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US006013597A
Ulllted States Patent [ 1 9 ] [ 1 1 ] P a t e n t N u m b e r : 6 , 0 1 3 , 5 9 7
Karim e t a l . [ 4 5 ] Date o f P a t e n t : J a n . 1 1 , 2000
[ 5 4 ] CATALYSTS FOR THE OXIDATION OF 4 , 5 9 6 , 7 8 7 6 / 1 9 8 6 Manyik e t a 1 . . . . . . . . . . . . . . . . . . . . . . . . . . 5 0 2 / 3 1 2
ETHANE T0ACETIC ACID PROCESSES )F 4 , 8 9 9 , 0 0 3 2 / 1 9 9 0 Manyik e t a l . . 5 8 5 / 3 1 3
M A K I N G S A M E A N D ’ P R O C E S S E S 0 F 2 1 2 3 2 3 5 3 1 1 3 3 5 $2” 3 * ‘ J r 2 5 5 2 / 5 2 1 3, , 0 am I. e a. . . .
USING SAME 5,198,580 3/1993 Bartek e t a 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . 562/542
[ 7 5 ] I n v e n t o r s : Khalid Karim, Manchester, United 5 , 3 0 0 , 6 8 2 4 / 1 9 9 4 Blum e t a 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 6 2 / 5 1 2 . 2
Kingdom; Mohammed - A l - H a z m i , FOREIGN PATENT DOCUMENTSR i y a d h , S a u d i A r a b i a ; EdouardMamedov Baku A z e r b a i j a n 0 5 1 8 5 4 8 1 2 / 1 9 6 2 E u r o p e a n P a t . O f f .
’ ’ 0 294 845 12/1988 European P a t . O f f .
[ 7 3 ] A s s i g n e e : S a u d i B a s i c I n d u s t r i e s C o r p o r a t i o n , 8 5 : 2 5 : 2 2 1 1 3 2 : ‘a u d l A r a b l a 0 6 2 0 2 0 5 1 0 / 1 9 9 4 E u r o p e a n P a t . O f f .
0 627 4 0 1 1 2 / 1 9 9 4 E u r o p e a n P a t . O f f .
[ 2 1 ] A p p l . N o . : 0 8 / 9 3 2 , 0 7 5OTHER PUBLICATIONS
[22] Filed: Sep. 17, 1997 _ _ _ _
E.M. T h o r s t e i n s o n e t a l . “The O x i d a t i v e D e h y d r o g e n e t i o n
[ 5 1 ] I n t . C ] . 7 . . . . . . . . . . . . . . . . . . . . . . . . . . B01J 2 7 / 1 9 8 ; B01] 2 7 / 1 9 o f E t h a n e _ _ _ ” J o u r n a l O f C a t a l y s i s V 0 1 , 5 2 , p p , 116—132[ 5 2 ] US . C l . . . . . . . . . . . . . . . . . . . . . . . . . 5 0 2 / 2 0 9 ; 5 0 2 / 2 0 6 ; 5 0 2 / 2 1 1 ; ( 1 9 7 8 ) .
5 0 2 / 2 1 5 ; 5 0 2 / 3 0 8 ; 5 0 2 / 3 1 1 ; 5 0 2 / 3 2 1 ; 5 0 2 / 3 4 9 ;5 0 2 / 3 5 3 ; 5 0 2 / 3 1 2 P r i m a r y E x a m i n e r — R o s a l y n d K e y s
[ 5 8 ] F i e l d of Search . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 0 2 / 2 0 6 , 2 0 9 , A t t o r n e y ) A g e n t » Or F irm—Whitman Breed Abbott &
5 0 2 / 2 1 1 , 2 1 5 , 3 0 8 , 3 1 1 , 3 2 1 , 3 4 9 , 3 5 3 , M o r g a n LLP
3 1 2 [ 5 7 ] ABSTRACT
[ 5 6 ] R e f e r e n c e s C i t e d An o x i d e c a t a l y s t c o m p r i s i n g t h e e l e m e n t s Mo, V n d Nb
W i t h s m a l l a m o u n t s o f p h o s p h o r u s , b o r o n , h a f n i u m , T eU ' S ' PATENT DOCUMENTS a n d / o r A s . The modi?ed a t a l y s t p r o v i d e s b o t h h i g h e r s e l e c
3 , 0 5 7 , 9 1 5 1 0 / 1 9 6 2 R i e m e n s c h n e i d e r e t a l . . . . . . . . . . . 2 6 0 / 5 3 3 t i v i t y and y i e l d o f a c e t i c a c i d i n t h e loW t e m p e r a t u r e
3 , 2 4 0 , 8 0 5 3 / 1 9 6 6 N a ' g l i e r i . . . . . . : . . . . . . . . . . . . . . . . . . . 2 6 0 / 5 3 3 Oxidation of ethane With molecular Oxygen-containing g a s ,
3 7 3 0 1 7 9 0 5 1 / 1 9 6 7 R e l m e n S c h n e l d e r e t a 1 ~ 2 6 0 / 5 9 7 A p r o c e s s f o r t h e h i g h e r s e l e c t i v e p r o d u c t i o n o f a c e t i c a c i d
4 , 1 4 8 , 7 5 7 4 / 1 9 7 9 B r a Z d i l e t a l . . . . . . . . . . . . . . . . 2 5 2 / 4 3 2 b y t h e C a t a l y t i c O x i d a t i o n of e t h a n e With Oxyge n, i n t h e4 , 2 5 0 , 3 4 6 2 / 1 9 8 1 Young e t a l . 5 8 5 / 6 5 8 r e s e n c e o f t h e im roved C a t a l S t4 , 3 3 9 , 3 5 5 7/1982 Decker e t a 1 . 252/464 p p y
4 , 5 2 4 , 2 3 6 6 / 1 9 8 5 McCain 5 8 5 / 6 5 8
4 , 5 6 8 , 7 9 0 2 / 1 9 8 6 McCain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 8 5 / 6 5 8 35 Claims, 2 D r awin g Sheets
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1
CATALYSTS FOR THEOXIDATION OF
ETHANE TOACETIC ACID PROCESSES OF
MAKING SAME ND, PROCESSESOF
USING SAME
BACKGROUND OF THE INVENTION
1 . F i e l d o f t h e I n v e n t i o n
The i n v e n t i o n r e l a t e s t o i m p r o v e d c a t a l y s t s , m e t h o d s o f
making t h e same and t o p r o c e s s e s o f u s i n g t h e same f o r loW
t e m p e r a t u r e o x y d e h y d r o g e n a t i o n o f e t h a n e t o a c e t i c a c i d
a n d e t h y l e n e p r o v i d i n g i n c r e a s e d e t h a n e c o n v e r s io n a n d
h i g h e r s e l e c t i v i t y t o a c e t i c a c i d .
2 . D e s c r i p t i o n o f t h e R e l a t e d A r t
D o cuments a r e c i t e d i n t h i s d i s c l o s u r e With a f u l l c i t a t i o n
f o r e a c h a p p e a r i n g t h e r e a t . T h e s e d o c u m e n t s p e r t a i n t o t h e
? e l d o f t h i s i n v e n t i o n ; a n d , e a c h document c i t e d h e r e i n i s
h e r e b y i n c o r p o r a t e d b y r e f e r e n c e .
The u s e o f molybdenum a n d vanadium c o n t a i n i n g c a t a
l y s t s y s t e m s f o r l o W t e m p e r a t u r e o x y d e h y d r o g e n a t i o n o f
e l t h a n e t o e t h y l e n e h a s become knoWn s i n c e t h e p u b l i c a t i o n
o f “The O x i d a t i v e D e h y d r o g e n a t i o n o f E t h a n e o v e r C a t a l y s t
C o n t a i n i n g Mixed O x i d e o f Molybdenum a n d V a n a d i u m ”
by E . M. T h o r s t e i n s o n , T . P . W i l s o n , F . G . Young a n d P . H .
K a s a i , J o u r n a l o f C a t a l y s i s , v o l . 5 2 , p p . 1 1 6 — 1 3 2 ( 1 9 7 8 ) .T h i s p a p e r d i s c l o s e s m i x e d o x i d e c a t a l y s t s c o n t a i n i n g
molybdenum a n d v a n a d i u m t o g e t h e r W i t h a n o t h e r t r a n s i t i o n
m e t a l o x i d e , s u c h a s T i , C r , Mn, F e , C o , N i , N b , T a , o r C e .
The d i s c l o s e d c a t a l y s t s a r e a c t i v e a t t e m p e r a t u r e s a s loW a s
2 0 0 ° C . f o r t h e o x y d e h y d r o g e n a t i o n o f e t h a n e t o e t h y l e n e .
Some a c e t i c a c i d i s p r o d u c e d a s a b y - p r o d u c t b y t h e s e
m e t h o d s .
S e v e r a l US. P a t . N o s . ( 4 , 2 5 0 , 3 46 , 4 , 5 2 4 , 2 3 6 , 4 , 5 6 8 , 7 9 0 ,
4 , 5 9 6 , 7 8 7 a n d 4 , 8 9 9 , 0 0 3 ) d i s c l o s e l o W t e m p e r a t u r e o x y d e
h y d r o g e n a t i o n o f e t h a n e t o e t h y l e n e . US. P a t . N o . 4 , 2 5 0 ,
346 d i s c l o s e s t h e u s e o f c a t a l y s t s o f t h e f o r m u l a MohVl-N
b J - A k i n W h i c h A s C e , K , P , N i , a n d / o r U , h i s 1 6 , i i s 1 t o
8 , j i s 0 . 2 t o 1 0 , a n d k s 0 . 1 t o 5 . The p a t e n t d i s c lo s e s one
p h o s p h o r u s - c o n t a i n i n g c a t a l y s t W h i c h i s s e t f o r t h i n t h e
e x a m p l e s h a v i n g a Mo16V4Nb4P4 o x i d e c o m p o s i t i o n s u p
p o r t e d b y s i l i c a - a l u m i n a . T h i s c a t a l y s t i s i n a c t i v e i n t h e
o x i d a t i o n o f e t h a n e a t 3 2 0 ° C . F u r t h e r m o r e , t h i s p a t e n t
r e f e r e n c e i s c o n c e r n e d W i t h o b t a i n i n g a h i g h s e l e c t i v i t y t o
e t h y l e n e , r a t h e r t h a n a c e t i c a c i d .US. a t . No. 4,454,326 s d i r e c t e d t o t h e use o f a c a l c i n e d
c a t a l y s t o f t h e f o r m u l a M o a V b N b C S b a X e .
The a b o v e c i t e d p a t e n t s r e f e r e n c e o t h e r p a t e n t s c o n c e r n e d
W i t h t h e p r o d u c t i o n o f e t h y l e n e f r o m e t h a n e b y t h e o x y d e
hydrogenation p r o c e s s Wherein a c e t i c a c i d i s formed a s a
b y - p r o d u c t .
European P a t . P u b l i c a t i o n EP 02 94 845 d i s c l o s e s a
p r o c e s s f o r t h e h i g h e r s e l e c t i v e p r o d u c t i on o f a c e t i c a c i d b y
t h e o x i d a t i o n o f e t h a n e With oxygen i n c o n t a c t W i t h a
m i x t u r e o f c a t a l y s t s c o n s i s t i n g o f ( A ) a c a t a l y s t f o r o x y d e
h y d r o g e n a t i o n o f e t h a n e t o e t h y l e n e a n d ( B ) a c a t a l y s t f o r
h y d r a t i o n / o x i d a t i o n o fe t h y l e n e .
T h e e t h a n e o x y d e h y d r o g e
n a t i o n c a t a l y s t i s r e p r e s e n t e d b y t h e f o r m u l a M o x V y Z Z ,
W h e r e i n Z c a n b e n o t h i n g o r Nb, S b , T a , W n d many o t h e r
m e t a l s .
European P a t e n t P u b li c a t i o n EP 04 80 594 i s d i r e c t e d t o
t h e u s e o f a n o x i d e c a t a l y s t c o m p o s i t i o n c o m p r i s i n g t u n g
10
1 5
20
25
30
35
40
45
55
60
6 5
2
s t e n vanadium, rhenium and a t l e a s t one of t h e a l k a l i n e
m e t a l s f o r t h e p r o d u c t i o n o f e t h y l e n e a n d a c e t i c a c i d b y
o x i d a t i o n o f e t h a n e W i t h a m o l e c u l a r oxygen c o n t a i n i n g g a s .
T h e r e p l a c e m e n t o f t u n g s t e n i n W h o l e o r p a r t b y m o l y b d e
num a r r i e d o u t i n EP 04 07 091 r e s u l t s i n an i n c r e a s e i n
s e l e c t i v i t y t o a c e t i c a c i d a t t h e e x p e n s e o f t h e s e l e c t i vi t y t oe t h y l e n e .
EP 05 1 8 548 r e l a t e s t o a p r o c e s s f o r making a c e t i c a c i d
by o x i d a t i o n o f e t h a n e i n c o n t a c t W i t h a s o l i d c a t a l y s t h a v i n g
e m p i r i c a l formula VPaMbOx, Where M s one o r more
o p t i o n a l e l e m e n t s s e l e c t e d f r o m C o , C u , R e , N b , W n d
many o t h e r e l e m e n t s , e x c l u d i n g molybdenum, a i s 0 . 5 t o 3 ,
b i s 0 t o 0 . 1 . The p a t e n t p u b li c a t i o n d i s c l o s e s t h a t t h e
c a t a l y s t c o n t a i n s a c r y s t a l l i n e v a n a d y l p y r op h o sp h a t e p h a s e .
European P a t e n t P u b li c a t i o n EP 0 6 27 401 d e s c r i b e s t h e
u s e o f a VaTibOx c a t a l y s t f o r o x i d a t i o n o f e t h a n e t o a c e t i c
a c i d . T h e c a t a l y s t c o m p o s i t i o n may c o m p r i s e a d d i t i o n a lc o m p o n e n t s f r o m a l a r g e l i s t o f p o s s ib l e e l e m e n t s .
I t Would b e d e s i r a b l e t o p r o d u c e a n i m p r o v e d c a t a l y s t f or
u s e i n t h e o x i d a t i o n o f e t h a n e t o a c e t i c a c i d W i t h h i g h e r
y i e l d s a n d i n c r e a s e d s e l e c t i v i t y o f a c e t i c a c i d .
SUMMARY OF THE INVENTION
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 i m p r o v e d MoVNb
c a t a l y s t u s e f u l f o r t h e c o n v e r s i o n o f e t h a n e t o a c e t i c a c i d i s
p r o v i d e d . U s i n g t h e i m p r o v e d c a t a l y s t , e t h a n e i s o x i d i Z e d
W i t h m o l e c u l a r oxygen o a c e t i c a c i d i n a g a s p h a s e r e a c t i o n
a t r e l a t i v e l y h i g h l e v e l s o f c o n v e r s i o n , s e l e c t i v i t y a n d p r o
d u c t i v i t y a n d a t t e m p e r a t u r e s 1 5 0 ° C . t o 4 5 0 ° C . a n d a t
p r e s s u r e s 1 — 5 0 b a r . The modi?ed MoVNb a t a l y t i c s y s t e m
p r o v i d e y i e l d o f a c e t i c a c i d up t o 40% a s compared t o t h e
u n m o d i ? e d c a t a l y s t . T h e i m p r o v e d c a t a l y s t i s f o r m e d f r o m
a c a l c i n e d c o m p o s i t i o n o f Mo aVbNb CXd W h e r e i n :
X s a t l e a s t one promoter element s e l e c t e d from h e group
c o n s i s t i n g o f : P , B , H f , T e , a n d A s ;
a i s a b o u t 1 t o 5 ;
b i s 1 ;
c i s a b o u t 0 . 0 1 t o 0 . 5 ;
d i s a b o u t 0 t o 0 . 1 .
The n u m e r i c a l v a l u e s o f a , b , c and d r e p r e s e n t t h e r e l a t i v e
g r a m - a t o m r a t i o s o f t h e e l e m e n t s Mo, V , Nb a n d X ,
r e s p e c t i v e l y , i n t h e c a t a l y s t . The e l e m e n t s a r e p r e s e n t i n
c o m b i n a t i o n W i t h oxygen i n t h e form o f v a r i o u s o x i d e s . The
c a t a l y s t s a r e p r e f e r a b l y p r o d u c e d u s i n g t h e m e t h o d s d i sc l o s e d h e r e i n .
BRIEF DESCRIPTION OF THE DRAWINGS
S p e c i ? c embodiments o f t h e p r e s e n t i n v e n t i o n W i l l noW
b e d e s c r i b e d f u r t h e r , by Way o f e x a m p l e , W i t h r e f e r e n c e t o
t h e a c c o m p a n y i n g d r a W i n g s , i n W h i c h :
F I G . 1 i s a n XRD a t t e r n f o r a c a t a l y s t modi?ed W i t h
p r o m o t e r P a c c o r d i n g t o o n e embodiment o f t h e i n v e n t i o n ;
a n d
F I G . 2 i s a g r a p h i c a l r e p r e s e n t a t i o n o f t h e r e l a t i o n s h i p
b e t W e e n s e l e c t i v i t y ( ) a n d e t h a n e c o n v e r s i o n ( ) s h o W i n g
s e l e c t i v i t y p l o t s f o r a c e t i c a c i d ( A A ) , e t h y l e n / e ( C 2 H 4 ) , a n d
a c e t i c a c i d a n d e t h y l e n e ( A A + C 2 H 4 ) , W h e r e i n t h e v e r t i c a l
a x i s r e p r e s e n t s s e l e c t i v i t y ( ) a n d h o r i Z o n t a l a x i s r e p r e s e n t s
e t h a n e c o n v e r s i o n ( ) .
DESCRIPTION OF THE PREFERRED
EMBODIMENTS
One a s p e c t o f t h e i n v e n t i o n r e l a t e s t o a c a t a l y s t f o r
s e l e c t i v e o x i d a t i o n o f e t h a n e t o a c e t i c a c i d c o n t a i n i n g a
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6 , 0 1 3 , 5 9 7
3c a t a l y s t c o m p o s i t i o n c o m p r i s in g t h e e l e m e n t s Mo, , Nb a n d
X , i n t h e f o r m o f o x i d e s , i n t h e f o l l o w i n g r a t i o :
M o A V B N b C X D
Wherein X s a t l e a s t one promoter element s e l e c t e d fromt h e g r o u p c o n s i s t i n g o f P , B , H f , T e , a n d A s ;
A s a number r a n g i n g from a b o u t 1 t o a b o u t 5 ;
B i s 1 ;
C s a number r a n g i n g from a b o u t 0 . 0 1 t o a b o u t 0 . 5 ; a n d
D s a number r a n g i n g from g r e a t e r t h a n 0 t o a b o u t 0 . 1 .
Another a s p e c t o f t h e i n v e n t i o n r e l a t e s t o a c a t a l y s t f o r
s e l e c t i v e o x i d a t i o n o f e t h a n e t o a c e t i c a c i d c o n t a i n i n g a
c a t a l y s t c o m p o s i t i o n c o m p r i s in g t h e e l e m e n t s M o , V , Nb a n d
X n d oxygen i n t h e f o l l o W i n g r a t i o :
MoAVBNbCXDOy
Wherein X s a t l e a s t one promoter element s e l e c t e d from
t h e g r o u p c o n s i s t i n g o f P , B , H f , T e , a n d A s ;
A s a number r a n g i n g from a b o u t 1 t o a b o u t 5 ;
B i s 1 ;
C i s a number r a n g i n g o f f r o m a b o u t 0 . 1 t o a b o u t 0 . 5 ;
D s a number r a n g i n g o f from g r e a t e r t h a n 0 t o a b o u t 0 . 1 ;
a n d
Y s 5 . 2 5 t o 20 and s a number d e t e r m i n e d by t h e v a l e n c e
r e q u ir e m e n t s o f t h e o t h e r e l e m e n t s i n t h e c a t a l y s tc o m p o s i t i o n .
A t i l l f u r t h e r a s p e c t o f t h e i n v e n t i o n r e l a t e s t o a c a t a l y s t
f o r s e l e c t i v e o x i d a t i o n o f e t h a n e t o a c e t i c a c i d made by
p r o c e s s c o m p r i s i n g t h e s t e p s o f :
( a ) c o m b i n i n g t h e e l e m e n t s Mo, V , Nb a n d X n t h ef o l l o W i n g r a t i o :
MOAVBNbCXDY
t o form a m i x t u r e ,
Wherein X s a t l e a s t one promoter element s e l e c t e d
f r o m t h e g r o u p c o n s i s t i n g o f P , B , H f , T e , a n d A s ;
A s a number r a n g i n g from a b o u t 1 t o a b o u t 5 ;
B i s a b o u t 1 ;
C s a number r a n g i n g o f from a b o u t 0 . 0 1 t o a b o u t 0 . 5 ;
and
D s a number r a n g i n g from g r e a t e r t h a n 0 t o a b o u t 0 . 1 ;
and
( b ) c a l c i n i n g t h e m i x t u r e t o f o r m t h e c a t a l y s t .According t o one embodiment o f t h e i n v e n t i o n , X o m
p r i s e s P , A a n g e s f r o m a b o u t 2 t o a b o u t 3 , C r a n g e s f r o m
a b o u t 0 . 2 0 t o a b o u t 0 . 4 5 and D a n g e s from a b o u t 0 . 0 1 t o
0 . 1 . A c c o r d i n g t o a n o t h e r embodiment o f t h e i n v e n t i o n , X
c o m p r i s e s P , A s a b o u t 2 . 5 , C i s a b o u t 0 . 3 a n d D s a b o u t
0 . 0 1 t o 0 . 1 . A c c o r d i n g t o y e t a n o t h e r embodiment o f t h e
i n v e n t i o n , X o m p r i s e s P , A s 2 . 5 , C s 0 . 3 2 a n d D s a b o u t
0 . 0 3 t o a b o u t 0 . 0 5 . P r e f e r a b l y , D s a b o u t 0 . 0 4 .
The p r i o r a r t h a s n o t d i s c l o s e d o r s u g g e s t e d t h e advan
t a g e s o f t h e c a t a l y s t s d i s c l o s e d i n p r e s e n t in v e n t i o n p r o v i d e d
b y a d d i n g o n l y s m a l l a m o u n t s o f p h o s p h o r u s , B , H f , T e ,
a n d / o r As o c a t a l y s t s f o r o x i d a t i o n o f e t h a n e t o a c e t i c a c i d .I t i s W e l l knoWn t h a t c a t a l y s t p e r f o r m a n c e , a s a f u n c t i o n o f
t h e amount o f d o p a n t , f r e q ue n t l y p a s s e s t h r o u g h a maxi
mum. T h i s i s o b s e r v e d i n t h e p r e s e n t i n v e n t i o n a s W e l l ( s e e
T a b l e 3 ) . As c a n b e s e e n from t h e Examples 1—6 d e s c r i b e d
b e l o W , MoVNb x i d e c a t a l y s t s modi?ed W i t h s m a l l a m o u n t s
10
1 5
20
25
30
35
40
45
55
60
6 5
4
o f p h o s p h o r u s d i s p l a y e d c o n s i d e r a b l y h i g h e r s e l e c t i v i t y t oa c e t i c a c i d t h a n t h e unmodi?ed c a t a l y s t . The same c a t a l y s t
m o d i ? e d W i t h l a r g e r a m o u n t s o f p h o s p h o r u s i n E x a m p l e s 7
a n d 8 shoWed l o W e r s e l e c t i v i t y t o a c e t i c a c i d a s compared o
t h e u n m o d i ? e d c a t a l y s t u s e d i n E x a m p l e 1 . And ? n a l l y , t h e
c a t a l y s t u s e d i n E x a m p l e 9 c o n t a i n e d t h e a m o u n t o f p h o s
p h o r u s commensurable W i t h t h e amounts o f b a s ic e l e m e n t s .
T h i s s a m p l e d i d n o t shoW a n y a c t i v i t y i n t h e o x i d a t i o n o f
e t h a n e i n a g r e e m e n t W i t h Example 4 8 o f t h e US. P a t . N o .
4 , 2 5 0 , 3 4 6 . S i m i l a r r e s u l t s f o r b o r o n ( e x a m p l e 1 1 ) a n d t e l
l u r i u m ( e x a m p l e 1 0 ) m o d i ? e d c a t a l y s t s , h a v i n g a h i g h e r
s e l e c t i v i t y t o a c e t i c a c i d a s compared t o unmodi?ed
( e x a m p l e 1 ) a r e o b t a i n e d .
The c a t a l y s t o f t h e i n v e n t i o n can be formed W i t h o r
W i t h o u t a s u p p o rt . S u i t a b l e s u p p o r t s f o r t h e c a t a l y s t i n c l u d e
a l u m i n a , s i l i c a , t i t a n i a , Z i r c o n i a , Z e o l i t e s , m o l e c u l a r s i e v e sa n d o t h e r m i c r o / n a n o p o r o u s m a t e r i a l s a n d m i x t u r e s t h e r e o f .
When u s e d o n a s u p p o r t , t h e s u p p o r t e d c a t a l y s t u s u a l l y
c o m p r i s e s f r o m a b o u t 1 0 t o 50% b y W e i g h t o f t h e c a t a l y s tc o m p o s i t i o n , W i t h t h e r e m a i n d e r b e i n g t h e s u p p o r t m a t e r i a l .
A t i l l f u r t h e r a s p e c t o f t h e 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
o f f o r m i n g t h e i n v e n t i v e c a t a l y s t c o m p r i s i n g t h e s t e p s o f :
( a ) f o r m i n g a m i x t u r e c o n t a i n i n g Mo, V , Nb a n d X n a
s o l u t i o n ;( b ) d r y i n g t h e m i x t u r e t o f o r m a d r i e d s o l i d m a t e r i a l ; a n d
( c ) c a l c i n i n g t h e d r i e d s o l i d m a t e r i a l t o f o r m t h e c a t a l y s t .
The s e l e c t i o n o f t h e compounds used a s W e l l a s t h e
s p e c i ? c p r o c e d u r e s f o l l o W e d i n p r e p a r i n g a c a t a l y s t c a n
have a s i g n i ? c a n t e f f e c t on t h e performance o f a
c a t a l y s t . The e l e m e n t s o f t h e c a t a l y s t ’ s r e s u l t a n t com
p o s i t i o n a r e p r e f e r a b l y i n c o m b i n a t i o n W i t h oxygen a s
o x i d e s .
T h e c a t a l y s t a c c o r d i n g t o t h e i n v e n t i o n may b e p r e p a r e d
f r o m a s o l u t i o n o f s o l u b l e compounds ( s a l t s , c o m p l e x e s o r
o t h e r compounds) o f e a c h o f t h e m e t a l s . The s o l u t i o n i s
p r e f e r a b l y a n a q u e o u s s y s t e m h a v i n g a pH f 1 t o 1 0 , more
p r e f e r a b l y a t a pH f 1 t o 7 , and a t a t e m p e r a t u r e o f from
a b o u t 3 0 ° C . t o a b o u t 1 0 0 ° C .
According t o one p r e f e r r e d embodiment, a m i x t u r e o f
c o m p o u n d s c o n t a i n i n g t h e e l e m e n t s i s p r e p a r e d b y d i s s o l vi n g s u f ? c i e n t q u a n t i t i e s o f s o l u b l e c o m p o u n d s a n d d i s p e r s
i n g t h e i n s o l u b l e compounds s o a s t o p r o v i d e t h e d e s i r e d
g r a m - a t o m r a t i o s o f t h e e l e m e n t s i n t h e c a t a l y s t c o m p o s i
t i o n . T h e c a t a l y s t c o m p o s i t i o n i s t h e n p r e p a r e d b y r e m o v i n g
t h e W a t e r o r / a n d o t h e r s o l ve n t from t h e m i x t u r e o f t h e
compounds i n t h e s o l u t i o n s y s t e m . The d r i e d m a t e r i a l i s t h e n
c a l c i n e d by h e a t i n g t o a t e m p e r a t u r e from a b o u t 2 5 0 ° C . t o
a b o u t 4 5 0 ° C . , p r e f e r a b l y 3 0 0 ° C . t o 3 8 0 ° C . , i n a i r o r
oxygen f o r a p e r i o d o f t i m e from a b o u t one hour t o a b o u t 1 6
h o u r s t o p r o d u c e t h e d e s i r e d c a t a l y s t c o m p o s i t i o n .
The molybdenum may b e i n t r o d u c e d i n t o t h e s o l u t i o n i n
t h e form of ammonium s a l t s such a s ammonium
p a r a m o l y b d a t e , o r o r g a n i c a c i d s a l t s o f molybdenum s u c h a s
a c e t a t e s , o x a l a t e s , m a n d e l a t e s , a n d g l y c o l a t e s . Some o t h e r
p a r t i a l l y W a t e r s o l u b l e molybdenum co mpound W h i c h may
a l s o b e u s e d i n c l u d e m o l y b d e n u m o x i d e s , m o l y b d i c a c i d ,
a n d c h l o r i d e s o f m o l y b d e n u m .The vanadium may b e i n t r o d u c e d i n t o t h e s o l u t i o n i n t h e
form o f amm onium s a l t s such a s amm onium metavanadate
a n d ammonium d e c a v a n a d a t e , o r o r g a n i c s a l t s o f vanadium
s u c h a s a c e t a t e s , o x a l a t e s , and t a r t r a t e s . P a r t i a l l y W a t e r
s o l u b l e vanadium compounds s u c h a s vanadium o x i d e s , a n d
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s u l f a t e s o f vanadium can be u s e d . To a c h i e v e a complete
s o l u b i l i t y , a c e r t a i n amount of o x a l i c o r t a r t a r i c a c i d can a l s o
b e a d d e d .
The niobium may b e u s e d i n t h e form o f o x a l a t e s . O t h e r
s o u r c e s o f t h i s m e t a l i n s o l u b l e form i n c l u d e compounds i n
Which t h e m e t a l i s c o o r d i n a t e d , bonded o r complexed t o a
b e t a - d i k e t o n a t e , c a r b o x y l i c a c i d , a n d a m i n e , a n d a l c o h o l , o r
a n alkanolamine.
The p h o s p h o r u s may e i n t r o d u c e d i n t o t h e s o l u t i o n i n t h e
f o r m o f diammonium h y d r o g e n p h o s p h a t e . O t h e r s o l u b l e
compounds o f p h o s p h o r u s c a n a l s o b e u s e d s u c h a s p h o s
p h o r i c a c i d . T e l l e r i u m may b e i n t r o d u c e d i n t o t h e s o l u t i o n i n
t h e form o f t e l l e u r i c a c i d o r s a l t o f t e l l u r i u m . Boron m ay be
added i n t o t h e s o l u t i o n i n t h e form o f b o r i c a c i d o r s a l t o f
b o r o n .
A c c o r d i n g t o a n o t h e r embodiment o f t h e i n v e n t i o n , t h e
c a t a l y s t i s p r e p a r e d b y t h e f o l l o w i n g g e n e r a l p r o c e d u r e . T h e
vanadium compound s mixed W i t h W a t e r a n d o x a l ic a c i d t o
form a ? r s t s o l ut i o n , t h e n i o b i u m compound i s mixed W i t hW a t e r t o f o r m a s e c o n d s o l u t i o n , t h e molybdenum compound
i s mixed W i t h W a t e r t o form a t h i r d s o l u t i o n , and phosphorus
compound s mixed i t h W a t e r t o form a f o u r t h s o l u t i o n . The
? r s t a n d s e c o n d s o l u t i o n s a r e h e a t e d s e p a r a t e l y a n d m i x e d ,
a n d t h e n combined and h e a t e d f o r a b o u t ? f t e e n m i n u t e s W i t h
c o n t i n u o u s s t i r r i n g . The t h i r d s o l u t i o n i s h e a t e d a n d m i x e d ,
and t h e n added t o t h e combined ? r s t and second s o l u t i o n s t o
form a combined e l . The f o u r t h s o l u t i o n i s s l o W l y a d d e d t o
t h e c o m b i n e d g e l s o l u t i o n . A f t e r m i x i n g a n d h e a t i n g f o r
a b o u t ? f t e e n m i n u t e s , t h e r e s u l t a n t g e l i s d r i e d t o i n c i p i e n t
W e t n e s s W i t h c o n t i n u o u s s t i r r i n g a t a b o u t 1 0 0 ° C .
A f t e r d r y i n g t h e r e s ul t a n t g e l m i x t u r e a t 1 2 0 ° C . f o r 1 6
h o u r s , t h e d r i e d m a t e r i a l i s h e a t e d t o 3 5 0 ° C . a t t h e r a t e o f2 ° C . p e r m i n u t e and c a l c i n e d a t t h i s t e m p e r a t u r e i n a i r f o r
4 h o u r s t o p r o d u c e t h e d e s i r e d o x i d e c o m p o s i t i o n . T h i s
p r o c e s s i n g r e g i m e a p p e a r s t o b e c l o s e t o optimum a s i t
a l l o W s t h e c o m p o s i t i o n t o f o r m a c a t a l y st W i t h t h e d e s i r e d
s t r u c t u r e .
T h e c a t a l y s t e m p l o y e d f o r p r a c t i c e o f 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 h a s a s t r u c t u r e Which s p o o r l y c r y s t a l l i Z e d
a n d c a n b e c h a r a c t e r i Z e d b y t h e X - r a y d i f f r a c t i o n (XRD)
p a t t e r n p r e s e n t e d i n T a b l e 1 .
TABLE
C a t a l y s t XRD h a r a c t e r i s t i c s
I n t e r p l a n a r d i s t a n c e ( A ) I n t e n s i t y ( a . u . )
4 . 0 3 100
3 . 5 7 60-85
2 . 0 1 40-60
1 . 8 6 50-70
T o o b t a i n t h i s s t r u c t u r e , t h e c a t a l y s t i s p r e f e r a b l y p r e p a r e d
a s s t a t e d h e r e i n a b o v e . A f t e r t h e c a t a l y s t p r e c u r s o r i s
o b t a i n e d , i t i s t h e n a c t i v a t e d b y c a l c i n i n g . D u r i n g c a l c i n i n g
a t 3 5 0 ° C . , t h e p a r t i a l l y c r y s t a l l i Z e d p h a s e s p e c i? e d a b o v e i s
formed Which i s b e l i e v e d t o be t h e a c t i v e s t r u c t u r e i n t h e
o x i d a t i o n o f e t h a n e t o a c e t i c a c i d . B o t h t h e amorphous p h a s e
t y p i c a l l y o b t a i n e d b y c a l c i n a t i o n a t t e m p e r a t u r e s l o W e r t h a n3 5 0 ° C . a n d t h e W e l l - c r y s t a l l i z e d s t r u c t u r e t y p i c a l ly o b t a i n e d
by c a l c i n a t i o n a t t e m p e r a t u r e s h i g h e r t h a n 3 5 0 ° C . a r e l e s s
e f f e c t i v e W i t h r e s p e c t t o p r o d u c t i o n o f a c e t i c a c i d .
The c a t a l y s t can be promoted W i t h one o r more promoters
e l e m e n t s W i t h o ut a f f e c t i n g t h e f o r e g o i n g XRD a t t e r n . We
10
1 5
20
25
30
35
40
45
50
55
60
6 5
6
h a v e f o u n d t h a t t h e a d d i t i o n o f s m a l l amounts o f t h e
p r o m o t e r e l e m e n t , up t o 0 . 1 atom p e r atom o f v a n a d i u m ,
d o e s n o t Weaken o r d e s t r o y t h e a c t i v i t y o f t h e c a t a l y s t b y
c h a n g i n g i t s s t r u c t u r e , b u t r a t h e r m a i n t a i n s t h e d e s i r e d
p o o r - c r y s t a l l i Z e d s t r u c t u r e . I t i s b e l i e v e d t h e p r o m o t e r e l e
ment i n c r e a s e s t h e c a t a l y s t a c i d i t y . T h i s f a c i l i t a t e s t h e
a d s o r p t io n o f e t h y l e n e a s W e l l a s t h e d e s o r p t io n o f a c e t i c
a c i d , b o t h l e a d i n g t o a n i n c r e a s e i n t h e s e l e c t i v i t y t o a c e t i c
a c i d .
The p r e s e n t i n v e n t i o n a l s o r e l a t e s t o methods 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 t h e c a t a l y t i c o x id a t i o n o f e t h a n e
W i t h o x y g e n i n c o n t a c t W i t h t h e i m p r o v e d c a t a l y s t .
A c c o r d i n g l y , y e t a n o t h e r a s p e c t o f t h e i n v e n t i o n r e l a t e s t o
a c a t a l y t i c p r o c e s s f o r p r e p a r i n g a c e t i c a c i d by means o f
e t h a n e o x i d a t i o n c o m p r i s i n g t h e s t e p o f o x i d i Z i n g e t h a n e i n
a r e a c t i o n mixture comprising e t h a n e and o xygen o r a
compound a p a b l e o f p r o v id i n g oxygen n a r e a c t i o n Z o n e i n
t h e p r e s e n c e o f a c a t a l y s t c o n t a i n i n g a c a t a l y s t c o m p o s i t i o n
c o m p r i s i n g t h e e l e m e n t s Mo, V , Nb a n d X , i n t h e f o r m o f
o x i d e s , i n t h e r a t i o
MoAVBNbCXD
Wherein X s a t l e a s t one promoter element s e l e c t e d from
t h e g r o u p c o n s i s t i n g o f P , B , H f , T e , a n d A s ;
A s a number r a n g i n g from a b o u t 1 t o a b o u t 5 ;
B i s 1 ;
C s a number r a n g i n g from a b o u t 0 . 0 1 t o a b o u t 0 . 5 ; a n d
D s a number r a n g i n g from g r e a t e r t h a n 0 t o a b o u t 0 . 1 .
A c c o r d i n g t o o n e p r e f e r r e d e m b o d i m e n t , t h e c a t a l y s t i s i n
t h e form o f a ? x e d o r ? u i d i Z e d bed and t h e o x i d a t i o n i s
c a r r i e d o u t by f e e d i n g a f e e d m i x t u r e c o m p r i s i n g e t h a n e i n t ot h e r e a c t i o n Z o n e . The f e e d m i x t u r e may f u r t h e r c o m p r i s e s
a i r , o x y g e n , e t h a n e , s t e a m o r m i x t u r e s t h e r e o f . P r e f e r a b l y ,
t h e f e e d m i x t u r e c o m p r i s e s 1 t o 70% b y volume o f e t h a n e .
A c c o r d i n g t o a n o t h e r p r e f e r r e d e m b o d i m e n t , t h e f e e d m i x
t u r e c o m p r i s e s m o l e c u l a r oxygen r a n g i n g f r o m 0 . 1 t o 50%
by volume o f t h e f e e d a n d / o r i s d i l u t e d W i t h s t e a m i n a n
amount r a n g i n g f r o m 0 t o 40% by v o l u m e .
A c c o r d i n g t o y e t a n o t h e r p r e f e r r e d e m b o d i m e n t , t h e o x i
d a t i o n i s a c h i e v e d W h i l e o p e r a t i n g i n g a s p h a s e a t a tem
p e r a t u r e o f fro m 150 t o 4 5 0 ° C . , u n d e r a p r e s s u r e o f from 1
t o 50 b a r s , a n d / o r W i t h a c o n t a c t t i m e betWeen t h e r e a c t i o n
m i x t u r e a n d c a t a l y s t o f from 0 . 1 t o 1 0 s e c o n d s .
The g a s e o u s c o m p o n e n t s o f t h e r e a c t i o n m i x t u r e p r e f e r
a b l y i n c l u d e e t h a n e , oxygen a n d a d i l u e n t , a n d t h e s e c om
p o n e n t s a r e u n i f o r m l y a d m i x e d p r i o r t o b e i n g i n t r o d u c e d
i n t o t h e r e a c t i o n Z o n e . The components may b e p r e h e a t e d ,
i n d i v i d u a l ly o r a f t e r b e i n g a d m i x e d , p r i o r t o b e i n g i n t r o
duced i n t o t h e r e a c t i o n Zone Which s h o u l d have t e m p e r a t u r e
o f from a b o u t 1 5 0 ° C . t o a b o u t 4 5 0 ° C .
Another embodiment r e l a t e s t o a method Wherein t h e
r e a c t i o n m i x t u r e u s e d i n c a r r y i n g o u t t h e c a t a l y t i c p r o c e s s
g e n e r a l l y c o n t a i n s o n e mole o f e t h a n e , 0 . 0 1 t o 2 . 0 moles o f
m o l e c u l a r oxygen e i t h e r a s p u r e oxygen o r i n t h e form o f a i r ,
and Z e r o t o 4 . 0 moles o f Water i n t h e form o f s t e a m . The
Water or steam i s used a s a reaction diluent and a s a heatmoderator f o r t h e r e a c t i o n . Other g a s e s m ay b e used a s
r e a c t i o n d i l ue n t o r h e a t m o d e r a t o r s s u c h a s h e l i u m , n i t r o g e n ,
a n d c a r b o n d i o x i d e .
The raW m a t e r i a l used a s t h e source of t h e ethane can be
a g a s s t r e a m Which c o n t a i n s a t l e a s t ?ve volume p e r c e n t o f
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7
e t h a n e . The g a s stream can a l s o c o n t a i n minor amounts o f
t h e C3—C4 a l k a n e s a n d a l k e n e s , p r e f e r a b l y l e s s t h a n ? v e
volume p e r c e n t o f e a c h . The g a s s t r e a m can a l s o c o n t a i n
m a j o r a m o u n t s , more t h a n ? v e volume p e r c e n t , o f n i t r o g e n ,
c a r b o n d i o x i d e , and W a t e r i n t h e form o f s t e a m .
The r e a c t i o n Zone g e n e r a l l y h a s a r e a c t i o n p r e s s u r e o f
from 1 t o 50 b a r , p r e f e r a b l y from 1 t o 30 b a r . The r e a c t i o n
p r e s s u r e i s i n i t i a l l y p r o v i d e d b y t h e f e e d o f t h e g a s e o u s
r e a c t a n t a n d d i l u e n t a n d , a f t e r t h e r e a c t i o n h a s commenced,
i s m a i n t a i n e d by t h e u s e o f s u i t a b l e b a c k - p r e s s u r e c o n t r o l l e r
p l a c e d on t h e r e a c t o r o u t l e t s t r e a m . The r e a c t i o n t e m p e r a t u r e
i s g e n e r a l l y f r o m a b o u t 1 5 0 ° C . t o a b o u t 4 5 0 ° C . , p r e f e r a b l y
from 2 0 0 ° C . t o 3 0 0 ° C . The r e a c t i o n t e m p e r a t u r e i s p r o
v i d e d b y p l a c i n g t h e c a t a l y st b e d W i t h i n a t u b u l a r c o n v e r t e r
h a v i n g W a l l s p l a c e d i n a f u r n a c e h e a t e d t o t h e d e s i r e d
r e a c t i o n t e m p e r a t u r e .
The r e a c t i o n c o n t a c t t i m e betWeen t i e r e a c t i o n m i x t u r e
a n d t h e c a t a l y st i s f r o m a b o u t 0 . 0 1 s e c o n d t o 1 0 0 s e c o n d s ,p r e f e r a b l y 0 . 1 t o 5 0 s e c o n d s , a n d a d v a n t a g e o u s l y f r o m 0 . 1
second t o 10 s e c o n d s . The c o n t a c t t i m e i s de?n ed a s t h e r a t i o
b e t W e e n t h e a p p a r e n t volume o f t h e c a t a l y s t b e d a n d t h e
volume o f t h e g a s e o u s r e a c t i o n m i x t u r e f e e d t o t h e c a t a l y s t
bed u n d e r t h e g i v e n r e a c t i o n c o n d i t i o n s i n a u n i t o f t i m e . The
r e a c t i o n Z o n e g e n e r a l l y h a s a s p a c e h o u r ly v e l o c i t y o f f r o m
a b o u t 5 0 t o a b o u t 5 0 , 0 0 0 h _ 1 , p r e f e r a b l y f r o m 1 0 0 t o 1 0 , 0 0 0
h - 1 a n d m o s t p r e f e r a b l y f r o m 2 0 0 t o 3 , 0 0 0 h _ 1 .
T h e s p a c e v e l o c i t y may e c a l c u l a t e d b y d e t e r m i n i n g t o t a l
r e a c t o r o u t l e t g a s e q u i v a l e n t i n l i t e r s o f t h e t o t a l e f f l u e n t
e v o l v e d o v e r a p e r i o d o f one hour d i v i d e d by t h e l i t e r s o f
c a t a l y s t i n t h e r e a c t o r . T h i s room t e m p e r a t u r e volume i s
c o n v e r t e d t o t h e volume a t 0 ° C . a t 1 b a r .
The oxygen c o n c e n t r a t i o n i n t h e f e e d g a s m i x t u r e can
v a r y W i d e l y , from 0 . 1 t o 50% o r h i g h e r o f t h e f e e d m i x t u r e
b y a p p l y i n g o f p r o p e r m e a s u r e s t o a v o i d e x p l o si o n p r o b
l e m s . A i r i s t h e p r e f e r r e d s o u r c e o f oxygen i n t h e f e e d . The
amount o f oxygen p r e s e n t m a y be a s t o i c h i o m e t r i c amount,
o r h i g h e r , o f t h e h y d r o c a r b o n s i n t h e f e e d .
The p r o c e s s i s g e n e r a l l y c a r r i e d o u t i n a s i n g l e s t a g e W i t h
a l l t h e oxygen a n d r e a c t a n t s b e i n g s u p p l i e d a s a s i n g l e f e e d
W i t h u n r e a c t e d i n i t i a l r e a c t a n t s b e i n g r e c y c l e d .
T h e p r o c e s s may f u r t h e r c o m p r i s e t h e s t e p o f i n t r o d u c i n g
oxygen i n t o t h e f e e d m i x t u r e a n d / o r r e a c t i o n Zone t o
i n c r e a s e t h e y i e l d , s e l e c t i v i t y o r b o t h y i e l d a n d s e l e c t i v i t y o f
a c e t i c a c i d .
The o x i d a t i o n p e r f o r m e d a c c o r d i n g t o t h e i n v e n t i o n p r o
v i d e s a s e l e c t i v i t y t o a c e t i c a c i d o f a b o u t 50 t a 50
c o n v e r s i o n o f e t h a n e p e r s i n g l e p a s s t h r o u g h s a i d r e a c t i o n
Zone.
The c a t a l y s t o f t h e i n v e n t i o n i s n o t l i m i t e d t o u s e i n t h e
o x y d e h y d r o g e n a t i o n o f e t h a n e t o e t h y l e n e a n d a c e t i c a c i d
a n d may b e a p p l i e d , f o r e x a m p l e , i n o x i d i Z i n g a l p h a - b e t a
u n s a t u r a t e d a l i p h a t i c a l d e h y d e s i n t h e v a p o u r p h a s e W i t h
m o l e c u l a r o x y g e n t o p r o d u c e t h e c o r r e s p o n d i n g a l p h a - b e t a
u n s a t u r a t e d c a r b o x y li c a c i d s .
A c c o r d i n g l y , t h e i n v e n t i o n a l s o r e l a t e s t o a p r o c e s s f o r
p e r f o r m i n g a c a t a l y t i c c h e m i c a l r e a c t i o n i n ? u i d p h a s e ( i . e . ,l i q u i d , v a p o r o r m i x t u r e s t h e r e o f ) c o m p r i s i n g c o n t a c t i n g a t
l e a s t one r e a c t a n t i n ? u i d p h a s e under s u i t a b l e r e a c t i o n
c o n d i t i o n s W i t h a c a t a l y s t c o n t a i n i n g a c a t a l y s t c o m p o s i t i o n
c o m p r i s i n g t h e e l e m e n t s Mo, V , Nb a n d X , i n t h e f o r m o f
o x i d e s , i n t h e r a t i o
10
1 5
20
25
30
35
40
45
50
55
60
6 5
MoAVBNbCXD
Wherein X s a t l e a s t one promoter element s e l e c t e d from
t h e g r o u p c o n s i s t i n g o f P , B , H f , T e , a n d A s ;
A s a number r a n g i n g from a b o u t 1 t o a b o u t 5 ;
B i s a b o u t 1 ;
C s a number r a n g i n g from a b o u t 0 . 0 1 t o a b o u t 0 . 5 ; a n d
D s a number r a n g i n g from g r e a t e r t h a n 0 t o a b o u t 0 . 1 .
Another a s p e c t r e l a t e s t o a p r o c e s s f o r performing a
c a t a l y t i c c h e m i c a l r e a c t i o n c o m p r i s i n g t h e s t e p o f i n t r o d u c
i n g a r e a c t a n t i n ? u i d p h a s e i n t o a r e a c t i o n Zone c o n t a i n i n g
a c a t a l y s t h a v i n g a c a t a l y s t c o m p o s i t i o n c o m p r i s i n g t h e
e l e m e n t s Mo, , Nb a n d X , i n t h e f o r m o f o x i d e s , i n t h e r a t i o
MoAVBNbCXD
Wherein X s a t l e a s t one promoter element s e l e c t e d from
t h e g r o u p c o n s i s t i n g o f P , B , H f , T e , a n d A s ;
A s a number r a n g i n g from a b o u t 1 t o a b o u t 5 ;
B i s 1 ;
C s a number r a n g i n g from a b o u t 0 . 0 1 t o a b o u t 0 . 5 ; a n d
D s a number r a n g i n g from g r e a t e r t h a n 0 t o a b o u t 0 . 1 .
One embodiment r e l a t e s t o a c a t a l y t i c c h e m i c a l r e a c t i o n
Which converts one or more ?uid phase reactants t o one or
more ?uid phase p r o d u c t s . P r e f e r a b l y , t h e one o r more ? u i d
phase r e a c t a n t s comprise e t h a n e and t h e one o r more ?uid
p h a s e p r o d u c t s c o m p r i s e a c e t i c a c i d . M o r e p r e f e r a b l y , t h eone or m o r e ?uid phase reactants and/or one or more ?uid
p h a s e p r o d u c t s c o m p r i s e s one o r more g a s e o u s c o m p o n e n t s .
According t o a n o t h e r embodiment, t h e one o r more ?uid
p h a s e r e a c t a n t s c o m p r i s e a l p h a - b e t a u n s a t u r a t e d a l i p h a t i ca l d e h y d e s and oxygen and t h e one o r more ?uid phase
p r o d u c t s c o m p r i s e a l p h a - b e t a u n s a t u r a t e d c a r b o x y l i c a c i d s .
EXAMPLES
The f o l l o W i n g examples a r e i l l u s t r a t i v e o f some o f t h e
p r o d u c t s a n d m e t h o d s o f making t h e same a l l i n g W i t h i n t h e
s c o p e o f t h e p r e s e n t i n v e n t i o n . They r e , o f c o u r s e , n o t t o b e
c o n s i d e r e d i n a n y Way l i m i t a t i v e o f t h e i n v e n t i o n . Numerous
c h a n g e s a n d m o d i ? c a t i o n c a n b e made W i t h r e s p e c t t o t h e
i n v e n t i o n .
C a t a l y t i c p r o c e s s e s u s i n g t h e v a r i o u s c a t a l y s t s Were c a r
r i e d o u t i n a t u b u la r r e a c t o r under t h e f o l l o W i n g c o n d i t i o n s .
Gas f e e d c o m p o s i t i o n Was 15% by volume e t h a n e a n d 85%
by volume a i r . A l l e x p e r i m e n t s Were r u n a t a t e m p e r a t u r e o f
2 6 0 ° C . , a p r e s s u r e o f 200 p s i g a n d a s p a c e v e l o c i t y o f a b o u t
1 , 1 0 0 h _ 1 . The r e a c t o r c o n s i s t e d o f a 6 m i l l i m e t e r d i a m e t e r
s t a i n l e s s s t e e l s t r a i g h t t u b e h e a t e d i n an o v e n . The r e a c t o r
c o n t a i n e d 3 . 0 grams o f t h e c a t a l y s t . The r e a c t o r bed d e p t h
Was a b o u t 6 . 0 c e n t i m e t e r s s o t h a t t h e depth t o c r o s s - s e c t i o n
r a t i o Was a b o u t t e n . R e a c t i o n p r o d u c t s Were a n a l y Z e d
o n - l i n e b y g a s c h r o m a t o g r a p h y . O x y g e n , n i t r o g e n a n d c a r
bon monoxide Were a n a l y Z e d u s i n g a 3 mm y 3 mm olumn
o f 13X m o l e c u l a r s i e v e . C a r b o n d i o x i d e , e t h a n e a n d e t h y l
ene and Water Were analyZed using a 1 . 8 m y 3 mm olumn
p a c k e dW i t h m a t e r i a l s o l d u n d e r t h e t r a d e n a m e
HAYASEPTMQ . A c e t i c a c i d Was Were a n a l y Z e d u s i n g a 0 . 5 m y 3 mm
column p a c k e d W i t h m a t e r i a l s o l d u n d e r t h e t r a d e m a r k
PORAPACKTM .
I n a l l c a s e s , t h e c o n v e r s i o n a n d s e l e c t i v i t y c a l c u l a t i o n s
Were based on t h e s t o i c h i o m e t r y :
8/12/2019 Us 6013597
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9
The y i e l d o f a c e t i c a c i d Was a l c u l a t e d by m u l t i p l y i n g t h e
s e l e c t i v i t y t o a c e t i c a c i d by e t h a n e c o n v e r s io n .
EXAMPLE
A a t a l y s t Was p r e p a r e d t o h a v e t h e f o l l o w i n g c o m p o s i
t i o n :
Ammonium metavanadate i n t h e amount o f 1 1 . 4 grams
Was added t o 120 ml o f d i s t i l l e d Water and h e a t e d t o 90° C .
W i t h s t i r r i n g . 2 . 5 grams o f o x a l ic a c i d Were a d d e d . t o o b t a i n
a c l e a r y e l l o W c o l o u r s o l u t i o n W i t h a pH etWeen 5 and 6
( S o l u t i o n A ) . 1 9 . 4 g r a m s o f n i o b i u m o x a l a t e c o n t a i n i n g21.5% by W e i g h t c a l c u l a t e d a s Nb2O5 Were a d d e d t o 86 ml
o f W a t e r a n d h e a t e d t o 6 5 ° C . W i t h c o n t i n u o u s s t i r r i n g t o
o b t a i n a c l e a r W h i t e c o l o u r s o l u t i o n W i t h a pH o f 1 ( S o l u t i o n
B ) . S o l u t i o n B Was t h e n combined W i t h S o l u t i o n A . The
combination Was h e a t e d a t 9 0 ° C . and 28 grams o f o x a l i c
a c i d W e r e a d d e d v e r y s l o W l y W i t h c o n t i n u o u s s t i r r i n g t o g i v e
S o l u t i o n C . Ammonium p a r a m o l y b d a t e i n t h e amount o f
4 3 . 2 grams Was added t o 45 ml o f Water and h e a t e d t o 6 0 °
C . t o g i v e a c o l o u r l e s s s o l u t i o n W i t h a pH etWeen 6 . 0 and
6 . 5 ( S o l u t i o n D) . S o l u t i o n Was c o m b i n e d s l o W l y W i t h
S o l u t i o n C o g i v e d a r k b l u e t o d a r k g r a y c o l o u r p r e c i p i t a t e s
( M i x t u r e T h i s d a r k c o l o u r c o m b i n a t i o n Was s t i r r e d
v i g o r o u s l y t o a c h i e v e a homogeneous g e l m i x t u r e W h i c h
Was t h e n d r i e d s l o W l y t o i n c i p i e n t d r y n e s s W i t h i n 6 0 t o 120
m i n u t e s a t 9 5 — 9 8 ° C . W i t h c o n t i n u o u s s t i r r i n g .
The r e s u l t i n g s o l i d Was p u t i n a China d i s h and d r i e d
f u r t h e r i n an oven a t 120° C . f o r s i x t e e n h o u r s . The d r i e d
m a t e r i a l Was cooled t o room t e m p e r a t u r e and placed i n a
f u r n a c e . The t e m p e r a t u r e Was r a i s e d from r o o m t e m p e r a t u r e
t o 350° C . a t t h e r a t e o f 2°/min and t h e r e a f t e r h e l d a t 350°
C . f o r f o u r h o u r s .
C a l c i n e d c a t a l y s t Was f o r m u l a t e d i n t o u n i f o r m p a r t i c l e s o f
t h e 40—60 mesh s i Z e a n d t e s t e d a c c o r d i n g t o t h e d e s c r i b e d
t e s t . The r e s u l t s a r e shoWn i n T a b l e 3 .
EXAMPLES TO
U s i n g t h e p r o c e d u r e o f E x a m p l e 1 , p h o s p h o r u s c o n t a i n i n gc a t a l y s t s o f t h e f o l l o W i n g g e n e r a l f o r m u l a W e r e p r e p a r e d :
Where X s 0 . 0 1 t o 1 . 0 .
T h e r e q u i r e d a m o u n t o f diammonium h y d r o g e n p h o s
p h a t e Was added t o a b o u t 5 t o 1 0 ml o f d i s t i l l e d W a t e r and
c o m b i n e d s l o W ly W i t h t h e g e l m i x t u r e f o r m e d f r o m m i x i n g
ammonium m e t a v a n a d a t e , n i o b i u m o x a l a t e a n d ammonium
p a r a m o l y b d a t e s o l u t i o n s ( M i x t u r e E i n E x a m p l e 1 ) . A f t e r
a c h i e v i n g a homogeneous m i x t u r e , t h e r e s u l t a n t g e l Was
d r i e d s l o W l y t o i n c i p i e n t d r y n e s s a t 9 5 — 9 8 ° C . W i t h c o n t i n uo u s s t i r r i n g . The d r y i n g a n d c a l c i n a t i o n p r o c e d u r e s W e r e t h e
same a s u s e d i n Example 1 . T a b l e 2 shoWs W e i g h t o f t h e
p h o s p h o r u s s a l t a d d e d t o t h e b a s e c a s e c a t a l y s t , grams o f
p h o s p h o r u s s a l t p e r g r a m o f c a t a l y s t a n d c a t a l y s t c o m p o s i
t i o n .
10
1 5
20
25
30
35
40
45
55
60
6 5
1 0EXAMPLE 10
U s i n g t h e p r o c e d u r e o f E x a m p l e 1 , t e l l u r i u m c o n t a i n i n gc a t a l y s t Was p r e p a r e d b y a d d i n g o f 3 . 8 1 E - o 4 g o f t e l l e u r i c
a c i d t o t h e g e l m i x t u r e E i n Example 1 . D r y i n g a n d c a l c i
n a t i o n o f t h e c a t a l y s t Was d o n e b y f o l l o W i n g t h e p r o c e d u r em e n t i o n e d i n Example 1 .
EXAMPLE 1
U s i n g t h e p r o c e d u r e o f E x a m p l e 1 , b o r o n c o n t a i n i n gc a t a l y s t Was r e p a r e d b y a d d i n g o f 1 . 3 4 4 E - o 3 g o f b o r i c a c i d
t o t h e g e l m i x t u r e E i n Example 1 . D r y i n g a n d c a l c i n a t i o n
o f t h e c a t a l y st Was d o n e by f o l l o W i n g t h e p r o c e d u r e men
t i o n e d i n Example 1 .
TABLE
P h o s p h o r u s c o n t a i n i n g c a t a l y s t s
g o f p h o s . / g
E x a m p l e ( N H 4 ) 2 H P O 4 ( g ) o f c a t a l y s t C a t a l y s t c o m p o s i t i o n
2 0 . 1 3 3 0 . 0 0 2 8 9 M O 2 _ 5 V 1 _ 0 N b 0 _ 3 2 P 0 _ 0 1
3 0 . 1 6 6 0 . 0 0 3 6 0 M O 2 _ 5 V 1 _ U N b U _ 3 2 P U _ U 1 3
4 0 . 3 3 3 0 . 0 0 8 6 7 M 6 , _ 5 v 1 _ 0 1 8 1 1 0 5 2 1 1 , 0 3
5 0 . 5 3 4 0 . 0 1 1 6 0 M O 2 _ 5 V 1 _ U N b U _ 3 2 P U _ U 4 2
6 0 . 8 0 0 0 . 0 1 7 3 0 M o 2 _ 5 V 1 _ D N b D _ 3 2 P D _ D 6
7 1 . 1 9 0 0 . 0 2 5 0 0 M 6 , _ 5 v 1 _ 0 1 8 1 1 0 5 2 1 ’ , 1
8 2 . 0 8 0 0 . 0 4 5 0 0 M 6 , _ 5 v 1 _ 0 1 8 1 1 0 5 2 1 ’ , 2
9 1 0 . 0 4 0.21800 Mo2_5V1_0Nb0_32 1D
10 3 81 X 1 0 * 4 2 . 1 2 X 1 0 * 4 M 6 , _ 5 v 1 _ U 1 ~ I 1 > D _ 3 2 T 6 1 _ 6 , E , D 5
1 1 1 35 X 1 0 * 3 2 . 3 6 X 1 0 * 4 MOZSVLONbQQBZBEDS
The r e s u l t s o f t h e t e s t s W i t h t h e s e c a t a l y s t s 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 d e s c r i b e d above a r e g i v e n i n T a b l e 3 .
TABLE
R e s u l t s o f t e s t i n g c a t a l y s t a c t i v i t y a n d s e l e c t i v i t y
C o n - S . S e l e c t i v i t y
v e r s i o n Conv.* AA i e l d BET u r f .
E x a m p l e ( ) ( ‘ V a / m 2 ) AA C 2 H 4 ( ) a r e a ( m Z / g )
1 6 5 . 0 0 . 8 5 3 0 . 5 2 6 . 9 1 9 . 8 2 5 . 6
2 6 0 . 0 1 . 0 4 3 8 . 5 2 4 . 1 2 3 . 1 1 9 . 3
3 6 3 . 2 1 . 1 1 3 3 . 8 2 5 . 3 2 1 . 3 1 8 . 9
4 6 2 . 2 1 . 2 1 3 6 . 6 2 4 . 1 2 2 . 8 1 7 . 1
5 5 3 . 3 0 . 9 9 4 9 . 9 1 0 . 5 2 6 . 6 1 7 . 9
6 3 3 . 6 1 . 2 9 5 0 . 2 1 4 . 7 1 6 . 9 8 . 7
7 5 2 . 8 1 . 2 0 2 3 . 3 4 3 . 6 1 2 . 3 1 4 . 78 2 0 . 1 1 . 2 8 1 1 . 7 5 8 . 7 2 . 4 5 . 2
9 0 — 0 0 0 0.5
10 6 2 . 8 6 0 . 8 4 3 7 . 2 2 8 . 4 0 2 3 . 3 5 25
1 1 6 4 . 4 1 0 . 9 3 3 8 . 2 26.32 2 4 . 6 1 23
*AA e n o t e s a c e t i c a c i d
**S.Conv s Speci?c c o n v e r s i o n o f e t h a n e p e r u n i t a r e a = C o n v e r s i o n / s p e c i ? c
s u r f a c e a r e a (%/m2)
As shoWn i n T a b l e 3 , When i n c r e a s i n g t h e amount o f
p h o s p h o r u s i n t r o d u c e d i n t o t h e MoVNb o x i d e c a t a l y s t ,
e t h a n e c o n v e r s i o n a n d s e l e c t i v i t i e s t o m i l d o x i d a t i o n p r o d
u c t s change a s f o l l o W s :
c o n v e r s i o n t e n d s t o d e c r e a s e ,
t o t a l s e l e c t i v i t y t o e t h y l e n e a n d a c e t i c a c i d someWhati n c r e a s e s ,
s e l e c t i v i t y t o e t h y l e n e g o e s t h r o u g h a minimum,
s e l e c t i v i t y t o a c e t i c a c i d p a s s e s t h r o u g h a maximum.
S i n c e t h e a c t i v i t i e s o f a l l s a m p l e s W e r e m e a s u r e d u s i n g
t h e same a m o u n t o f c a t a l y s t ( 3 g ) , t h e d i f f e r e n c e s i n e t h a n e
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6 , 0 1 3 , 5 9 7
1 1
c o n v e r s i o n m i g h t b e c a u s e d b y d i f f e r e n t s p e c i ? c s u r f a c e
a r e a s o f c a t a l y s t s . I n d e e d , c a t a l y t i c a c t i v i t y e x p r e s s e d a s t h e
conversion p e r s u r f a c e a r e a , a s i s seen from T a b l e 3 , does n o t
c h a n g e s t r o n g l y W i t h t h e a m o u n t o f p h o s p h o r u s i n t h e
c a t a l y s t . T h i s means t h a t s m a l l amounts o f p h o s p h o r u s
r a n g i n g from 0 t o 0 . 2 atom p e r atom o f vanadium do n o t
a l t e r p r a c t i c a l l y t h e s p e c i ? c o v e r a l l a c t i v i t y o f t h e M o V N b
o x i d e c a t a l y s t i n t h e o x i d a t i o n o f e t h a n e .
G e n e r a l l y , t o t a l s e l e c t i v i t y t o e t h y l e n e a n d a c e t i c a c i d
d e c r e a s e s W i t h t h e c o n v e r s i o n o f e t h a n e . F I G . 2 shoWs a
t y p i c a l c u r v e r e l a t i n g s e l e c t i v i t y t o e t h y l e n e p l u s a c e t i c a c i d
t o c o n v e r s i o n o f e t h a n e f o r t h e unmodi?ed MoVNb x i d e
c a t a l y s t o v e r t h e p r e f e r r e d o p e r a t i n g r e g i m e . From t h i s
? g u r e , i t c a n b e s e e n a l s o t h a t t h e s e l e c t i v i t y t o e t h y l e n e
d e c l i n e s W h i l e t h e s e l e c t i v i t y t o a c e t i c a c i d i n c r e a s e s W i t h
i n c r e a s i n g e t h a n e c o n v e r s i o n . T a k i n g i n t o a c c o u n t t h e s e
d e p e n d e n c i e s , a s l i g h t i n c r e a s e o f t h e t o t a l s e l e c t i v i t y t o
e t h y l e n e a n d a c e t i c a c i d W i t h t h e amount o f p h o s p h o r u s i nt h e c a t a l y s t can be r e l a t e d t o t h e d e c r e a s e o f e t h a n e conver
s i o n o b s e r v e d o n F - d o p e d c a t a l y s t s .
T h i s e x p l a n a t i o n i s n o t v a l i d f o r t h e s i n g l e s e l e c t i v i t i e s t o
e t h y l e n e a n d a c e t i c a c i d W h i c h c h a n g e d n o n - m o n o t o n i c a l l y
W i t h t h e c o n c e n t r a t i o n o f p h o s p h o r u s i n t h e c a t a l y s t . I t i s
b e l i e v e d t h a t s m a l l amounts o f p h o s p h o r u s , betWeen 0 . 0 1
a n d 0 . 1 a t o m p e r a t o m o f v a n a d i u m , m a i n l y i n c r e a s e c a t a l y s t
s u r f a c e a c i d i t y t o t h e e x t e n t Which i s s u b s t a n t i a l f o r t h e
c o n s e c u t i v e o x i d a t i o n o f e t h y l e n e t o a c e t i c a c i d . As a r e s u l t ,
t h e s p e c i ? c c a t a l y t i c a c t i v i t y d o e s n o t c h a n g e c o n s i d e r a b l y ,b u t t h e s e l e c t i v i t y t o a c e t i c a c i d i n c r e a s e s . S i m i l a r e f f e c t s o f
a n i n c r e a s e i n a c e t i c a c i d s e l e c t i v i t y o r y i e l d by a d d i t i o n o f
Te and B a s a promoter t o MoVNb a t a l y t i c s y s t e m i s
a c h i e v e d , T a b l e 3 .
The a b o v e d e s c r i p t i o n o f t h e i n v e n t i o n i s i n t e n d e d t o b e
i l l u s t r a t i v e a n d n o t l i m i t i n g . V a r i o u s c h a n g e s o r modi?ca
t i o n s i n t h e embodiments d e s c r i b e d may o c c u r t o t h o s e
s k i l l e d i n t h e a r t . These c a n b e made W i t h o u t d e p a r t i n g from
t h e s p i r i t o r s c o p e o f t h e i n v e n t i o n .
I t i s c l a i m e d :
1 . A a t a l y s t f o r s e l e c t i v e o x i d a t i o n o f e t h a n e t o a c e t i c
a c i d c o n t a i n i n g a c a t a l y s t c o m p o s i t i o n c o n s i s t i n g e s s e n t i a l l y
o f t h e e l e m e n t s Mo, V , Nb a n d X , i n t h e f o r m o f o x i d e s , i n
t h e f o l l o W i n g r a t i o :
M o A V B N b C X D
W h e r e i n X s P ;
A s a b o u t 2 . 5 ;
B i s 1 ;
C i s a b o u t 0 . 3 ; a n d
D s a number r a n g i n g from g r e a t e r t h a n a b o u t 0 . 0 1 t o
a b o u t 0 . 1 .
2 . A a t a l y s t f o r s e l e c t i v e o x i d a t i o n o f e t h a n e t o a c e t i c
a c i d c o n t a i n i n g a c a t a l y s t c o m p o s i t i o n c o n s i s t i n g e s s e n t i a l l y
o f t h e e l e m e n t s Mo, V , Nb a n d X a n d oxygen i n t h e
f o l l o W i n g r a t i o :
MoAVBNbCXDOy
W h e r e i n X s P ;
A s a b o u t 2 . 5 ;
B i s 1 ;
C i s a b o u t 0 . 3 ;
10
1 5
20
25
30
35
40
45
55
60
6 5
1 2
D s a number r a n g i n g from g r e a t e r t h a n a b o u t 0 . 0 1 t o
a b o u t 0 . 1 ; a n d
Y s a number d e t e r m i n e d by t h e v a l e n c e r e q u i r e m e n t s o f
t h e o t h e r e l e m e n t s i n t h e c a t a l y s t c o m p o s i t i o n .
3 . A a t a l y s t f o r s e l e c t i v e o x i d a t i o n o f e t h a n e t o a c e t i c
a c i d made b y p r o c e s s c o m p r i s i n g t h e s t e p s o f :
( a ) c o m b i n i n g t h e e l e m e n t s Mo, V , Nb a n d X n t h e
f o l l o W i n g r a t i o :
MoAVBNbCXD
t o form a m i x t u r e ,
W h e r e i n X s P ;
A s a b o u t 2 . 5 ;
B i s a b o u t 1 ;
C i s a b o u t 0 . 3 ; a n d
D s a number r a n g i n g from g r e a t e r t h a n a b o u t 0 . 0 1 t o
a b o u t 0 . 1 ; a n d
( b ) c a l c i n i n g s a i d m i x t u r e t o f o r m s a i d c a t a l y s t .4 . The c a t a l y s t o f c l a i m 1 , W h e r e i n D s a b o u t 0 . 0 3 t o
a b o u t 0 . 0 5 .
5 . The c a t a l y s t o f c l a i m 2 , W h e r e i n D s a b o u t 0 . 0 3 t o
about 0 .0 5
6 . The c a t a l y s t o f c l a i m 1 , W h e r e i n D s a b o u t 0 . 0 4 .
7 . The c a t a l y s t o f c l a i m 2 , W h e r e i n D s a b o u t 0 . 0 4 .
8 . The c a t a l y s t o f c l a i m 1 , W h e r e i n s a i d c a t a l y s t i s a
s u p p o r t e d c a t a l y s t c o m p r i s i n g a s u p p o r t .
9 . T h e c a t a l y s t o f c l a i m 8 , W h e r e i n s a i d s u p p o r t i s s e l e c t e d
f r o m t h e g r o u p c o n s i s t i n g o f a l u m i n a , s i l i c a , t i t a n i a ,
Z i r c o n i a , Z e o l i t e s a n d m o l e c u l a r s i e v e s .
1 0 . The c a t a l y s t o f c l a i m 8 , W h e r e i n s a i d s u p p o r t com
p r i s e s a m i c r o p o r o u s m a t e r i a l , n a n o p o r o u s m a t e r i a l o r mixt u r e s t h e r e o f .
1 1 . T h e c a t a l y s t o f c l a i m 8 , W h e r e i n s a i d s u p p o r t e d
c a t a l y s t c o m p r i s e s f r o m 1 0 t o 50% b y W e i g h t c a t a l y s t
c o m p o s i t i o n a n d 9 0 t o 50% b y W e i g h t s u p p o r t .
1 2 . A r o c e s s o f f o r m i n g t h e c a t a l y s t o f c l a i m 1 , com
p r i s i n g t h e s t e p s o f :
( a ) f o r m i n g a m i x t u r e c o n s i s t i n g e s s e n t i a l l y o f Mo, , Nb
and X n a s o l u t i o n ;
( b ) d r y i n g s a i d m i x t u r e t o f o r m a d r i e d s o l i d m a t e r i a l ; a n d
( c ) c a l c i n i n g s a i d d r i e d s o l i d m a t e r i a l t o f o r m s a i d c a t a
1 s t .
1 3 . y T h e p r o c e s s o f c l a i m 1 2 , W h e r e i n s a i d m i x t u r e i s a n
a q u e o u s s y s t e m h a v i n g a pH from 1 t o 1 0 .
1 4 . The p r o c e s s o f c l a i m 1 2 , Wherein s a i d m i x t u r e i s a n
a q u e o u s s y s t e m h a v i n g a pH from 1 t o 7 .
1 5 . The p r o c e s s o f c l a i m 1 2 , W h e r e i n s a i d m i x t u r e i s
formed by combining a ? r s t s o l u t i o n W i t h a s e c o n d s o l u t i o n ,
W h e r e i n s a i d ? r s t s o l u t i o n and s a i d s e c o n d s o l u t i o n e a c h
c o n t a i n a t l e a s t one element s e l e c t e d from t h e group con
s i s t i n g o f Mo, V , Nb a n d X .
1 6 . The p r o c e s s o f c l a i m 1 2 , W h e r e i n s a i d c a l c i n i n g
c o m p r i s e s h e a t i n g s a i d d r i e d s o l i d m a t e r i a l t o a c a l c i n i n g
t e m p e r a t u r e from a b o u t 250° C . t o a b o u t 450° C . i n a i r o r
oxygen f o r a p e r i o d o f t i m e r a n g i n g from a b o u t one h o u r t o
a b o u t 1 6 h o u r s .1 7 . The p r o c e s s o f c l a i m 1 2 , W h e r e i n s a i d m i x t u r e f u r t h e r
c o m p r i s e s a s u p p o r t .
1 8 . The p r o c e s s o f c l a i m 1 7 , W h e r e i n s a i d s u p p o r t i s
s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g o f a l u m i n a , s i l i c a , t i t a n i a ,
Z i r c o n i a , Z e o l i t e s a n d m o le c u l a r s i e v e s .
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1 3
1 9 . The c a t a l y s t o f c l a i m 2 , w h e r e i n s a i d c a t a l y s t i s a
s u p p o r t e d c a t a l y s t c o m p r i s i n g a s u p p o r t .2 0 . T h e c a t a l y s t o f c l a i m 1 9 , W h e r e i n s a i d s u p p o r t i s
s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g o f a l u m i n a , s i l i c a , t i t a n i a ,
Z i r c o n i a , Z e o l i t e s a n d m o l e c u l a r s i e v e s .
2 1 . The c a t a l y s t o f c l a i m 3 , W h e r e i n s a i d c a t a l y s t i s a
s u p p o r t e d c a t a l y s t c o m p r i s i n g a s u p p o r t .
2 2 . The c a t a l y s t o f c l a i m 3 , W h e r e i n D s a b o u t 0 . 0 3 t o
a b o u t 0 . 0 5 .
2 3 . The c a t a l y s t o f c l a i m 2 2 , W h e r e i n s a i d c a t a l y s t i s a
s u p p o r t e d c a t a l y s t c o m p r i s i n g a s u p p o r t .
2 4 . T h e c a t a l y s t o f c l a i m 2 3 , W h e r e i n s a i d s u p p o r t i s
s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g o f a l u m i n a , s i l i c a , t i t a n i a ,
Z i r c o n i a , Z e o l i t e s a n d m o l e c u l a r s i e v e s .
2 5 . The c a t a l y s t o f c l a i m 2 3 , W h e r e i n s a i d s u p p o r t c o m
p r i s e s a m i c r o p o r o u s m a t e r i a l , n a n o p o r o u s m a t e r i a l o r miX
t u r e s t h e r e o f .
2 6 . T h e c a t a l y s t o f c l a i m 2 3 , W h e r e i n s a i d s u p p o r t e dc a t a l y s t c o m p r i s e s f r o m 1 0 t o 50% b y W e i g h t c a t a l y s t
c o m p o s i t i o n a n d 9 0 t o 50% b y W e i g h t s u p p o r t .
2 7 . A r o c e s s o f f o r m i n g t h e c a t a l y s t o f c l a i m 2 , com
p r i s i n g t h e s t e p s o f :
( a ) f o r m i n g a m i X t u r e c o n s i s t i n g e s s e n t i a l l y o f Mo, , Nb
and X n a s o l u t i o n ;
( b ) d r y i n g s a i d m i X t u r e t o f o r m a d r i e d s o l id m a t e r i a l ; a n d
( c ) c a l c i n i n g s a i d d r i e d s o l i d m a t e r i a l t o f o r m s a i d c a t a
l y s t .
10
1 5
20
25
1 4
2 8 . The p r o c e s s o f c l a i m 2 7 , Wherein s a i d m i X t u r e i s a n
a q u e o u s s y s t e m h a v i n g a pH from 1 t o 1 0 .
2 9 . The p r o c e s s o f c l a i m 2 7 , Wherein s a i d m i X t u r e i s a n
a q u e o u s s y s t e m h a v i n g a pH from 1 t o 7 .
3 0 . The p r o c e s s o f c l a i m 2 7 , W h e r e i n s a i d m i x t u r e i s
formed by combining a ? r s t s o l u t i o n W i t h a s e c o n d s o l u t i o n ,
W h e r e i n s a i d ? r s t s o l u t i o n and s a i d s e c o n d s o l u t i o n e a c h
c o n t a i n a t l e a s t one element s e l e c t e d from t h e group con
s i s t i n g o f Mo, V , Nb a n d X .
3 1 . The p r o c e s s o f c l a i m 2 7 , W h e r e i n s a i d c a l c i n i n g
c o m p r i s e s h e a t i n g s a i d d r i e d s o l i d m a t e r i a l t o a c a l c i n i n g
t e m p e r a t u r e from a b o u t 250° C . t o a b o u t 450° C . i n a i r o r
oxygen f o r a p e r i o d o f t i m e r a n g i n g from a b o u t one h o u r t o
a b o u t 1 6 h o u r s .
3 2 . The c a t a l y s t o f c l a i m 3 , W h e r e i n s a i d c a t a l y s t i s a
s u p p o r t e d c a t a l y s t c o m p r i s i n g a s u p p o r t .
3 3 . T h e c a t a l y s t o f c l a i m 3 2 , W h e r e s a i d s u p p o r t i s
s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g o f a l u m i n a , s i l i c a , t i t a n i a ,Z i r c o n i a , Z e o l i t e s a n d m o le c u l a r s i e v e s .
3 4 . The c a t a l y s t o f c l a i m 3 2 , W h e r e i n s a i d s u p p o r t com
p r i s e s a m i c r o p o r o u s m a t e r i a l , n a n o p o r o u s m a t e r i a l o r miX
t u r e s t h e r e o f .
3 5 . T h e c a t a l y s t o f c l a i m 3 2 , W h e r e i n s a i d s u p p o r t e d
c a t a l y s t c o m p r i s e s f r o m 1 0 t o 50% b y W e i g h t c a t a l y s t
c o m p o s i t i o n a n d 9 0 t o 50% b y W e i g h t s u p p o r t .
* * * * *