Kids&Us · Kids&Us Kids&Us Kids&Us Kids&Us Kids&Us Kids&Us . Created Date: 5/26/2015 9:49:45 AM
Us 5672743
of 14
-
Upload
martin2104 -
Category
Documents
-
view
218 -
download
0
Transcript of Us 5672743
-
8/11/2019 Us 5672743
1/14
United States Patent
[ 1 9 ]
Garland e t
a 1 .
US005672743A
[ 1 1 ] Patent
Number:
[ 4 5 ] Date o f P a t e n t :
5 , 6 7 2 , 7 4 3
S e p . 3 0 , 1 9 9 7
[ 5 4 ] PROCESS
FOR THE
PRODUCTION OF
ACETIC A CID
[ 7 5 ]
I n v e n t o r s : C a r l
Sherman G a r l a n d . C o l u m b i a .
M d . ; M a r t i n
F r a n c i s
G i l e s . M i d d l e s e x ;
John
G l e n n S u n l e y ,
N o r t h H u m b e r s i d e .
b o t h o f
E n g l a n d
[ 7 3 ] A s s i g n e e : BP C h e m i c a l s L i m i t e d . L o n do n . ~
E n g l a n d
[ 2 1 ]
A p p l . N o . : 2 8 4 , 0 7 8
[ 2 2 ]
F i l e d : A u g . 1 , 1 9 9 4
[ 3 0 ] F o r e i g n A p p l i c a t i o n
P r i o r i t y
D a t a
S e p . 1 0 , 1993 [GB] United
Kingdom
. . . . . . . . . . . . . . . . .
.
9318809
May 5,1994
[GB] United Kingdom . . . . . . . . . . . . . . . . . . 9 4 08 9 6 6
[ 5 1 ] I n t .
C l . 6
. . . . . . . . . . . . . . . . . . . . . . . . . . . CWC 1 / 1 0 ;
C07C 51/12
[ 5 2 ]
US. C l .
5 6 2 / 5 1 9
[ 5 8 ] Field of S ea rch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5 6 2 / 5 1 9
[ 5 6 ] R e f e r e n c e s C i t e d
U . S .
PATENT DOCUMENTS
3,285,948 1 1 / 1 9 6 6 Butter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 6 0 / 6 4 2
3,772,380
11/1973 Paulik e t a 1 .
3,813,428 5 / 1 9 7 4
Paulik
e t
a 1 .
. . . . . . . . . . . . . . . . . . . . . . . . . .
.
2 6 0 / 5 3 2
4 , 0 2 9 , 7 4 8 6 / 1 9 7 7
F o r s t e r e t
a 1 . 4 2 3 / 4 1 8
4 , 0 4 6 , 8 0 7
9 / 1 9 7 7 K u c k e r t z
2 6 0 / 5 4 9
4 , 1 0 1 , 4 5 0 7 / 1 9 7 8
Hwang
t
a l . 2 5 2 / 4 6 0
4 102 921
7/1978
Bartish . . . . . . . . .
.. 260/532
4 , 1 3 6 , 1 0 4
1 / 1 9 7 9
Hwang t a 1 .
. . 260/449 R
4,333,884 6/ 1 982 Kiibbeler
e t
a 1 . . . . . . . . 2 6 0 / 5 4 6
4 , 3 5 6 , 1 2 6
l 0 / l 9 8 2 Drent
. . . . . . . . . . . . . . .
.
4 , 4 3 0 , 2 7 3
2/1984
Erpenbach
e t
a 1 .
4, 48 4, 00 2
11/1984 Lin . . . . . . . . . . . . . . .
.
, 48 7, 40 6
1 2 / 1 9 8 4
Steinmetz
e t a 1 . ............. .
5 6 0 / 8 0
4 , 5 0 0 , 4 7 4
2 / 1 9 8 5
G a u t h i e r - L a f a y e
e t
a 1 .
4 , 5 1 4 , 3 3 6 4/1985 Ryan e t a ] . . . . . . . . . . . . . . .
. ., 5 1 9 , 9 5 6
5/1985 Lin e t a l . 260/549
4 , 5 8 8 ,8 3 4
5/1986
L a r ki n
. . . . . . . . . . . . . .
. .
4,629,809
12/1986 Vanderpool e t a 1 .
. .
4 , 6 4 0 , 8 0 2
2/1987 Drent
, 6 5 8 , 0 5 3
4/1987 Green
4 , 6 6 1 , 6 2 3 4/1987 Chang e t a ] .
4,664,851
5/ 1 987 Drent
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
2 6 0 / 4 1 0 9
R
4,681,707 7/1987 Alper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2 6 0 / 4 1 0 9
R
4 , 9 9 7 , 9 7 8 3 / 1 9 9 1 G a u t h i e r - L a f a y e
e t
a ] .
5 6 0 / 2 6 5
5,268,505 1 2/ 1 9 9 3 Delis
e t
a 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562/ 51 7
FOREIGN PA TENT DOCUMENTS
3 8 0 3 7 / 8 9
1 / 1 9 9 0
Australia
1 2 3 4 1 5 0 3 1 1 9 8 8 Canada
1 2 5 8 4 6 9 8 / 1 9 8 9
Canada
1 2 6 7 1 2 9
3 / 1 9 9 0 Ca n a d a
0 031 606
7 1 1 9 8 1
0 072 0 5 5
2 1 1 9 8 3
0 075
3 3 5 3 / 1 9 8 3
0 075 3 3 7 3 / 1 9 8 3
0 083 1 2 1 7 / 1 9 8 3
0
09 0
443
1 0 / 1 9 8 3
0 120
6 3 1 1 0 / 1 9 8 4
0 1 3 1 998 1 / 1 9 8 5
0
1 5 5
1 2 2 9 / 1 9 8 5
0 6 1 8 1 8 3 1 0 / 1 9 9 4
1 9 4 1 449
I 9 4 1
448
1767150B2
5 / 1 9 7 2
5 6 - 0 8 3 4 3 9 - A
7 / 1 9 8 1
5 8 - l 6 7 5 3 1 - A
1 0 / 1 9 8 3
5 8 - l 7 2 3 3 1 - A 1 0 / 1 9 8 3
6 0 - 0 3 2 7 2 4 - A 2 1 1 9 8 5
6 0 - 0 3 2 7 2 6 - A
2 / 1 9 8 5
6 0 - 1 9 9 8 4 1 1 0 /1 9 8 5
6 0 - 2 5 5 7 4 1 - A 1 2 / 1 9 8 5
6 2 - 1 3 5 4 4 5 - A
6 /
1 9 8 7
3197441-A
8 / 1 9 9 1
4046139-A
2 1 1 9 9 2
1 2 3 4 6 4 1
6 / 1 9 7 1
1 2 3 4 6 4 2
6 / 1 9 7 1
1 2 7 6 3 2 6 6 / 1 9 7 2
1 4 4 8 0 1 0 9 / 1 9 7 6
1 4 5 0 9 9 3 9 / 1 9 7 6
1 5 2 3 3 4 6
8 /
1 9 7 8
2029409 3 / 1 9 8 0
OTHER
PUBLICATIONS
J .
M o l .
C a t a l ,
8 5
( 1 9 9 3 )
L 1 0 9 - L 1 1 6 .
C a r b o n y l a t i o n
o f t h e
Ru-Me
Bond
o f
Ru(Me) ( I )
( C O ) 2 ( i P r - N = C H C H = N - " P r ) C a t a l y z e d b y R u ( C O ) , , ( P R 3 ) .
Z n C l 2 . a n d HP;
O r g a n o m e t a l l i c s ; M a r c o .
A .
K r a a l n n a n e t
a l . ; 1 1 , 3 7 7 4 - 3 7 8 5
( 1 9 9 2 ) .
R u t h e n i u m - C a t a l y z e d
C a r b o n y l a t i o n R e a c t i o n s
o f
A 1 0 0
h o l s t o A c i d s a n d E s t e r s J o u r n a l o f
M o l e c u l a r
C a t a l y s i s ; G .
J e n n e r e t a l . ; 4 0
( 1 9 8 7 )
7 1 - 8 2 .
C ,
t o A c e t y l s : C a t a l y s i s a n d
P r o c e s s ;
C a t a l y s i s T o d a y ;
M.
J .
Howard
t a l . ; 1 8 ( 1 9 9 3 )
3 2 5 - 3 5 4 .
M e t h a n o l
C a r b o n y l a t i o n
t o
A c e t i c A c i d " ;
A p p l i e d
I n d u s
t r i a l
C a t a l y s i s . v o l . 1 ; R . Eby a n d T . S i n g l e t o n ;
( 1 9 8 3 )
2 7 5 - 2 9 6 .
A b s t r a c t f o r
S c h r o d
&
L u f t ; 2 7 t h DGMK Annu. M e e t .
( A a c h e n
O c t . 6 - 8
1 9 8 2 ) ( C o n d e n s . )
( D t s c h .
G e s . ) .
C h e m . L e t t . ( 9 ) 1 6 1 1 - 1 2 .
M e t h a n o l a n d C a r b o n y l a t i o n ; R h d n e - P o u l e n c R e c h e r
c h e s ; J . G a u t h i e r - L a f a y e e t a l . ; ( 1 9 8 7 ) 1 3 6 - 2 0 1 .
" K i n e t i c
a n d
S p e c t r o s c o p i c S t u d i e s o f t h e C a r b o n y l a t i o n o f
Methanol
w i t h
a n
I o d i d e - P r o m o t e d I r i d i u m C a t a l y s t ;
D .
F o r s t e r ;
( 1 9 7 9 ) 1 6 3 9 - 1 6 4 5 .
H a l i d e C a t a l y s i s o f t h e O x i d a l i v e A d d i t i o n o f A l k y l
H a l i d e s
t o R h o d i u r n ( I ) C o m p l e x e s ; J A C S ; D . F o r s t e r ;
( 1 9 7 5 )
9 7 : 4 .
9 5 1 - 9 5 2 .
3 / 1 9 7 0
4 / 1 9 7 0
Germany
Germany
Germany
J a p a n
J a p a n
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
United
Kingdom
United
Kingdom
United Kingdom
United Ki n gd om
United Ki n gd om
United
Kingdom
United
Kingdom
( L i s t
c o n t i n u e d o n n e x t p a g e . )
P r i m a r y
E x a m i n e r J o s e G . D e e s
A s s i s t a n t E x a m i n e r - R o s a l y n d
A . W i l l i a m s
A t t o m e ) ; A g e n t , o r
FirmBrooks
H a i d t H a f f n e r
&
D e l a h u n t y
[ 5 7 ] ABSTRACT
A
r o c e s s f o r t h e p r o d u c t i o n o f a c e t i c a c i d b y
c a r b o n y l a t i o n
o f m e t h a n o l o r a r e a c t i v e
d e r i v a t i v e t h e r e o f by c o n t a c t i n g
t h e m e t h a n o l o r d e r i v a t i v e w i t h c a r b o n monoxide i n a l i q u i d
r e a c t i o n
c o m p o s i t i o n c o m p r i s i n g ( a ) a c e t i c a c i d , ( b ) a n
i r i d i u m
c a t a l y s t .
( c )
m e t h y l i o d i d e ,
( d )
a t l e a s t
a ? n i t e
q u a n t i t y
o f w a t e r
a n d
( e )
m e t h y l
a c e t a t e
i s
i m p r o v e d b y
t h e
u s e a s p r o m o t e r o f
a t l e a s t
one o f r u t h e n i u m and
osmium.
2 9 C l a i m s , No
D r a w i n g s
-
8/11/2019 Us 5672743
2/14
5 , 6 7 2 , 7 4 3
P a g e 2
OTHER PUBLICATIONS
M e c h a n i s t i c S t u d y
o f M e t h a n o l
C a r b o n y l a t i o n
C a t a l y z e d
b y
a n I r i d i u m
C o m p l e x
i n
t h e
P r e s e n c e o f
M e t h y l
I o d i d e ;
J o u r n a l o f a t a l y s i s ; T .
M a t s u m o t o
e t a 1 . ; 5 1
( 1 9 7 8 )
9 6 - 1 0 0 .
F u r t h e r S t u d y o f M e t h a n o l C a r b o n y l a t i o n C a t a l y z e d b y
C o b a l t . R h o d i u m , a n d
I r i d i u m
C a t a l y s t s ; B u l l e t i n
o f
t h e
C h e m i c a l
S o c e i t y
o f J a p a n ;
T .
M i z o r o k i e t
a l . ;
5 2 ( 1 9 7 9 )
4 7 9 - 4 8 2 .
M e c h a n i s t i c
P a t h w a y s
i n t h e C a t a l y t i c
C a r b o n y l a t i o n o f
M e t h a n o l b y Rhodium
a n d
I r i d i u m C o m p l e x e s ;
A d v a n c e s
i n O r g a n o m e t a l l i c C h e m i s t r y ; D .
F o r s t e r ;
1 7 ( 1 9 7 9 )
2 5 5 - 2 6 7 .
Homogeneous C a t a l y t i c
R e a c t i o n s
o f
M e t h a n o l
w i t h C a r
b o n M o n o x i d e ; J o u r n a l o f M o l e c u l a r C a t a l y s i s ; D . F o r s t e r ;
1 7 ( 1 9 8 2 )
2 9 9 - 3 1 4 .
M e c h a n i s t i c
A s p e c t s
o f T r a n s i t i o n - M e t a l - C a t a l y z e d
A l c o
h o l C a r b o ny l a t i o n s ; A d v .
i n
C a n a l ;
T .
D e k l e v a a n d
D .
F o r s t e r ; 3 4 ( 1 9 8 6 ) 8 1 - 1 3 0 .
C a r b o n y l a t i o n o f E t h a n o l
U s i n g M o n o g e n e o u s
I r C o m p l e x
C a t a l y s t : E f f e c t
o f
L i g a n d s
a n d
R e a c t i o n C o n d i t i o n s ;
J o u r
n a l o f
M o l e c u l a r C a t a l y s i s ;
R .
P . P a t i l e t a l . ;
4 7 ( 1 9 8 8 )
8 7 - 9 7 .
C a r b o n y l a t i o n
o f E t h a n o l
U s i n g
H o m o g e n e o u s I r i d i u m
C o m p l e x C a t a l y s t :
A
i n e t i c S t u d y ; J o u r n a l
o f M o l e c u l a r
C a t a l y s i s ;
R .
P .
P a n ' l e t
a l . ; 7 2 ( 1 9 9 2 )
1 5 3 - 1 6 5 .
C h e m i s t s D e t a i l
C a t a l y s i s
Work
w i t h
C 1 S y s t e m s ; C &
E N ; J o s e p h
H a g g i n ; ( 1 9 8 4 )
2 1 - 2 2 .
-
8/11/2019 Us 5672743
3/14
5 , 6 7 2 , 7 4 3
1
PROCESS
FOR THE
PRODUCTION
OF
A CETIC ACID
The p r e s e n t
i n v e n t i o n r e l a t e s t o
a p r o c e s s f o r t h e
p r o
d u c t i o n o f a c e t i c a c i d by c a r b o n y l a t i o n o f m e t h a n o l o r a
r e a c t i v e d e r i v a t i v e
t h e r e o f i n
t h e
p r e s e n c e
o f a n
i r i d i u m
c a t a l y s t
and a s p r o m o t e r ,
a t
l e a s t one o f r u t h e n i u m and
o s m i u m .
C a r b o n y l a t i o n p r o c e s s e s i n
t h e
p r e s e n c e o f i r i d i u m
c a t a
l y s t s a r e known and
a r e d e s c r i b e d f o r
example i n U . S .
P a t .
N o . 3 7 7 2 3 8 0 . UK a t e n t
GB 2 7 6 3 2 6
d e s c r i b e s
p r e p a r a t i o n
o f m o n o c a r b o x y l i c a c i d s a n d
t h e i r
e s t e r s
b y c a r b o n y l a t i o n
o f
a l c o h o l s . h a l i d e s . e t h e r s . e s t e r s o r
1 . 2
epoxy a l i p h a t i c com
p o u n d s i n
t h e p r e s e n c e o f
rhodium
o r i r i d i u m c a t a l y s t s .
h a l o g e n promoters and
water o r
an
a l c o h o l . e t h e r o r
e s t e r .
C a r b o n y l at i o n p r o c e s s e s
i n t h e
p r e s e n c e o f
r u t h e n i u m
a n d
osmium a t a l y s t s a r e a l s o k n o w n . T h u s ,
UK
a t e n t s GB
1 2 3 4 6 4 1
and GB 1234642 d e s c r i b e
a p r o c e s s
f o r t h e
p r o
d u c t i o n
o f
an
o r g a n i c
a c i d
o r a n e s t e r
by
c a r b o n y l a t i o n o f a n
a l c o h o l , h a l i d e , e s t e r . e t h e r o r p h e n o l i n
t h e
p r e s e n c e o f
a
n o b l e m e t a l
c a t a l y s t
s e l e c t e d f r o m i r i d i u m . p l a t i n u m .
p a l l a d i u m . osmium a n d r u t h e n i u m a n d t h e i r c o m p o u n d s a n d
a
p r o m o t e r w h i c h i s h a l o g e n o r h a l o g e n c o m p o u n d .
A c c o r d
i n g t o
J e n n e r
e t a l i n J . M o l . C a t a l y s i s 4 0 ( 1 9 8 7 ) 7 1 - 8 2
r u t h e n i u m c o m p o u n d s a r e
e t f e c t i v e c a r b o n y l a t i o n
c a t a l y t s
f o r c o n v e r t i n g p r i m a r y a l c o h o l s i n t o a c i d s a n d e s t e r s
a t h i g h
CO
r e s s u r e s .
S t a n d a r d
c o n d i t i o n s o f 450 b a r CO r e s s u r e
w e r e u s e d
i n
t h e r e p o r t e d
e x p e r i m e n t s a n d l o w CO r e s s u r e s
w e r e s a i d t o l e a d t o
h i g h
y i e l d s o f
h y d r o c a r b o n s
a n d
a l o w e r
y i e l d o f e s t e r . UK a t e n t a p p l i c a t i o n G B 2 0 2 9 4 0 9
d e s c r i b e s
a p r o c e s s f o r t h e
p r e p a r a t i o n
o f a l i p h a t i c
c a r b o x y l i c
a c i d s
and e s t e r s
by r e a c t i n g
c a r b o n monoxide w i t h
a l c o h o l s
a t a n
e l e v a t e d p r e s s u r e o f 34 a t m o s p h e r e s o r
g r e a t e r
i n t h e p r e s
e n c e o f a r u t h e n i u m c a t a l y s t and h a l o g e n - c o n t a i n i n g p r o
m o t e r .
US.
a t . N o .
5 2 6 8 5 0 5
d e s c r i b e s t h e p r e p a r a t i o n
o f
a d i p i c
a c i d b y
h y d r o c a r b o x y l a t i n g
a p e n t e n i c
a c i d
i n
t h e p r e s e n c e
o f
rhodium c a t a l y s t and
a
c o - c a t a l y s t
o f a t
l e a s t one
o f
i r i d i u m ,
r u t h e n i u m
a n d
o s m i u m .
E u r o p e a n
p a t e n t
p u b l i c a t i o n EP 0 0 3 1 6 0 6 - A d e s c r i b e s a
p r o c e s s
f o r
t h e c o - p r o d u c t i o n o f c a r b o x y l i c
a c i d s a n d
e s t e r s
b y
r e a c t i o n o f e s t e r s a n d / o r
e t h e r s
w i t h c a r b o n monoxide
a n d
h y d r o g e n i n
t h e
p r e s e n c e o f
a c a t a l y s t
s y s t e m which
c o m p r i s e s
a r u t h e n i u m compound, a
Group
1 1 m e t a l
i o d i d e
a n d / o r bromide
o r
t r a n s i t i o n
m e t a l
i o d i d e
a n d / o r b r o m i d e ,
a n d a f u r t h e r
Group V I I I
m e t a l
c o m p o u n d . The Group V 1 1 1
m e t a l
i s
s a i d t o b e e s p e c i a l l y
r h o d i u m
a n d
p a l l a d i u m . O n l y
t h e s e
Group
V 1 1 1 m e t a l s a r e i l l u s t r a t e d i n
t h e
e x a m p l e s .
A c c o r d i n g t o E u r o p e a n p a t e n t p u b l i c a t i o n s EP
0075335-A a n d B I 0075337-A t h e Group
I I
o r t r a n s i t i o n
m e t a l i o d i d e a n d / o r b r o m i d e i n t h e c a t a l y t i c s y s t e m o f EP
0031606-A c a n
b e
r e p l a c e d
b y m e t h y l
i o d i d e
o r b r o m i d e o r
a c e t y l
i o d i d e
o r bromide o r a n y m i x t u r e t h e r e o f p r o v i d e d
t h a t t h e r e a c t i o n i s c a r r i e d o u t i n t h e
p r e s e n c e
o f an amine
o r
phosphine r e s p e c t i v e l y
i n an amount
n o t e x c e e d i n g a
c e r t a i n l e v e l . The use
o f
i r i d i u m i s n o t d i s c l o s e d .
I t h a s n o w
been
found t h a t ruthenium
a n d / o r
osmium
h a v e
b e n e ? c i a l
e f f e c t s on t h e r a t e o f c a r b o n y l a t i o n
o f
methanol o r a r e a c t i v e d e r i v a t i v e
t h e r e o f
i n t h e p r e s e n c e
o f
a n i r i d i u m
c a t a l y s t .
T h u s , a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n t h e r e
i s
p r o
v i d e d a
p r o c e s s
f o r t h e p r o d u c t i o n
o f
a c e t i c a c i d b y c a r b o
n y l a t i o n o f m e t h a n o l
a n d / o r
a r e a c t i v e d e r i v a t i v e t h e r e o f
which
r o c e s s
c o m p r i s e s c o n t a c t i n g m e t h a n o l
a n d / o r
a
r e a c
t i v e
d e r i v a t i v e
t h e r e o f w i t h
c a r b o n monoxide i n
a
l i q u i d
r e a c t i o n c o m p o s i t i o n
i n
a c a r b o n y l a t i o n r e a c t o r c h a r a c t e r
i s e d
i n
t h a t t h e l i q u i d r e a c t i o n c o m p o s i t i o n
c o m p r i s e s : ( a )
10
20
25
35
4 5
50
55
6 5
2
a c e t i c
a c i d .
( b ) a n i r i d i u m
c a t a l y s t .
( c )
m e t h y l i o d i d e . ( d )
a t
l e a s t
a f i n i t e
c o n c e n t r a t i o n o f
w a t e r ,
( e ) m e t h y l a c e t a t e and
( f ) a s
p r o m o t e r , a t l e a s t o n e o f r u t h e n i u m and os mium.
A l s o a c c o r d i n g
t o t h e p r e s e n t
i n v e n t i o n t h e r e i s p r o v i d e d
a
c a t a l y s t
s y s t e m f o r t h e p r o d u c t i o n o f
a c e t i c
a c i d b y
c a r b o n y l a t i o n
o f
m e t h a n o l
o r a
r e a c t i v e d e r i v a t i v e t h e r e o f i n
t h e p r e s e n c e o f a t l e a s t a ? n i t e c o n c e n t r a t i o n o f w a t e r which
c a t a l y s t s y s t e m
c o m p r i s e s :
( a )
a n
i r i d i u m c a t a l y s t . ( b )
m e t h y l
i o d i d e
and
c ) a t
l e a s t o n e
o f r u t h e n i u m a n d o s m i u m .
S u i t a b l e r e a c t i v e d e r i v a t i v e s
o f
m e t h a n o l i n c l u d e
m e t h y l
a c e t a t e .
d i m e t h y l e t h e r a n d m e t h y l i o d i d e . A
i x t u r e
o f
methanol and
r e a c t i v e
d e r i v a t i v e s t h e r e o f
may
be
used
a s
r e a c t a n t s i n t h e p r o c e s s
o f t h e
p r e s e n t i n v e n t i o n . P r e f e r a b l y .
methanol a n d / o r methyl a c e t a t e a r e u s e d a s r e a c t a n t s .
A t
l e a s t some
o f
t h e m e t h a n o l a n d / o r r e a c t i v e d e r i v a t i v e t h e r e o f
w i l l b e c o n v e r t e d
t o , a n d
h e n c e p r e s e n t a s , m e t h y l a c e t a t e
i n
t h e l i q u i d r e a c t i o n c o m p o s i t i o n b y r e a c t i o n w i t h a c e t i c
a c i d
p r o d u c t
o r s o l v e n t . The c o n c e n t r a t i o n
i n
t h e l i q u i d r e a c t i o n
c o m p o s i t i o n .
o f m e t h y l a c e t a t e i s s u i t a b l y i n t h e r a n g e 1 t o
7 0%
b y
w e i g h t .
p r e f e r a b l y
2
t o
50%
b y
w e i g h t .
m o s t
p r e f e r a b l y
3 t o 35% b y w e i g h t .
W a t e r
may b e formed i n s i t u
i n
t h e l i q u i d r e a c t i o n
c o m p o s i t i o n . f o r e x a m p l e , b y t h e
e s t e r i ? c a t i o n
r e a c t i o n
b e t w e e n m e t h a n o l
r e a c t a n t
a n d a c e t i c a c i d
p r o d u c t .
W a t e r
may e i n t r o d u c e d
t o
t h e c a r b o n y l a t i o n r e a c t o r
t o g e t h e r
w i t h
o r
s e p a r a t e l y
f r o m o t h e r c o m p o n e n t s o f t h e
l i q u i d r e a c t i o n
c o m p o s i t i o n .
W a t e r may b e s e p a r a t e d f r o m o t h e r compo
n e n t s o f r e a c t i o n c o m p o s i t i o n w i t h d r a w n from t h e r e a c t o r
and may
b e
r e c y c l e d i n c o n t r o l l e d a m o u n t s t o
m a i n t a i n
t h e
r e q u i r e d
c o n c e n t r a t i o n o f
w a t e r i n t h e
l i q u i d
r e a c t i o n
com
p o s i t i o n . P r e f e r a b l y . t h e c o n c e n t r a t i o n o f
w a t e r i n t h e
l i q u i d
r e a c t i o n c o m p o s i t i o n i s i n t h e r a n g e
0 . 1
t o
15%
by w e i g h t ,
more
p r e f e r a b l y 1
t o 15%
b y w e i g h t , m o s t p r e f e r a b l y 1
t o
10%
b y
w e i g h t ,
The
i r i d i u m c a t a l y s t
i n
t h e
l i q u i d
c a r b o n y l a t i o n r e a c t i o n
c o m p o s i t i o n
may c o m p r i s e a n y i r i d i u m c o n t a i n i n g com
p o u n d w h i c h
i s s o l u b l e
i n t h e l i q u i d
r e a c t i o n c o m p o s i t i o n .
The i r i d i u m c a t a l y s t may b e a d d e d
t o t h e
l i q u i d r e a c t i o n
c o m p o s i t i o n
f o r
t h e
c a r b o n y l a t i o n
r e a c t i o n i n a n y s u i t a b l e
f o r m w h i c h d i s s o l v e s i n t h e l i q u i d r e a c t i o n c o m p o s i t i o n o r
i s c o n v e r t i b l e t o a s o l u b l e f o r m . Examples o f
s u i t a b l e
i r i d i u m - c o n t a i n i n g c o m p o u n d s w h i c h may b e a d d e d t o t h e
l i q u i d r e a c t i o n c o m p o s i t i o n i n c l u d e I r C l 3 , I r I 3 I r B r 3 , [ I r ( C O )
2 H 2 .
[ I r ( C 0 ) 2 C l ] 2 ~ [ I r ( C 0 ) = B R ] 2 , [ I r ( C 0 ) 2 I 2 ] ' . [ I r ( C O )
2 B R 2 ] _ u [ I I ( C O ) 4 I 2 l _ ~ l I 1 ( C H 3 ) I 3 ( C 0 ) z l ~ I 1 ' 4 ( C O ) 1 2
I r C l 3 . 4 H 2 O . I r B r 3 . 4 H 2 O , I r 3 ( C O ) 1 2 , i r i d i u m m e t a l ,
b 2 0 3 ,
I 1 0 2 ,
I r ( a c a c ) ( C O ) 2 , I r ( a c a c ) 3 . i r i d i u m a c e t a t e [ I r 3 O ( O A c ) 6
( H 2 O ) 3 ] [ O A c ] , a n d
h e x a c h l o r o i r i d i c a c i d
[ l l z l r C l ? ]
p r e f e r a b l y . c h l o r i d e - f r e e c o m p l e x e s
o f i r i d i u m s u c h a s
a c e t a t e s .
o x a l a t e s
and a c e t o a c e t a t e s .
P r e f e r a b l y , t h e i r i d i u m
c a t a l y s t c o n c e n t r a t i o n i n
t h e l i q
u i d r e a c t i o n c o m p o s i t i o n i s i n t h e
r a n g e
1 0 0 t o 6 0 0 0
ppm y
w e i g h t o f i r i d i u m .
The r u t h e n i u m
a n d / o r
osmium
p r o m o t e r
may
c o m p r i s e
a n y r u t h e n i u m a n d / o r
osmium
c o n t a i n i n g
compound
w h i c h
i s
s o l u b l e
i n t h e
l i q u i d
r e a c t i o n c o m p o s i t i o n . The
p r o m o t e r
may
b e a d d e d
t o t h e l i q u i d r e a c t i o n c o m p o s i t i o n f o r t h e
c a r b o n y l a t i o n
r e a c t i o n i n a n y s u i t a b l e
form
w h i c h d i s s o l v e s
i n t h e
l i q u i d
r e a c t i o n
c o m p o s i t i o n o r
i s
c o n v e n i b l e t o
s o l u b l e
f o r m .
E x a m p l e s o f s u i t a b l e r u t h e n i u m - c o n t a i n i n g c o m p o u n d s
w h i c h
may
b e
u s e d
i n c l u d e
r u t h e n i u m
( 1 1 1 )
c h l o r i d e ,
r u t h e
n i u m ( I I I ) c h l o r i d e
t r i h y d r a t e . r u t h e n i u m
( I V ) c h l o r i d e ,
r u t h e n i u m
( 1 1 1 ) b r o m i d e ,
r u t h e n i u m
m e t a l , r u t h e n i u m
o x i d e s , r u t h e n i u m ( I H ) f o r m a t e . [ R u ( C O ) 3 I 3 ] " H + , t e t r a
( a c e t c ) c h l o r o r u t h e n i u m ( 1 1 , [ [ l ) ,
r u t h e n i u m
( I I I )
a c e t a t e ,
r u t h e n i u m ( H I ) p r o p i o n a t e . r u t h e n i u m ( I I I ) b u t y r a t e . r u t h e
-
8/11/2019 Us 5672743
4/14
5 , 6 7 2 , 7 4 3
3
n i u m p e n t a c a r b o n y l .
t r i r u t h e n i u m d o d e c a c a r b o n y l
a n d
m i x e d r u t h e n i u m h a l o c a r b o n y l s
s u c h
a s d i c h l o r o t r i c a r b o n
y l r u t h e n i u m ( H ) d i m e r . d i b r o m o t r i c a r b o n y l r u t h e n i u m
( I I )
d i m e r . a n d
o t h e r
o r g a n o r u t h e n i u m
c o m p l e x e s
s u c h
a s
t e t r a
c h l o r o b i s ( 4 - c y m e n e ) d i r u t h e n i u m ( l I ) . t e t r a c h l o r o b i s
( b e n z e n e ) d . i r u t h e n i u m ( [ l ) . d i c h l o r o ( c y c l o o c t a - 1 , 5 - d i e n e )
r u t h e n i u m
( H ) p o l y m e r a n d n i s ( a c e t y l a c e t o n a t e ) r u t h e n i u m
E x a m p l e s
o f
s u i t a b l e
o s m i u m
c o n t a i n i n g c o m p o u n d s
w h i c h
may
b e u s e d i n c l u d e osmium ( I l l ) c h l o r i d e
h y d r a t e
a n d a n h y d r o u s .
osmium
m e t a l ,
osmium t e t r a o x i d e .
t r i o s m i u m d o d e c a c a r b o n y l . p e n t a c h l o r o - p -
n i t r o d o d i o s m i u m
a n d m i x e d osmium a l o c a r b o n y l s
s u c h a s
n i c a r b o n y l d i c h l o
r o o s m i u m ( I I )
d i m e r
a n d
o t h e r o r g a n o o s m i u m c o m p l e x e s .
The m o l a r r a t i o o f e a c h p r o m o t e r
t o
i r i d i u m c a t a l y s t i s
s u i t a b l y
i n
t h e
r a n g e 0111
t o
1 5 : 1 , p r e f e r a b l y
0 . 5 : 1
t o 1 0 : 1 .
P r e f e r a b l y . t h e c o n c e n t r a t i o n o f m e t h y l i o d i d e i n t h e
l i q u i d
r e a c t i o n
c o m p o s i t i o n i s
i n
t h e r a n g e 1
t o
20% b y
w e i g h t . p r e f e r a b l y 2 t o 15% b y w e i g h t .
The
c a r b o n
monoxide e a c t a n t may
be s s e n t i a l l y p u r e
o r
may
c o n t a i n
i n e r t
i m p u r i t i e s
s u c h
a s
c a r b o n
d i o x i d e .
m e t h a n e . n i t r o g e n , n o b l e g a s e s , w a t e r a n d C 1 t o C4 a r a ? n i c
h y d r o c a r b o n s . The
p r e s e n c e
o f
h y d r o g e n
i n t h e
c a r b o n
m o n o x i d e a n d g e n e r a t e d i n s i t u
b y
t h e
w a t e r
g a s s h i f t
r e a c t i o n
i s p r e f e r a b l y
k e p t l o w .
f o r
e x a m p l e . l e s s t h a n 1
b a r
p a r t i a l
p r e s s u r e . a s i t s
p r e s e n c e
may e s u l t i n t h e f o r m a t i o n
o f
h y d r o g e n a t i o n p r o d u c t s . The p a r t i a l p r e s s u r e o f
c a r b o n
monoxide i n
t h e r e a c t i o n i s
s u i t a b l y
i n t h e
r a n g e
1
t o 70
b a r
p r e f e r a b l y 1 t o 35 b a r and
most
p r e f e r a b l y 1 t o 1 5 b a r .
The c a t a l y s t
s y s t e m o f
t h e
p r e s e n t i n v e n t i o n h a s
b e e n
f o u n d t o
b e
p a r t i c u l a r l y
b e n e ? c i a l a t
r e l a t i v e l y
l o w p a r t i a l
p r e s s u r e s o f c a r b o n monoxide where t h e r a t e o f r e a c t i o n
may b e d e p e n d e n t u p o n t h e c a r b o n
m o n o x i d e
p a r t i a l
p r e s
s u r e .
Under
t h e s e
c o n d i t i o n s . i t h a s
been found
t h a t t h e
c a t a l y s t
s y s t e m
o f t h e p r e s e n t i n v e n t i o n h a s t h e a d v a n t a g e o f
p r o v i d i n g
a n
i n c r e a s e d r a t e o f r e a c t i o n o v e r c a t a l y s t s y s t e m s
W i t h o u t
t h e p r o m o t e r s o f
t h e
p r e s e n t i n v e n t i o n . T h i s
a d v a n
t a g e a l l o w s
f o r i n c r e a s e d
r a t e
o f
r e a c t i o n u n d e r c o n d i t i o n s
when h e c a r b o n m o n o x i d e
p a r t i a l
p r e s s u r e
i s r e l a t i v e l y l o w .
f o r example d u e
t o a low
o t a l
p r e s s u r e i n t h e c a r b o n y l a t i o n
r e a c t o r
o r
due
t o h i g h vapour r e s s u r e o f
components
o f t h e
l i q u i d
r e a c t i o n c o m p o s i t i o n . f o r e x a m p l e a t h i g h m e t h y l
a c e t a t e
c o n c e n t r a t i o n
i n t h e l i q u i d
r e a c t i o n c o m p o s i t i o n
o r
d u e
t o a
h i g h c o n c e n t r a t i o n o f i n e r t g a s e s ( f o r
e x a m p l e
n i t r o g e n a n d c a r b o n
d i o x i d e ) i n t h e c a r b o n y l a t i o n r e a c t o r .
T h e c a t a l y s t s y s t e m
may
l s o
h a v e
a d v a n t a g e s o f i n c r e a s i n g
r a t e
o f
c a r b o n y l a t i o n
when
h e r a t e o f r e a c t i o n i s r e d u c e d b y
t h e a v a i l a b i l i t y
o f
c a r b o n
m o n o x i d e
i n
s o l u t i o n
i n t h e l i q u i d
r e a c t i o n
c o m p o s i t i o n
r e s u l t i n g
from mass
t r a n s f e r
l i m i t a t i o n s .
f o r
e x a m p l e d u e
t o
p o o r
a g i t a t i o n .
Under
some
c o n d i t i o n s i t
i s
b e l i e v e d p o s s i b l e t h a t s m a l l
amounts
o f t h e
i r i d i u m c a t a l y s t
may
be
v o l a t i l e .
I t i s
b e l i e v e d
t h a t
t h e p r e s e n c e o f a t
l e a s t ruthenium may r e d u c e
t h e v o l a t i l i t y o f t h e i r i d i u m
c a t a l y s t .
A l s o , t h e u s e o f r u t h e
n i u m o r
osmium
r o m o t e r ,
b y
i n c r e a s i n g t h e
c a r b o n y l a t i o n
r a t e
may
a l l o w o p e r a t i o n a t r e d u c e d i r i d i u m c o n c e n t r a t i o n
w h i c h
c a n h a v e b e n e ? t s
f o r
r e d u c e d b y - p r o d u c t f o r m a t i o n .
T h e p r e s s u r e o f t h e c a r b o n y l a t i o n
r e a c t i o n
i s s u i t a b l y i n
t h e r a n g e 1 0 t o
200
b a r g . p r e f e r a b l y 1 0 t o 1 0 0 b a r g , m o s t
p r e f e r a b l y 1 5 t o
5 0
b a r g .
The
t e m p e r a t u r e
o f t h e c a r b o n y
l a t i o n r e a c t i o n i s s u i t a b l y i n t h e
r a n g e 1 0 0
t o
3 0 0
C . ,
p r e f e r a b l y i n
t h e r a n g e
1 5 0
t o
2 2 0 C .
A c e t i c a c i d may b e used
a s
a s o l v e n t
f o r
t h e r e a c t i o n .
C o r r o s i o n
m e t a l s .
p a r t i c u l a r l y n i c k e l .
i r o n
a n d
c h r o m i u m
s h o u l d b e k e p t
t o
a
minimum
i n t h e
l i q u i d
r e a c t i o n compo
s i t i o n
a s t h e s e may have an a d v e r s e e f f e c t i n
t h e
r e a c t i o n .
The
p r o c e s s o f t h e p r e s e n t i n v e n t i on may b e
p e r f o r m e d
a s a b a t c h
o r continuous
p r o c e s s .
p r e f e r a b l y a s
a
continuous
p r o c e s s .
25
30
3 5
4 5
50
5 5
6 5
4
The c e t i c a c i d p r o d u c t may e removed from h e r e a c t o r
b y
w i t h d r a w i n g
l i q u i d
r e a c t i o n
c o m p o s i t i o n
a n d s e p a r a t i n g
t h e
a c e t i c
a c i d p r o d u c t
by
one o r more
a s h
a n d / o r
f r a c t i o n a l
d i s t i l l a t i o n
s t a g e s f r o m
t h e o t h e r
c o m p o n e n t s o f
t h e
l i q u i d
r e a c t i o n
c o m p o s i t i o n s u c h
a s i r i d i u m
c a t a l y s t . r u t h e n i u m
a n d / o r
osmium
r o m o t e r ,
m e t h y l
i o d i d e .
w a t e r a n d u n c o n
sumed r e a c t a n t s which may be r e c y c l e d t o
t h e
r e a c t o r t o
m a i n t a i n t h e i r c o n c e n t r a t i o n s
i n t h e l i q u i d
r e a c t i o n compo
s i t i o n . The c a r b o x y l i c a c i d a n d / o r e s t e r
p r o d u c t
may
a l s o b e
removed a s
a
vapour
from
t h e
r e a c t o r .
The n v e n t i o n w i l l
now
b e i l l u s t r a t e d
b y
way o f
e x a m p l e
o n l y
b y
r e f e r e n c e t o t h e f o l l o w i n g e x a m p l e s .
I n
t h e e x a m p l e s r e a c t i o n r a t e s a r e q u o t e d a s number o f
m o l e s
o f p r o d u c t / r e a c t a n t p r o d u c e d / c o n s u m e d p e r l i t e r o f
c o l d
d e g a s s e d r e a c t o r c o m p o s i t i o n p e r h o u r ( m o l I l / h r ) .
A
5 0 ml
a s t e l l o y B2
( T r a d e
M a r k ) a u t o c l a v e
e q u i p p e d
w i t h
a M a g n e d r i v e ( T r a d e
M a r k ) s t i r r e r
a n d
l i q u i d i n j e c t i o n
f a c i l i t y was
u s e d
f o r a s e r i e s o f b a t c h c a r b o n y l a t i o n e x p e r i
m e n t s . A a s s u p p l y t o t h e a u t o c l a v e was p r o v i d e d
from a
g a s
b a l l a s t v e s s e l .
f e e d g a s
b e i n g p r o v i d e d t o m a i n t a i n t h e
a u t o c l a v e
a t a
c o n s t a nt p r e s s u r e and
t h e
r a t e
of g a s
u p t a k e
b e i n g
c a l c u l a t e d ( w i t h
a n
a c c u r a c y b e l i e v e d t o
b e
i1%) f r o m
t h e
r a t e a t
which
t h e p r e s s u r e
f a l l s
i n t h e g a s b a l l as t v e s s e l .
A t
t h e e n d o f e a c h e x p e r i m e n t l i q u i d a n d
g a s
s a m p l e s
f r o m
t h e
a u t o c l a v e w e r e a n a l y s e d b y g a s c h r o m a t o g r a p h y .
F o r e a c h
b a t c h
c a r b o n y l a t i o n e x p e r i m e n t t h e a u t o c l a v e
was c h a r g e d w i t h t h e ruthenium o r osmium r o m o t e r and
h e
l i q u i d c o m p o n e n t s o f t h e l i q u i d r e a c t i o n c o m p o s i t i o n
e x c l u d i n g
p a r t
o f
t h e a c e t i c a c i d a n d
w a t e r
c h a r g e , i n w h i c h
t h e i r i d i u m c a t a l y s t
was
d i s s o l v e d .
The a u t o c l a v e w a s ?ushed once w i t h n i t r o g e n and once
w i t h
c a r b o n
monoxide
a n d
was t h e n h e a t e d w i t h s t i r r i n g
( 1 0 0 0 r p m ) t o 1 9 5
C . A f t e r
a l l o w i n g t h e s y s t e m t o s t a b i l i s e
f o r
a b o u t
3 0 m i n u t e s . t h e i r i d i u m c a t a l y s t i n
a c e t i c a c i d
w a t e r s o l u t i o n Was
t h e n i n j e c t e d
i n t o
t h e
a u t o c l a v e u n d e r
p r e s s u r e o f c a r b o n m o n o x i d e . The r e s s u r e i n
t h e a u t o c la v e
was
s u b s e q u e n t l y
m a i n t a i n e d
a t
30
b a r g
w i t h c a r b o n
mon
o x i d e f e d f r o m
t h e
g a s b a l l a s t v e s s e l
t h r o u g h
t h e
l i q u i d
i n j e c t i o n f a c i l i t y .
Gas u p t a k e
from
t h e
b a l l a s t
v e s s e l was
measured e v e r y
3 0 s e c o n d s
and
from t h i s w a s c a l c u l at e d t h e r a t e
o f
c a r b o n y l a t i o n . e x p r e s s e d a s m o l e s
o f
c a r b o n monoxide
p e r
l i t e r
o f l i q u i d r e a c t i o n c o m p o s i t i o n p e r h o u r ( m o l / 1 h r ) .
A f t e r u p t a k e o f c a r b on monoxide from h e b a l l a s t v e s s e l
h a d
c e a s e d
t h e
a u t o c l a v e
was
i s o l a t e d
from h e
g a s
s u p p l y , was
c o o l e d
t o
room e m p e r a t u r e
and
h e g a s e s
were
v e n t e d from
t h e
a u t o c l a v e ,
s a m p l e d
a n d
a n a l y s e d . T h e
l i q u i d r e a c t i o n
c o m p o s i t i o n
was
d i s c h a r g e d from t h e a u t o c l a v e and
was
a n a l y s e d
f o r l i q u i d
p r o d u c t s
a n d
b y - p r o d u c t s .
To
o b t a i n
a r e l i a b l e b a s e l i n e
a
number
of i d e n t i c a l
b a s e l i n e
r u n s
may
have t o
be performed t o
c o n d i t i o n
t h e
a u t o c l a v e
s u c h t h a t
c o n s i s t e n t
r a t e s
a r e a c h i e v e d . T h i s
c o n d i t i o n i n g p e r i o d i s o f t e n d i l f e r e n t f r o m a u t o c l a v e t o
a u t o c l a v e a n d may d e p e n d u p o n i t s p r e v i o u s h i s t o r y . A n
i n d u c t i o n p e r i o d i s
a l s o s o m e t i m e s
o b s e r v e d ,
p a r t i c u l a r l y
a t
l o w p r e s s u r e i n t h e a b s e n c e o f
a n y
p r o m o t e r s . T h i s
i n d u d i o n
p e r i o d
i s
n o t
p r e s e n t when t h e
p r o m o t e r s o f
t h e p r e s e n t
i n v e n t i o n
a r e p r e s e n t .
EXPERIMENTA
A
a s e l i n e
e x p e r i m e n t
was
p e r f o r m e d w i t h
t h e a u t o c l a v e
c h a r g e d
w i t h
m e t h y l
a c e t a t e
( 4 1 9
m m o l ) .
w a t e r ( 3 8 3
m m o l ) .
m e t h y l
i o d i d e
( 2 7
m m o l ) . a n d
a c e t i c
a c i d
( 8 0 6 m m o l ) .
T h e i r i d i u m c a t a l y s t s o l u t i o n
c o m p r i s e d I r C l 3 . 3 H 2 O
( 0 . 5 4
mmol) d i s s o l v e d i n a c e t i c a c i d
( 8 3 mmol)
a n d
w a t e r ( 5 0
m m o l ) .
The
r e a c t i o n
was
performed
a t
a
c o n s t a n t p r e s s u r e
o f
3 0
b a r g
and
t a t e m p e r a t u r e o f 1 9 5 C .
The r a t e
o f r e a c t i o n .
-
8/11/2019 Us 5672743
5/14
5 , 6 7 2 , 7 4 3
5
m e a s u r e d 5 m i n u t e s a f t e r i n j e c t i o n o f t h e i r i d i u m c a t a l y s t
s o l u t i o n , b a s e d upon c a r b o n
monoxide
u p t a k e r a t e was 9 . 8
m o l / Mn. High
c o n v e r s i o n
t o a c e t i c a c i d was o b s e r v e d
w i t h
o n l y 2 0 mmol
m e t h y l a c e t a t e r e m a i n i n g i n
t h e
l i q u i d r e a c
t i o n c o m p o s i t i o n a t t h e e n d o f t h e e x p e r i m e n t . The n o n
c o n d e n s i b l e g a s e s i n t h e
a u t o c l a v e
a t
room t e m p e r a t u r e
a t
t h e
end
o f
t h e
e x p e r i m e n t
were a n a l y s e d
a n d w e r e
f o u n d
t o
c o n t a i n b y
v o l u m e . 3 . 6 %
c a r b o n
d i o x i d e
a n d 1 . 6 % m e t h a n e ,
t h e
b a l a nc e c o m p r i s i n g h y d r o g e n
( n o t
m e a s u r e d ) a n d c a r b o n
m o n o x i d e .
T h i s i s n o t
a n
e x a m p l e a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n
because no ruthenium o r
o smium
promoter
was p r e s e n t
i n
t h e l i q u i d
r e a c t i o n
c o m p o s i t i o n .
EXPERIMENTB
E x p e r i m e n t
A
a s r e p e a t e d . The r e a c t i o n
r a t e ,
m e a s u r e d
i n an i d e n t i c a l
manner t o Experiment
A
a s
1 0 . 1 m o l / l / h r .
The a m o u n t o f m e t h y l a c e t a t e r e m a i n i n g i n t h e l i q u i d
r e a c t i o n c o m p o s i t i o n a t
t h e
e n d o f
t h e
e x p e r i m e n t
was
2 5
mmol.
The e n t e d g a s
a t
t h e e n d o f t h e
e x p e r i m e n t
was
a n a l y s e d
a s i n
Experiment
A nd was
found
t o c o n t a i n 1.5% c a r b o n
d i o x i d e
and 1.1%
m e t h a n e .
EXAMPLEl
E x p e r i m e n t
A was
r e p e a t e d
w i t h
d i c h l o r o t r i c a r b o n y l
r u t h e n i u m
( H ) d i m e r
( 0 . 5 4
mmol) c h a r g e d t o t h e
a u t o c l a v e
a t t h e
s t a r t b e f o r e
t h e i r i d i u m
c a t a l y s t s o l u t i o n
was a d d e d .
The
t o t a l a m o u n t
o f
a c e t i c
a c i d c h a r g e d ( 8 8 4 mmol) w a s
a d j u s t e d s o
t h a t t h e
p e r c e n t a g e
c o n c e n t r a t i o n s
b y w e i g h t
o f
t h e i r i d i u m
c a t a l y s t , m e t h y l a c e t a t e . m e t h y l
i o d i d e
a n d w a t e r
were t h e same a s
i n
Experiments A nd B .
The
a t e
o f
r e a c t i o n
b a s e d upon
c a r b o n
monoxide
u p t a k e ,
m e a s u r e d
5 m i n u t e s a f t e r i n j e c t i o n o f t h e
c a t a l y s t
s o l u t i o n
was 1 1 . 7 m o l / l / h r which s a b o u t 19% and
16% h i g h e r t h a n
t h e
r a t e s m e a s u r e d i n
E x p e r i m e n t s
A n d B r e s p e c t i v e l y .
The l i q u i d
r e a c t i o n
c o m p o s i t i o n a t t h e e n d o f t h e e x p e r i
ment w a s a n a l y s e d and w a s found t o
c o n t a i n
1 7 . 7 mmol
m e t h y l
a c e t a t e . The g a s v e n t e d a t t h e e n d o f t h e e x p e r i m e n t
was f o u n d t o c o n t a i n by volume
0.7%
m e t h a n e
and 0.6%
c a r b o n
d i o x i d e .
T h i s E x a m p l e i s a c c o r d i n g
t o t h e p r e s e n t i n v e n t i o n
a n d
shows
t h e
b e n e ? t
o f t h e
p r e s e n c e o f r u t h e n i u m
i n t h e l i q u i d
r e a c t i o n
c o m p o s i t i o n on
t h e c a r b o n y l a t i o n
r a t e .
EXAMPLE
Example
1
was
r e p e a t e d e x c e p t
t h a t
1 . 6
mmol
o f
1 5
d i c h l o r o t r i c a r b o n y l r u t h e n i u m
( I I )
d i m e r
a n d
8 8 0 mmol
o f
a c e t i c a c i d were charged
t o
t h e
a u t o c l a v e .
The a t e
o f r e a c t i o n b a s e d upon
c a r b o n
monoxide u p t a k e ,
m e a s u r e d
5
m i n u t e s
a f t e r
i n j e c t i o n o f t h e
c a t a l y s t ,
was 1 5 . 7
m o l / l l h r w h i c h i s a b o u t
6 0 %
a n d 55.5% h i g h e r
t h a n
t h e
r a t e s
m e a s u r e d i n E x p e r i m e n t s
A n d B
e s p e c t i v e l y .
The
i q u i d r e a c t i o n
c o m p o s i t i o n
a t t h e e n d o f t h e e x p e r i
ment c o n t a i n e d
1 3 . 8 mmol m e t h y l a c e t a t e .
The
g a s
v e n t e d
a t
t h e e n d o f t h e e x p e r i m e n t c o n t a i n e d b y
volume 1 . 3 % m e t h a n e a n d 1 . 9 % c a r b o n d i o x i d e .
T h i s
Example s a c c o r d i n g t o
t h e
p r e s e n t i n v e n t i o n a n d
shows t h e
b e n e ? t o f an i n c r e a s e i n t h e c o n c e n t r a t i o n o f
r u t h e n i u m
i n
t h e l i q u i d r e a c t i o n c o m p o s i t i o n o n t h e c a r b o
n y l a t i o n
r a t e .
EXAMPLE
Example
1 was
r e p e a t e d e x c e p t t h a t 2 . 7 mmol o f
d i c h l o
r o t r i c a r b o n y l
r u t h e n i u m
( l 1 ) d i m e r
a n d
8 7 6 mmol o f a c e t i c
a c i d were c h a r g e d t o t h e a u t o c l a v e .
1 0
20
2 5
35
4 5
50
SS
65
6
The
a t e
o f
r e a c t i o n
b a s e d upon c a r b o n
monoxide u p t a k e .
m e a s u r e d
5 m i n u t e s a f t e r
i n j e c t i o n
o f t h e
c a t a l y s t s o l u t i o n ,
was 1 6 . 5 m o l / l / h r
which
s a b o u t 6 8 % and 6 3 % h i g h e r t h a n
t h e r a t e s
measured i n
t h e b a s e l i n e
E x p e r i m e n t s A
and
B
r e s p e c t i v e l y .
The i q u i d
r e a c t i o n c o m p o s i t i o n
a t
t h e e n d
o f
t h e
e x p e r i
ment c o n t a i n e d 6 . 4
mmol
m e t h y l
a c e t a t e .
The g a s v e n t e d a t t h e
e n d
o f t h e e x p e r i m e n t c o n t a i n e d b y
volume
1 . 1 % methane a n d
1.1%
c a r b o n
d i o x i d e .
T h i s E x a m p l e
i s
a c c o r d i n g
t o t h e p r e s e n t i n v e n t i o n a n d
shows
t h e b e n e ? t o f a
f u r t h e r
i n c r e a s e i n t h e c o n c e n t r a t i o n
o f r u t h e n i u m
i n
t h e l i q u i d r e a c t i o n
c o m p o s i t i o n
o n t h e
c a r b o n y l a t i o n r a t e .
EXAMPLE
Example 1 was
r e p e a t e d
e x c e p t t h a t
3 . 8
mmol o f d i c h l o
r o t r i c a r b o n y l
r u t h e n i u m ( I I )
d i m e r
a n d 8 7 1 mmol o f
a c e t i c
a c i d
w e r e c h a r g e d t o
t h e a u t o c l a v e .
The a t e o f r e a c t i o n b a s e d
u p o n
c a r b o n monoxide u p t a k e ,
m e a s u r e d
5
m i n u t e s a f t e r
i n j e c t i o n
o f t h e c a t a l y s t s o l u t i o n
was 1 5 . 9 m o l / l / h r w h i c h i s a b o u t 6 2% a n d 57.5% h i g h e r
t h a n t h e
r a t e s measured
i n t h e b a s e l i n e
E x p e r i m e n t s
A
nd
B
e s p e c t i v e l y .
The
i q u i d r e a c t i o n c o m p o s i t i o n
a t t h e e n d o f t h e e x p e r i
ment
c o n t a i n e d 8 . 7 mmol m e t h y l
a c e t a t e .
The g a s v e n t e d a t t h e e n d o f
t h e
e x p e r i m e n t
c o n t a i n e d
by
volume
1 . 5 % methane a n d
2.2%
c a r b o n
d i o x i d e .
T h i s
E x a m p l e
i s a c c o r d i n g
t o
t h e p r e s e n t
i n v e n t i o n a n d
s h o w s t h a t , a t
l e a s t
u n d e r t h e
r e a c t i o n
c o n d i t i o n s g i v e n i n
E x p e r i m e n t s
A n d
B , t h e
i n c r e a s e i n r e a c t i o n r a t e
w i t h
i n c r e a s i n g r u t h e n i u m c o n c e n t r a t i o n r e a c h e d a maximum
EXAMPLE
Example I
was r e p e a t e d
e x c e p t
t h a t
5 . 4 r m n o l o f d i c h l o
r o t r i c a r b o n y l
r u t h e n i u m ( I I )
d i m e r
a n d 8 0 2 mmol
o f
a c e t i c
a c i d
were c h a r g e d t o t h e a u t o c l a v e .
The a t e o f
r e a c t i o n
b a s e d
upon
c a r b o n monoxide
u p t a k e .
m e a s u r e d
5 m i n u t e s
a f t e r
i n j e c t i o n
o f t h e c a t a l y s t s o l u t i o n
was
1 5 . 1 m o l / l / h r
w h i c h i s
a b o u t 5 4%
a n d
49.5% h i g h e r
t h a n t h e r a t e s m e a s u r e d i n E x p e r i m e n t s A n d B
r e s p e c
t i v e l y .
The l i q u i d
r e a c t i o n c o m p o s i t i o n a t
t h e end o f
t h e r e a c t i o n
c o n t a i n e d
5 . 2 mmol m e t h y l a c e t a t e .
The
g a s
v e n t e d a t
t h e e n d o f t h e
e x p e r i m e n t c o n t a i n e d
b y
volume
1 . 9
ethane a n d
2.8%
c a r b o n
d i o x i d e .
T h i s
Example
i s
a c c o r d i n g
t o t h e p r e s e n t i n v e n t i o n a n d
s h o w s
t h a t , a t l e a s t u n d e r
t h e
r e a c t i o n c o n d i t i o n s g i v e n
i n
E x p e r i m e n t s
A nd B , t h a t a b o v e a c e r t a i n
c o n c e n t r a t i o n
o f
r u t h e n i u m
t h e
d e g r e e o f
r a t e e n h a n c e m e n t b e g a n
t o
d e c l i n e .
EXPERIMENTC
The
a u t o c l a v e was c h a r g e d
w i t h m e t h y l a c e t a t e ( 4 2 0
m m o l ) , w a t e r
( 4 3 4
m m o l ) ,
m e t h y l
i o d i d e ( 2 7 m m o l ) , a c e t i c
a c i d ( 8 0 2 r m n o l ) a n d
d i c h l o r o t r i c a r b o n y l
r u t h e n i u m ( l 1 )
d i m e r
( 4 . 1 m m o l ) . No r i d i u m
c a t a l y s t s o l u t i o n
was a d d e d t o
t h e
a u t o c l a v e .
The a u t o c l a v e w a s
e a t e d a t 195
C .
a t
a
o n s t a n t
p r e s s u r e
o f
30
b a r g
f o r
a b o u t
1
h o u r
b u t
no
u p t a k e o f
c a r b o n
monoxide g a s from t h e b a l l a s t v e s s e l was o b s e r v e d .
T h e a m o u n t
o f
m e t h y l
a c e t a t e
i n
t h e l i q u i d r e a c t i o n
c o m p o s i t i o n a t t h e end o f t h e e x p e r i m e n t was measured t o
b e
a b o u t 3 3 8 mmol t h i s
m i g h t
b e
s u b j e c t t o
some d e g r e e o f
c a l i b r a t i o n
e r r o r a t
t h i s
h i g h
l e v e l ) .
-
8/11/2019 Us 5672743
6/14
5 . 6 7 2 . 7 4 3
7
The n o n - c o n d e n s i b l e g a s e s i n
t h e
a u t o c l a v e
a t
r o o m
t e m p e r a t u r e a t t h e
e n d o f
t h e e x p e r i m e n t were a n a l y s e d a s
b e f o r e
a n d c o n t a i n e d . b y v o l u m e . 0 . 4 %
m e t h a n e
a n d 0 . 4 %
c a r b o n d i o x i d e .
T h i s i s n o t a n e x a m p l e
a c c o r d i n g
t o t h e p r e s e n t i n v e n t i o n
b e c a u s e
no
r i d i u m
c a t a l y s t
was r e s e n t i n t h e l i q u i d r e a c t i o n
c o m p o s i t i o n . T h i s
e x a m p l e
s h o w s t h a t
r u t h e n i u m
a l o n e d i d
n o t a c t
a s a c a t a l y s t f o r t h e c a r b o n y l a t i o n o f methyl a c e t a t e .
EXPERIMENTD
E x p e r i m e n t s
A n d B w e r e
r e p e a t e d
a t h i g h e r m e t h y l
i o d i d e c o n c e n t r a t i o n . The a u t o c l a v e was
c h a r g e d
w i t h
m e t h y l
a c e t a t e ( 4 2 0
m m o l ) .
w a t e r ( 3 8 4
m m o l ) , m e t h y l
i o d i d e ( 5 6 m m o l ) . a n d
a c e t i c
a c i d ( 7 3 7 m m o l ) . T h e a m o u n t
o f
a c e t i c
a c i d
was
a d j u s t e d s o
t h a t
t h e
p e r c e n t a g e c o n c e n
t r a t i o n s
b y
w e i g h t s
o f
i r i d i u m c a t a l y s t ,
m e t h y l a c e t a t e a n d
water
were
t h e same
a s
i n
Experiments
A nd B.
The
a t e o f
r e a c t i o n
b a s e d
upon
c a r b o n
monoxide u p t a k e .
m e a s u r e d
5
m i n u t e s
a f t e r
i n j e c t i o n
o f
t h e c a t a l y s t s o l u t i o n
w a s
1 2 . 2 m o l / l/ h r .
The
l i q u i d
r e a c t i o n
c o m p o s i t i o n a t
t h e e n d
o f t h e
e x p e r i
ment
was a n a l y s e d
a n d
c o n t a i n e d 8 . 5 mmol m e t h y l
a c e t a t e .
The g a s v e n t e d a t
t h e e n d
o f
t h e
e x p e r i m e n t c o n t a i n e d by
volume 1 . 4 % m e t h a n e a n d 2.4% c a r b o n d i o x i d e .
T h i s e x p e r i m e n t i s n o t
a n
e x a m p l e a c c o r d i n g t o t h e
p r e s e n t
i n v e n t i o n
b e c a u s e
no p r o m o t e r
was
p r e s e n t i n t h e
l i q u i d r e a c t i o n
c o m p o s i t i o n .
EXAMPLE6
E x p e r i m e n t D
w a s r e p e a t e d
w i t h d i c h l o r o t r i c a r b o n y l
r u t h e n i u m I l ) d i m e r ( 5 . 4 mmol) h a r g e d t o t h e r e a c t o r
a t
t h e
s t a r t b e f o r e t h e c a t a l y s t
was
added The t o t a l amount o f
a c e t i c
a c i d
c h a r g e d ( 7 9 6
mmol)
was
a d j u s t e d s o
t h a t
t h e
p e r c e n t a g e
c o n c e n t r a t i o n s
b y
w e i g h t o f t h e
i r i d i u m
c a t a l y s t .
m e t h y l a c e t a t e . m e t h y l i o d i d e
a n d
w a t e r were
t h e same a s
i n
E x p e r i m e n t D .
The a t e o f r e a c t i o n b a s e d upon c a r b o n
monoxide u p t a k e ,
m e a s u r e d
5 m i n u t e s a f t e r
i n j e c t i o n
o f
t h e c a t a l y s t s o l u t i o n
was 2 3 . 9 m o l / l l h r
which
s a b o u t
9 6 % h i g h e r
t h a n t h e r a t e
m e a s u r e d
i n c o m p a r a t i v e E x p e r i m e n t D .
The l i q u i d
r e a c t i o n c o m p o s i t i o n a t
t h e
e n d o f
t h e e x p e r i
ment
w a s
a n a l y s e d and
w a s
found t o
c o n t a i n
7 . 3 mmol
m e t h y l a c e t a t e .
T h e
g a s v e n t e d
a t
t h e
e n d o f t h e e x p e r i m e n t c o n t a i n e d b y
volume
1 . 4 %
m e t h a n e
a n d 2.4%
c a r b o n
d i o x i d e .
T h i s e x p e r i m e n t
i s
a n
e x a m p l e
a c c o r d i n g
t o
t h e
p r e s e n t
i n v e n t i o n and shows
t h a t
a t a
h i g h e r m e t h y l
i o d i d e
c o n c e n
t r a t i o n
ruthenium
w a s m o r e
e i f e c t i v e a s a prom ot e r
f o r
t h e
i r i d i u m c a t a l y s e d c a r b o n y l a t i o n o f m e t h y l a c e t a t e .
EXPERDIIENT
E
The a u t o c l a v e
w a s
c h a r g e d w i t h m e t h y l a c e t a t e ( 4 2 0
m m o l ) . w a t e r
( 4 3 0
m m o l ) . m e t h y l i o d i d e ( 5 7
m m o l ) ,
a c e t i c
a c i d ( 8 7 1 m m o l )
a n d
d i c h l o r o t r i c a r b o n y l
r u t h e n i u m ( l 1 )
d i m m ' ( 5 . 4 m m o l ) . No r i d i u m c a t a l y s t s o l u t i o n was a d d e d t o
t h e
a u t o c l a v e .
The u t o c l a v e w a s h e a t e d
a t 1 9 5 C . a t
a c o n s t a n t p r e s s u r e
o f 30 b a r g f o r a b o u t 1
h o u r
b u t no
u p t a k e
o f c a r b o n
monoxide g a s from t h e b a l l a s t
v e s s e l
w a s o b s e r v e d .
The
amount
o f
m e t h y l
a c e t a t e
i n
t h e l i q u i d r e a c t i o n
c o m p o s i t i o n
a t t h e end o f t h e
e x p e r i m e n t
wa s measured a s
p r e v i o u s l y
t o
b e
a b o u t 3 5 7 mmol.
The n o n - c o n d e n s i b l e g a s e s i n
t h e
a u t o c l a v e
a t
r o o m
t e m p e r a t u r e a t t h e e n d
o f
t h e
e x p e r i m e n t
w e r e
a n a l y s e d
a n d
were
found
n o t t o c o n t a i n any methane o r
carbon d i o x i d e .
10
2 5
35
4 0
45
5 0
55
8
T h i s i s
n o t
a n
example
a c c o r d i n g
t o t h e
p r e s e n t i n v e n t i o n
b e c a u s e
n o
i r i d i u m
c a t a l y s t
was r e s e n t i n
t h e
l i q u i d
r e a c t i o n
c o m p o s i t i o n .
T h i s
e x a m p l e
s h o w s
t h a t
r u t h e n i u m
a l o n e
d i d
n o t
a c t
a s a c a t a l y s t
f o r t h e
c a r b o n y l a t i o n
o f
m e t h y l
a c e t a t e
u n d e r t h e c o n d i t i o n s
o f
t h i s e x p e r i m e n t
EXAMPLE
The a u t o c l a v e
was
c h a r g e d w i t h m e t h y l
a c e t a t e
( 4 1 9
m m o l ) ,
w a t e r
( 4 3 4 m m o l ) .
m e t h y l
i o d i d e ( 2 7 m m o l ) . a c e t i c
a c i d
( 8 6 4
m m o l )
a n d
osmium t r i c h l o r i d e
O s C l 3
( 0 . 5 4
m m o l ) .
The a u t o c l a v e w a s
h e a t e d
a s p r e v i o u s l y a t
1 9 5
C . a t a
c o n s t a n t p r e s s u r e
o f
30 a r g .
The r e a c t i o n
r a t e measured
a s p r e v i o u s l y was 1 3 . 9
m o l
l l h r . The
a m o u n t o f
m e t h y l a c e t a t e i n t h e l i q u i d c o m p o s i t i o n
a t t h e
end
o f t h e e x p e r i m e n t was
measured
o
be
1 2 . 8 mmol.
The methane and c a r b o n d i o x i d e
were
measured a s p r e v i
o u s l y t o b e 0 . 9 % a n d 0 . 8 % b y v o l u m e r e s p e c t i v e l y .
T h i s
i s
a n e x a m p l e
a c c o r d i n g
t o t h e
p r e s e n t
i n v e n t i o n .
FURTHER EXPERIMENTS USING A OLID
INJECTION FA CILITY
T h e s e
f u r t h e r
e x p e r i m e n t s w e r e
p e r f o r m e d
u s i n g a 1 5 0 ml
H a s t e l l o y
B2
( T r a d e M a r k ) a u t o c l a v e e q u i p p e d w i t h a
D i s p e r s i m a x
( T r a d e
M a r k ) s t i r r e r . s o l i d c a t a l y s t i n j e c t i o n
f a c i l i t y
a n d c o o l i n g c o i l s . A a s s u p p l y t o t h e
a u t o c l a v e
was
p r o v i d e d
from
a g a s b a l l a s t v e s s e l . f e e d g a s b e i n g p r o v i d e d
t o m a i n t a i n t h e a u t o c l a v e a t a
c o n s t a n t
p r e s s u r e . The r a t e o f
g a s
uptake
a t a
c e r t a i n p o i n t i n
a
r e a c t i o n run
w a s
used t o
c a l c u l a t e t h e
r a t e
a t
a
p a r t i c u l a r r e a c t o r c o m p o s i t i o n
( r e a c t o r
c o m p o s i t i o n
b a s e d
on
a
c o l d d e g a s s e d v o l u m e ) .
F o r e a c h b a t c h c a r b o n y l a t i o n
e x p e r i m e n t
a s m a l l g l a s s
v i a l
c h a r g e d w i t h
t h e
c a t a l y s t
a n d
o p t i o n a l l y
a
c a t a l y s t
p r o m o t e r w a s p l a c e d
i n t h e i n j e c t i o n
f a c i l i t y
w h i c h f a c i l i t y
was ? t t e d
t o
t h e
u n d e r s i d e
o f t h e l i d o f t h e a u t o c la v e .
The
a u t o c l a v e
was
s e a l e d ,
p r e s s u r e
t e s t e d
w i t h
n i t r o g e n a n d
? u s h e d w i t h c a r b o n
m o n o x i d e
( 2 > 6 b a r g ) . The
i q u i d com
p o n e n t s
o f t h e r e a c t i o n c o m p o s i t i o n were
h e n
c h a r g e d t o t h e
a u t o c l a v e v i a a l i q u i d a d d i t i o n p o r t . The a u t o c l a v e
wa s
h e n
p r e s s u r i s e d
w i t h
c a r b o n m o n o x i d e ( t y p i c a l l y 6 b a r g ) a n d
h e a t e d
w i t h
s t i r r i n g ( 1 5 0 0
r . p . m . )
t o r e a c t i o n t e m p e r a t u r e .
The o t a l p r e s s u r e was t h e n
r a i s e d
t o a p p r o x i m a t e l y
4 b a r g
b e l o w
t h e
d e s i r e d o p e r a t i n g p r e s s u r e b y f e e d i n g c a r b o n
monoxide from a b a l l a s t v e s s e l . Once
s t a b l e a t t e m p e r a t u r e
( 1 5
m i n u t e s )
t h e c a t a l y s t a n d o p t i o n a l l y
t h e
c a t a l y s t p r o
m o t e r were
i n j e d e d
u s i n g a n o v e r p r e s s u r e o f c a r b o n
mon
o x i d e .
The
r e a c t o r p r e s s u r e
was
m a i n t a i n e d
c o n s t a n t ( 1 0 . 5
b a r g )
b y
f e e d i n g g a s f r o m t h e b a l l a s t v e s s e l t h r o u g h o u t t h e
c o u r s e o f t h e e x p e r i m e n t . Gas u p t a k e from h e b a l l a s t v e s s e l
was
m e a s u r e d u s i n g d a t a l o g g i n g f a c i l i t i e s
t h r o u g h o u t t h e
c o u r s e o f t h e e x p e r i m e n t . The
r e a c t i o n
t e m p e r a t u r e was
m a i n t a i n e d w i t h i n 1 1 C .
o f t h e
d e s i r e d r e a c t i o n t e m p m ' a t u r e
by means o f
a h e a t i n g
m a n t l e
c o n n e c t e d
t o
a E u r o t h e r r n
( T r a d e
Mark) o n t r o l l e r . I n
a d d i t i o n .
e x c e s s h e a t
o f
r e a c t i o n
was removed
by
means o f c o o l i n g
c o i l s .
A t t h e e n d
o f
e a c h e x p e r i m e n t l i q u i d a n d
g a s
s a m p l e s
f r o m
t h e a u t o c l a v e w e r e a n a l y s e d
b y
g a s c h r o m a t o g r a p h y
and
w a t e r
c o n c e n t r a t i o n s
i n
l i q u i d
s a m p l e s
w e r e
d e t e r m i n e d
by t h e K a r l F i s c h e r m e t h o d .
E x p e r i m e n t s
F t o
H show
h o w a n i r i d i u m c a t a l y s e d
c a r b o n y l a t i o n
r e a c t i o n
i s
a f f e c t e d
b y
r e d u c e d
t o t a l
p r e s s u r e
o f
c a r b o n
m o n o x i d e a n d
b y r e d u c e d
s t i r r e r s p e e d .
EXPERIMENTF
The
b a t c h a u t o c l av e w a s c h a r g e d w i t h m e t h y l i o d i d e ( 7 . 5
g . 0 . 0 5 3 m o l e s ) , a c e t i c a c i d ( 8 0
g .
1 . 3 3
m o l e s ) .
m e t h y l
-
8/11/2019 Us 5672743
7/14
5 , 6 7 2 , 7 4 3
a c e t a t e ( 4 8 . 1
g .
0 . 6 5
m o l e s )
a n d
w a t e r ( 1 4
g .
0 . 7 8 0
m o l e s ) .
The a u t o c l a v e was ?ushed w i t h
c a r b o n
monoxide
and
t h e n
p r e s s u r i s e d
w i t h
c a r b o n monoxide o a n a m b i e n t
p r e s s u r e
o f
6 b a r g .
The a u t o c l a v e c o n t e n t s
w e r e
s t i r r e d ( 1 5 0 0 r . p . r n . ) a n d
h e a t e d t o
1 9 5 C . Once s t a b l e a t
t e m p e r a t u r e t h e
c a t a l y s t
( I r C l 3 . h y d r a t e ;
0 . 2 8 9
g .
0 . 7 8
m m o l e s ) was
i n t r o d u c e d u s i n g
a n o v e r p r e s s u r e o f
carbon
monoxide t o g i v e a r e a c t i o n
p r e s s u r e
o f 20
b a r g . The r e a c t i o n
was
a r r i e d
o u t
a t
c o n s t a n t
p r e s s u r e
( 2 0 b a r g )
f o r
a p e r i o d o f
o n e h o u r .
The e x p e r i m e n t
was r e p e a t e d and t h e mean
o f
t h e r e a c t i o n c o m p o s i t i o n s
a t
t h e
e n d
o f t h e two
e x p e r i m e n t s i s
a s
f o l l o w s :
85.1%
A c e t i c
Acid
3 . 9 % M e t h y l I o d i d e
4.4% M e t h y l
A c e t a t e
5.7% W a t e r
T r a c e
l e v e l s
o f
l i q u i d b y - p r o d u c t s ( e t h y l i o d i d e .
e t h y l
a c e t a t e a n d
p r o p i o n i c a c i d )
a n d g a s e o u s b y - p r o d u c t s c a r b o n
d i o x i d e . h y d r o g e n a n d
m e t h a n e w e r e
f o r m e d .
The m e t h y l a c e t a t e
c o n c e n t r a t i o n s
i n t h e l i q u i d r e a c t i o n
c o m p o s i t i o n s d e c r e a s e d d u r i n g t h e two r e a c t i o n s a n d
w e r e
c a l c u l a t e d from t h e c a r b o n monoxide u p t a k e s
a s
t h e r e a c
t i o n s
p r o g r e s s e d . No a l l o w a n c e was
made i n
t h e s e c a l c u l a
t i o n s f o r t h e p a r t i t i o n i n g o f l i q u i d r e a c t i o n
c o m p o n e n t s t o
t h e
v a p o u r s p a c e o f
t h e
a u t o c l a v e .
t h e
c o m p o s i t i o n s
b e i n g
c a l c u l a t e d
a s c o l d d e g a s s e d l i q u i d .
W h e n t h e
m e t h y l a c e t a t e
c o n c e n t r a t i o n s
were
c a l c u l a t e d
t o
b e
2 6 %
b y w e i g h t t h e mean o f t h e two e x p e r i m e n t s
r e a c t i o n
r a t e was
c a l c u l a t e d t o
be
3 . 4 m o l / l l h r . At 1 6 % by
w e i g h t m e t h y l
a c e t a t e
c o n c e n t r a t i o n
t h e
mean r e a c t i o n r a t e
was 2 . 9
m o l / l / h r .
T h i s i s n o t
a n e x a m p l e
a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n
because no promoter w a s
u s e d .
EXPERIMENTG
E x p e r i m e n t F
was r e p e a t e d e x c e p t
t h a t
t h e t o t a l p r e s s u r e
i n
t h e
a u t o c l a v e
was m a i n t a i n e d a t
28
b a r g a f t e r
i n j e c t i n g
t h e
c a t a l y s t . The
r e a c t i o n
was
c a r r i e d
o u t
a t
c o n s t a n t p r e s s u r e
( 2 8 b a r g ) f o r
a p e r i o d o f o n e h o u r .
y i e l d i n g a s o l u t i o n
c o n t a i n i n g t h e f o l l o w i n g
d i s t r i b u t i o n
o f p r o d u c t s b y w e i g h t :
8 8 . 5 %
A c e t i c A c i d
3 . 2 % M e t h y l
I o d i d e
0 . 8 % M e t h y l A c e t a t e
5.3%
Water
T r a c e
l e v e l s
o f l i q u i d b y - p r o d u c t s ( e t h y l i o d i d e .
e t h y l
a c e t a t e
a n d p r o p i o n i c
a c i d )
a n d g a s e o u s b y - p r o d u c t s
( c a r b o n
d i o x i d e . h y d r o g e n a n d m e t h a n e ) w e r e f o r m e d . W h e n t h e
m e t h y l
a c e t a t e
c o n c e n t r a t i o n was a l c u l a t e d
from
a s u p t a k e
t o b e
2 6 %
by w e i g h t
t h e r e a c t i o n
r a t e
was c a l c u l a t e d
t o b e
1 0 . 0
m o l / l / h r .
A t 16%
b y
w e i g h t m e t h y l a c e t a t e
t h e
r e a c t i o n
r a t e
w a s 6 . 0
m o l l l / h r .
T h i s
i s
n o t a n
e x a m p l e
a c c o r d i n g t o
t h e p r e s e n t
i n v e n t i o n
because no promoter w a s u s e d .
EXPERIMENT H
T h i s e x p e r i m e n t i l l u s t r a t e s t h e e ? e c t o f s t i r r e r s p e e d o n
t h e
c a r b o n y l a t i o n
r a t e a t a
t o t a l p r e s s u r e o f
2 8
b a r g .
E x p e r i m e n t
G
as
r e p e a t e d e x c e p t
t h a t
t h e
s t i r r e r
s p e e d
wa s
reduced t o 7 5 0 r . p . m . . When h e
methyl a c e t a t e
con
c e n t r a t i o n
w a s
c a l c u l a t e d
from g a s u p t a k e
t o b e 2 6 % b y
w e i g h t t h e r e a c t i o n r a t e was c a l c u l a t e d t o
b e
6 . 5
m o l /
/ h r . At
16% b y
w e i g h t m e t h y l a c e t a t e
t h e
r e a c t i o n r a t e was
3 . 8
m o l / l l h r .
1 5
20
25
3 0
3 5
4 5
5 5
1 0
EXAMPLE
T h i s e x a m p l e d e m o n s t r a t e s t h e p r o m o t i o n a l e t T e c t o f
i n t r o d u c i n g
r u t h e n i u m p r o m o t e r . o n e m o l a r
e q u i v a l e n t , t o
a n
i r i d i u m c a t a l y s e d
c a r b o n y l a t i o n a t
l o w t o t a l
p r e s s u r e .
E x p e r i m e n t
F
was
r e p e a t e d e x c e p t
t h a t
some
o f
t h e
a c e t i c
a c i d
c h a r g e
( 0 . 2 0 g )
w a s s u b s t i t u t e d w i t h a n
e q u a l
w e i g h t o f
[ { R u ( C O ) 3 C 1 2 } 2 ]
( 0 . 3 9 m m o l e s ) . s u c h t h a t
t h e
t o t a l
a u t o
c l a v e
c h a r g e
w e i g h t
r e m a i n e d c o n s t a n t .
The
r u t h e n i u m
was
i n j e c t e d . t o g e t h e r
w i t h
t h e
I r C l 3 . h y d r a t e .
The r e a c t i o n
w a s
c a r r i e d
o u t
a t c o n s t a n t p r e s s u r e ( 2 0 b a r g ) f o r a
p e r i o d o f o n e
h o u r .
y i e l d i n g a s o l u t i o n c o n t a i n i n g t h e
f o l l o w i n g d i s t r i b u
t i o n o f p r o d u c t s
b y
w e i g h t :
89.1% A c e t i c Acid
2 . 8 % M e t h y l I o d i d e
3 . 5 %
M e t h y l
A c e t a t e
4.8%
W a t e r
T r a c e
l e v e l s
o f
l i q u i d
b y - p r o d u c t s
( e t h y l i o d i d e . e t h y l
a c e t a t e a n d p r o p i o n i c a c i d ) a n d g a s e o u s
b y - p r o d u c t s
( c a r b o n
d i o x i d e . h y d r o g e n a n d m e t h a n e ) w e r e
f o r m e d .
When h e m e t h y l a c e t a t e c o n c e n t r a t i o n
was c a l c u l a t e d
from
g a s
u p t a k e t o b e 2 6 %
b y
w e i g h t t h e r e a c t i o n r a t e was
c a l c u l a t e d
t o b e 8 . 1 m o l / l / h r .
A t
16% b y w e i g h t m e t h y l
a c e t a t e t h e r e a c t i o n r a t e w a s 5 . 3 m o l / l /h r . The r a t e s quoted
a r e t h e
mean o f two i d e n t i c a l e x p e r i m e n t s .
EXAMPLE 9
T h i s e x a m p l e d e m o n s t r a t e s
t h e
p r o m o t i on a l e ? e c t o f
i n t r o d u c i n g
r u t h e n i u m p r o m o t e r .
t w o
m o l a r e q u i v a l e n t s .
t o
a n i r i d i u m c a t a l y s e d
c a r b o n y l a t i o n a t
l o w
t o t a l
p r e s s u r e .
E x p e r i m e n t
F
was
r e p e a t e d
e x c e p t
t h a t
some
o f
t h e
a c e t i c
a c i d c h a r g e ( 0 . 4 0 g )
w a s
s u b s t i t u t e d w i t h a n e q u a l
w e i g h t
o f
[ { R u ( C O ) 3 C l 2 } - _ . ] ( 0 . 7 8 m m o l e s ) . s u c h t h a t t h e t o t a l
a u t o
c l a v e c h a r ge w e i g h t r e m a i n e d
c o n s t a n t .
The r u t h e n i u m was
i n j e c t e d . t o g e t h e r w i t h t h e I r C l 3 . h y d r a t e .
The
r e a c t i o n w a s
c a r r i e d o u t a t c o n s t a n t p r e s s u r e
( 2 0 b a r g ) f o r a
p e r i o d
o f
o n e
h o u r .
When
h e
m e t h y l a c e t a t e c o n c e n t r a t i o n
was
c a l c u l a t e d
t o
b e
26 by
w e i g h t t h e r e a c t i o n
r a t e
was c a l c u l a t e d t o b e
8 . 7
m o l / l / h r .
A t 16%
b y
w e i g h t m e t h y l a c e t a t e
t h e
r e a c t i o n r a t e
was
7 . 2
m o l / l / h r .
EXAMPLE 0
T h i s
e x a m p l e d e m o n s t r a t e s t h e p r o m o t i o n a l e t f e c t
o f
i n t r o d u c i n g r u t h e n i u m
p r o m o t e r ,
h a l f a m o l a r e q u i v a l e n t .
t o
a n i r i d i u m c a t a l y s e d c a r b o n y l a t i o n a t low t o t a l
p r e s s u r e .
E x p e r i m e n t
F was r e p e a t e d
e x c e p t
t h a t some
o f
t h e a c e t i c
a c i d
c h a r g e
( 0 . 1 0 g ) was u b s t i t u t e d w i t h
a n e q u a l
w e i g h t
o f
[ { R u ( C O ) 3 C l 2 } 2 ]
( 0 . 2 0
m m o l e s ) . s u c h t h a t
t h e
t o t a l
a u t o
c l a v e
c h a r g e
w e i g h t
r e m a i n e d c o n s t a n t . The r u t h e n i u m was
i n j e c t e d . t o g e t h e r w i t h
t h e I r C L 3 . h y d r a t e .
The
r e a c t i o n
w a s
c a r r i e d o u t
a t
c o n s t a n t
p r e s s u r e ( 2 0
b a r g )
f o r a p e r i o d o f o n e
h o u r .
When
h e
methyl
a c e t a t e c o n c e n t r a t i o n w a s
c a l c u l a t e d
t o
be
2 6 %
by w e i g h t t h e r e a c t i o n r a t e was
c a l c u l a t e d
t o b e 5 . 6
m o l l l / h r . At 16% b y w e i g h t
m e t h y l a c e t a t e
t h e r e a c t i o n
r a t e
w a s 4 . 5 m o l / l / h r .
EXAMPLE 1
T h i s
e x a m p l e
d e m o n s t r a t e s t h e
p r o m o t i o n a l
e f f e c t o f
i n t r o d u c i n g r u t h e n i u m p r o m o t e r . o n e m o l a r
e q u i v a l e n t . t o
a n
i r i d i u m
c a t a l y s e d c a r b o n y l a t i o n
a t r e d u c e d
s t i r r e r
s p e e d ( 7 5 0
r . p . m . ) .
-
8/11/2019 Us 5672743
8/14
5 , 6 7 2 , 7 4 3
1 1
E x p e r i m e n t
H
as
r e p e a t e d e x c e p t t h a t some o f t h e a c e t i c
a c i d c h a r g e ( 0 . 2 0 g ) w a s s u b s t i t u t e d w i t h a n e q u a l w e i g h t
o f
[ { R u ( C O ) 3 C l 2 } 2 ]
( 0 . 3 9 r n m o le s ) . s u c h t h a t t h e
t o t a l
a u t o
c l a v e
c h a r g e
w e i g h t r e m a i n e d c o n s t a n t . The r u t h e n i u m w a s
i n j e c t e d .
t o g e t h e r
w i t h
t h e
I r C 1 . 3 . h y d r a t e . The
r e a c t i o n
w a s
c a r r i e d o u t
a t
c o n s t a n t p r e s s u r e
( 2 8
b a r g ) . w i t h t h e s t i r r e r s e t
a t 7 5 0
r . p . r n . ,
f o r
a p e r i o d
o f one h o u r . y i e l d i n g
a
s o l u t i o n
c o n t a i n i n g t h e f o l l o w i n g d i s t r i b u t i o n o f p r o d u c t s
b y
w e i g h t :
91.5% A c e t i c Acid
2 . 8 %
M e t h y l
I o d i d e
1 . 9 %
M e t h y l A c e t a t e
4.1% W a t e r
T r a c e l e v e l s o f
l i q u i d b y - p r o d u c t s
( e t h y l i o d i d e ,
e t h y l
a c e t a t e
a n d
p r o p i o n i c a c i d )
a n d
g a s e o u s
b y - p r o d u c t s ( c a r b o n
d i o x i d e .
h y d r o g e n a n d m e t h a n e ) w e r e
f o r m e d . W h e n
t h e
m e t h y l
a c e t a t e
c o n c e n t r a t i o n
was
c a l c u l a t e d t o
b e
2 6 %
by
w e i g h t t h e r e a c t i o n r a t e
was
c a l c u l a t e d t o be 1 0 . 5 m o l / l / h r .
At
1 6%
by
w e i g h t m e t h y l a c e t a t e
t h e r e a c t i o n r a t e was 7 . 3
m o l / / h r .
The
r e a c t o r c h a r g e s a r e g i v e n
i n
T a b l e 1 .
T h e g a s e o u s
a n d
l i q u i d p r o d u c t
y i e l d s
f o r
C o m p a r a t i v e
E x p e r i m e n t s F-H
a n d E x a m p l e s 8 - 1 1 a r e
g i v e n
i n T a b l e s 2 a
a n d
2 b .
T h e s e p r o d u c t
y i e l d s
a r e n o t d i r e c t l y c o m p a r a t i v e t o
t h o s e
r e c o r d e d
f o r
C o m p a r a t i v e
E x a m p l e s
A - G a n d
Examples 1 - 7 b e c a u s e
t h e a u t o c l a v e s
were d i t f e r e n t i n
p a r t i c u l a r
b e i n g
o p e r a t e d w i t h
d i ? e r e n t a m o u n t s o f
r e a g e n t s
a n d h a v i n g
d i f f e r e n t
h e a d s p a c e s a n d
s t i r r e r s p e e d s .
TABLE
REACTOR AUTOCIAVE
CHARGES
COMPONENTS
M e t h y l A c e t i c M e t h y l
EXPERIMENT
A c e t a t e
Acid
W a t e r
I o d i d e
P r o m o t e r
F
48.1 80.1 1 4 . 1 7.5
48.1
80.1 14.0 7.6
G 48.1
80.1
14.0 7.5
H 48.1 80.2 1 4 . 1 7.6
~
8
4 8 . 2
8 0 . 1
1 4 . 0
7 . 5
0 . 2 0
4 8 . 1 8 0 . 2
1 4 . 0 7 . 6 0 . 2 0
9 4 8 . 1
7 9 . 9 1 4 . 1 7 . 4 0 . 4 0
1 0
4 8 . 1 8 0 . 3
1 4 . 5 7 . 5 0 . 1 0
1 1 4 8 . 2 8 0 . 3
1 4 . 0
7 . 4 0 . 2 0
1 2 4 8 . 2 8 0 . 2
1 4 . 1
7 . 6 0 . 2 0
1 3
4 8 . 1 7 9 . 9 1 4 . 3 7 . 6
0 . 4 6
TABLE a
Gaseom P r o d u c t s i n
O t I - g a s
G a s e o l m B y - p r o d u c t s G a s e o u s B y - p r o d u c t s
(% v / v ( m m o l )
E x p e r i m e n t H ; C O ; C H H 2 C O ; C H ,
F
1 . 6
2 . 0 6 . 8
2 . 8
3 . 4 1 2 . 0
G
1 . 4 1 . 0 2 . 1 5 . 6 4 . 0 7 . 9
H 1 . 3 1 . 1 2 . 2 5 . 4
4 . 6
8 . 7
8 * 1 . 5 2 . 3 7 . 7 3 . 1 4 . 7 1 6 . 6
9 1 . 4 2 . 1 6 . 6 2 . 8 4 . 2 1 3 . 3
1 0
1 . 7
2 . 1 6 . 8 3 . 5 4 . 3 1 4 . 0
1 1 1 9
0 . 7 0 . 8
6 . 9 2 . 6
3 . 0
Mean o f
t w o e x p e r i m e n t s .
10
30
35
45
50
5 5
6 5
1 2
TABLE 1 :
L i g u i d P r o d u c t s
b y W e i g h t
E t h y l
i o d i d e
E t h y l
a c e t a t e
A c e t i c
E x p e r i m e n t 9 5 P t o p o i o u i c A c i d A c i d
F 0 . 0 2 0 . 0 1 0 . 0 2
8 5 . 1
G
0 . 0 5
0 . 0 3
0 . 0 3 3 8 5
H
0 . 0 3
0 . 0 2
0 . 0 3
9 2 . 2
8 '
0 . 0 7 0 . 0 2
0 . 0 3
8 9 . 1
9
0 . 0 4 0 . 0 1 0 . 0 4 9 0 . 2
1 0 0 . 0 2
0 . 0 2 0 . 0 2 8 8 . 8
1 1
0 . 0 9
0 . 0 2
0 . 0 6
9 1 . 5
I M e a n o f t w o
e x p e r i m e n t s
EXAMPLE 2
T h i s
e x p e r i m e n t
i l l u s t r a t e s t h e
e ? e c t o f a d d i n g
r u t h e n i u m
p r o m o t e r .
one m o l a r e q u i v a l e n t . on t h e c a r b o n y l a t i o n r a t e
a t
a t o t a l p r e s s u r e o f 2 8 b a r g . The
e x p e r i m e n t
a l s o i l l u s t r a t e s
t h a t
t h e r e l a t i v e p r o m o t i o n a l e ? e c t o f a d d i t i o n o f
one
m o l a r
e q u i v a l e n t
o f
r u t h e n i u m
i s grem
t
l o w e r t o t a l p r e s s u r e
s u c h a s 20 b a r g t h e n a t h i g h e r p r e s s u r e s
s u c h
a s 28
b a r g .
E x p e r i m e n t G as r e p e a t e d e x c e p t t h a t
some o f
t h e a c e t i c
a c i d c h a r g e ( 0 . 2 0
g )
was u b s t i t u t e d
w i t h a n
e q u a l w e i g h t o f
[ { R u ( C O ) 3 C l 2 } 2 ]
( 0 . 3 9
m m o l e s ) . s u c h
t h a t t h e
t o t a l
a u t o
c l a v e c h a r ge w e i g h t
r e m a i n e d c o n s t a n t .
The
r u t h e n i u m was
i n j e c t e d . t o g e t h e r w i t h t h e l r c l s h y d r a t e . The r e a c t i o n w a s
c a r r i e d o u t a t
c o n s t a n t p r e s s u r e
( 2 8
b a r g )
f o r
a p e r i o d o f o n e
h o u r .
y i e l d i n g
a
s o l u t i o n c o n t a i n i n g t h e
f o l l o w i n g
d i s t r i b u
t i o n o f p r o d u c t s
b y
w e i g h t :
88.8%
A c e t i c Acid
3 . 0 %
M e t h y l I o d i d e
1 . 9 % M e t h y l
A c e t a t e
5.3% W a t e r
T r a c e l e v e l s
o f
l i q u i d b y - p r o d u c t s ( e t h y l
i o d i d e , e t h y l
a c e t a t e a n d
p r o p i o n i c
a c i d ) a n d
g a s e o u s
b y - p r o d u c t s ( c a r b o n
d i o x i d e ,
h y d r o g e n
a n d m e t h a n e ) w e r e f o r m e d . W h e n t h e
m e t h y l a c e t a t e c o n c e n t r a t i o n was
c a l c u l a t e d t o
be
2 6 % by
w e i g h t t h e r e a c t i o n r a t e was c a l c u l a t e d
t o be
1 1 . 3 m o l / l / h r .
At
1 6% wlw methyl a c e t a t e
t h e r e a c t i o n r a t e was 7 . 9
m o i / 1 1 h r . T a b l e 3 b e l o w s h o w s t h e
l e v e l s
o f b y - p r o d u c t s .
TABLE
tl2
mg d B y i r o d u c t s k
b y
w e i g g
P r o p i o n i c
A c i d
0 . 0 4
G a s e o u s
B y - p r o d u c t s
y v o l u m e
( m m o l )
H .
C O .
C H .
1 . 3
( 4 . 5 )
1 . 0 ( 3 . 7 ) 1 . 4 ( 4 . 9 )
E t l
0 . 1 1
EtOAc
0 . 0 1
T h u s , a c o m p a r i s o n
o f E x a m p l e 8 a g a i n s t
E x p e r i m e n t F
s h o w s
t h a t a t 2 0 b a r g t h e
r a t e
o f
r e a c t i o n
a t 2 6 % by w e i g h t
m e t h y l a c e t a t e i s 2 . 4
t i m e s
g r e a t e r w i t h r u t h e n i u m p r o m o t e r
w h e r e a s
a t 2 8
b a r g a
c o m p a r i s o n
o f E x a m p l e 1 2 a g a i n s t
E x p e r i m e n t G h o w s t h e i m p r o v e m e n t w i t h
r u t h e n i u m
i n
r e a c t i o n
r a t e
a t 2 6 % b y
w e i g h t m e t h y l a c e t a t e i s o n l y
1 . 1
t i m e s .
EXAMPLE 3
T h i s
e x a m p l e
d e m o n s t r a t e s
t h e p r o m o t i o na l e ? e c t
o f
i n t r o d u c i n g
osmium
p r o m o t e r . a p p r o x i m a t e l y t w o m o l a r
e q u i v a l e n t s .
t o a n
i r i d i u m
c a t a l y s e d c a r b o n y l a t i o n a t low
t o t a l
p r e s s u r e .
-
8/11/2019 Us 5672743
9/14
5 , 6 7 2 , 7 4 3
1 3
E x p e r i m e n t F
was
e p e a t e d e x c e p t t h a t some
o f t h e
a c e t i c
a c i d c h a r g e ( 0 . 4 6
g )
w a s s u b s t i t u t e d w i t h a n e q u a l w e i g h t o f
osmium
t r i c h l o r i d e h y d r a t e ( 0 . 4 6 g ) . s u c h t h a t t h e
t o t a l
a u t o c l a v e c h a r g e
w e i g h t r e m a i n
