r h e n i u s a c t i v a t i o n e n e r g i e s (Table
V I I I and F i g u r e 7) based on f i r s t o r d e r r a t e c o n s t a n t s
i n d i c a t e d t h a t t h e r a t e s o f h y d r o c r a c k i n g were con
t r o l l e d b y c h e m i c a l r e a c t i o n s . The r a t e d a t a o f
phenanthrene and c o a l o i l were t e s t e d f o r c o m p a t i b i l i t y
w i t h t h e d u a l - s i t e mechanism o f Langmuir and H i n s h e l -
wood. The model shown i n e q u a t i o n ( i i ) was e a r l i e r
used f o r t e s t i n g h y d r o c r a c k i n g d a t a o f naphthalene,
anthracene and pyrene by Qader e t a l (5, 6 ) .
Κ h
2
1^ = 1 + a . C (ii)
2
κ (κ* \ \ c )h (κ* \ c h ) h r
where Κ = e x p e r i m e n t a l r a t e c o n s t a n t
= c o n c e n t r a t i o n o f hydrogen
= c o n c e n t r a t i o n o f r e a c t a n t hydrocarbon or o i l
Κ*, K a # = constants
A t c o n s t a n t hydrogen p r e s s u r e , e q u a t i o n ( i i ) becomes
e q u a t i o n ( i i i ) s i n c e C_ becomes c o n s t a n t .
h
l i = M + NC (iii)
2
K

0.0
I I I I I 1
0 0+10 0+20 0+30 0+40 0+60
TIME, MINUTES
Figure S. First order plot of anthracene
TIME, MINUTES
Figure 4. First order plot of phenanthrene

0 , 5
Ο 04-10 0+20 0+30 0+40
TIME, MINUTES
Figure 6. First order plot of coal

rH
•Η π σ\
Ο VO CO CN
Ο Ο ι—ι
rH Ο Ο Ο
rd . . .
Ο ο ο ο
ω
ω >ι
U ιΗ
ιη Γ- cx>^
,α VD Ο Μ 03
-Ρ ο Η Η ω ω
s C Ο Ο Ο C ι-Η
rH rd . . . WO
I G Ο Ο Ο CO Ë
CL) W β σο ο oo
-ρ — Λ H ο ε L T W m ko
Ρί -Ρ CU Ο Ή Cil · · · ·
-HO p$ -Ρ \ vo r> ο
Sffi H (d rH H H H ÎN
— — ïs > (d
W -HO
C0 -H (U -P
EH 03 β «ζ; U «
2 α CU O O O Ï O Ο •< ^
<; υ σ\ ^ co H H
H EH Ο (d Ο H CN H EH
H CO Ο M O O O H <C
> Ζ Ο Λ . . . > >
Ο on -Ρ ο ο ο Η
W U β W ΕΗ
§ go, S «
EH <Ç M EH CO
Κ 0 rH CN VD KO |D
03 rd σ\ H
03 Ο H H ( M S
H (U CJ o o o pq
Ρ . . . w
PS pu o o o «
Ο «
< CD
EH β
CO 0 0
CM
H H
PLI -H ο -P
Ο id G
M rd
rd <d -Ρ ω
ο ο q Λ
υ υ pu
ο
ο
eu
+3
rd
u
eu
g Ο If) ο
eu m ο
EH m

QADER A N D M C O M B E R Complex Aromatic Structures
-1.5 μ
1.40
1/TxlC?
Figure 7. Arrhenius plots

Where M = 1
h = constant
Κ
Ν =, a
= constant
At constant c o n c e n t r a t i o n of hydrocarbon or o i l , C
becomes c o n s t a n t and e q u a t i o n ( i i ) becomes e q u a t i o n
(iv)
Κ = Ζ · c,
h
Where Ζ = Κ* Κ Κ
(1 + Κ C ) = constant (iv)
The e x p e r i m e n t a l d a t a o b t a i n e d i n t h e h y d r o
c r a c k i n g o f c o a l , c o a l o i l and phenanthrene were
t e s t e d w i t h e q u a t i o n s ( i i i ) and ( i v ) as shown i n
F i g u r e s 8 and 9 and t h e d a t a were found c o m p a t i b l e
w i t h t h e model. This c o m p a t i b i l i t y confirmed that the
r a t e s o f h y d r o c r a c k i n g were c o n t r o l l e d by s u r f a c e
c h e m i c a l r e a c t i o n s as were a l s o i n d i c a t e d b y a r r h e n i u s
a c t i v a t i o n e n e r g i e s (Table V I I I ) .
Acknowledgement
T h i s work was done under t h e s p o n s o r s h i p o f t h e
O f f i c e o f C o a l Research and t h e U n i v e r s i t y o f Utah.
Some o f t h e h y d r o c r a c k i n g experiments on c o a l and c o a l
o i l were done b y B i l l B e r r e t t and t h e a n a l y t i c a l work
was done by Jim L i g h t and E a r l E v e r e t t .

REACTANT (gm.)
Figure 8. Variation of rate constant with weight
Figure 9. Variation of rate constant with pressure

Literature Cited
1. S c h r o e d e r , W.C., U. S. P a t e n t 30,030,297 and
3,152,063
2. Qader, S . A . - The Oil and Gas J o u r n a l , 72,
No. 29, 58 (1974)
3. G i v e n , P. H. - F u e l , 39, 147 (1960)
4. Qader, S. Α., D. B. McOmber and W. H. W i s e r , 166th
N a t i o n a l M e e t i n g , ACS, F u e l C h e m i s t r y Division,
p r e p r i n t s 18, No. 4, 127 (1973)
5. Qader, S. A. - J o u r n a l o f t h e Institute o f
Petroleum 59, No. 568, 178 (1973)
6. Qader, S. Α., L. Chun Chen and D. B. McOmber,
165th N a t i o n a l M e e t i n g , ACS, F u e l C h e m i s t r y
Division - p r e p r i n t s 18, No. 1, 60 (1973)

6
Diesel and Burner Fuels from Hydrocracking in
Situ Shale Oil
PHILIP L. COTTINGHAM and L E O G. NICKERSON

Laramie Energy Research Center, Energy Research and Development Administration,
Laramie, Wyo. 82070
For several years, the Laramie Energy Research Center has

conducted research in recovering shale o i l through in situ retort-
ing by the underground combustion method. Crude shale o i l s pro-
duced by this method normally have lower specific gravities, vis-
cosities, and pour points than do crude shale o i l s produced in the
gas combustion or N-T-U retorts. They also contain somewhat less
nitrogen, but the sulfur content is not greatly different from
that of the crude o i l s from these aboveground retorts. Percent-
ages of both elements are higher than desirable in liquid fuels or
in feedstocks that are to be processed to high-quality liquid
fuels by most catalytic refining processes.
Catalytic hydrogenation at cracking conditions, referred to
here as "hydrocracking," has been found by previous experiments to
be a suitable method for producing low-sulfur, low-nitrogen "syn-
thetic crude" o i l s from in situ crude shale o i l s (1,2,1). One of
the primary objectives of these previous experiments has been to
increase the quantity of gasoline contained in the hydrocracked
synthetic crudes. A limited investigation of the s u i t a b i l i t y of
fractions of the hydrocracked o i l s as catalytic reforming and
catalytic cracking feedstocks for the production of gasoline has
been made however, little attention has been given to the
types of diesel fuels and fuel oils that can be prepared from the
fractions.
The purpose of the present work was to investigate the quan-
t i t y and quality of diesel fuels and fuel o i l s that could be pre-
pared from the liquid product obtained by hydrocracking of in situ
combustion shale oil. A sample of the in situ crude o i l was hydro-
cracked at operating conditions that had been found by previous
experiments to be effective in eliminating most of the nitrogen
and sulfur from the o i l and in greatly reducing the average b o i l -
ing point of the oil. The hydrocracked o i l was d i s t i l l e d into a
350° F end-point reforming stock and small-volume heavier frac-
tions. Diesel fuels, suitable for use also as fuel o i l s , were
prepared by blending small-volume fractions.
99

Apparatus and Operating Procedure
A simplified flow diagram of the hydrocracking equipment is

shown in Figure 1. The reactor was a type 316 stainless steel
tube 40 inches long, with 9/16-inch inside diameter and 1-inch
outside diameter. A stainless steel screen 10^ inches from the
bottom of the reactor supported 50 ml of catalyst that extended
approximately 12% inches above the screen. A second screen on top
of the catalyst supported 50 ml of quartz chips in the upper, pre-
heating section of the reactor. The reactor was surrounded by
a c y l i n d r i c a l , 3-inch-outside-diameter aluminum block, contained
in a 36-inch-long electric furnace that covered essentially a l l
but the exposed high-pressure fittings at the ends of the reactor.
Temperatures were measured by five thermocouples placed at uni-
formly spaced intervals along the catalyst-containing section of
the reactor in a groove in the inner wall of the aluminum block.
Other thermocouples were used to control the temperature of the

surrounding furnace.
Before the hydrocracking experiment, the catalyst was pre-
treated in the reactor for 16 hours at 700° F with a mixture of
1.1 standard cubic feet of a i r and 0.41 pound of steam per pound
of catalyst per hour. After the pretreatment, the reactor was
cooled to 500° F; then the steam was cut off. When the reactor
cooled to 350° F, the a i r flow was cut off. The reactor was next
purged with helium and pressurized to 250 psig with hydrogen. A
stream of hydrogen containing 5 volume-percent hydrogen sulfide at
a total pressure of 250 psig was then passed through the reactor
at a rate of 1 scf per hour for 4 hours. During this time the
reactor was heated from 350° to 600° F. The reactor was then
heated to the planned hydrocracking temperature, and brought to
the planned total reaction pressure with hydrogen, and a stream of
hydrogen at the proposed experimental rate was passed through the
reactor for 30 minutes. The o i l feed pump was then started.
During the experiment, o i l pumped by positive displacement
was mixed with hydrogen at the top of the reactor and passed down-
ward through the catalyst. The resulting products passed through
a backpressure regulator into a separator maintained at 200 psig
and 75° F. Gas from the separator passed through a second back-
pressure regulator and was metered and sampled for gas chromato-
graphic analysis. The liquid product was drained from the separa-
tor at the end of each 24-hour period and was washed with water to
remove hydrogen sulfide and ammonia before i t was analyzed. Hy-
drogen flow was metered with a mass flowmeter, but total hydrogen
feed was measured by the volume removed from calibrated storage
vessels. Hydrogen consumption was calculated from the analyses
of feed and product gases.
After the experiment, the used catalyst was purged with steam
and then regenerated with a mixture of steam and a i r ; the regener-
ation gas was dried and any carbon dioxide formed was absorbed by
Ascarite for determination of the percent carbon deposit.

6. coTTiNGHAM A N D NiCKERSON Diesel and Burner Fuels 101
PRESSURE ROTAMETER
-REGULATOR
BACK-PRESSURE REGULATOR
METERING VALVE
TO GAS HOLDER
SOR
œ.
ζ
</> g
LU LU
oc
α.
ο
Ο
CO.
YDR
ecu
PRODUCT OIL
χ
< TO DISTILLATION
OIL BACK PRESSURE REGULATOR
Figure 1. Simplified flow diagram of hydrogénation unit

TABLE I. - Hydrocracking of in situ crude shale oil

over nickel-molybdena catalyst
Operating conditions:
Temperature, F 0
800
Pressure, psig 1500
Space velocity, V /V /hr 0 c 0.48
Throughput, V / V 0 c 125
Hydrogen feed, scf/bbl 5000
Hydrogen consumed, scf/bbl 1760
In situ Hydrocracked
crude oil
Yield, volume-percent 100.0 97.6
Yield, weight-percent 100.0 89.7
Properties:
Specific gravity, 60/60° F 0.8800 0.8086

0
API 28.75 43.56
Nitrogen, weight-percent 1.62 0.02
Sulfur, weight-percent 0.82 0.02
Carbon/hydrogen weight ratio 7.01 ND
Carbon residue, weight-percent 1.8 ND
Pour point, 0
F 40 ND
Viscosity at 100° F:
Kinematic, cs 5.82 ND
Saybolt Universal Seconds 45 ND
ASTM d i s t i l l a t i o n , F: 0
IBP 293 138

5 volume-percent recovered 346 258
90 volume-percent recovered - 672
EP 704 717
Recovery, volume-percent 92.0 94.5
Residue, volume-percent 6.0 2.5
Loss, volume-percent 2.0 3.0
ND, not determined

6. C O T T I N G H A M A N D NICKERSON Diesel and Burner Fuels 103
Preparation of Hydrocracked Oil
The in situ crude shale o i l feedstock was obtained during

the 28th through the 37th day of operation of a 42-day in situ
combustion retorting experiment at a site near Rock Springs, Wyo.
(4^5,6). The crude contained 0.01 weight-percent ash, which was
removed by f i l t r a t i o n with diatomaceous s i l i c a f i l t e r aid before
the o i l was hydrocracked. The f i l t e r e d o i l was hydrocracked in a
once-through operation at 800° F, 1,500 psig, and 0.48 volume of
o i l per volume of catalyst per hour (V /V /hr) over a catalyst
0 c
that contained nickel oxide and molybdenum oxide on alumina in the

form of 1/8-inch by 1/16-inch extrusions. Total throughput of
crude o i l in the planned 10-day run was 125 volumes of o i l per
volume of catalyst (V /V ). 0 cOperating conditions, properties of
the feedstock, yields, and properties of the hydrocracked o i l
(total liquid product) are shown in Table I.
The yield of synthetic crude was 97.6 volume-percent, or 89.7

weight-percent. The decrease in quantity of liquid was accompani
ed by considerable reduction in the average boiling point, and
specific gravity of the liquid product compared with those of the
in situ crude. At the same time, about 98 percent of the nitrogen
and sulfur content was eliminated. Gas formed was 9.4 weight-per
cent of the feed, and carbon deposited on the catalyst was 0.13
weight-percent of the feed.
The analysis of the product gas, calculated to a hydrogen-
free basis, is shown in Table II. The high percentage of methane
and the predominance of η-butane and n-pentane over the branched
compounds suggest that they were produced by a thermal cracking
reaction with hydrogénation of the olefins.
TABLE II. - Analysis of gas from hydrocracking in situ crude
Gas Volume-percent of gas
Methane 45.8
Ethane 33.6
Propane 14.0
i-Butane 1.2
n-Butane 4.2
i-Pentane 0.5
n-Pentane 0.7
Diesel Fuels and Fuel Oil
As a means of preparing high percentages of diesel fuels with

good quality from the hydrocracked o i l , a batch d i s t i l l a t i o n of
the o i l was made in a packed laboratory d i s t i l l a t i o n column in
which a f i r s t fraction was removed at a corrected column head

temperature of 364° F (at 760 mm). This fraction, considered as a

catalytic reforming feedstock, had an ASTM-disti"Nation [7) end
point of 350° F. Its Research Method octane numbers were only 39,
clear, and 69 with 3 ml of tetraethyllead, and i t would require
reforming before use in gasoline. The remainder of the d i s t i l l a -
tion was conducted at 10 mm absolute pressure, and 54 small-volume
d i s t i l l a t e fractions were collected at 5° F intervals between dis-
t i l l a t i o n column head temperatures of 145° F and 428° F (at 10 mm),
corresponding to temperatures of 364° and 725° F at 760 mm.
The d i s t i l l a t i o n residuum contained a large amount of wax
that separated when the residuum was cooled to room temperature.
The wax was removed by mixing the residuum with three times its
volume of acetone, c h i l l i n g the mixture to 32° F, and f i l t e r i n g
out the precipitated wax. Acetone was removed from both the f i l -
trate and precipitate by d i s t i l l a t i o n . Total wax removed, includ-
ing a small quantity washed from the d i s t i l l a t i o n column with
boiling acetone, amounted to 48 weight-percent of the residuum.

From a study of the d i s t i l l a t i o n data for the hydrocracked
o i l , i t was estimated that quantities of city bus (C-B), truck-
tractor (T-T), and stationary-marine (S-M) diesel fuels in the
volume ratios of 2:2:1 and f i t t i n g the average d i s t i l l a t i o n char-
acteristics (8) of diesel fuels now being sold could be made from
the hydrocracked small-volume d i s t i l l a t e fractions. Beginning
with the type C-B diesel f u e l , appropriate amounts of the small-
volume fractions were calculated that would produce a fuel approx-
imately f i t t i n g the 10, 50, and 90 percent ASTM d i s t i l l a t i o n
points of typical diesel fuels now being sold. Similar calcula-
tions were made for the desired types T-T and S-M fuels. The c a l -
culated quantity of each fuel was then adjusted to use up as much
as possible of the available small-volume fractions without great-
ly changing the desired d i s t i l l a t i o n characteristics of the pro-
posed fuels. According to these calculations, portions of some of
the small-volume fractions would be l e f t over, and these leftover
portions were considered suitable for mixing with the dewaxed dis-
t i l l a t i o n residuum to make fuel o i l .
The small-volume fractions were blended according to the
above procedure, producing the quantities of diesel fuels shown
(as percentages) in Table III. The dewaxed residuum was mixed
with approximately four times i t s volume of lower boiling oil not
used in the diesel fuel blends, and is reported in Table III as
fuel o i l . Properties of the blended diesel fuels and fuel o i l are
shown in Table IV.
The total yield of diesel fuels was 51.6 volume-percent of
the in situ crude. The properties of these fuels f e l l within the
limits (Table V) of those of corresponding petroleum diesel fuels
currently marketed in the United States (8) except for the carbon
residue of the S-M shale-oil diesel f u e l ; this residue was slight-
ly higher than those of the petroleum diesel fuels but was prob-
ably acceptable. The value of 0.36 weight-percent for the carbon
residue on the 10-percent bottoms of the S-M fuel was only a

6. coTTiNGHAM A N D NiCKERsoN Diesel and Burner Fuels 105
TABLE III. - Yields of products from d i s t i l l a t i o n and blending
Weight-percent Volume-percent
of of
in situ crude in situ crude
Reforming stock 16.0 18.5

C-B diesel fuel 19.7 21.3
T-T diesel fuel 18.5 19.6
S-M diesel fuel 10.1 10.7
Fuel o i l 20.4 21.5
Wax 3.8 ND
Light ends from d i s t i l l a t i o n 0.6 ND
D i s t i l l a t i o n loss 0.6 ND
ND, not determined

t r i f l e greater than the upper ASTM limit of 0.35 percent for the
lighter grade 2-D diesel fuels (7J, and no limit is listed for the
grade 4-D which corresponds to type S-M. With the exception of
the carbon residue and high flash point, the properties of the S-M
shale-oil diesel fuel also f e l l within the limits of the proper-
ties of the type R-R (railroad) diesel fuels now being marketed.
Most of the properties of the fuel o i l blend containing the de-
waxed residuum were within the range of properties of the petrol-
eum S-M diesel fuels shown in Table V, Its high cetane index of
65 suggests that this fuel o i l be used as an S-M diesel fuel
rather than as a burner f u e l .
The sulfur percentages of 0.02 weight-percent or less in the
shale oil diesel fuels would permit these fuels to be classed as
low-sulfur diesel fuels. Nitrogen percentages were low, ranging
from 141 to 202 parts per million (ppm). Cetane indexes, calcu-
lated by ASTM method D-976 (7), were excellent, ranging from 48 to
56.
Table VI shows the range of properties of grades 1, 2, and 4
burner fuel o i l s marketed in the United States in 1974 (9). Most
of these fuels were also marketed as diesel fuels (8,9). The
shale-oil types C-B and T-T diesel fuels would, respectively, f i t
with the grades 1 and 2 burner fuels. The shale-oil S-M diesel
fuel would also f i t with the grade 2 burner fuels. The shale-oil
fuel o i l fraction had a d i s t i l l a t i o n range resembling the grade 2
fuels, but i t s viscosity was intermediate between those of the
grade 2 and grade 4 fuels.
The C-B, T-T, and S-M shale oil diesel fuels respectively met
the ASTM requirements []) for grades 1-D, 2-D, and 4-D diesel
fuels and Nos. 1, 2, and 4 fuel o i l s , with some minor exceptions.
Thus, the 90-percent d i s t i l l a t i o n temperature of the T-T diesel
fuel was 3° F lower than the ASTM lower limit for grade 2-D diesel
and No. 2 fuel o i l . Also, the viscosity of the S-M diesel fuel
was slightly lower than the lower limit specified for grade 4-D

TABLE IV. - Properties of reforming stock, diesel fuels,

and fuel o i l
Reforming C-B T-T S-M Fuel

stock diesel diesel diesel oil
Specific gravity,
60/60° F 0.7600 0.8159 0.8262 0.8300 0.8367
A P I
54.68 41.93 39.75 38.98 37.62
° 0
Flash point, F NAp 188 212 265 325
Pour point, F 0
NAp -50 -30 -20 30
C residue on 10 pet
bottoms, wt-pct NAp 0.14 0.16 0.36 0.42
Ash, wt-pct NAp <0.001 <0.001 <0.001 <0.001
Kinematic, cs NAp 1.66 2.40 2.96 5.07
SUS NAp 32 34.0 35.8 42.6

Sulfur, wt-pct <0.001 0.01 0.02 0.02 0.02
Nitrogen, ppm 20 141 166 202 396
Cetane index NAp 48 54 56 65
ASTM d i s t i l l a t i o n ,
F at 760 mm:
0
IBP 158 379 404 410 394

10 vol-pet recovered 223 400 442 450 528
EP 350 517 554 628 667
Recovery, vol-pet 97.0 95.0 98.0 97.5 92.0
Residue, vol-pet 2.0 2.0 1.0 2.0 7.0
Loss, vol-pet 1.0 3.0 1.0 0.5 1.0
NAp, not applicable

TABLE V. - Range of diesel fuels produced

in the United States during 1974
Type C-B Type T-T Type R-R Type S-M

Test Min. Max. Min. Max. Min. Max. Min. Max.
0
Gravity, API 33.3 47.4 27.3 47.4 27.2 43.4 9.6 41.1
0
Flash point, F 124 194 112 230 136 198 136 290
Kinematic, cs 1.50 4.34 1.30 4.55 1.60 4.34 1.94 22.1
0
Pour point, F -70 25 <-60 25 -40 25 -35 65
Sulfur, weight-percent 0.004 0.52 0.001 1.07 0.01 0.85 0.06 2.85
C res. on 10 percent, weight-percent 0.000 0.18 0.001 0.26 0.014 0.26 0.05 0.18
Ash, weight-percent 0.000 0.005 0.000 0.010 0.000 0.005 0.000 0.02
Cetane no. or index 39.8 65.8 38.1 65.8 34.1 65.8 38.0 63.1
0
D i s t i l l a t i o n temperature, F:
IBP 320 488 301 488 310 488 327 535
10 percent recovered 357 520 329 520 376 520 384 595
EP 476 663 476 700 514 688 582 700

TABLE VI. - Range of properties of d i s t i l l a t e burner fuels

produced in the United States during 1974
Grade 1 Grade 2 Grade 4

Test Min. Max. Min. Max. Min. Max.
0
Gravity, API 36.2 47.9 29.5 43.0 17.6 28.2
0
Flash point, F 104 160 114 192 156 216
Kinematic, cs 1.28 2.60 1.70 3.70 9.64 30.1
0
Pour point, F -70 0 -50 25 -50 75
Sulfur, weight-percent 0.002 0.38 0.03 0.64 0.46 1.44
C res. on 10 percent, weight-percent 0.00 0.18 0.002 0.27 NR NR
C res. on 100 percent, weight-percent NR NR NR NR 0.52 7.6
Ash, weight-percent NR NR NR NR 0.002 0.03
Water and sediment, volume-percent 0.000 0.025 0.00 0.10 0.06 0.2
0
D i s t i l l a t i o n temperature, F:
IBP 303 380 293 416 NR NR
10 percent recovered 336 413 333 469
EP 464 614 575 698

6. coTTiNGHAM A N D NiCKERSON Diesel and Burner Fuels 109
diesel fuel and No. 4 fuel o i l . The pour points met the ASTM
requirements for burner fuel o i l s . The ASTM pour point require-
ments for diesel fuels depend on the ambient temperature at the
place of use; for most purposes, the pour points of the shale-oil
diesel fuels would be satisfactory.
The properties of the fuel o i l blend met the requirements for
ASTM No. 4 fuel o i l (usually considered a d i s t i l l a t e fuel) except
that its viscosity was low, f a l l i n g between the specified require-
ments for No. 2 and No. 4 fuel oils (7), and i t s pour point of
30° F was higher than the ASTM-recommended maximum of 20° F. The
fuel could be used as a low-sulfur, high-cetane-index grade 4-D
diesel fuel in warm weather or where preheating f a c i l i t i e s were
available.
The yield of fuel oil prepared from the blended dewaxed
residuum was 21.5 volume-percent of the in situ crude. The total
of this, plus the 51.6 volume-percent of diesel fuels, amounted to
73.1 volume-percent of the in situ crude that could be used as

low-sulfur diesel fuels or Nos. 1 through 4 burner fuels.
Summary
In situ crude shale o i l , produced by the underground combus-

tion retorting method, was hydrocracked over a nickel-molybdena
catalyst at 800° F and 1,500 psig. The liquid product was dis-
t i l l e d into a low-octane reforming feedstock amounting to 18.5
volume-percent of the in situ crude plus a large number of small-
volume higher boiling fractions and a small quantity of waxy
residuum. Most of the small-volume d i s t i l l a t e fractions were
blended into types C-B, T-T, and S-M diesel fuels whose properties
resembled those of diesel fuels and d i s t i l l a t e fuels now being
marketed. The diesel fuels also met the ASTM requirements for
diesel fuels and d i s t i l l a t e fuel o i l s with minor exceptions. All
of the shale-oil diesel fuels had very low sulfur contents and
very high cetane indexes.
The dewaxed d i s t i l l a t i o n residuum was blended with a portion
of the small-volume d i s t i l l a t e fractions to form a fuel oil f i t -
ting the requirements for No. 4 fuel o i l except that its viscosity
was between the viscosity limits for No. 2 and No. 4 fuels and its
pour point of 30° F was higher than ASTM recommendations, although
in the range of No. 4 fuel o i l s now being marketed. This fuel oil
could also be used as a low-sulfur, high-cetane-index S-M diesel
fuel.
The yield of diesel fuels was 51.6 volume-percent of the in
situ crude, and the yield of No. 4 fuel oil was 21.5 volume-per-
cent, for a total of 73.1 volume-percent of the in situ crude that
could be used as low-sulfur, high-cetane-index diesel fuels or
Nos. 1 through 4 burner fuels.

Literature Cited
1. Frost, C. Μ., and P. L. Cottingham. BuMines RI 7844 (1974).

2. Frost, C. M., R. E. Poulson, and H. B. Jensen, Preprints, Div.
of Fuel Chem., Inc., ACS (1974) 19 (2) 156.
3. Poulson, R. E., C. M. Frost, and H. B. Jensen, Preprints, Div.
of Fuel Chem., Inc., ACS (1974) 19 (2) 175.
4. Burwell, E. L., H. C. Carpenter, and H. W. Sohns. BuMines
TPR 16 (1969).
5. Burwell, E. L., T. E. Sterner, and H. C. Carpenter. J .
Petrol. Technol. (1970) 1520.
6. Carpenter, H. C., E. L. Burwell, and H. W. Sohns. J . Petrol.
Technol. (1972) 21.
7. American Society For Testing Materials. 1973 Book of ASTM
Standards. Part 17: Petroleum Products.
8. Shelton, Ella Mae. BuMines PPS 87 (1974).
9. . BuMines PPS 86 (1974).

7
Synthoil Process and Product Analysis
HEINZ W. STERNBERG, RAPHAEL RAYMOND, and SAYEED AKHTAR
Energy Research and Development Administration, Pittsburgh Energy Research Center,
4800 Forbes Ave., Pittsburgh, Penn. 15213
Many power generating stations i n the United States burn im

ported fuel oils, instead of coal, to meet environmental protec
tion regulations. Large quantities of fuel oils are imported
annually at considerable strain to the nation's balance of pay
ment, a strain that could be removed by burning environmentally
acceptable coal-derived fuels prepared from internal resources.
Towards this end, the Energy Research and Development Administra
tion is developing a process known as the SYNTHOIL process to
convert coal to a low-sulfur, low-ash utility fuel. In the
process, coal is liquefied and hydrodesulfurized catalytically
in a turbulent-flow, packed-bed reactor (1-3). The gross liquid
product on centrifugation yields a nonpolluting fuel oil suitable
for power generation. The results of a study of the chemical
composition and viscosity of the product oils obtained at differ
ent operating conditions are presented in this paper. The inter
relationship of chemical composition and viscosity i s of special
interest in view of the importance of the latter in centrifugation
of the gross liquid products and in pipeline transportation of
the product oil.
Plant and Operating Conditions
The flowsheet of a 1/2-ton (slurry) per day SYNTHOIL bench

scale plant, currently i n operation at the Energy Research and
Development Administration laboratory in Bruceton, Pennsylvania,
is shown i n figure 1. The v e r t i c a l l y placed reactor is made
of two interconnected stainless steel tubings of 1.1-inch ID
χ 14.5-ft long each. The upper end of the f i r s t section i s
connected to the lower end of the second section with a 5/16-inch
ID empty tubing. Thus, the plant may be operated with one or
both sections of the reactor packed with catalyst while the fluids
flow upwards through each.
Hydrogen and a slurry of 35 to 45 percent coal i n recycle
o i l are introduced concurrently in a 3-inch ID χ 11-ft long
preheater packed with 3/4-inch χ 3/4-inch ceramic pellets which
111

proirote heat t r a n s f e r . The heated feed stream enters the r e a c t o r

at the lower end of the f i r s t s e c t i o n and the product stream
e x i t s at the upper end of the second s e c t i o n . The l i q u i d s and
unreacted s o l i d s are separated from the gases and c e n t r i f u g e d
to o b t a i n the product o i l . The gases, a f t e r scrubbing out H2S
and NH3, are r e c y c l e d without d e p r e s s u r i z a t i o n . The flow of
E2 through both the preheater and the r e a c t o r i s i n t u r b u l e n t
regime.
The o p e r a t i n g c o n d i t i o n s f o r the three runs FB-38, FB-39,
and FB-40, the r e s u l t s from which are discussed i n t h i s paper,
are given i n t a b l e I . The l e n g t h of the 1 . 1 - i n c h ID r e a c t o r
was 29 f t i n run FB-38 and 14.5 f t i n FB-39 and FB-40. Runs
FB-38 and FB-39 were both conducted at 4,000 p s i but the r e a c t o r
temperature was 4 1 5 ° C i n FB-38 and 4 5 0 ° C i n FB-39. Run FB-40
was conducted at 2,000 p s i and 4 5 0 ° C .
TABLE I . - Run numbers and operating conditions
Run No. FB-38 FB-39 FB-40

Length of the 1 . 1 - i n c h ID 29 14.5 14.5
reactor, ft
Charge weight of C o - M o / S i 0 2 - A l 0
2 3 11 5.5 5.5
catalyst, lb
Plant pressure, psig 4,000 4,000 2,000
Reactor temperature, 0
C 415 450 450
Feed r a t e o f (35 c o a l + 65 r e c y c l e 25 25 25
oil) slurry, lb/hr
Time on stream, h r 30 380 360
The a n a l y s i s of the c o a l used i n these runs i s given i n

table II. The c o a l contained 5.5 percent s u l f u r and 16.5 percent
ash. The p y r i t i c s u l f u r i n c o a l was 3.08 percent and the organic
s u l f u r 1.95 p e r c e n t .
Product A n a l y s i s
The l i q u i d products were c o l l e c t e d i n 4-hour batches, c e n t r i -

fuged, sampled, and analyzed f o r asphaltene, o i l , elementary
composition (C, H , N , S ) , a s h , s p e c i f i c g r a v i t y , and v i s c o s i t y .
In runs FB-38 and FB-40, the asphaltene content i n c r e a s e d
w i t h time. In run FB-39, on the other hand, the asphaltene
content decreased during the f i r s t 120 hours from 18 percent
to 7 p e r c e n t , remained around 7 percent f o r about 60 h o u r s , and

STERNBERG E T A L . Synthoil Process
1
TABLE I I . - Analysis o f feed c o a l , as received
Proximate a n a l y s i s , wt pet
Moisture 4.2
1 6 5
Ash ·
V o l a t i l e matter 36.2
F i x e d carbon 43.1
U l t i m a t e a n a l y s i s , wt pet
Hydrogen 4.8
6 0 7
Carbon ·
2
Nitrogen I ·
Oxygen 11.3
5 5
Sulfur ·
1 6 5
Ash ·
Forms o f s u l f u r , wt pet
7
Sulfate °-^
Pyritic 3.08
Organic · · 1.95
C a l o r i f i c value, Btu/lb 11,020
Rank: hvBb
A b l e n d from Kentucky seams #9, 11, 12, and 13 which are

mined t o g e t h e r . Ohio County, Western Kentucky.

during the l a s t 200 hours i n c r e a s e d from 7 percent to 25 p e r c e n t .

The analyses o f some of the samples c o l l e c t e d from runs
FB-38, FB-39, and FB-40 are l i s t e d i n t a b l e s I I I , IV, and V .
I n s p e c t i o n of the data shows that the v i s c o s i t y o f the product
o i l i n c r e a s e s w i t h asphaltene content. To l e a r n more about the
nature o f asphaltenes and t h e i r e f f e c t on v i s c o s i t y , we f r a c t i o n
ated samples of product o i l from runs FB-38 and FB-40 according
to the scheme shown i n f i g u r e 2. U l t i m a t e analyses and molecular
weights o f the v a r i o u s f r a c t i o n s a r e shown i n t a b l e s V I , V I I ,
and V I I I . In a d d i t i o n to heavy o i l and asphaltene, these t a b l e s
a l s o l i s t p y r i d i n e s o l s and p y r i d i n e i n s o l s . These two f r a c t i o n s
are always lumped together as "benzene i n s o l s " , but we separated
the benzene i n s o l s (toluene i n s o l s i n our case) i n t o a p y r i d i n e
s o l u b l e and a p y r i d i n e i n s o l u b l e f r a c t i o n . I t i s a common p r a c
t i c e to measure the e f f i c i e n c y of a c o a l l i q u e f a c t i o n process
by the percent coal-to-benzene s o l s conversion on a m o i s t u r e -
and a s h - f r e e b a s i s , the assumption being that the benzene i n

s o l u b l e m a t e r i a l i s unreacted c o a l and, by i m p l i c a t i o n , that
i t i s not s o l u b l e i n the product o i l and does not c o n t r i b u t e
to i t s v i s c o s i t y . These assumptions are m i s l e a d i n g . Tables
V I , V I I , and V I I I show that i n a l l cases more than 50 percent
of the toluene i n s o l s are p y r i d i n e s o l u b l e and therefore cannot
be considered unreacted c o a l . I t i s only the p y r i d i n e i n s o l s
that may be unreacted c o a l , carbon, or ash. Moreover, removal
of the toluene i n s o l s r e s u l t s i n a considerable decrease i n the
v i s c o s i t y o f the product o i l . F o r example, the v i s c o s i t y of
a product o i l (FB-40, batch 88) dropped from 1,433 to 907 a f t e r
removal o f 8.1 percent toluene i n s o l s . I t i s reasonable to assume
that o f the 8.1 percent toluene i n s o l s removed, o n l y the 4.8
percent p y r i d i n e s o l s are r e s p o n s i b l e f o r t h i s decrease i n
viscosity. A f u r t h e r and much l a r g e r decrease i n v i s c o s i t y
occurred when the asphaltenes, r e p r e s e n t i n g 40.2 percent o f the
sample, were removed. The v i s c o s i t y then dropped from 907 to
16, as shown i n f i g u r e 3.
TABLE I I I . - Analyses o f c e n t r i f u g e d l i q u i d product samples

taken d u r i n g run FB-38
Vis Analyses5, Wt pet

Sp g r , c o s i t y , As
Batch 60°F/ SSF at phal
No. 60°F 180° F OBI 1
tenes O i l Ash C H Ν S
1 1.061 39.4 2.6 21.2 75.3 0.9 87.4 9.2 0.8 0.36
4 1.064 44.3 2.2 22.8 73.8 1.2 86.6 9.1 0.8 0.42
7 1.079 85.6 2.8 24.3 70.9 2.0 85.9 8.9 0.8 0.56
Organic benzene insolubles

7. STERNBERG E T A L . Synthoil Process 115
TABLE IV.- Analyses o f c e n t r i f u g e d l i q u i d product samples

taken from run FB-39
Analyses, wt pet
S
P gr, V i s - As-
Batch 60°F/ c o s i t y phal-
1
No. 60°F SSF OBI tenes O i l Ash _C _H_ _N_ _S
1 1.082 21.5 a t 2.4 18.0 79.1 0.50 88.8 8.5 0.8 0.30
180° F
31 1.023 29.1 a t 0.4 7.2 92.3 0.01 88.7 9.5 0.6 0.17
77° F
49 1.034 67.2 a t 0.9 11.4 87.6 0.10 88.1 9.3 0.8 0.14
77° F
91 1.094 32.5 a t 1.6 25.4 71.9 1.06 86.5 8.4 1.2 0.51
180° F
1
Organic benzene i n s o l u b l e s
TABLE V.- Analyses o f c e n t r i f u g e d l i q u i d product samples

taken d u r i n g run FB-40
Vis- Analyses, wt pet

Sp g r , c o s i t y , As-
Batch 60°F/ SSF a t phal-
1
No. 60°F 180° F OBI tenes O i l Ash _C _H__ _N_ _S
1 1.060 13.5 1.1 17.3 81.4 0.2 88.5 8.6 1.0 0.22
43 1.130 56.2 4.6 29.4 64.3 1.7 86.5 7.5 1.5 0.55
90 1.146 75.7 5.7 28.9 62.5 2.9 85.3 7.3 1.6 0.71
Organic benzene i n s o l u b l e s

Reactor
Recycle oi
COAL- Flare stack
»H S,NH
2 3 l H 0
2
Scrubber
Furnaces-^ — H 0
Gas
9
Whole
meter product
Centrifuge
Oil
Light oil
Cake
-Or
Recycle gas
N E T P R O D U C T OIL compressor
Figure 1. Synthoil pilot plantflowsheet
Centrifugea liquid
product
Toluene
Toluene Toluene
insolubles solubles
Pyridine Pentane
Pyridine Pyridine Pentane Pentane

insolubles solubles insolubles solubles
(asphaltenes) (oil)
Figure 2. Fractionation scheme for centrifugea liquid product

(CLP)

TABLE V I . - A n a l y s i s of c e n t r i f u g e d l i q u i d product (CLP) from

run FB-38, batch 7 ( 4 1 5 ° C, 4,000 p s i ) .
V i s c o s i t y of CLP; 85.6 SSF at 1 8 0 ° F
Pet of
Total Ultimate a n a l y s i s , wt pet Mol Viscos-
1
Fraction product C H Ν S Ash 0 H/C wt ity
Oil 71.7 89.01 9.69 0.43 0.18 0.01 0.68 1.30 289 53 at
100° F
Asphaltenes 23.5 85.44 6.78 1.12 0.77 0.36 5.53 0.95 671
Pyridine 2.6 81.97 5.69 2.03 0.91 2.68 6.72 0.83

solubles
Pyridine 2.2 71.9

insolubles

In c e n t i s t o k e s

TABLE VII.- A n a l y s i s of c e n t r i f u p e d l i q u i d product (CLP) from

run FB-40, batch 7 (450° C, 2,000 p s i ) .
V i s c o s i t y of CLP: 58.9 c e n t i s t o k e s at 140° F, 14.3 SSF at 180° F
Pet of
total U l t i m a t e a n a l y s i s , v t pet Mol V i s cos-
1
Fraction product C H Ν S Ash 0 H/C wt ity
Oil 75.2 88.52 8.89 0.83 0.23 0.0 1.53 1.20 227 11.8 at
e
140 F
Asphaltenes 22.3 89.03 6.13 2.10 0.27 0.0 2.47 0.82 459
Pyridine 1.8 86.80 4.75 2.63 0.46 2.29 3.07

solubles
Pyridine 0.7 28.5

Insolubles

In centistokes °

ο
H
M
M
a
ο
TABLE V I I I . - A n a l y s i s o f c e n t r i f u g e d l i q u i d product (CLP) from
run FB-40, batch 88 (450° C, 2,000 p s i T T
V i s c o s i t y o f CLP; 1,433 c e n t i s t o k e s a t 140° F, 97.6 SSF a t 180° F ρ
___
total Ultimate a n a l y s i s , wt pet Mol V i s cos- <s?
1
Fraction product C H Ν S Ash 0 H/C wt ity si
Oil 2.42
2.
51.7 87.57 8.49 1.10 0.42 0.0 1.16 225 16.5 at
140° F *a
3
Asphaltenes 40.2 87.33 6.27 2.14 0.62 0.0 3.64 0.86 417
Pyridine 4.8 73.06 4.39 2.32 1.41 14.28 4.54 0.72

solubles
Pyridine 3.3 65.5

insolubles

1
In c e n t i s t o k e s

A comparison of data in tables VI and VII shows that for

a given asphaltene content the viscosity of the product o i l
depends on the molecular weight of the asphaltenes: FB-40, batch
7, containing 22.3 percent of asphaltenes with a molecular weight
of 459 has a viscosity of 14.3; while FB-38, batch 7, containing
approximately the same amount of asphaltenes but with a molecular
weight of 671 has a viscosity of 85.6.
The increase in viscosity of the product o i l during a run
is due primarily to an increase in asphaltenes and possibly
pyridine sols content and not to a change in the molecular weight
of the asphaltenes or to an increase in the viscosity of the
heavy o i l . This may be seen by comparing batches 7 and 88 of
run FB-40 in tables VII and VIII. The viscosity of the centri-
fuged liquid product increases from 59 to 1,433 with an increase
in asphaltene content from 22 to 40 and an increase in pyridine
sols content from 2 to 5. In contrast, the viscosity of the
heavy o i l increases only from 12 to 17. There is no increase

but rather a slight decrease in the molecular weight of asphal-
tenes from 459 to 416.
The increase in viscosity of centrifuged liquid product
with asphaltene content is shown in figure 4, where viscosities
for runs FB-39 and FB-40 are plotted against asphaltene content.
Abstract
In the Energy Research and Development Administration's
SYNTHOIL process, slurries of coal in recycle o i l are hydrotreated
on Co-Mo/SiO2-Al2O3 catalyst in turbulent flow, packed-bed re-
actors. The reaction is conducted at 2,000 to 4,000 psi and
about 450° C under which conditions coal is converted to low--
sulfur liquid hydrocarbons and sulfur is eliminated as H2S.
Product oils from SYNTHOIL runs carried out at 415° and
450° C and 2,000 and 4,000 psi H2 pressures were analyzed with
respect to asphaltene and o i l content, elementary compositions
(C, H, S, N), ash and physical properties (specific gravity and
viscosity). Asphaltenes exert a large effect on the viscosity
of the product oil, the viscosity increasing exponentially with
asphaltene content. Viscosity of product o i l is not only depen-
dent on the amount but also on the molecular weight of asphaltenes
present. At 415° C, asphaltenes with a molecular weight of 670
are formed and at 450° C asphaltenes with a molecular weight
of 460.
Product o i l containing 24 percent asphaltenes of 670 molec-
ular weight has a viscosity of 86 (SSF at 180° F, ASTM D88),
while product o i l containing almost the same amount of asphaltenes
(22 percent) but with a molecular weight of 460 has a viscosity
of only 14. Benzene insolubles, heretofore regarded as unreacted
coal, were found to be soluble in pyridine and to exert a large
effect on viscosity.

STERNBERG E T A L . Synthoil Process
• • Pyridine solubles (toluene insolubles)
777Ά Asphaltenes
I I Oil
58
42
16 907 1400
VISCOSITY IN C E N T I S T O K E S AT I40°F
Figure 3. Effect of pyridine solubles (toluene insolubles) and

of asphaltenes on viscosity
•—ι 500
' I 1
I 1
I
• SYNTHOIL product FB-39
(lower scale,right ordinate)
• SYNTHOIL product FB-40
(upper scale .left ordinate ) H 400
o
CO 60 300
a
u_ CO
to CO
CO 50
> >-
CO CO
ο 40 200 3
CO to
> >
H 100
3
çP .
16 20 22 24 26 28 30 32
L_ _L_ I _JL_ - J
10 15 20
ASPHALTENES .percent
Figure 4. Viscosity of CLP vs. asphaltene content

122 HYDROCRACKING AND HYDROTREATTNG
Literature Cited
1. Akhtar, Sayeed, Lacey, James J., Weintraub, Murray, Reznik,

Alan Α., and Yavorsky, Paul M. The SYNTHOIL Process--Material
Balance and Thermal Efficiency. Presented at the 67th Annual
AIChE Meeting, December 1-5, 1974, Washington, D.C.
2. Akhtar, Sayeed, Mazzocco, Nestor J., Weintraub, Murray, and
Yavorsky, Paul M. SYNTHOIL Process for Converting Coal to
Nonpolluting Fuel Oil. Presented at the 4th Synthetic Fuels
from Coal Conference of the Oklahoma State University,
Stillwater, Oklahoma, May 6-7, 1974.
3. Yavorsky, Paul Μ., Akhtar, Sayeed, and Friedman, Sam. Process
Developments: Fixed-Bed Catalysis of Coal to Fuel O i l . AIChE
Symposium Series, v. 70, No. 137, pp. 101-105, 1974.

8
Coal Liquifaction by Rapid Gas Phase Hydrogenation
MEYER STEINBERG and PETER FALLON

Department of Applied Science, Brookhaven National Laboratory, Upton, Ν. Y.
11973
The Increased awareness in this nation's dependence on

foreign sources of crude oil has generated much interest in de
veloping and u t i l i z i n g U.S. domestic energy resources. Since
coal is in such great abundance, it is of particular interest to
find an economical method of converting it to a low sulfur al
ternate fuel capable of being transported through existing pipe
lines and used in existing equipment. This would have the three
fold effect of 1) revitalizing the coal industry, 2) providing a
greater domestic supply of fuel to the power industry, and 3) i n
creasing the availability of feedstock to the petrochemical indus
try. A number of coal gasification processes have been developed
to the point where large scale application has become feasible.
The development of the liquifaction of coal has lagged and when
taken together with the advantages of handling, transporting, and
higher conversion efficiency, the incentive to perform additional
work in converting coal to liquid products becomes apparent.
The technology for liquid phase coal hydrogenation has been
in existence for a number of years. (J.) For example, during
World War II Germany produced much of its liquid fuel via the
Bergius Process. This involves forming a slurry of coal, oil and
catalyst and heating it under high pressure (10,000 psi) for up
to an hour while purging the mixture with hydrogen. Being essen
tially a batch process involving the s o l i d , l i q u i d , and gas phase,
a more direct less stringent method of hydrogenation was desired.
In 1962, Schroeder (2) described a process whereby dry particles
of coal entrained in a stream of hydrogen at total pressures in
the range of from 500 to 6000 psi are rapidly heated to tempera
tures in the range of 600 to 1000°C; the resulting stream contain
ing the organic products is then quickly cooled to below the re
action temperature and the products separated. This system i s
claimed to u t i l i z e less hydrogen than the liquid phase method be
cause the liquids produced are primarily unsaturated aromatics
rather than saturated paraffins and cycloparaffins. Conversion
of almost 50% of the coal (on a moisture and ash free basis) to
123

l i q u i d p r o d u c t s , was obtained a t pressures above 2000 p s i , and

temperatures i n the order o f 5 0 0 ° C , and when a molybdenum c a t a l y s t
was used. Outside t h i s patent l i t e r a t u r e there appears to be no
f u r t h e r information on t h i s system. Moseley and Paterson (3) p e r -
formed experiments s i m i l a r to Schroeder but were p r i m a r i l y i n t e r -
ested i n the production of methane. The fact that they d i d not
r e p o r t the p r o d u c t i o n o f any l i q u i d product i s probably due p r i -
m a r i l y to the higher temperatures u t i l i z e d , 9 0 0 - 9 2 5 ° C
Qader, et a l . , (4) reported work on h y d r o g é n a t i o n i n a d i l u t e
phase free f a l l r e a c t o r at temperatures i n the order o f 5 1 5 ° C ,
pressures of 2000 p s i and w i t h a heavy dose of c a t a l y s t , 15%
stannous c h l o r i d e by weight o f c o a l . Up to 75% conversion was r e -
ported with a product d i s t r i b u t i o n of 43% o i l , 32% gas and 25%
char. The residence time o f the c o a l feed p a r t i c l e s was estimated
to be i n the order of seconds, however, no measurement was made
and aromatics were reported a f t e r f u r t h e r h y d r o r e f i n i n g i n a
second stage h y d r o g é n a t i o n .
More r e c e n t l y , Yavorsky, et a l . , (5) have r e p o r t e d on the
development o f a l i q u i d phase ( s o l v e n t ) h y d r o g é n a t i o n of c o a l i n a
h i g h l y t u r b u l e n t tubular r e a c t o r i n the presence of a packed s o l i d
catalyst. Residence times i n the order o f s e v e r a l minutes were
r e p o r t e d and an o i l product i s formed. This system i s a c o n s i d e r -
a b l e improvement over the Bergius Process since reduced p r e s s u r e ,
i n the order o f 4000 p s i and lower temperature o f 4 5 0 ° C are em-
ployed. From t h i s l i t e r a t u r e i t thus appears that coal can be
converted to l i q u i d and gaseous hydrocarbon products i n substan-
t i a l y i e l d s by means of an elevated temperature ( 4 5 0 - 9 5 0 ° C ) high
pressure (2000-6000 p s i ) contact of coal with hydrogen gas. L i -
quid hydrocarbons are favored i n the lower temperature range and
shorter contact time ( i n the order o f seconds), while gaseous
hydrocarbons increase i n y i e l d a t the higher temperatures and
longer residence times. The b a s i c mechanism appears to i n v o l v e a
thermally induced opening o f the polymeric aromatic hydrocarbon
s t r u c t u r e i n c o a l , a l l o w i n g h y d r o g é n a t i o n to occur i n a hydrogen
atmosphere, followed by a r a p i d removal o f the l i q u i d and gaseous
hydrocarbon products formed so that e i t h e r f u r t h e r dehydrogenation,
r e p o l y m e r i z a t i o n and c a r b o n i z a t i o n i s prevented or further exces-
s i v e h y d r o g é n a t i o n i s minimized.
The purpose o f the present experiments i s to s u b s t a n t i a t e
previous work and to gather a d d i t i o n a l process and k i n e t i c i n f o r -
mation e s p e c i a l l y i n a n o n - l i q u i d non-catalyzed gas phase hydro-
g é n a t i o n system. S p e c i a l e f f o r t was made to o b t a i n o v e r a l l ma-
t e r i a l balances i n determining y i e l d s .
A f t e r a few p r e l i m i n a r y runs using a caking eastern bituminous
coal and s e v e r a l r e a c t o r c o n f i g u r a t i o n s , i t was found that b e t t e r
r e s u l t s could be obtained w i t h a non-caking coal i n an e n t r a i n e d
down-flow tubular r e a c t o r . The coal was dropped down i n t o a tubu-
l a r r e a c t o r through which hydrogen was passed down-flow and en-
t r a i n e d and c a r r i e d the coal down through the heated tube.

8. STEINBERG A N D F A L L O N Coal Liquifaction 125
D e s c r i p t i o n of Equipment, and Experimental and A n a l y t i c Procedures
The experimental equipment (Figure 1) was designed to r a p i d l y

heat c o a l i n the presence o f hydrogen a t elevated temperature and
pressure, to maintain these conditions long enough f o r hydrogéna-
t i o n to take p l a c e , to cool the products preventing f u r t h e r reac-
t i o n and f i n a l l y to separate and c o l l e c t the products. Hydrogen
i s s u p p l i e d from standard 200 cubic f o o t c y l i n d e r s and the opera-
t i n g pressure i s c o n t r o l l e d by a 4000 p s i pressure r e g u l a t o r .
Argon i s s u p p l i e d a t low pressure to f l u s h the system before and
a f t e r each run and to a c t i v a t e the normally c l o s e d pneumatic v a l v e
which shuts the hydrogen supply o f f i n case o f sudden l o s s o f pres-
sure. The hydrogen can then pass through e i t h e r or both o f two
5000 p s i s e r v i c e rotameters. The gas from one meter goes to the
top o f the r e a c t o r through an e l e c t r i c a l l y heated preheater con-
s t r u c t e d from a ten foot length of 1/4 inch tubing formed i n t o a
6 i n c h diameter c o i l . Since heating i s by d i r e c t connection to a

v a r i a b l e v o l t a g e transformer, one s i d e o f the system i s e l e c t r i -
c a l l y i s o l a t e d from the other. Gas from the other meter i s used
to c o o l the l i n e between the r e a c t o r and the c o a l feeder and en-
ters j u s t below the feeder. Experience has shown that even w i t h
a non-caking c o a l , t h i s s e c t i o n w i l l become plugged i f the tem-
perature i s not c o n t r o l l e d . This i s probably caused by a combina-
t i o n o f reduced cross s e c t i o n , small p a r t i c l e s i z e and d e v o l a t i l i -
z a t i o n o f the c o a l .
The r e a c t o r column i s f a b r i c a t e d from an e i g h t foot length of
1 i n . O.D. χ 0.120 i n . w a l l thickness type 304 s t a i n l e s s s t e e l
tubing. The c o a l feeder i s a p r e s s u r i z e d 40 gram c a p a c i t y hopper
having an o r i f i c e i n the base and a tapered plug operated by an
electromagnet a c t i n g through a non-magnetic s t a i n l e s s s t e e l w a l l
of the hopper. The feed r a t e i s c o n t r o l l e d by both a p u l s e gener
a t o r operating an e l e c t r o n i c r e l a y which actuates the s o l e n o i d and
by c o n t r o l l i n g the distance the tapered plug i s r a i s e d o f f the
seat during i t s v e r t i c a l c y c l i n g .
A North Dakota l i g n i t e and a New Mexico sub-bituminous c o a l
were mainly used i n these experiments. Coal p r e p a r a t i o n c o n s i s t e d
o f s i z e reduction and d r y i n g . I d e a l l y , the p a r t i c l e s i z e should
f a l l somewhere between the l a r g e s t s i z e with which the maximum
r a t e o f hydrogénation takes place and a s i z e l a r g e enough so that
i n t e r - p a r t i c l e a t t r a c t i o n and agglomeration does not occur. With
the b a l l m i l l used i n these experiments f o r s i z e r e d u c t i o n , a
l a r g e q u a n t i t y of f i n e s were produced when g r i n d i n g to a maximum
p a r t i c l e s i z e o f £ 50 or ^ 150 μ . The i n s i d e of the feeder had to
be coated with a fluorοcarbon r e l e a s e agent which was baked i n
p l a c e . The coal was magnetically a g i t a t e d by pieces of a finned
rod attached to the tapered plug to prevent aggregation and c l o g
ging o f the feeder.
To prevent o x i d a t i o n a l l g r i n d i n g was conducted i n an i n e r t
atmosphere. Drying i n a i r a t temperatures s l i g h t l y above 100°C
was a l s o found to cause o x i d a t i o n and f o r t h i s reason drying and
storage was performed i n a vacuum oven.

A n a l y s i s o f the c o a l used i n these experiments and of a

t y p i c a l char from the l i g n i t e c o a l produced during a s e r i e s of
runs through the hydrogenator are shown i n Table 1. The analyses
are on a m o i s t u r e - f r e e b a s i s and were obtained by the U . S . Bureau
of Mines u s i n g standard ASTM a n a l y t i c a l procedures.
A f t e r the c o a l passed through the r e a c t o r , the char and any
unreacted c o a l were c o l l e c t e d i n an a i r cooled tubular trap con-
t a i n i n g a s t a i n l e s s s t e e l wool f i l t e r attached to the base o f the
column. The q u a n t i t y c o l l e c t e d i s determined by weighing the trap
before and a f t e r each r u n .
The products pass through the trap along with the excess
hydrogen which i s s t i l l a t elevated temperature and r e a c t o r p r e s -
sure. These gases then pass through a double U-tube water cooled
trap ( 2 5 - 3 0 ° C ) , which removes any o i l s produced and most o f the
moisture. The o i l deposits on the w a l l s o f the trap and due to
the r e l a t i v e l y small q u a n t i t y produced and the l a r g e trap surface
a r e a , c o l l e c t i o n becomes d i f f i c u l t . By c l e a n i n g w i t h a cotton
swab, the o i l c o l l e c t e d appears to be l i g h t i n c o l o r and r e l a t i v e -
l y low i n v i s c o s i t y , s i m i l a r to a motor o i l . The q u a n t i t y p r o -
duced i s determined by weighing the trap before and a f t e r the r u n .
The gases are then passed through a metering valve reducing the
pressure to atmospheric. The remaining l i q u i d s contained i n the
gases are c o l l e c t e d i n a l c o h o l - d r y i c e cooled glass trap ( - 7 2 ° C ) .
Samples o f the hydrocarbons c o l l e c t e d i n t h i s trap have c o n s i s -
t e n t l y been analyzed to contain over 98% benzene, the remainder
being toluene w i t h a t r a c e o f xylene. The q u a n t i t y produced i s
determined by weighing the trap before and a f t e r the run and by
volume i n a small graduate attached to the glass t r a p . Water from
the r e a c t o r u s u a l l y c o l l e c t i n t h i s trap and appears as a separ-
ate l a y e r i n the graduate. This water and that c o l l e c t e d i n the
U-tube trap have been analyzed on a Beckman Carbon A n a l y z e r and
shows some i n s i g n i f i c a n t amount o f d i s s o l v e d hydrocarbons. The
l i q u i d hydrocarbons c o l l e c t e d i n t h i s trap are analyzed by gas
chromatography u s i n g a column o f 50-80 mesh Porapak Q and a flame
i r o n i z a t i o n detector. The chromatograph i s c a l i b r a t e d to detect
benzene, toluene, xylene C6 l i q u i d s ) and a l l the l i g h t hydro-
carbon gases, methane, ethane, propane, hexane and pentane
C5 gases). The remaining gas i s then vented to the atmosphere.
At about two-thirds o f the time p e r i o d through the r u n , a 300 cc
gas sample i s taken i n a g l a s s sampling v e s s e l i n s e r t e d i n the
vent l i n e . Due to the l i m i t e d capacity of the c o a l feed hopper,
the duration o f most runs was i n the order of 10 to 15 minutes.
Steady s t a t e operation i s u s u a l l y obtained q u i c k l y s i n c e i n about
one or two minutes a t the flow r a t e s used s e v e r a l r e a c t o r volume
changes have o c c u r r e d . The gas sample i s analyzed i n the same
manner as the l i q u i d sample mentioned above. A s i d e from excess
hydrogen, the gas sample u s u a l l y contains mostly methane and
ethane, the methane being present i n approximately twice the
abundance as the ethane. The next g r e a t e s t c o n s t i t u e n t i s u s u a l l y
benzene i n the vapor phase. There appears to be very l i t t l e C3,
C4, and C5 hydrocarbons p r e s e n t . P e r i o d i c a l l y these same samples

8. STEINBERG A N D F A L L O N Coal Liquifaction 127
VENT
VENT
REACTOR TUBE
H E A T E D IN F O U R
TWO FOOT SECTIONS
Figure 1. Coal hydrogénation tubular reaction experiment
TABLE 1
COAL AND CHAR FEED ANALYSIS

% by wt - Moisture Free Basis
North Dakota New Mexico Char from

Lignite Sub Bituminous Lignite
Hydrogen 4.29% 4.86% 2.74%
Carbon 62.39 64.21 73.63
Nitrogen 0.97 1.41 0.85
Oxygen 21.75 12.26 0.37
Sulphur 1.17 0.61 1.42
Ash 9.43 16.65 20.99
100.00 100.00 100.00

were a l s o analyzed by mass spectrometry as a check on the gas

chromatography and a l s o to determine the concentration o f con-
s t i t u e n t s not detected by the gas chromatograph, such as oxides
of carbon.
Experimental and C a l c u l a t e d Results
Table 2 contains a summary of some of the experimental r e -

sults. Except as otherwise noted, most o f the runs were made
u s i n g ground North Dakota l i g n i t e with no a d d i t i o n of c a t a l y s t .
The r e a c t o r operating temperature c o n d i t i o n o f 700°C was chosen
on the basis that t h i s was s l i g h t l y above 650°C found i n previous
experiments to be the temperature below which l i t t l e r e a c t i o n w i t h
the l i g n i t e was noted. The 1500 p s i operating pressure i s the
upper s a f e t y l i m i t o f the r e a c t o r at the 700°C temperature. Lower
pressures tended to r e s u l t i n lower l i q u i d y i e l d s . A thorough
i n v e s t i g a t i o n o f the e f f e c t of pressure i s yet to be made.

The residence time o f the c o a l p a r t i c l e s i n the r e a c t i o n zone
was estimated by combining the l i n e a r gas v e l o c i t y through the
tube with the free f a l l v e l o c i t y of the p a r t i c l e s as c a l c u l a t e d
from data c o r r e l a t e d by Zenz and Othmer (6). The p a r t i c l e s were
assumed to be uniform spheres d i s t r i b u t e d i n a h i g h l y d i l u t e gas
phase. A t a f i x e d r e a c t o r operating temperature and p r e s s u r e , the
residence time becomes dependent upon the p a r t i c l e s i z e and the
gas flow r a t e . Most o f the o r i g i n a l experiments were conducted
u s i n g £ 50 micron coal p a r t i c l e s . In an attempt to improve the
u n i f o r m i t y of the coal feed flow and decrease the residence time,
t h i s was increased to £ 150 microns. As shown i n Table 3, i t was
not p o s s i b l e with the frequent s i e v i n g and g r i n d i n g method used
to reduce the presence o f s i g n i f i c a n t amounts o f ^ 50 micron p a r -
ticles.
Using Figure 2, which i s a p l o t o f residence time as a func-
t i o n of coal p a r t i c l e s i z e based on the Zenz and Othmer c o r r e l a -
t i o n , i t can be shown that due to the r e l a t i v e l y l a r g e q u a n t i t y
of fines p r e s e n t , i n c r e a s i n g the maximum s i z e by a f a c t o r of three
only reduces the average residence time by about 30%. F i g u r e 2
a l s o shows the e f f e c t o f reducing residence time by i n c r e a s i n g the
hydrogen flow r a t e from the minimum used i n these experiments
(0.7 gm/min) to the maximum (4.5 gm/min).
Brown and Essenhigh (7) have suggested that the free f a l l
v e l o c i t y may be much greater than that c a l c u l a t e d here. In t h e i r
experiments u s i n g cork p a r t i c l e s f a l l i n g through an a i r f i l l e d
tube, the p a r t i c l e cloud acted as a porous p l u g , f a l l i n g a t a
r a t e o f approximately 57 f t / m i n . Using the Zenz and Othmer c o r r e -
l a t i o n , t h i s v e l o c i t y i s c a l c u l a t e d to be only 17 f t / m i n . Thus,
the coal residence time may be much shorter than determined from
Figure 2. A d d i t i o n a l experimental e f f o r t i s r e q u i r e d to measure
the a c t u a l residence i n the system.
The hydrogen fed to the system i s much i n excess o f that
u t i l i z e d i n the h y d r o g é n a t i o n r e a c t i o n . The net use o f hydrogen

TABLE 2
HYDROGENATION OF COAL IN AN ENTRAINED TUBULAR REACTOR
Coal - North Dakota Lignite
Reactor - 0.75" I.D . χ 8ft Long Stainless Steel
Run No. 5/3 5/21 6/3 6/7 6/14 7/30 9/9 9/13 9/16 11/21 9/11
H Pressure (psi) (3)
2 1000 1400 1500 1500 1500 1500 1500 1500 1500 1500 1500
Reactor Temp (°C) 700 700 700 700 700 700 700 700 700 700 700
H Preheat Temp (°C)
2 350 350 350 350 R.T. 300 600 600 600 R.T. 600
(1 2
Coal Rate (gm/min) 1.5 (
0.7β ' 1.47 1.66 2.93 1.63 2.53 1.4 3.7<' 1.08 0.94 (4)
H Rate (gm/min) 3)
2 0.7 0.74 4.14 4.14 2.5 1.6 1.75 1.75 2.1 21.3< 1.75
H Linear Velocity Pt/Sec
2 0.056 0.059 0.33 0.33 0.20 0.128 0.14 0.14 0.168 0.086 0.14
Max.Coal Particle Size (Microns) <50 <50 <50 <50 <50 <150 <150 <150 <150 <150 <150
Est. Max. Coal Residence Time (Sec) 38 36 16 16 22 20 18 18 16 30 18
Duration of Run (Min) 10 15 20 17.5 10 11.5 10 10 10 10 10
Raw Carbon Balance - % C Converted
% C as Liquid HC (^Cg) 8.4 7.3 35.8 21.2 17 .5 25 .0 19.1 23.8 12.9 4.0 0
Gaseous HC (C.-C ) 19.6 34.3 45.7 10.6 19.5 5.3 1.7 26.8 30.6 7.7 0
C Oxides * ' 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 16.2 -
Unreacted 49.5 48.3 34.1 32.9 44.0 41.9 27.9 42.9 44.1 68.8 95.3
% Total Conversion of C to
Gas & Liquid 28.0 41.6 81.5 31.8 37.0 30.3 20.8 50.6 43.5 11.7 0
% c Accounted for 83.5 95 .9 121.6 70.7 87.0 78.2 54.7 99.5 93.6 96.7 95.3
Modified C Balance - % C Converted
% C as Liquid HC {zC^ 8.4 7.3 35 .8 21.2 17.5 25 .0 19.1 23.8 12.9 4.0 0
38.4 24.1

Gaseous HC (C -C ) 36.1 39.9 32.5 27.1 47.0 27.3 37.0 11.0 4.7
(5) 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 16.2 -
v 1
C Oxides
Unreacted 49.5 48.3 34.1 32.9 44.0 41.9 27.9 42.9 44.1 68.8 95.3
% Total Conversion of C to
Gas & Liquid 44.5 45.7 59.9 61.1 50.0 52.1 66.1 51.1 49.9 15.0 4.7

(1) 1% Ammonium Molybdate Added
(2) New Mexico Sub-Bituminous Coal
(3) Argon Used in Place of Hydrogen
(4) Char Collected from Previous Lignite Coal Runs Used in Place of Coal as Feed Material to the Tubular Reactor
(5) For Hydrogen Runs, Analysis Indicates 1% COn and 5% CO
For Argon Run, Analysis Indicates 11.5% CO_ and 4.7 % CO
TABLE 3
COAL PARTICLE SIZE DISTRIBUTION
P a r t i c l e Size (Microns) Weight Percent

150 - 125 4.8
125 - 90 21.4
90 - 50 21.0
£ 50 52.8
H F L O W RATE
2
- Ο q /min
-0.7 q/min
ς4.5 q/min
20 40 60 80 100 120 140

PARTICLE SIZE (μ)
Fluidization and Fluid-Particle Systems

Figure 2. Coal particle residence time vs. particle size.
e
H at 1500 psi + 700 C.
2

8. STEINBERG A N D F A L L O N Coal Liquifdction 131
for a high y i e l d run where, for example, 60% o f the a v a i l a b l e

carbon from the l i g n i t e i s hydrogenated i n t o equal parts o f l i q u i d
and gas, i s o n l y about 5 grams hydrogen per 100 grams o f c o a l .
An a d d i t i o n a l 50% of t h i s amount of hydrogen, o r i g i n a t e s from the
coal i t s e l f to make up the hydrogen balance i n the hydrocarbon
products. Hydrogen for r e a c t i o n w i t h the s u l f u r , n i t r o g e n and
oxygen contained i n the coal i s taken i n t o account for t h i s b a l -
ance. I t should be noted that the l i g n i t e has an e s p e c i a l l y high
oxygen content. The l a r g e excess hydrogen feed serves the purpose
o f t r a n s f e r r i n g heat to the c o a l , t r a n s p o r t i n g the products out o f
the r e a c t o r and producing v a r i a t i o n s i n the coal residence time by
changes i n hydrogen v e l o c i t y .
The carbon balance given i n Table 2 was made by weighing the
l i q u i d s and char c o l l e c t e d i n each t r a p , determining a n a l y t i c a l l y
o r , as i n the case o f the l i g h t o i l , estimating the carbon content
and a n a l y s i s o f a sample o f the e f f l u e n t gas. The o i l was assumed
to contain some amount of aromatic w i t h approximately 90% carbon

content. I f t h i s o i l was p r i m a r i l y a l i p h a t i c , the carbon content
would be c l o s e r to 85%. This would only a f f e c t the o v e r a l l b a l -
ance by a small amount s i n c e the o i l s make up approximately 40%
of the l i q u i d s c o l l e c t e d , the r e s t being chromatographically
analyzed as benzene, toluene and xylene (BTX) with the major f r a c -
t i o n (^ 98%) being benzene.
As mentioned p r e v i o u s l y , a sample o f the e f f l u e n t gas i s
analyzed chromatographically for l i g h t hydrocarbons (C1-C5). Only
a small f r a c t i o n of higher hydrocarbons (^ 05) i s found i n the gas
sample and t h i s i s added to the t o t a l l i q u i d formed. The t o t a l
carbon content o f the gas i s obtained from the r e s u l t s o f t h i s
a n a l y s i s , the gas flow r a t e and the d u r a t i o n o f the r u n . T y p i c a l
r e s u l t s o f mass spectrometric analyses a l s o i n d i c a t e that about
5% o f the a v a i l a b l e carbon appears as carbon monoxide and 1% as
carbon dioxide i n the e f f l u e n t gas. As shown i n Table 2, most of
the experiments i n d i c a t e over 70% o f the carbon can be accounted
f o r by d i r e c t a n a l y s i s . Since the amounts o f c o a l used and con-
densed l i q u i d and char produced were measured g r a v i m e t r i c a l l y and
there was no holdup i n the system, any i n a b i l i t y to account f o r
a l l the carbon fed to the r e a c t o r must be a t t r i b u t e d to l o s s i n
the e f f l u e n t gas. The carbon balance was therefore modified by
assuming the missing carbon to be i n the form o f a l i g h t hydro-
carbon i n the e f f l u e n t gas. This modified carbon balance i s given
i n the lower h a l f o f Table 2.
Figure 3 shows the e f f e c t o f coal p a r t i c l e residence time on
the f r a c t i o n o f carbon converted to l i q u i d and gaseous p r o d u c t s .
Based on t h i s c o r r e l a t i o n , the p r o d u c t i o n of gaseous products
appears to be l e s s s e n s i t i v e to c o a l residence time than the p r o -
duction of l i q u i d s . I t a l s o appears that the p r o d u c t i o n of l i -
quids i s favored by shorter residence time.
F i g u r e 4 gives a p l o t o f the conversion to l i q u i d s as a
function o f coal feed r a t e for the shorter c o a l residence times
(16-22 s e c ) . This f i g u r e i n d i c a t e s a trend towards lower l i q u i d

70
60
50
GAS + LIQUID
40
Ο
ο
— —" GAS
·
g 30
<
ο
aS 2 0
LIQUID
22 26 30 34 38 42
COAL PARTICLE RES. TIME (sec)
Figure 3. Gas phase coal hydrogénation yield vs. coal

residence time. North Dakota lignite—reactor, 0.75" i.d.
X 8 ft; pressure, 1000-1500 psi; temperature, 700°C; par-
ticle size, < 150 μ.
Figure 4. Gas phase coal hydrogénation

liquid yield vs. coal feed rate. North Dakota
lignite—reactor, 0.75" i.d. X 8 ft; pressure,
1500 psi; temperature, 700°C; particle size,
COAL F E E D RATE (q/min) < 150 μ; residence time, 16-22 sec.

8. STEINBERG AND FALLON Coal LiquifaCtlOYl 133
conversion a t higher coal feed r a t e s - Even a t the higher feed

r a t e s , the c o a l i s i n a very d i l u t e phase i n the gas, so that
there should be no tendency towards a c o a l s a t u r a t i o n e f f e c t i n
the system. Since much of the heat needed to b r i n g the c o a l to
r e a c t i o n temperature can be obtained as r a d i a n t heat from the r e -
a c t o r w a l l , t h i s e f f e c t o f coal feed r a t e could be a t t r i b u t e d to
a shadowing e f f e c t , reducing the heating rate a t higher coal feed
rates. This assumes that r a p i d heating of the c o a l p a r t i c l e s i s
needed for optimum l i q u i d y i e l d . From experience i n running the
equipment, i t was a l s o found that while preheating the hydrogen
increased the o v e r a l l y i e l d , the d i f f e r e n c e i n preheating between
3 5 0 ° C and 600°C d i d not appear a p p r e c i a b l e .
Several runs were made with the a d d i t i o n o f 1% ammonium
molybdate to the l i g n i t e for purposes o f t e s t i n g c a t a l y t i c ef-
fects. Under s i m i l a r flow conditions there appears to be l i t t l e
e f f e c t on the y i e l d s .
In the run made with a New Mexico sub-bituminous c o a l , an

a p p r e c i a b l e q u a n t i t y of gaseous hydrocarbons was produced. The
main d i f f e r e n c e between the New Mexico c o a l and the North Dakota
l i g n i t e i s that the sub-bituminous coal has a lower oxygen con-
tent and a higher ash content.
Runs were a l s o made using an i n e r t gas, argon, i n place of
hydrogen at the s i m i l a r pressure and l i n e a r v e l o c i t y through the
reactor. The r e s u l t s o f a t y p i c a l one o f these runs i s given i n
Table 2. Although almost 11 grams o f coal was f e d , no measurable
q u a n t i t y of product was found i n the high pressure water cooled
t r a p , and only a few drops o f what was predominantly benzene was
c o l l e c t e d i n the a l c o h o l - d r y i c e cooled t r a p . A n a l y s i s o f the
gas sample showed methane and about o n e - f i f t h as much ethane. The
char contained a higher carbon content (77%) than when hydrogen
was used (72%). Almost 70% of the a v a i l a b l e carbon remained un-
reacted. The production of oxides o f carbon was much higher with
argon (16%) than for a t y p i c a l hydrogen run (6%). A l s o , the CO
to CO2 r a t i o was much higher (5 times) with hydrogen than with
argon (2 t i m e s ) . These r e s u l t s i n d i c a t e that v o l a t i l i z a t i o n of
l i g n i t e i n an i n e r t gas stream produces much l e s s gaseous and
l i q u i d hydrocarbon products (15% o f C) under s i m i l a r conditions
of p r e s s u r e , temperature and residence time than when hydrogen i s
present (45 to 66% o f C) and thus a p p r e c i a b l e h y d r o g é n a t i o n i s
occurring.
A t e s t was made to determine the r e a c t i v i t y of the char r e -
maining a f t e r a h y d r o g é n a t i o n r u n . For t h i s purpose, char c o l -
l e c t e d from a s e r i e s o f previous runs was r e c y c l e d through the
system. A n a l y s i s of t h i s char appears i n Table 1. Over 95% o f
the m a t e r i a l fed was recovered as a s o l i d i n the f i r s t t r a p . No
l i q u i d was produced and only a trace of l i g h t hydrocarbons were
found i n the gas. S i m i l a r r e s u l t s were obtained when feeding a
coconut charcoal to the system. There thus appears to be l i t t l e
r e a c t i v i t y towards hydrogen i n the char produced from an o r i g i n a l
l i g n i t e h y d r o g é n a t i o n run.

Conclusions
The o b j e c t i v e s o f t h è s e h y d r o g é n a t i o n experiments were main-

l y d i r e c t e d toward producing the l a r g e s t q u a n t i t y o f l i q u i d p r o -
duct and reducing the unreacted carbon remaining. Although f r a g -
mented, t h i s experimental study i n d i c a t e s that s i g n i f i c a n t y i e l d s
o f l i q u i d and gaseous hydrocarbon products can be obtained by an
elevated temperature and pressure gas phase h y d r o g é n a t i o n of
North Dakota l i g n i t e without the a d d i t i o n o f a c a t a l y s t . Based
on a modified carbon balance, a range o f y i e l d s obtained i n a
number o f experimental runs under the operating conditions i n d i -
cated can be l i s t e d as f o l l o w s :
Pressure 1500 p s i
Temperature 700°C
Coal p a r t i c l e s i z e £ 150 μ
Coal residence time 16 to 22 sec.
Y i e l d as % conversion o f carbon i n lignite
Liquids %) 18-25% (~60% C H ) 6 6
Gas C5) 27-40 (mainly CH4 & C H ) 2 6
Oxides of C 6
Unreacted C 33- 44
Several general trends were noted. The y i e l d o f l i q u i d p r o

ducts i s s t r o n g l y favored by s h o r t e r coal residence times, while
the y i e l d of gaseous hydrocarbons increases only s l i g h t l y with
increases i n coal residence times. A t shorter residence times,
i n c r e a s i n g the coal feed r a t e decreases the y i e l d o f l i q u i d p r o
ducts.
V o l a t i l i z a t i o n of l i g n i t e i n an i n e r t gas stream under s i m i
l a r flow conditions produced much smaller y i e l d s o f l i q u i d and
gaseous hydrocarbon p r o d u c t s . A d d i t i o n o f a c a t a l y s t caused no
a p p r e c i a b l e e f f e c t s on the y i e l d .
The r e s u l t s o f t h i s study should be considered as work i n
progress. Much a d d i t i o n a l work needs to be performed to r e f i n e
the experimental procedure and to o b t a i n a d d i t i o n a l information
and a f u l l e r understanding o f the r e s u l t s .
Acknowledgement
The a u t h o r s w o u l d l i k e t o t h a n k M r . G e r a l d F a r b e r
f o r t h e c o n s t r u c t i o n and o p e r a t i o n o f t h e equipment,
the U . S . Bureau of Mines for the c o a l a n a l y s i s and
R o b e r t S m o l , J o e F o r r e s t , and R o b e r t D o e r i n g o f B r o o k -
h a v e n N a t i o n a l L a b o r a t o r y f o r t h e g a s e o u s and liquid
product a n a l y s i s . A c k n o w l e d g e m e n t i s a l s o made t o
t h e g r o u p a t C i t y U n i v e r s i t y o f New Y o r k , A r t h u r S q u i r e s ,
R o b e r t G r a a f f , a n d Sam D o b n e r f o r t h e i r h e l p f u l dis
c u s s i o n s on r a p i d r e a c t i o n s o f c o a l w i t h h y d r o g e n .

8. STEINBERG AND F A L L O N Coal Liquifaction 135
Abstract
The short contact time, high temperature, non-catalyzed gas

phase reaction of hydrogen with coal in a tubular reactor has been
investigated. A North Dakota lignite coal was hydrogenated by
entraining fine coal particles (≤ 150 μ) in a hydrogen stream
through a 0.75" I.D. by 8 ft long tubular reactor at 700°C and
1000 to 1500 p s i . The coal flow rate varied between 0.8 and 3.7
gm/min. and the hydrogen flow rate varied between 0.7 and 4.1
gm/min. Residence times were calculated to vary between 16 and
38 seconds. The unreacted carbon was collected in an a i r cooled
trap, the light o i l s in a water cooled trap on the high pressure
side of the system and the lighter liquids consisting predomin
antly of benzene with smaller amounts of xylene and toluene (BTX)
were collected in an alcohol-dry ice cooled trap after reducing
the pressure to one atmosphere for venting. The exit gas was
analyzed. Based on a modified carbon balance, the y i e l d , or con

version of carbon in the feed coal, to liquid products (≥ C6)
usually varied between 18 and 25%, approximately 60% of which is
benzene. The gases ( ≤ C5) varied between 27 and 40% consisting
mainly of methane and ethane, and the oxides of carbon were 6%
of the available carbon feed in the l i g n i t e . A trend indicating
higher liquid yields at shorter coal residence times was noted.
A decrease in liquid yield at increased coal feed rate when the
residence time remained approximately constant was also noted.
Volatilization of lignite in an inert gas stream under simi
lar flow conditions produced much smaller yields of l i q u i d and
gaseous hydrocarbon products. Addition of a catalyst caused no
appreciable effects on the y i e l d . Much additional work is re
quired to obtain a fuller understanding of the results obtained.
Literature Cited
1. M i l l s , G. Alex, Ind & Eng. Chem. (1969), 61, 6-17.

2. Schroeder, W. C. (assigned to Fossil Fuels, Inc.), U.S.
Pat. 3,030,298 (April 17, 1962) and U.S. Pat. 3,152,063 (October
6, 1964).
3. Moseley, F. and Paterson, D . , J. Inst. Fuel (November
1967), 523-530.
4. Qader, S. Α . , Haddadin, R. Α . , Anderson, L . L., and Hill,
G. R . , Hydrocarbon Processing (September 1969) 48, 147-152.
5. Yavorsky, P . , Akktar, S., and Friedman, S., Chem. Eng.
Progress (1973) 69, 51-2.
6. Zenz, F. A. and Othmer, D. F., Fluidization and Fluid-
Particle Systems, ρ 236, Reinhold Publishing, New York, 1960.
7. Brown, K. C. and Essenhigh, R. Η . , Dust Explosions in
Factories : A New Vertical Tube Test Apparatus, Safety in Mines
Research Establishment Research Report, No 165, Ministry of Power,
Sheffield, England (April 1959).

9
Consideration of Catalyst Pore Structure and
Asphaltenic Sulfur in the Desulfurization of Resids
RYDEN L. RICHARDSON and STARLING K. ALLEY
Union Oil Co. of California, Union Research Center, Brea, Calif. 92621
The residuum f r a c t i o n of a full range crude is that f r a c t i o n

remaining a f t e r all of the distillate i s taken overhead. As noted
in Figure 1, t h i s residuum f r a c t i o n or r e s i d may be obtained with
e i t h e r atmospheric or vacuum f r a c t i o n a t i o n , y i e l d i n g e i t h e r long
or short r e s i d .
Table I shows t h a t , upon distillation of a Kuwait crude i n t o
s e v e r a l f r a c t i o n s , s u l f u r components concentrate mostly i n the
r e s i d f r a c t i o n . Upon h y d r o t r e a t i n g each f r a c t i o n at f i x e d r e a c t o r
c o n d i t i o n s , the r e s i d s u l f u r i s more difficult to remove than the
gasoline s u l f u r or the gas oil s u l f u r .
CHARACTERIZATION OF RESIDS
The d i s t i n g u i s h i n g features of r e s i d feedstocks are (1) the

presence of asphaltenes or p e n t a n e - i n s o l u b l e s , (2) high carbon
r e s i d u e s , (3) the presence of metals, mainly n i c k e l and vanadium,
and (4) unknown endpoints i n s o f a r as b o i l i n g range is concerned.
Table II compares two atmospheric r e s i d s , West Coast and K u -
w a i t , i n a t r a d i t i o n a l manner. The obvious d i f f e r e n c e s i n c l u d e
s u l f u r , n i t r o g e n , asphaltenes, t o t a l metals and m i d - b o i l i n g p o i n t .
Apart from s u l f u r content, one might surmise a greater c a t a l y s t
demand by the West Coast feedstock i n that the boxed values sug-
gest heavy coke laydown and metals d e p o s i t i o n . Neither of the
s u l f u r values i s boxed because there i s no i n d i c a t i o n as to (1)
what f r a c t i o n of the s u l f u r i s r e f r a c t o r y or "hard" s u l f u r , nor
(2) the degree of d e s u l f u r i z a t i o n to be achieved.
Table I I I extends the comparison of these r e s i d s with an
emphasis on r e a c t i v i t y , asphaltene c h a r a c t e r i s t i c s , compound types
and the r e f r a c t o r y forms of s u l f u r , such as benzothiophenes and
asphaltenic s u l f u r .
The lower r a t e constant of the Kuwait feed i n d i c a t e s i t s
greater r e f r a c t o r i n e s s or r e s i s t a n c e toward d e s u l f u r i z a t i o n .
These second order r a t e constants were measured at 6 7 5 ° F w i t h a
p r e s u l f i d e d c o b a l t moly c a t a l y s t having a c a t a l y s t age of 10 days.
Conversion l e v e l s d i d not exceed 75% and hence d i d not go deeply
136

9. RICHARDSON A N D A L L E Y Desulfurization of Resids 137
TABLE I
FRACTIONATION AND HYDROTREATING
HYDROTREATED
BOILING SULFUR PRODUCT SULFUR
FRACTION RANGE, °F VOL. % WT. % S,% REMOVAL, %
GASOLINE X-400 25 0.5 0.02* 96
GAS OIL 400-650 25 1.8 0.5 * 72
LONG RESID 650 + 50 3.7 1.6· 57

SHORT RESID 1050 + (20) (5)
e
• 780 F , 1000 psig, 1 LHSV, 4000 SCF/B
TABLE II
COMPARISON OF WEST COAST AND KUWAIT
ATMOSPHERIC RESIDS
FEED DESIGNATION WEST COAST KUWAIT
GRAVITY, *API 11.5 17.4
DISTILLATION, °F
IBP/10 536/725 447 / 6 3 4

50/60 996/1051 937/1020
SULFUR, % 1.73 3.66

NITROGEN, % 0.90 0.203
ASPHALTENES,% 1 1.2 6.3

CONRADSON CARBON,% 10.7 8.1
POUR POINT, F e
75 30
METALS, ppm
COPPER 1
IRON 53 2
NICKEL 75 11
VANADIUM 63 38

TABLE III
EXTENDED COMPARISON OF WEST COAST AND

KUWAIT RESIDS
RATE CONSTANT 52 38
TOTAL SULFUR,% 1.73 3.66

ASPHALTENIC SULFUR, % 0.22 0.38
GEL. PERM. CHROMO.
ASPHALTENE MODE DlAM., A 60 70

RELATIVE AMOUNT OF
ASPHALTENES AT D - 150 λ 0.72 0.78
LIQUID CHROMO
C O M P O U N D TYPE
SATURATES, Jo 20.6 26.7

AROMATICS, % 41.2 50.4
POLAR AROMATICS, % 22.9 10.4
ASPHALTENES, % 10.7 6.3
SULFUR CONT ENT
SATURATES, ppm 22 34
AROMATICS, % 0.94 2.36
POLAR AROMATICS, % 0.4 1 0.59
ASPHALTENES, % 0.22 0.38
HIGH MASS O N X-1100 °F Q.H.
THIOPHENES 2.9 2.3

BENZOTHIOPHENES 7.4 15.0
TRI BENZOTHIOPHENES 0.0 0.0
IR ABSORBANCE
AROMATIC RINGS 0.43 0.33

ALKYL GROUPS 0.38 0.42
RATIO OF NMR PEAK HEIGHTS
CH /CH
2 3 LOW HIGH

into asphaltenic s u l f u r . F i g u r e 2 shows the GPC curves of the

c i t e d r e s i d s and t h e i r asphaltene f r a c t i o n s . Note the s l i g h t p r e -
dominance of very l a r g e asphaltenes i n the Kuwait r e s i d . A l s o
note that very l a r g e molecules e x i s t i n the non-asphaltenic f r a c -
t i o n of both r e s i d s . For the conversion l e v e l s under c o n s i d e r a -
t i o n , we regard the l a r g e p r o p o r t i o n of s t e r i c a l l y hindered aroma-
t i c s u l f u r i n the Kuwait r e s i d l a r g e l y r e s p o n s i b l e f o r i t s greater
refractoriness. Returning to Table I I I , one notes the h i g h values
for aromatic s u l f u r (2.36 v s . 0.94%) and benzothiophenes (15.0 v s .
7.4%) i n the Kuwait feed. A l s o , the IR and NMR s p e c t r a i n d i c a t e d
that the Kuwait aromatics are more h i g h l y s u b s t i t u t e d , the R
groups being naphthenes and/or long p a r a f f i n s .
A p e r t i n e n t example of s t e r i c hindrance on the d e s u l f u r i z a -
t i o n of thiophenes has been reported by a Gulf i n v e s t i g a t o r (1).
A l k y l or r i n g a d d i t i o n at the 2 p o s i t i o n can reduce the r e a c t i o n
r a t e by a f a c t o r of 100.
REFRACTORINESS OF ASPHALTENES
When s u l f u r conversion l e v e l s are pushed above 90%, the

unique r e f r a c t o r i n e s s of asphaltenes becomes dominant. The tend-
ency of a f i n e pore c a t a l y s t to p a r t i a l l y exclude asphaltenes and
the complete s t e r i c hindrance or "burying" of s u l f u r i n a s p h a l -
tenes c o n t r i b u t e to t h i s r e f r a c t o r i n e s s .
However, before c o n s i d e r i n g the f a t e of a s p h a l t e n i c s u l f u r at
high r e a c t o r s e v e r i t i e s , some patent aspects of c a t a l y s t pore
s t r u c t u r e would be of i n t e r e s t . Table IV shows a divergence of
o p i n i o n as to the d e s i r a b i l i t y of asphaltene e x c l u s i o n .
I t i s noted that patent (2) favors the e x c l u s i o n of a s p h a l -
tenes by maximizing surface area contained by pore diameters of
30-70 Â. Patent (3) d i s c l o s e s an upper l i m i t on the amount of
macropore volume represented by pore diameters greater than 100 A .
Patents (4) and (5) suggest that c a t a l y s t s c o n t a i n i n g mostly m i c r o -
pores w i l l be poisoned soon; asphaltenes p e n e t r a t i n g the l a r g e r
pores subsequently w i l l block entrance to the smaller p o r e s .
Patent (6) claims the d e s i r a b i l i t y of intermediate pores (100-1000
Â) p l u s channels (>1000 Â) "to take up p r e f e r e n t i a l l y adsorbed
l a r g e molecules without causing blockage, so that the smaller s i z e
1
pores can d e s u l f u r i z e ' s m a l l e r molecules." Patent (7) a l s o p r e -
f e r s the open s t r u c t u r e for c o l l e c t i o n of coke and metals. It
s p e c i f i e s 0.3 c c / g of pore volume i n diameters l a r g e r than 150 Â
and "many pores from 1,000-50,000 A . "
With t h i s b r i e f c o n s i d e r a t i o n of v a r i a t i o n s i n c a t a l y s t pore
s t r u c t u r e , l e t us examine the pore s t r u c t u r e of two c a t a l y s t s used
i n t h i s r e f r a c t o r i n e s s study. One observes i n Table V only s l i g h t
d i f f e r e n c e s between the two c o b a l t moly c a t a l y s t s , Τ and R. They
are t y p i f i e d by h i g h surface a r e a , small micropore mode diameters
and low macropore volumes.
Upon processing Kuwait r e s i d over these c a t a l y s t s , a s i m i l a r
trend i n product d i s t r i b u t i o n i s shown i n Table V I . Saturates i n -

140 HYDROCRACKING A N D HYDROTRLATING
ATMOS FRACTIONATION
GASOLINE
TURBINE FUEL
DIESEL FUEL
Λ 20 mm Hg
CRUDE
OIL VAC
COLUMN
LGO
HEATER
HG Ο
Λ LVGO
HVGO
HEATER
A T M O S . RESID
OR L O N G RESID
e
650 F +
V A C RESID
OR SHORT RESID.
e
1050 F +
Figure 1. Distillation of crude oil
DIAMETER, Â
Figure 2. GPC molecular size distribution

RICHARDSON A N D A L L E Y Desulfurization of Resids 141
TABLE IV
SOME PATENTS O N PORE STRUCTURE

OF RESID HYDROTREATING CATALYSTS
PATENT CATALYST SPECIAL FEATURES

CODE NUMBER COMPOSITION PORE VOLUME PORE DIAMETER
(2) CoMo, NiMo SURFACE AREA (SA)

OF 3 0 - 7 0 Â PORES
2
> 100 m / g .
(3) CoMo, NiMo,WMo. <0.25 c c / g IN TOTAL SA > 150 m V g .

ALUMINA WITH PORES > 1 0 0 Â SA OF 3 0 - 7 0 Â PORES
2
1-6% SILICA. > 100 m / g .
(4) APPROX. 85 7. OF PORE

VOLUME IN 5 0 - 2 0 0 A
RANGE.
PATENT CATALYST SPECIAL FEATURES

CODE NUMBER COMPOSITION PORE VOLUME PORE DIAMETER
(5) N i C o M o . NO 0.46 c c / g REGULAR DISTRIBUTION

SILICA WITH 0 - 2 4 0 A. A V E R A G E =
ALUMINA. 1 4 0 - 1 8 0 A.
(6) CoMo (+ Ni) 0.45-0.50 cc/g 6 0 - 7 0 A PLUS 100-1000

Â PLUS CHANNELS >
1000 A. S A * 260-355 m /g. 2
(7) CoMo, NiW. NO 0.3 c c / g IN MANY PORES

SILICA WITH PORES >150 A 1,000-50,000 Â
ALUMINA

TABLE V
PORE STRUCTURE OF COBALT MOLY CATALYSTS
USED IN REFRACTORINESS STUDY
CATALYST DESIGNATION Τ R
2
SURFACE AREA (SORPT.), m / g 284 307
MODE DIAMETER, Â 67 65
TOTAL PORE VOL., m l / g 0.44 0.52
MACRO ( D > 100 A) PORE VOL., ml/g 0.012 0.035

T A B L E VI
CHANGE IN PRODUCT C O M P O U N D TYPE A N D

ASPHALTENIC SULFUR CONTENT WITH
CONVERSION LEVEL
REACTOR CONDITIONS FEED CATALYST Τ CATALYST R
TEMPERATURE, *F 65 5 655 709 665 670 710
PRESSURE, psig 800 1292 1292 800 1292 1292
LHSV, V O L . / ( V O L . ) (HR) 0.5 0.3 0.3 0.5 0.3 0.3
CONVERSION LEVEL, 74 83 92 74 85 94
COMPOUND TYPE,'/.
SATURATES 30.6 36.8 42.8 43.1 37.5 39.7 45.5

AROMATICS 45.8 47.6 46.8 43.5 47.6 46.4 44.3
POLAR AROMATICS 17.3 10.7 6.2 10.3 10.8 11.3 8.2
ASPHALTENES 6.3 4.9 4.2 3.1 4. 1 2.6 2.0
TOTAL SULFUR, % 3.66 0.95 0.63 0.29 0.96 0.55 0.23
ABSOLUTE ASPHALTENIC SULFUR, % 0.45 0.32 0.26 0.18 0.24 0.15 0.09
RELATIVE ASPHALTENIC SULFUR, % 12 34 41 62 25 27 39

crease, aromatics remain f a i r l y constant and both p o l a r aromatics

and asphaltenes decrease. Adsorption chromatography i s the b a s i s
f o r type s e p a r a t i o n : pentane e l u t e s the s a t u r a t e s , ether e l u t e s
the aromatics, and benzene-methanol e l u t e s the p o l a r aromatics.
Quite c l e a r l y , the r e l a t i v e amount of a s p h a l t e n i c s u l f u r increases
as the product t o t a l s u l f u r decreases. This i s depicted i n F i g u r e
3.
Whereas the r e l a t i v e amount of aromatics remained f a i r l y con-
stant as s u l f u r conversion l e v e l was increased to 92-94%, the r e l -
a t i v e amount of s u l f u r i n the aromatic f r a c t i o n decreased markedly.
T h i s a l s o i s depicted i n F i g u r e 3. P o l a r aromatics are interme-
d i a t e to the aromatics and asphaltenes i n regard to t h i s behavior.
These d i f f e r e n t d i s t r i b u t i o n s of s u l f u r with conversion l e v e l
resemble those reported by Drushel f o r Safaniya r e s i d (8).
The removal of metals with the a s p h a l t e n i c s u l f u r i s observed
i n F i g u r e 4. T h i s response i s c o n s i s t e n t with an asphaltene model
i n which vanadium and n i c k e l are b u r i e d as porphyrins or sandwich

compounds (9). The s l i g h t l y higher removal of vanadium r e f l e c t s a
general tendency f o r vanadium to deposit on the c a t a l y s t more r e a -
d i l y than n i c k e l .
EFFECT OF COKE DEPOSITION

ON PORE SIZE DISTRIBUTION
A f i r s t step toward c a t a l y s t design i s to r e l a t e pore s t r u c -

ture roughly to asphaltene dimensions. Another step i s to c o n s i -
der pore s t r u c t u r e of the used c a t a l y s t and the probable s i z e of
asphaltenes at r e a c t o r temperature.
Figure 5 i s a histogram showing the d i s t r i b u t i o n of pore v o l -
ume v s . pore diameter f o r alumina c a r r i e r , f r e s h c o b a l t molybdenum
c a t a l y s t and used cobalt molybdenum c a t a l y s t . There was a s l i g h t
change i n mode diameter when the c a r r i e r was loaded with about 20%
a c t i v e metal oxides. The pore volume was reduced from 0.60 to
0.53 m l / g . However, accumulation of about 17% coke during the p r o -
c e s s i n g of West Coast r e s i d g r e a t l y s h i f t e d the mode downward and
reduced the t o t a l pore volume from 0.53 to 0.30 m l / g . ( A l l of
these pore volumes have been normalized to 1.0 gram of alumina).
A d d i t i o n a l comparisons of f r e s h v s . used c a t a l y s t are shown
i n Table V I I . The coke laydown occurred mainly i n the micropore
r e g i o n , causing a s u b s t a n t i a l l o s s of surface a r e a . Coke laydown
a l s o was observed i n the macropore r e g i o n of the bimodal c a t a l y s t
shown at the bottom of the t a b l e .
ASPHALTENE EXCLUSION AS A
FUNCTION OF TEMPERATURE
The e x c l u s i o n of asphaltenes f i r s t was approached by the sim-

p l e method of immersing a given amount of c a t a l y s t i n a volume of
r e s i d equal to 3 times the pore volume of the c a t a l y s t . If asphal-
tene e x c l u s i o n were to occur to a s i g n i f i c a n t degree, then there

CATALYST R
-CATALYST Τ
SATURATES
, •^ •
0 20 40 60 80 100 Figure 3. Distribution of sulfur with con-
7. DESULFURIZATION version level

20 40 60 80 100 140
PORE DIAMETER, Â
Figure 5. Histograms of pore volumes vs. pore diameter for carrier, fresh
catalyst, and used catalyst
TABLE VII
CHANGE IN PORE STRUCTURE

DUE TO COKE DEPOSITION
MODE SURFACE
SAMPLE DESCRIPTION PORE VOLUME, ml/g DIAMETER AREA
AND DESIGNATION MACRO MICRO TOTAL A m /g 2
S - 0293 - A 0.03 0.3 6 0.39 90 207
USED S - 0 2 9 3 - A 0.04 0.13 0.17 55 164
V-8477-Β 0.02 0.35 0.37 85 136
USED V-8477-Β 0.02 0.15 0.17 60 102
X - 02 34 - A 0.02 0.41 0.43 90 167
USED X - 0234 - A 0.02 0.21 0.23 60 140
H-6013 0.70 0.4 5 1.15 95, 350 350
USED H-6013 0.39 0.30 0.69 80, 400 174

would be an enrichment of asphaltenes i n the e x t e r n a l l i q u i d .

Using a 24-hour e q u i l i b r a t i o n p e r i o d of 2 1 2 ° F , the four sam-
p l e s shown i n Table V I I I a l l give an enrichment of asphaltenes.
The e x t e r i o r l i q u i d s contained 12.0-13.8% asphaltenes compared to
6.3% i n the Kuwait feed. These r e s u l t s q u a l i t a t i v e l y agree with
observations of Drushel who used a d i f f e r e n t technique w i t h Safan-
i y a r e s i d at room temperature (8).
The e x c l u s i o n of asphaltenes as a f u n c t i o n of temperature sub-
sequently was approached w i t h the a i d of g e l permeation chromoto-
graphy (GPC) i n a manner s i m i l a r to that described by D r u s h e l .
C a t a l y s t was e q u i l i b r a t e d 4 hour at constant temperatures w i t h a
volume of r e s i d equal to 3 times the pore volume of the c a t a l y s t .
During t h i s time, the system was n i t r o g e n blanketed and a g i t a t e d
every 1/2 hour. The e x t e r n a l l i q u i d subsequently was drained
through a screen and submitted f o r GPC analyses and metals content.
The i n t e r n a l l i q u i d was e x t r a c t e d from the c a t a l y s t pores f i r s t by
benzene and then 50/50 methanol-benzene. A f t e r evaporation of

these s o l v e n t s , the i n t e r n a l l i q u i d was submitted f o r i d e n t i c a l
analyses.
The GPC curves i n Figure 6 show asphaltene or "large molecule"
e x c l u s i o n at the nominal temperatures of 200, 400 and 6 0 0 ° F . The
e f f e c t decreases with i n c r e a s i n g temperature: planimeter areas
f a l l i n the r a t i o of 1.00, 0.65, and 0.40.
Metals d i s t r i b u t i o n , which i n some degree should r e l a t e to
asphaltene d i s t r i b u t i o n , are shown f o r the a c t u a l e q u i l i b r a t i o n
temperatures i n Table IX. N i c k e l showed the expected enrichment
at a l l temperatures. Vanadium responded s i m i l a r l y except at 403
and 6 0 3 ° F . Progressive s u l f i d i n g (0.6, 0.7, 1.4% S) and coke l a y -
down (0.8, 1.5, 7.8% C) were observed f o r the used c a t a l y s t s and
hence represent an experiment c o m p l i c a t i o n .
CONCLUSIONS
The p o i n t s to be emphasized i n c l u d e the f o l l o w i n g :

1. The r e f r a c t o r i n e s s of r e s i d feeds has been considered
from the standpoint of process s e v e r i t y and d i v i s i o n between
"hard" and "easy" s u l f u r .
2. For lower conversions l e v e l s , where a s p h a l t e n i c s u l f u r
removal i s not deep, r e f r a c t o r i n e s s appears to be l a r g e l y i n f l u -
enced by a l a r g e p r o p o r t i o n of s t e r i c a l l y hindered aromatic s u l -
fur compounds. S u b s t i t u t e d thiophenes, benzothiophines and d i -
benzothiophenes are r e p r e s e n t a t i v e compounds.
3. A s p h a l t e n i c s u l f u r i s the most r e f r a c t o r y specie i n r e -
s i d s and the removal of metals, p a r t i c u l a r l y n i c k e l , c o r r e l a t e s
w e l l with removal of a s p h a l t e n i c s u l f u r .
4. Coke d e p o s i t i o n a l t e r s c a t a l y s t pore s i z e d i s t r i b u t i o n s
s i g n i f i c a n t l y and i s an e f f e c t to be followed i n regard to c a t a -
l y s t aging.
5. The e x c l u s i o n of asphaltenes i n Kuwait r e s i d i s observed
by an autoclave technique at 2 1 2 ° F with s e v e r a l c a t a l y s t s having

RICHARDSON A N D A L L E Y Desulfurization of Resids
Figure 6. GPC molecular size distributions at vari-

ous temperatures

TABLE VIII
ASPHALTENE EXCLUSION EXPERIMENTS

AT 212 *F A N D Ί ATMOS.
. CATALYST
CATALYST WEIGHT, g 24.00 23.00 25.50 26-60
RESID WEIGHT, g 36.49 35.00 35.07 47.00
ASPHALTENE CONTENT
INITIAL, % 6.3 6.3 6.3 6.3

FINAL, OBS., % 13.8 12.8 12.0 13.4
PORE V O L U M E , ml/g 0.50 0.52 0.47 1.15
MICROPORE VOLUME, ml/g 0.42 0.50 0.44 0.45
MODE DIAMETER, λ 65 60 75 95
TABLE IX
METALS DISTRIBUTION IN RESID

FRACTIONS
Ni (PPM) V (PPM)
FEED 9 40
e
197 F INTERNAL 4 18
e
197 F EXTERNAL 15 58
403 F e
INTERNAL 2 48
403 F e
EXTERNAL 12 35
603 F e
INTERNAL 5 49
603 F e
EXTERNAL 10 27

9. RICHARDSON AND A L L E Y Desulfurization of Resids 149
mode diameters of 60-95 Â.

6. Exclusion of asphaltenes and/or large molecules i s also
observed at 200, 400 and 600°F by similar technique involving GPC.
The effect diminishes moderately with increasing temperature due
to thermal dissociation into smaller particles.
7. The exclusion of asphaltenes is matched by the distribu-
tion of nickel inside and outside the catalyst pore structure.
Vanadium distribution is inconsistent, probably influenced by
coke deposition at the higher temperatures.
ACKNOWLEDGEMENT
The authors acknowledge Dr. Dennis L . Saunders for the GPC

analytical work and many useful discusssions.
LITERATURE CITED
(1) Larson, O. Α . , Pittsburgh Catalysis Society, Spring Symposium,

(April, 1972).
(2) US 3,509,044 (Esso)
(3) US 3,531,398 (Esso)
(4) US 3,563,886 (Gulf)
(5) UK 1,122,522 (Gulf)
(6) NPA 6,815,284 (Hydrocarbon Research)
(7) German 1,770,996 (Nippon Oil)
(8) Drushel, Η. V., Preprints, Div. Petrol. Chem.,
ACS, 17, No. 4, F-92 (1972).
(9) Dickie, J. P . , Yen, T. F., Preprints, Div. Petrol. Chem.,
ACS, 12, No. 2, B-117 (1967).

10
The Structural Form of Cobalt and Nickel
Promoters in Oxidic HDS Catalysts
R. MONÉ and L. MOSCOU

Akzo Chemie Nederland bv, Research Centre Amsterdam, P. O. Box 15,
Amsterdam, The Netherlands
H y d r o d e s u l f u r i z a t i o n c a t a l y s t s c o n s i s t of CoO and M o O or
3
NiO and M o O on a3 2 3-Al O c a r r i e r ( 1 - 3 ) . The c a t a l y s t s are pro-

duced i n the o x i d i c form; t h e i r a c t u a l a c t i v e s t a t e is obtained
by s u l f i d i n g before or during usage i n the r e a c t o r .
Molybdenum oxide - alumina systems have been s t u d i e d i n
d e t a i l (4-8). Several authors have pointed out that a molybdate
surface l a y e r is formed, due to an i n t e r a c t i o n between molybdenum
oxide and the alumina support (9-11). Richardson (12) s t u d i e d the
s t r u c t u r a l form of c o b a l t i n s e v e r a l o x i d i c cobalt-molybdenum-
alumina c a t a l y s t s . The presence of an a c t i v e cobalt-molybdate
complex was concluded from magnetic s u s c e p t i b i l i t y measurements.
Moreover c o b a l t aluminate and c o b a l t oxide were found. Only the
a c t i v e c o b a l t molybdate complex would c o n t r i b u t e to the a c t i v i t y
and be c h a r a c t e r i z e d by o c t a h e d r a l l y coordinated c o b a l t . L i p s c h
and Schuit (10) s t u d i e d a commercial o x i d i c h y d r o d e s u l f u r i z a t i o n
c a t a l y s t , c o n t a i n i n g 12 wt% M o O and 4 wt% CoO. They concluded
3
that a c o b a l t aluminate phase was present and could not f i n d

i n d i c a t i o n s f o r an a c t i v e c o b a l t molybdate complex. Recent magnetic
s u s c e p t i b i l i t y s t u d i e s of the same type of c a t a l y s t (13) confirmed
the c o n c l u s i o n of L i p s c h and Schuit.
Schuit and Gates (30 proposed a model f o r the o x i d i c c a t a l y s t ,
i n which the promotor ions l a y j u s t below the molybdate l a y e r .
These c o b a l t ions would s t a b i l i z e the molybdate l a y e r on the
c a t a l y s t surface.
The promoting a c t i o n of c o b a l t on the a c t i v i t y f o r hydrodesul-
f u r i z a t i o n has been shown already i n the p i o n e e r i n g work of Byrns,
Bradley and Lee ( 1A). This promoting a c t i o n might be l i n k e d with
the s u l f i d i n g step, s i n c e the a c t u a l c a t a l y s t i s the s u l f i d e d form
of c o b a l t - or nickel-molybdenum-alumina. Voorhoeve and S t u i v e r (15)
and Farragher and Cossee (lj3) demonstrated the promoting a c t i o n f o r
the unsupported N1-WS2 system. T h e i r i n t e r c a l a t i o n model was based
on these experiments.
I t i s expected that the a c t i v a t o r system i n the o x i d i c
c a t a l y s t has a s t r u c t u r e from which the r i g h t c o n f i g u r a t i o n i s
obtained on s u l f i d i n g . We f e e l that the promotor ions have to be
150

10. M O N É A N D Moscou Cobalt and Nickel Promoters 151
present i n the neighbourhood of the surface molybdate l a y e r and

that the assumption of a cobalt-aluminate phase might be an i n s u f -
f i c i e n t d e s c r i p t i o n of the o x i d i c h y d r o d e s u l f u r i z a t i o n c a t a l y s t .
Therefore we have examined the presence of i n t e r a c t i o n s between
c o b a l t and molybdenum from which a more d e t a i l e d p i c t u r e of the
o x i d i c c a t a l y s t can be deduced. We have s t u d i e d t h e r e f o r e UV-VIS
r e f l e c t a n c e s p e c t r a of adsorbed p y r i d i n e , a technique that has
been used before f o r t h i s type of c a t a l y s t s by K i v i a t and P e t r a k i s
(19).
Experimental Methods.
C a t a l y s t Preparation. The c a t a l y s t s were prepared by impreg-

2
n a t i o n of îf-alumina extrudates ( SA=253 m /g ). Each impregnation
was followed by drying overnight at 120°C and c a l c i n a t i o n at the
i n d i c a t e d temperatures during one hour. Molybdenum was brought on
the support as an ammonium molybdate s o l u t i o n ; c o b a l t and n i c k e l

as n i t r a t e s o l u t i o n s . Each component was impregnated s e p a r a t e l y .
The impregnation of c o b a l t on the blanc support took place step-
wise (1 wt% CoO i n each s t e p ) .
C a t a l y s t s . MoCo-124: Alumina was impregnated f i r s t w i t h

molybdenum, then c a l c i n e d at 650°C, followed by the c o b a l t impreg-
n a t i o n . The f i n a l c a l c i n a t i o n was v a r i e d from 400 - 700°C. Compo-
sition: 12 wt% M0O3 and 4 wt% CoO.
MoCo-122 and MoCo-123 were obtained by impregnation as c a r r i e d
out f o r MoCo-124. Only 2 and 3 wt% CoO resp. were brought on the
c a t a l y s t . F i n a l c a l c i n a t i o n temperature 650 C.
CoMo-124: Alumina was impregnated f i r s t with c o b a l t stepwise.
e
The sample was d r i e d at 120°C and c a l c i n e d at 650 C a f t e r each
impregnation step. Afterwards the c a t a l y s t was impregnated w i t h
molybdenum. F i n a l c a l c i n a t i o n temperature 650°C. The composition
was the same as f o r MoCo-124.
CoMo-124 B: Cobalt was brought on uncalcined boehmite, 4 wt%
i n one step. Afterwards the sample was c a l c i n e d at 650°C, impreg-
nated w i t h molybdenum oxide (12 wt%) and c a l c i n e d at 650°C f o r a
2
second time. The surface area was 241 m /g.
MoCo-153: Alumina was impregnated f i r s t w i t h molybdenum, d r i e d
and c a l c i n e d at 650°C. Then the c o b a l t was brought hereupon. Two
f i n a l c a l c i n a t i o n temperatures were a p p l i e d , 480 and 650*C. The
composition was 15 wt% M0O3 and 3 wt% CoO.
NiMo-124: The c a t a l y s t s were prepared according to the Dutch
Patent 123195 (17). The alumina c a r r i e r was impregnated f i r s t w i t h
n i c k e l . Two f i n a l c a l c i n a t i o n temperatures were a p p l i e d , 480 and
650°C. These samples were impregnated w i t h molybdenum. F i n a l c a l -
c i n a t i o n temperatures 480 and 650°C. The composition of the four
c a t a l y s t s , which were obtained was 12 wt% M0O3 and 4 wt% NiO, The
c a t a l y s t s are i n d i c a t e d by the a p p l i e d c a l c i n a t i o n temperatures
a f t e r each impregnation; e.g. NiMo-124 480/480.
MoNi-153: Molybdenum was brought on the alumina c a r r i e r f i r s t ,

( c a l c i n a t i o n temperature 650°C), followed by the n i c k e l impreg-

n a t i o n . The f i n a l c a l c i n a t i o n temperature was v a r i e d . The composi-
t i o n was 15 wt% M0O3 and 3 wt% NiO.
R e f l e c t i o n Spectroscopy. The r e f l e c t i o n s p e c t r a were r e c o r -

ded with an O p t i c a Milano CF 4 spectrophotometer, using magnesium
oxide as the r e f e r e n c e . The samples were m i l l e d i n a mortar during
20 minutes. The r e f l e c t a n c e d i d not change s i g n i f i c a n t l y when t h i s
m i l l i n g time was increased. The s p e c t r a of the c o b a l t c o n t a i n i n g
samples are shown, as they have been recorded (% r e f l e c t a n c e
against wavelength). The s p e c t r a of the n i c k e l c o n t a i n i n g samples
are p l o t t e d as a remission f u n c t i o n (18) against wavenumber.
I n f r a r e d Spectroscopy. The procedure of K i v i a t and P e t r a k i s

(19) was followed f o r the greater p a r t . The s p e c t r a of adsorbed
p y r i d i n e were recorded with a Perkin Elmer 621 spectrophotometer.
2
The d i s c s (15 mg/cm ) were pressed i n a RIIC d i e , using a pressure
2
of 1000 kg/cm . These d i s c s were rehydroxylated f i r s t on standing
i n humid a i r during two days before they were placed i n the IR
c e l l . Outgassing took place at 420*C. P y r i d i n e was adsorbed at
room temperature and the excess was removed by evacuation at 150,
250 and 350°C during one hour.
Pore s t r u c t u r e . The surface area and pore volume were deter-

mined by N2 adsorption. No s i g n i f i c a n t changes were observed when
the c a t a l y s t was c a l c i n e d i n the temperature r e g i o n of 400 - 700°C
i n d i c a t i n g that no s t r u c t u r a l c o l l a p s e took place i n t h i s tempera-
ture range.
Results.
V i s i b l e R e f l e c t i o n Spectra. The f i n a l c a l c i n a t i o n tempera-

ture of MoCo-124 samples has been v a r i e d i n order to study i t s
i n f l u e n c e on the c o o r d i n a t i o n of the c o b a l t i o n s . The r e f l e c t i o n
s p e c t r a are shown i n F i g u r e 1. The s p e c t r a of MoCo-124, c a l c i n e d
at 400 and 500°C show a broad absorption band, covering the whole
s p e c t r a l region, with a weak s u p e r p o s i t i o n of the c h a r a c t e r i s t i c
t r i p l e t of c o b a l t aluminate. T h i s i n d i c a t e s that the c o b a l t ions
are f o r the greater part s t i l l on the c a t a l y s t surface and not i n
the alumina l a t t i c e . The s p e c t r a of the MoCo-124 samples, c a l c i n e d
at 650-700 °C show a strong increase i n i n t e n s i t y of the t r i p l e t
band, while the broad absorption band has disappeared. T h i s i n d i c a -
tes the formation of a c o b a l t aluminate phase.
I n f r a r e d Spectra. F i g u r e 2 shows the s p e c t r a of p y r i d i n e

adsorbed on /-alumina. Two types of Lewis a c i d s i t e s are present;
strong Lewis a c i d s i t e s , which s t i l l bind p y r i d i n e on evacuation
1
at 350°C and c h a r a c t e r i z e d by the 1622 and 1454 cm" bands and
1
weak Lewis a c i d s i t e s , c h a r a c t e r i z e d by the 1614 and 1450 cm"
bands. BrSnsted a c i d s i t e s , which have c h a r a c t e r i s t i c bands around

10. ΜΟΝΕ AND MOSCOU Cobalt and Nickel Promoters 153
1636 and 1540 cm~l (19,21) are not observed i n t h i s spectrum. The
spectrum of p y r i d i n e adsorbed upon cobalt-alumina (4 wt% CoO) i s
shown i n F i g u r e 2d. No change i n the p y r i d i n e spectrum i s observed
i n comparison with the spectrum of p y r i d i n e on y-alumina, i n d i c a
t i n g that the surface a c i d i t y i s not markedly changed. A same
behaviour has been observed f o r n i c k e l alumina. These r e s u l t s
agree w i t h those o f K i v i a t and P e t r a k i s (19).
The adsorption of p y r i d i n e on molybdenum-alumina (12 wt%
M0O3) has been i n v e s t i g a t e d f o r samples i n both o r i g i n a l and
rehydroxylated form. The s p e c t r a are shown i n F i g u r e 3. I t appears
1
that BriSnsted a c i d s i t e s , c h a r a c t e r i z e d by the 1636 and 1540 cm""
bands are observed only, when the d i s c s are rehydroxylated i n wet
a i r before the c a l c i n a t i o n under high vacuum i n the IR c e l l takes
p l a c e (Figure 3b). By consequence a l l s p e c t r a have been recorded
for such rehydroxylated samples. Only one Lewis band i s observed
for the molybdenum-alumina sample, opposite t o the observations
of K i v i a t and P e t r a k i s (19), who have observed two Lewis bands f o r

t h e i r samples.
Spectra of adsorbed p y r i d i n e have been recorded f o r the
MoCo-124 c a t a l y s t s , f o r which the f i n a l c a l c i n a t i o n temperature
a f t e r the c o b a l t impregnation has been v a r i e d . I t turns out that
the 400 and 500°C c a l c i n e d samples and the 650 and 700°C c a l c i n e d
samples show very s i m i l a r s p e c t r a . Therefore we show only the
s p e c t r a o f the 400°C (low c a l c i n e d ) and the 650°C (high c a l c i n e d )
samples. F i g u r e 4 shows s p e c t r a a f t e r desorption at 150 and 250°C.
Few BrSnsted a c i d s i t e s are observed i n the low c a l c i n e d MoCo-124
samples. The r e f l e c t i o n s p e c t r a ( F i g u r e 1) i n d i c a t e f o r these low
c a l c i n e d samples the presence of c o b a l t on the c a t a l y s t s u r f a c e ,
because no c o b a l t aluminate phase could be detected. The high
c a l c i n e d samples do show the presence of BrSnsted a c i d s i t e s ; the
presence of a c o b a l t aluminate phase i s concluded from the r e f l e c
t i o n s p e c t r a (Figure 1) f o r these samples.
These experiments i n d i c a t e that at low c a l c i n a t i o n tempera
tures the c o b a l t ions are present on the c a t a l y s t surface and
n e u t r a l i z e the BrBnsted a c i d s i t e s of the molybdate surface l a y e r .
At the higher c a l c i n a t i o n temperatures, the c o b a l t ions move i n t o
the alumina l a t t i c e . The BrGnsted a c i d s i t e s reappear, i n d i c a t i n g
that the s i t u a t i o n on the molybdate surface i s r e s t o r e d .
However, the molybdenum-alumina and the high c a l c i n e d c o b a l t -
molybdenum-alumina samples s t i l l show an important d i f f e r e n c e . The
p y r i d i n e s p e c t r a of MoCo-124 i n d i c a t e a second Lewis a c i d s i t e ,
1
c h a r a c t e r i z e d by the 1612 cm" band. T h i s band d i f f e r s from the
1
weak Lewis a c i d s i t e s of the alumina support (1614 cm* ) because
the p o s i t i o n i s s i g n i f i c a n t l y d i f f e r e n t . I t a l s o appears that the
s t r e n g t h of the bond between p y r i d i n e and the c a t a l y s t i s stronger,
1
for the 1612 cm" band i s s t i l l present a f t e r evacuation at 250°C,
1
w h i l e the weak Lewis band (1614 cm" ) o f the alumina has d i s a p
peared at t h i s desorption temperature. Obviously the second Lewis
band f o r the MoCo-124 c a t a l y s t i s introduced by the i n t e r a c t i o n of
c o b a l t with the surface molybdate l a y e r . T h i s i n t e r a c t i o n i s

Or
500 600 700 800

WAVELENGTH (nm)
Figure 1. Reflectance spectra of MoCo-124 cata-

lysts, calcined at different temperatures, a)
400°C, b) 500°C, c) 600°C, d) 650°C, and e)
750°C.
1700 1600 1500 1400

WAVENUMBER (cm-1)
170Ô 1600 1500 1400
WAVENUMBER (cm-1) Figure 3. Spectra of ad-
sorbed pyridine a) on
Figure 2. Spectra of ad- MoO -y-Al 0 ,
s 2 evacu-
3
sorbed pyridine a) on ated 1 hr, 150°C; b) on
y-Al O evacuated 1 hr,
2 s rehydroxylated MoCVy-
150°C; b) as a), evacu- Al O , evacuated 1 hr,
z s
ated 1 hr, 250°C; c) as 150° F; c) as b), evacu-
a), evacuated 1 hr, 350° ated 1 hr, 250°C; d) as
C; d) on CoO-y-Al O , z s b), evacuated 1 hr,
evacuated 1 hr, 150° C 350°C

c l e a r l y s t i l l present i n the high c a l c i n e d c a t a l y s t s , where c o b a l t

i s present i n the alumina l a t t i c e .
Reversed Impregnation. The reversed impregnation has been

s t u d i e d too. Impregnation of 4 wt% CoO on y-alumina i n one step
g e n e r a l l y leads t o the formation of C03O4 on c a l c i n a t i o n (black
extrudates (22,23)). A stepwise impregnation r e s u l t s i n c o b a l t
aluminate formation (blue extrudates), showing i t s c h a r a c t e r i s t i c
t r i p l e t i n the r e f l e c t i o n spectrum (Figure 5a). Impregnation of
molybdenum on the c o b a l t c o n t a i n i n g support does not i n f l u e n c e the
r e f l e c t i o n spectrum of the c o b a l t i o n s , as shown i n F i g u r e 5b.
Spectra of p y r i d i n e , adsorbed on t h i s CoMo-124 sample are
1
shown i n F i g u r e 6. The second Lewis band (1612 cm"" ) i s present,
i n d i c a t i n g that the i n t e r a c t i o n between the c o b a l t ions and the
s u r f a c e molybdate l a y e r i s present too.
Boehmite Based .Catalysts. Hedvall (24) has discussed the f o r

mation of c o b a l t aluminate from CoO and AI2O3. He has shown that a
r e l a t i v e l y f a s t s o l i d s t a t e r e a c t i o n takes place when the alumina
undergoes a phase change, v i z . y-Al2C>3-> rt-AÔg. T h i s phenomenon
i s known as the Hedvall e f f e c t .
Such an e f f e c t might be expected when boehmite supported
c o b a l t i s being c a l c i n e d , v i z . during the phase t r a n s i t i o n AIO(OH)
- * y - A l 0 3 . F i g u r e 7 shows s p e c t r a of p y r i d i n e , adsorbed on the
2
sample CoMo-124 B, which has been prepared i n t h i s way. Spectra f o r

MoCo-122, -123 and -124, c o n t a i n i n g 2, 3 and 4 wt% CoO resp.
are shown f o r comparison. A l l these c a t a l y s t s have had a f i n a l c a l
c i n a t i o n of 650°C. Comparison of the s p e c t r a of CoMo-124 Β and
1
MoCo-124 i n d i c a t e s that the i n t e n s i t y of the 1612 cm" band,
which i s introduced by the i n t e r a c t i o n of the c o b a l t ions and the
molybdate l a y e r , i s lower f o r CoMo-124 Β than f o r MoCo-124. The
spectrum f o r CoMo-124 Β resembles that of CoMo-123, i n d i c a t i n g that
a part of the c o b a l t ions does not p a r t i c i p a t e i n t h i s i n t e r a c t i o n .
N i c k e l Promoted C a t a l y s t s . N i c k e l c o n t a i n i n g c a t a l y s t s are
known to be s e n s i t i v e f o r too high temperatures. The Dutch patent
123195 (17) claims that a c t i v e nickel-molybdenum-alumina c a t a l y s t s
are obtained, when n i c k e l i s impregnated f i r s t . The c a l c i n a t i o n i s
c r i t i c a l however. According t o t h i s patent, c a t a l y s t s c a l c i n e d at
4 8 0 a r e twice as a c t i v e as c a t a l y s t s , c a l c i n e d at 650°C.
C a t a l y s t s NiMo-124 have been prepared according t o t h i s patent and
have been i n v e s t i g a t e d . The h y d r o d e s u l f u r i z a t i o n a c t i v i t y showed
indeed a pronounced decrease on c a l c i n a t i o n at 650°C i n comparison
w i t h the 480°C c a l c i n e d sample.
The s p e c t r a of adsorbed p y r i d i n e are shown i n F i g u r e 8. The
spectrum of the sample NiMo-124 480/480, which has been c a l c i n e d
1
twice at the lowest c a l c i n a t i o n temperature shows a c l e a r 1612 cm"
Lewis band. This band has a f a r weaker i n t e n s i t y f o r the 650/650
1
c a t a l y s t . The 480/650 sample shows a more intense 1612 cm" band
than the 650/650 and 650/480 samples. T h i s might i n d i c a t e that the

Figure 4. Spectra of ad-

sorbed pyridine a) on
MoCo-124,finalcalcina-
tion 400°C, evacuated 1
hr, 150°C; b) as a),
evacuated 1 hr, 250°C;

c) on MoCo-124, final
calcination 650°C, evac-
uated 1 hr, 150°C; d)
1700 1600 1500 1400 as c), evacuated 1 hr,
WAVENUMBER (cm-1) 250°C
Figure 5. Reflectance spectra: a) CoO-y-Al O , 2 s
calcined at 650°C; b) of CoMo-124,finalcalcina-

tion, 650°C

ΜΟΝΕ AND MOSCOU Cobalt and Nickel Promoters
Figure 6. Spectra of adsorbed pyri

dine a) on CoMo-124, evacuated 1 1400

hr, 150°C; b) as a) evacuated 1 hr, 1700 1600 1500
250°C WAVENUMBER (cm-1)
1700 1600 1500 1400 1700 1600 1500 1400

WAVENUMBER (cm-1) WAVENUMBER (cm-1)
Figure 7. Spectra of ad Figure 8. Spectra of ad

sorbed pyridine a) Mo- sorbed pyridine NiMo-
Co-122; b) MoCo-123; 124: a) 480/480; b) 480/
c) MoCo-124; d) CoMo- 650; c) 650/480; d) 650/
124 B. All after evacua 650. All after evacuation
tion 1 hr, 150°C. 1 hr, 150°C.

n i c k e l i o n s , which are s t i l l present i n the neighbourhood of the

alumina surface a f t e r the f i r s t c a l c i n a t i o n at 480°C, remain t i e d
to the molybdate l a y e r to some extent a f t e r the second c a l c i n a t i o n
at 650°C.
The s p e c t r a of adsorbed p y r i d i n e f o r MoCo-153 and MoNi-153
are compared i n F i g u r e 9. Two f i n a l c a l c i n a t i o n temperatures have
e
been a p p l i e d , 480 and 650 C. The s p e c t r a of the 480°C samples ( F i -
gure 9a and 9b) are n e a r l y i d e n t i c a l . The Brtfnsted a c i d bands are
weak, while the 1612 cm"l Lewis bands are strong. The i n t e n s i t y
of the Bro'nsted a c i d bands i n c r e a s e s f o r both 650 °C c a l c i n e d sam-
p l e s (Figure 9c and 9d). The Lewis a c i d bands show a marked d i f f e -
rence now. The 1612 band remains high i n i n t e n s i t y f o r the MoCo-
153 c a t a l y s t , but t h i s Lewis band decreases a p p r e c i a b l y i n i n t e n -
s i t y f o r the MoNi-153 c a t a l y s t .
R e f l e c t i o n s p e c t r a f o r the MoNi-153 c a t a l y s t s are shown i n
F i g u r e 10. The 480°C c a l c i n e d c a t a l y s t shows the c h a r a c t e r i s t i c
a b s o r p t i o n band (25) of o c t a h e d r a l l y coordinated n i c k e l i o n s . The

650°C c a l c i n e d c a t a l y s t shows the c h a r a c t e r i s t i c spectrum of
n i c k e l aluminate. These r e f l e c t i o n s p e c t r a i n d i c a t e that the
n i c k e l ions migrate from the c a t a l y s t surface i n t o the alumina, as
has been observed a l s o f o r the cobalt-molybdenum-alumina c a t a l y s t s .
Discussion.
R u s s e l l and Stokes (9) and Sonnemans and Mars (11) have presen-
ted strong evidence f o r the formation of a molybdate monolayer. I t
appears from t h e i r experiments that each molybdate group covers
2
20-25 Â of the alumina surface.The surface of the alumina support,
which has been used i n t h i s study, i s high enough f o r a complete
spreading of 15 wt% M 0 O 3 , so no bulk molybdenum oxide i s expected
to be present. T h i s has been confirmed by X-ray d i f f r a c t i o n
measurements.
The molybdate surface l a y e r i n the molybdenum-alumina samples
i s c h a r a c t e r i z e d by the presence of Bro'nsted a c i d s i t e s ( 1545
1 1
cm" ) and one type of strong Lewis a c i d s i t e s (1622 cm" ). Cobalt
or n i c k e l ions are brought on t h i s surface on impregnation of the
promotor. The absence of BrSnsted a c i d s i t e s i s observed f o r both
c o b a l t and n i c k e l impregnated c a t a l y s t s , c a l c i n e d at the lower tem-
peratures (400-500°C). A l s o a second Lewis band i s observed at 1612
1
cm" .The r e f l e c t i o n s p e c t r a of these c a t a l y s t s i n d i c a t e that no
c o b a l t or n i c k e l aluminate phase has been formed at these tempera-
t u r e s . T h i s i n d i c a t e s that the c o b a l t and n i c k e l ions are s t i l l
present on the c a t a l y s t surface and n e u t r a l i z e the BrSnsted a c i d
s i t e s of the molybdate l a y e r . These c o n f i g u r a t i o n s w i l l be c a l l e d
" c o b a l t molybdate" and " n i c k e l molybdate" and are shown schematic-
a l l y i n F i g u r e 11a.
For the high temperature c a l c i n e d cobalt-molybdenum-alumina
c a t a l y s t s , the presence of a c o b a l t aluminate phase has been con-
cluded from the r e f l e c t i o n s p e c t r a . The Bro'nsted a c i d s i t e s reap-
pear i n the spectrum of absorbed p y r i d i n e , i n d i c a t i n g that the

10. M O N É A N D Moscou Cobalt and Nickel Promoters
1612
1700 1600 1500 1400

WAVENUMBER (cm-1)
I 1 1 .
Figure 9. Spectra of ad- 20 15 10 χ 10 3
sorbed pyridine on Mo- WAVENUMBER (cm-1)

C0-153,finalcalcination:
a) 480°C; c) 650°C; Mo- Figure 10. Reflectance spectra of MoNi-
Ni-153,finalcalcination: 153: a)finalcalcination, 480°C; b)finalcal
b) 480°C; d) 650°C cination, 650°C
H
Ο
molybdate surface layer ι /
-Mo-
characterized by Brônsted -Mo-
and Lewis acid sites alumina
impregnation Cobalt Nickel
+
Co 2 +
Ni^
calcining 5 0 0 ° C
Cr
-Co ?" I
(5) -Mo<- -M6- (a) -Mo- -Mo-
alun alumina
calcining 6 5 0 ° C H Η
CE) -&>- -Mo-
surface CoA^Qj
Θ-some surface -NiAlÔj
Mo-
^^buTk^NiAl^^^
H
Ο
boehmite based φ -Ao<- -Mo-
CoMo-124
^ Î 5 % ζ»\ν€ο&\$£>
Figure 11. Schematic representation of the different surface

structures

bond between c o b a l t and the molybdate l a y e r i s broken. S t i l l the

presence of two types of Lewis a c i d s i t e s i s observed (1622 and
1
1612 cm" ). T h i s suggests that no bulk aluminate phase i s formed,
but that the c o b a l t ions remain present i n the f i r s t l a y e r of the
alumina l a t t i c e , s t i l l having an i n t e r a c t i o n with the surface
molybdate l a y e r .
The optimal a c t i v i t y f o r a cobalt-molybdenum-alumina c a t a l y s t
i s obtained by c a l c i n a t i o n at the higher temperatures. This means
that the c o b a l t i o n s , present as a c o b a l t aluminate phase according
to the r e f l e c t a n c e s p e c t r a and the magnetic s u s c e p t i b i l i t y measure
ments, s t i l l have a pronounced promoting a c t i o n a f t e r t h i s c a l c i
n a t i o n . The assumption of c o b a l t present i n the surface l a y e r of
the alumina l a t t i c e e x p l a i n s both the high a c t i v i t y due to the
c o b a l t promotion as w e l l as the presence of the second Lewis band.
T h i s c o n f i g u r a t i o n i s shown s c h e m a t i c a l l y i n F i g u r e l i b .
Some bulk c o b a l t aluminate formation i s expected to take
place f o r the boehmite based c a t a l y s t , owing to a Hedvall e f f e c t

(24).The spectrum of adsorbed p y r i d i n e on CoMo-124 Β shows indeed
1
a weaker 1612 cm" band, comparable with the i n t e n s i t y of t h i s
band f o r the MoCo-123 c a t a l y s t . This i n d i c a t e s that about 25 % of
the c o b a l t ions has disappeared in the bulk of the alumina. (Figure
lid).
The reappearance of Bro'nsted a c i d s i t e s has been observed f o r
the high c a l c i n e d nickel-molybdenum-alumina c a t a l y s t s . The presence
of a n i c k e l aluminate phase has been concluded from the r e f l e c
1
tance s p e c t r a . The second Lewis band (1612 cm" ) has a very low
i n t e n s i t y , i n comparison with the c o b a l t c o n t a i n i n g c a t a l y s t s of a
same composition and a f t e r the same c a l c i n a t i o n c o n d i t i o n s .
N i c k e l aluminate i s a p a r t l y inverse s p i n e l (26) i n which the
n i c k e l ions occupy both t e t r a h e d r a l and octahedral holes, opposite
to c o b a l t aluminate, which i s a normal s p i n e l . Romeyn (26)has
shown f o r the compound NIAI2O4 and Lo Jacono e t . a l . (25) f o r
n i c k e l alumina systems that the n i c k e l ions occupy only a f r a c t i o n
of the t e t r a h e d r a l s i t e s , never exceeding 25 %. The strong reduc
1
t i o n i n i n t e n s i t y of the 1612 cm" Lewis band might be due to the
octahedral p o s i t i o n of the greater part of the n i c k e l ions i n the
surface l a y e r of the alumina l a t t i c e . However i t i s a l s o known that
the a c t i v i t y decreases s t r o n g l y f o r the high c a l c i n e d n i c k e l -
molybdenum-alumina c a t a l y s t s (17), at temperatures normally a p p l i e d
i n the cobalt-molybdenum-alumina c a t a l y s t p r e p a r a t i o n . This i n d i
cates that only a f r a c t i o n of the n i c k e l ions are a v a i l a b l e f o r a
promoting a c t i o n i n the high c a l c i n e d c a t a l y s t s . We suggest that
t h i s i s due to bulk n i c k e l aluminate formation, by which the
n i c k e l ions are l o s t i n the alumina l a t t i c e . T h i s i s s c h e m a t i c a l l y
shown i n F i g u r e 11c.
K i v i a t and P e t r a k i s (19) have shown that the c o b a l t and n i c k e l
ions i n f l u e n c e the s p e c t r a of p y r i d i n e adsorbed on aolybdenum-
alumina. They have concluded that the i n t r o d u c t i o n of these ions
r e s u l t s i n a change of the r a t i o of the i n t e n s i t i e s of the bands of
the Lewis and Bro'nsted a c i d s i t e s . Our observations show that t h i s

r a t i o i s s t r o n g l y dependent on the c a l c i n a t i o n temperature. T h i s

temperature determines the i n t e r a c t i o n between the surface molyb
date l a y e r and the promotor ions and might be c o r r e l a t e d w i t h the
h y d r o d e s u l f u r i z a t i o n a c t i v i t y of the c a t a l y s t s .
Concerning the a c t i v i t y of the cobalt-molybdenum-alumina
c a t a l y s t s , i t i s the experience i n t h i s l a b o r a t o r y that the o p t i
mal a c t i v i t y i s obtained by c a l c i n a t i o n at high temperatures. The
high c a l c i n e d form i s probably p r e f e r r e d , because i n t h i s form the
c o b a l t ions are hidden i n the f i r s t l a y e r of the alumina l a t t i c e
and are not very s u s c e p t i b l e f o r reducing c o n d i t i o n s i n t h i s con
f i g u r a t i o n . I t i s w e l l known that t h i s i s the case f o r the ( low
c a l c i n e d ) nickel-molybdenum-alumina c a t a l y s t s . T h i s might be
expected from the f a r more exposed form of the n i c k e l ions (Figure
11a). No c o r r e l a t i o n s between a c t i v i t y and the presence of a
c o b a l t aluminate complex as i n d i c a t e d by Richardson (12) can be
concluded. The low c a l c i n e d cobalt-molybdenum-alumina c a t a l y s t s do
show the presence of a " c o b a l t molybdate" phase; however t h i s

phase disappears on c a l c i n a t i o n at 650-700°C, where the c a t a l y s t s
s t i l l have a high a c t i v i t y . T h i s shows that the c o b a l t ions are
not l o s t i n the alumina l a t t i c e .
Conclusions..
I t has been found by measuring s p e c t r a of adsorbed p y r i d i n e

on various C0O-M0O3-AI2O3 systems that there i s a c l e a r i n t e r a c
t i o n of the c o b a l t ions w i t h the M0O3-AI2O3 s u r f a c e l a y e r . T h i s
c o n c l u s i o n i s based upon the occurence of a second Lewis band i n
the spectrum of adsorbed p y r i d i n e , which has been observed i n the
whole r e g i o n of the c a l c i n a t i o n temperatures a p p l i e d .
A p i c t u r e has been formed of the way i n which the promotor
ions are b u i l t i n the M0O3-AI2O3 system. The n e u t r a l i z a t i o n of the
Bro'nsted a c i d s i t e s , as o r i g i n a l l y present i n M0O3-AI2O3 systems
by the c o b a l t ions f o r the c a t a l y s t s c a l c i n e d at low tempera
tures (^500°C) i n d i c a t e s that the c o b a l t ions are present on the
c a t a l y s t s u r f a c e . The l i b e r a t i o n of these s i t e s i n c a t a l y s t s c a l
c i n e d at high temperatures (~650°C) and the o b s e r v a t i o n of the
c h a r a c t e r i s t i c r e f l e c t a n c e spectrum of C0AI2O4 show that the c o b a l t
ions enter the alumina l a t t i c e . However the i n t e r a c t i o n between
c o b a l t and molybdenum, as i n d i c a t e d by the second Lewis band
remains present. T h i s leads to the c o n c l u s i o n that the c o b a l t ions
are present i n the surface l a y e r s of the alumina l a t t i c e .
S i m i l a r i n t e r a c t i o n s have been observed f o r the n i c k e l promo
t e d c a t a l y s t . However, the degree of i n t e r a c t i o n depends on the
c a l c i n a t i o n temperature. T h i s i n t e r a c t i o n disappears f o r a great
p a r t at i n c r e a s i n g temperatures. T h i s i s a s c r i b e d to bulk n i c k e l
aluminate formation.
These observations might c o n t r i b u t e to the understanding of
the d i f f e r e n c e s i n c a t a l y t i c performance between c o b a l t and
n i c k e l promoted h y d r o d e s u l f u r i z a t i o n c a t a l y s t s .

Literature Cited.
1) McKinley, J.B., i n "Catalysis", P.H. Emmett,(ed), Vol 5,

ρ 405, Reinhold, New York 1957.
2) Schuman, S.C. and Shalit, Η., Catal. Rev., (1970),4, 245.
3) Schuit, G.C.A. and Gates, B.C., AIChE, (1973),19, 417.
4) Seshadri, K.S. and Petrakis, L., J.Catal. (1973),30, 195.
5) Massoth, F.E., J. Catal. (1973),30, 204.
6) Dufaux, Μ., Che, M. and Naccache, C., J. Chim. Phys. Physico-
chim. B i o l . , (1970),67, 527.
7) Masson, J. and Nechtstein, J., B u l l . Soc. Chim. Fr., (1968),
3933.
8) Miller, A.W., Atkinson, W., Barber, M. and Swift, P., J. Catal.
(1970),22, 140.
9) Russell, A.S. and Stokes, J.J., Ind. Eng. Chem., (1946),38,
1071.
10) Lipsch, J.M.J.G. and Schuit, G.C.A., J. Catal., (1969),15, 174.

11) Sonnemans, J. and Mars,P., J. Catal., (1973),31, 209.
12) Richardson, J.T., Ind. Eng. Chem. Fundamentals, (1964),3, 154.
13) Roelofsen, J.W., unpublished results.
14) Byrns, A.C., Bradley, W.E., and Lee, M.W., Ind. Eng. Chem.,
(1943), 35, 1160.
15) Voorhoeve, R.J.H. and Stuiver, J.C.M., J. Catal., (1971),23,
228,236,243 (1971).
16) Farragher, A.L. and Cossee, P.,Proc F i f t h Intern. Congr.
Catal., Palm Beach, ρ 1301, North-Holland Publishing Company,
1973.
17) Chevron Researh Company, Dutch Patent 123195.
18) Wendlandt, W.Wm. and Hecht, H.G., "Reflectance Spectroscopy",
Interscience Publishers, New York, 1966.
19) Kiviat, F.E. and Petrakis, L., J. Phys. Chenu,(1973),77, 1232.
20) Parry, E.P., J. Catal., (1963),2, 317.
21) Grimblot, J., Pommery, J. and Beaufils, J.P., C.R. Acad. S c i . ,
Ser. C., (1973),276, 331.
22) Tomlinson, J.R., Keeling, R.O., Rymer, G.T. and Bridged, J.M.,
Actes du deuxième Congr. Intern, de Catalyse, ρ 1831, Ed.
Technip, Paris (1961).
23) Nishina, R., Yonemura, M. and Kotera, Y., J. Inorg.Nucl.Chem.,
(1972),34, 3279.
24) Hedvall, J.A. and L e f f l e r , L.,Z, Anorg. A l l g . Chem., (1937),
234, 235.
25) Lo Jacono, M., Schiavelo, M. and Cimino, Α., J. Phys. Chem.,
(1971),75, 1044.
26) Romeyn, F.C., Thesis, university of Leiden, 1953.

INDEX
A Catalysts (continued)
Acid function of the catalyst 29 chromia-alumina 66,72
Acid sites, Bronsted 158 deactivation 46
Acidic halides 29 Ε hydrocracking 45
Activation energies, Arrhenius 94 effects on yields and product prop
Activity, hydrogénation 1, 11, 30 erties 28
n-Alkanes 1, 2, 18 experimental 34
Alkylbenzenes 82 faujasite 46
Alkylcarbenium ions 2 fouling 45
hydrocracking 29
Publication Date: June 1, 1975 | doi: 10.1021/bk-1975-0020.ix001
γ-Alumina 151 hydrodesulfurization 150

Alumina catalyst, chromia- 66,72 hydrogenation-dehydrogenation
Amorphous catalysts 42
Anthracene 83,92 component of 29
Argon 133 monofunctional 7
Aromatic structures, complex 82 nickel-molybdena 102
Aromatics, condensed ring 65 nickel promoted 155
Arrhenius activation energies 94 NIS-H-zeolon 88
Arrhenius plots 95 noble metal 29
Asphaltenes 112, 121, 139, 143 nonacidic 65
Asphaltenic sulfur 136 oxidic HDS 150
palladium-nickel containing syn
thetic mica-montmorillonite .... 52
Β preparation and processing 53, 151
Batch distillation 103 presulfided cobalt moly 136
Batch stirred tank reactor 84 pore structure 136
Benzene 88,126 Pt/Ca-Y-zeolite 2
insolubles 114 reduced 60
Berguid process 123 sulfided 57
Bifunctional catalysts 1,9 sulfided metal 29
Blending, products from 105 treatment on LPG yields, effect of 61
Boehmite based catalysts 155 Catalytic cracking 5
Branched isomers, multiple 8 Catalytic sites 40
Branching in the cracked products .... 19 Cation, mono-branched decyl 20,22
Bronsted acid sites 158 Cation, primary 18
Burner fuels 99, 108 Cetane index 105
η-Butane hydrocracking, isobutane/ .39,41
Centrifuged liquid product 114, 116
Chain length 1,3
C
Char feed analysis 127
C yield hydrocracking
5 40,44 Chemisorption, competitive 7
C - 180°F product
5 36 Chromia-alumina catalysts 66
C M , conversion to 67 Chromia-alumina reactor 72
California gas oil 34,37
Carbenium ions 5 City bus diesel fuel 104
Carbon balance 131 Cleavage 9,18
Carbon number 11, 79 Coal 93
Carbonization of coal 82 carbonization of 82
Catalyst(s) -derived fuels Ill
acid function of 29 feed analysis 113, 127
aging effects 42 feed rate 132
amorphous 42 hydrocracking of 83, 84
bifunctional 1,9 hydrogénation tubular reaction
boehmite based 155 experiment
165

Coal (continued) Free radical mechanisms 67

liquefaction 114, 123 Fuel(s)
New Mexico sub-bituminous 125 burner 99
oil 83, 85, 93 coal-derived Ill
particle residence time 128, 130 diesel 99, 103, 106, 107
particle size distribution 130 distillate burner 108
properties of 85 oil 106
solvent refined 65
Cobalt G
moly catalyst, presulfided 136
-molybdate complex 150 Gas
promotors 150 from hydrocracking in situ crude .... 103
Coke deposition 143 oil, California 34,37
Competitive chemisorption 7 oil, mid-continent 47
Condensed-ring aromatics 65 phase hydrogénation, rapid 123
Cracked products, branching in the .. 19 GPC molecular size distributions 147
Cracked products, distribution of 11,12
Cracking H
catalytic 5 Halides, acidic 29
primary •••• 13
reactions, overall 14 HDS catalysts, oxidic 150

Crude η-Heptane 24
in situ 103 n-Hexane hydrocracking, isohexanes/ 38
Kuwait 136 Hydrocarbons, polynuclear aromatic .. 82
oil, distillation of 140 Hydrocracked oil 103
oils, synthetic 99 Hydrocracked products 89
residuum fraction of 136 Hydrocracking 2
shale oil feedstock 103 of n-alkanes, ideal 1,18
CycloparafEns 36 anthracene 83
C liquid yield
5 44
of California gas oil 37
D catalysts 29
n-Decane 11 of coal 83, 84
Decyl cations, mono-branched 20,22 coal oil 83
Dehydrogenation 11,29 condensed-ring aromatics 65
Desorption 7 extinction recycle 31
Desulfurization of resids 136 ideal 1
Diesel fuels 99, 103, 104, 106, 107 incorporating sulfur on 58
9,10-Dihydrophenanthrene 66 in situ crude, gas from 103
Distillate burner fuels 108 in situ shale oil 99
Distillation product yields from 28,59
of crude oil 140 ionic 19
of the hydrocracked oil, batch 103 isobutane/n-butane 41
product from 105 isohexanes/n-hexane 38
isopentane/n-pentane 38
£ of phenathrene 79,83
raffinate 52,56
Entrained down-flow tubular reactor 124 Hydrogénation
Extinction recycle hydrocracking 31 activity 1, 30
acidity 30
F /dehydrogenation activity 11
/dehydrogenation component of a
Faujasite catalyst 46 catalyst 29
Feed(s) 32 product ratios 74
char 127 rapid gas 123
coal 113, 127, 132 reactions 76
properties 33 tubular reaction experiment 127
sulfur level 57,60 unit 101
Feedstocks 90, 103, 136 Hydrogenolysis 7,21
First order rate constants 94 Hydroisomerization 1, 2, 7, 11
Fractionation scheme 116 Hydrodesulfurization catalysts 150

INDEX 167
I Ν
Infrared spectroscopy 152 NIS-H zeolon catalyst 88

Ionic hydrocracking 19 New Mexico sub-bituminous coal 125
Isoalkanes 16 Nickel 143
Isobutane 52 containing synthetic mica-mont-
/n-butane hydrocracking 41 morillonite catalysts 52
/n-butane ratio 39 molybdena catalyst 102
production 60 promoted catalysts 155
yields 62 promotors in oxidic HDS catalysts .. 150
Isohexanes/n-hexane hydrocracking .. 38 Noble metal catalysts 29
Isomer (s) Nonacidic catalysts 65
distributions 61,63 n-Nonane 10
from hydroisomerization of n- North Dakota lignite 125
octane and n-nonane 10
monomethyl 11 Ο
multiple branched 8 η-Octane 4, 9,19, 24
Isoparaffins 36 Octane number 28
Isopentane/n-pentane hydrocracking 38
J Palladium nickel-containing synthetic

Jet product 46 mica-montmorillonite catalysts .. 52
Jet yield 40 Paring reaction 39
n-Pentane hydrocracking, isopentane/ 38
Pentane insolubles 136
Κ Phenanthrene 67, 79, 83, 92
Kinetics 91 Poisoning of catalytic sites 40
Kuwait crude 136 Polynuclear aromatic hydrocarbons .... 82
Pore
size distribution 143
L structure, catalyst 136, 152
volume vs. pore diameter 145
LPG yields 61 Power generation, fuel oil for Ill
Lewis band 158 Preferential poisoning of catalytic
Lignite, North Dakota 125 sites 40
Liquefied petroleum gas 52 Primary cation 18
Liquid product, centrifuged 114,116 Primary cracking 13
Liquid ( C + ) yield
5 40, 44 Product 78
analysis Ill
M composition 45
distributions 34, 62, 78, 79
Metal catalysts 29 properties 28
Metals, removal of 144 yields 59
Methylnonane 11 Promotor ions 150
Mica-montmorillonite catalysts, Promotors, cobalt and nickel 150
palladium nickel-containing Pt/Ca-Y zeolite catalyst 2
synthetic 52 Pyridine 114, 181, 151, 154
Microreactor, steady state 72
Mid-continent gas oil 47
Molecular size distributions, GPC 147
Moly catalyst, presulfided cobalt 136 Raffinite analysis 54
Molybdate complex, cobalt- 150 Raffinitate hydrocracking 52, 56
Molybdate monolayer 158 Rate constant, first order 94
Molybdena catalyst, nickel- 102 Rate constant, variation of 97
Mono-branched decyl cations 20, 22 Reaction rates 3
Monofunctional catalysts 7 Reaction zone 128
Monolayer, molybdate 158 Reactor, entrained down-flow tubular 124
Monomethyl isomers 11 Recycle hydrocracking, extinction 31
Montmorillonite catalysts, palladium Reflection spectroscopy 152, 154
nickel-containing synthetic mica 52 Reforming stock 106

168 HYDROCRACKING A N D H Y D R O T R E A T I N ^
Refractoriness of asphaltenes 139 Τ

Resid (residuum fraction) 136 Tank reactor, batch stirred 84
Residence time, coal particle 128, 130 Temperature on product distribtuion,
Reversed impregnation 155 effect of 78
γ-Ring opening of a saturated termi Terminal ring, saturated 73
nal 73 Tetrahydrophenanthrene 73
Tetralin 73
S Toluene 91, 126
insolubles 114, 121
β-Scission 7, 18, 20, 22 Truck-tractor diesel fuel 104
Shale oil, in situ 99, 103 Tubular reactor, entrained down-flow 124
Solvent refined coal 65 Tubular reaction experiment, coal
Stationary-marine diesel fuel 104 hydrogénation 127
Steady state microreactor 72
Steric hindrance 139 U
Sulfur n-Undecane 9
distribution of 144
in the desulfurization of resids 136 V
in hydrocracking 58 Vanadium 143
level 57, 59, 60, 61 X
in raffinate hydrocracking 56
Sulfided catalysts 29,57 Xylene 126
Supports for hydrocracking catalysts 29 Y
Surface structures, different 159 Yields in hydrocracking 28
Sym-octahydrophenanthrene 73
Synthetic crude oils 99 Ζ
Synthoil process Ill Zeolites 29


Hydrocracking and Hydrotreating

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Hydrocracking and Hydrotreating

Union Oil Co. of California

Burns and Roe Industrial Service Corp.

the Division of Petroleum

Chemistry, Inc. at the

169th Meeting of the

American Chemical Society,

ACS SYMPOSIUM SERIES 20

AMERICAN CHEMICAL SOCIETY

American Chemical Society

1155 16th St., N.W.

In Hydrocracking and Hydrotreating; Ward, J., el al.;

Library of Congress Œ Data

American Chemical Society

ACS Symposium Series

Robert F. Gould, Series Editor

In Hydrocracking and Hydrotreating; Ward, J., el al.;

a medium for publishing symposia quickly in book form. The

In Hydrocracking and Hydrotreating; Ward, J., el al.;

'"phe efficient upgrading of energy resources to desirable products is an

tial polluting contaminants from fuels and their precursors.

Union Oil Co. of California JOHN W. WARD

In Hydrocracking and Hydrotreating; Ward, J., el al.;

Since 1960 catalytic hydrocracking has received considerable

T h e e x p e r i m e n t s w e r e c a r r i e d out i n a s m a l l flow type f i x e d

It was found that h y d r o i s o m e r i z a t i o n and h y d r o c r a c k i n g of

In Hydrocracking and Hydrotreating; Ward, J., el al.;

In Hydrocracking and Hydrotreating; Ward, J., el al.;

SUPERFICIAL HOLDING TIME [s]

Figure 1. Hydroisomerization and hydrocracking of n-alkanes with different

In Hydrocracking and Hydrotreating; Ward, J., el al.;

c r a c k i n g (13), w h e r e l i t t l e o r no i s o m e r i z a t i o n of the feed t a k e s

In Hydrocracking and Hydrotreating; Ward, J., el al.;

240 260 280 300 320 340

Figure 3. Influence of reaction temperature on hydroisomerization conversion

Figure 4. Influence of reaction temperature on hydrocracking conversion of

In Hydrocracking and Hydrotreating; Ward, J., el al.;

In Hydrocracking and Hydrotreating; Ward, J., el al.;

In Hydrocracking and Hydrotreating; Ward, J., el al.;

n-ALKANE — CRACKED PRODUCTS

n-ALKENES SEC. n-ALKYL CATIONS — f * C R A C K E D PRODUCTS

i-ALKANES CRACKED PRODUCTS

Figure 5. Reaction scheme for hydroisomerization of n-alkanes on bifunctional cata-

FEED: n-OCTANE F E E D : n-UNDECANE

SUPERFICIAL HOLDING TIME [s] SUPERFICIAL HOLDING TIME [s]

Figure 6. Course of hydroisomerization of η-octane and n-undecane (T — 275°C)

In Hydrocracking and Hydrotreating; Ward, J., el al.;

Table II. Mole-% of Isomers Formed in Hydroisomerization of «-Octane and w-Nonane

3-Methylheptane 11 .4 22.3 23.3 17.3

n-Nonane 74.1 25.9 11.1 6.5

(a) Thermodynamic equilibrium calculated from ref. (Γ7)

In Hydrocracking and Hydrotreating; Ward, J., el al.;

(e. g . , m = 10) t h e n the m a i n c h a i n i n the m o n o m e t h y l i s o m e r s

τ °c j 224 250 274 300

v i r t u a l l y absent. P r o d u c t d i s t r i b u t i o n s l i k e this a r e t y p i c a l for

In Hydrocracking and Hydrotreating; Ward, J., el al.;

FEED Τ F -103 eXCR

Figure 7. Hydrocracking of n-alkanes with an even carbon number. Distribu­

Figure 8. Hydrocracking of n-alkanes with an odd carbon number. Distribu­

In Hydrocracking and Hydrotreating; Ward, J., el al.;

In Hydrocracking and Hydrotreating; Ward, J., el al.;

d i f f e r s s u b s t a n t i a l l y f r o m the one w h i c h i s v a l i d f o r the h i g h e r

In Hydrocracking and Hydrotreating; Ward, J., el al.;

Overall Cracking Reaction P r o b a b i l i t y (%)

Figure 7. Hydrocracking of n-alkanes with an even carbon number. Distribu

Figure 8. Hydrocracking of n-alkanes with an odd carbon number. Distribu

T h e v a l u e s defined i n t h i s m a n n e r do not r e p r e s e n t any p r o

M r s . H . Schlifkowitz and M r . G . Walter for their excellent ex