(2013) US20130324758 Process for Manufacturing Acrolein-Acrylic Acid

8/11/2019 (2013) US20130324758 Process for Manufacturing Acrolein-Acrylic Acid

1/13

US

20130324758A1

1 9 )

United

S t a t e s

1 2 ) Patent

Application

Publication 1 0 )

P u b .

N 0 . 2 US 2 0 1 3 / 0 3 2 4 7 5 8 A 1

Devaux t

a ] .

( 4 3 ) P u b . D a t e : Dec.

5 , 2 0 1 3

( 5 4 ) PROCESS FOR MANUFACTURING P u b l i c a t i o n

C l a s s i ? c a t i o n

ACROLEIN/ACRYLICACID ( 5 1 ) Int CL

C07C

1 / 1 6

( 2 0 0 6 . 0 1 )

C07C

1 9 / 0 2 ( 2 0 0 6 . 0 1 )

( 7 5 ) I n v e n t o r s : J e a n - F r a n c o i s D e v a u x ; S o u c i e u En C07C 5 / 2 8 ( 2 0 0 6 . 0 1 )

J a r r e s t ( F R ) ; J e a n - L u c

D u b o i s ;

M i l l e r y C07C 5 3 / 1 8 ( 2 0 0 6 - 0 1 )

( F R )

( 5 2 ) US. l .

CPC

. . . . . . . . . . . . .

. . C07C 1/16

(2013.01);

C07C 5 3 / 1 8

( 2 0 1 3 . 0 1 ) ;

C07C319/02

2 0 1 3 . 0 1 ) ; C07C

4 5 / 2 8

( 2 0 1 3 . 0 1 )

( 7 3 ) A s s i g n e e : Arkema r a n c e ,

C o l o m b i a / s

( F R )

USPC

. . . . . . . . . 5 5 8 / 3 1 5 ; 5 6 2 / 5 3 2 ; 5 6 2 / 5 3 4 ; 5 6 2 / 5 3 5 ;

5 6 2 / 5 4 9 ; 5 6 8 / 6 3 ; 5 6 8 / 4 4 9

( 2 1 )

A p p l .

N O . Z

1 3 / 9 8 1 , 9 2 7

( 5 7 )

ABSTRACT

The

r e s e n t i n v e n t i o n

r e l a t e s t o t h e s e l e c t i v e

e l i m i n a t i o n

of

( 2 2 )

PCT l l e d i J a n -

2 6 :

2 0 1 2 p r o p a n a l

i n a c r o l e i n - r i c h s t r e a m s

t o p r o d u c e a c r o l e i n

a n d / o r

a c r y l i c a c i d a n d / o r a c r y l o n i t r i l e a n d / o r m e t h y l m e r c a p t o p r o

( 8 6 )

PCT NO;

PCT/IB12/00396

p i o n a l d e h y d e

c o n t a i n i n g l o W

a m o u n t o f r o p a n a l

a n d / o r

p r o

p i o n i c a c i d

a n d / o r

p r o p i o n i t r i l e . One u b j e c t o f t h e p r e s e n t

3 7 1

( c ) ( 1 ) ;

i n v e n t i o n

i s

a

p r o c e s s

f o r

m a n u f a c t u r i n g

a c r o l e i n

c o m p r i s i n g

( 2 ) ( 4 ) D a t e . Aug 0

2 0 1 3

a s t e p o f s e l e c t i v e e l i m i n a t i o n o f r o p a n a l

i n

a n

a c r o l e i n - r i c h

stream

i n c o n t a c t With a c a t a l y s t

comprising

a t

l e a s t

molyb

_ _ _ _ _ denum. Another

subject

of he present invention

i s a

process

( 3 0 )

F o r e l g n

A p p h c a t l o n Pnonty a t a

f o r

m a n u f a c t u r i n g a c r y l i c a c i d f r o m

g l y c e r o l

i n c l u d i n g

a s t e p

of

e l e c t i v e e l i m i n a t i o n o f r o p a n a l i n

an c r o l e i n - r i c h

s t r e a m

J a n .

2 8 ; 2011

( I B )

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

201

/ 000468

i n

c o n t a c t With a

c a t a l y s t

comprising

a t l e a s t molybdenum.


2/13


3/13

US 2013/0324758

A 1

m e t a l s , a l k a l i n e - e a r t h m e t a l s , A l , S i , B ,

C o ,

C r , N i , V , Z n ,

Z r ,

S n , S b , A g , C u , N b , M o , Y ,

Mn,

t ,

Rh

n d t h e r a r e e a r t h s

L a ,

C e ,

S m .

[ 0 0 1 6 ]

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and

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r e s p e c t i v e l y o f t h e o b j e c t i v e c o m p o u n d s o f a c r o l e i n a n d

a c r y l i c

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t r i l e i f r o m p r o p y l e n e o r f r o m g l y c e r o l i s i n c e p r o p a n al

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[ 0 0 2 0 ]

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6 n EP 2 0 3 9 6 7 4 ) .

[ 0 0 2 6 ]

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o f

s a t u r a t e d

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a r t .

[ 0 0 2 7 ]

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i n I&EC

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a l d e h y d e s

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4/13


5/13

US 2013/0324758

A 1

t h a t

i s u s e d W i t h o t h e r f e e d s t o c k s t h a n

s a t u r a t e d

a l d e h y d e , f o r

e x a m p l e f o r m e t h a n o l

o x i d a t i o n

t o f o r m a l d e h y d e (Fei

M040 o p e d

o r

n o t ) a n d p r o p y l e n e

o x i d a t i o n t o

a c r o l e i n

( b a s e d o n

b i s m u t h

m o l y b d a t e , f o r e x a m p l e W i t h a

g e n e r a l

f o r m u l a

d e s c r i b e d

i n

EP

1 9 8 7 8 7 7 :

Mo

2 B i a F e b A c B

C e D f O , C

Wherein

A

s a t

l e a s t an

element s e l e c t e d from c o b a l t and

n i c k e l , B

s

a t

l e a s t

a n

e l e m e n t

s e l e c t e d from

a l k a l i

m e t a l s ,

a l k a l i n e

e a r t h

m e t a l s and

t h a l l i u m , C

s

a t l e a s t an e l e m e n t

s e l e c t e d

f r o m

t u n g s t e n , s i l i c o n , a l u m i n u m , Z i r c o n i u m

a n d

t i t a n i u m ; D s a t l e a s t an

e l e m e n t

s e l e c t e d from h o s p h o r u s ,

t e l l u r i u m , a n t i m o n y , t i n , c e r i u m , l e a d , n i o b i u m , m a n g a n e s e ,

a r s e n i c

a n d Z i n c , p o t a s s i u m ) .

[ 0 0 5 0 ] E x a m p l e s o f

FeiMoiO

r o n m o l y b d a t e c a t a l y s t s

a r e

d e s c r i b e d

i n C a t a l y s i s

R e v i e w , V o l

4 7 ( 2 0 0 4 ) ,

p p

1 2 5 - 1 7 4 .

[ 0 0 5 1 ] I r o n molybdenum

a s e d

a t a l y s t s

a r e

c o m m e r c i a l l y

a v a i l a b l e .

F o r e x a m p l e i i d Chemie u p p l i e s s e v e r a l g r a d e s o f

s u c h

c a t a l y s t s u n d e r t h e t r a d e name FAMAX: FAMAX 5 ,

FAMAX

S,

FAMAX

S,

FAMAX H.

[ 0 0 5 2 ]

E x a m p l e s

o f p r o p y l e n e

o x i d a t i o n

c a t a l y s t s t o

a c r o l e i n a r e

d e s c r i b e d

i n

EP

9 0 0 7 7 4 ,

EP

1 1 2 5 9 1 1 ,

EP

1 9 8 7 8 7 7 ,

EP

1 0 7 4 9 3 8 , US. a t . N o . 6 , 2 6 8 , 5 2 9 , US. a t . N o .

4 , 8 3 7 , 9 4 0 .

[ 0 0 5 3 ]

P r e f e r a b l y ,

t h e c a t a l y s t c o m p r i s e s m o l y b d e n u m a n d

a t

l e a s t

o n e e l e m e n t

s e l e c t e d f r o m

, S i ,

W,

r , Mn, e , C o ,

N i ,

B i , S b , C e .

[ 0 0 5 4 ]

I n o n e em b o d i m e n t ,

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

c o m p r i s e s

a t l e a s t o n e

h e t e r o p o l y a c i d c o n t a i ni n g

a t

l e a s t m o l y b d e n u m .

[ 0 0 5 5 ] A d v a n t a g e o u s l y , p r o t o n i n

t h e h e t e r o p o l y a c i d

c o n

t a i n i n g

a t l e a s t

m o l y b d e n u m ,

may

e

p a r t i a l l y

e x c h a n g e d b y

a t

l e a s t one

a t i o n s e l e c t e d from

l e m e n t s b e l o n g i n g

to Group

1

t o

1 6

of

h e P e r i o d i c T a b l e

of

l e m e n t s .

[ 0 0 5 6 ] The

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

e

r e p

r e s e n t e d

b y

t h e

g e n e r a l

f o r m u l a :

A a X b Y c Z d O e

i n Which

[ 0 0 5 7 ]

A

s more t h a n one c a t i o n s e l e c t e d

from

e l e m e n t s

b e l o n g i n g t o Group t o 1 6 o f

t h e

P e r i o d i c T a b l e o f E l e m e n t s

and l a n t h a n i d e s , p r e f e r a b l y one a l k a l i m e t a l c a t i o n s u c h a s

c e s i u m , r u b i d i u m o r p o t a s s i u m .

[ 0 0 5 8 ] X s P o r

S i ,

p r e f e r a b l y P

[ 0 0 5 9 ] Y

s Mo

[ 0 0 6 0 ] Z

i s

more

t h a n

one

element s e l e c t e d from t h e

g r o u p c o m p r i s i ng W ,

T i ,

Z r ,

V ,

N b ,

T a ,

C r , M n , F e ,

C o ,

N i ,

C u ,

Z n ,

G a ,

I n ,

T l , S n , A g , A s , G e , B , B i , L a ,

B a ,

S b ,

T e ,

C e a n d

P b ,

p r e f e r a b l y

F e , B i , C o , N i ,

W ,

V ,

C r ,

S b ,

Mn, Ce

[ 0 0 6 1 ]

a ,

b ,

c

a n d d

s a t i s f y i n g

f o l l o W i n g r a n g e s :

[ 0 0 6 2 ]

0 s a s 9 ,

p r e f e r a b l y

0 < a s 9

[ 0 0 6 3 ]

0 s b s 2

p r e f e r a b l y 0 . 1 s b s 1 . 5

[ 0 0 6 4 ] 0 < c s 1 2 p r e f e r a b l y 5 < c s 1 2

[ 0 0 6 5 ] 0 s d < 1 2 p r e f e r a b l y 0 s d s 4

[ 0 0 6 6 ] and i s a number

e t e r m i n e d by

h e o x i d a t i o n

o f

h e

e l e m e n t s .

[ 0 0 6 7 ]

Examples

o f

e f f e c t i v e c a t a l y s t s

a r e mixed x i d e s o r

h e t e r o p o l y a c i d

s a l t s o f FeMo,

CsPMo, CsPWMo

r

BiMoFe

c a t a l y s t s .

[ 0 0 6 8 ]

The

c a t a l y s t u s e d i n t h e p r e s e n t i n v e n t i o n c a n b e

p r e p a r e d b y a n y

knoWn

e c h n i q u e , f o r

e x a m p l e

a s d e s c r i b e d

i n

WO/09/

2 8 , 5 5 5 ( h e t e r o p o l y a c i d s ) o r i n C a t a l y s i s

R e v i e W ,

V o l 4 7

( 2 0 0 4 ) , pp

1 2 5 - 1 7 4

and t h e

r e f e r e n c e s d e s c r i b e d

t h e r e i n . G e n e r a l l y ,

t h e

r e s u l t i n g s o l i d c o m p o n e n t i s

? n a l l y

D e c .

5 , 2 0 1 3

?red o r c a l c i n e d t o o b t a i n

t h e c a t a l y s t

f o r

s e l e c t i v e e l i m i n a

t i o n o f

p r o p a n a l 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 .

[ 0 0 6 9 ]

The c a l c i n a t i o n can be

c a r r i e d

o u t

i n

a i r

o r under

i n e r t g a s such a s n i t r o g e n , helium and argon o r

under an

a t m o s p h e r e

o f

mixed

a s

o f

oxygen a n d

i n e r t

g a s ,

u s u a l l y

i n

a fumace

s u c h

a s muf?e f u r n a c e , r o t a r y

k i l n ,

? u i d i z e d bed

f u r n a c e . T y p e o f t h e f u r n a c e i s

n o t

l i m i t e d

s p e c i a l l y . The

c a l c i n a t i o n can

be

f f e c t e d

even

n a r e a c t i o n tube h a t i s used

f o r t h e g l y c e r i n d e h y d r a t i o n

r e a c t i o n .

T h e ? r i n g t e m p e r a t u r e

i s u s u a l l y 1 5 0

t o 9 0 0 C . ,

p r e f e r a b l y 200

o 8 0 0

C . and more

p r e f e r a b l y 200

o 6 0 0

C . The

a l c i n a t i o n

s c o n t i n u e d u s u a l l y

f o r 0 . 5 to

1 0 h o u r s .

[ 0 0 7 0 ] The a t a l y s t

i n

t h e p r o c e s s

a c c o r d i n g t o

t h e i n v e n

t i o n

may

be

a

b u l k and i s

u s e d ,

i n t h i s

c a s e , W i t h o u t

any

s u p p o r t .

[ 0 0 7 1 ]

The

c a t a l y s t may a l s o b e l o a d e d on a s u p p o r t ( o r

c a r r i e r ) , t h e a m o u n t

o f

s u p p o r t g e n e r a l l y

r e p r e s e n t i n g

f r o m 0

t o 90 , p r e f e r a b l y a t l e a s t

5

o f t h e t o t a l W e i g h t o f t h e

c a t a l y s t .

[ 0 0 7 2 ]

The

a r r i e r c a n b e g r a n u l e a n d p o W d e r a n d

may

a v e

a n y s h a p e s u c h a s s p h e r e ,

p e l l e t ,

c y l i n d r i c a l

b o d y ,

h o l l o W

c y l i n d e r b o d y , t r i l o b e a n d q u a d r i l o b e a n d b a r W i t h o p t i o n a l

m o l d i n g

a i d .

[ 0 0 7 3 ] I t i s p o s s i b l e t o u s e , a s

a su p p o r t , any

a t e r i a l s u c h

a s s i l i c a ,

a l u m i n a , m a g n e s i a , t i t a n i u m

o x i d e ,

Z i r c o n i a , s i l i c o n

c a r b i d e ,

s i l i c a / a l u m i n a m i x t u r e , s i l i c a t e s , d i a t o m a c e o u s

e a r t h , b o r a t e s

o r c a r b o n a t e s

on

o n d i t i o n

t h a t

t h e s e p r o d u c t s

a r e

s t a b l e 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 t o

Which h e c a t a l y s t

W i l l

b e

s u b j e c t e d . P r e f e r a b l y , t h e c a t a l y s t i s

n o t

a

s u p p o r t e d

c a t a l y s t .

[ 0 0 7 4 ]

The

a t a l y s t may a v e a n y s h a p e a n d c a n b e g r a n u l e

o r p o W d e r . I t

i s

p r e f e r a b l e t o

mold

h e c a t a l y s t i n t o a s h a p e

o f

s p h e r e , p e l l e t s , c y l i n d e r ,

h o l l o W

c y l i n d e r , b a r o r t h e l i k e ,

o p t i o n a l l y

W i t h a d d i n g

a

m o l d i n g

a i d .

The

c a t a l y s t

c a n b e

s h a p e d i n t o

t h e

a b o v e - c o n ? g u r a t i o n s t o g e t h e r W i t h c a r r i e r

a n d

o p t i o n a l a u x i l i a r y a g e n t s .

T h e m o l d e d c a t a l y s t

may a v e

a p a r t i c l e

s i Z e

o f

f o r

example

t o

1 0 mm

o r

a

?xed

bed

and

of

e s s than mm o r

a

?uidized

e d .

[ 0 0 7 5 ]

The c r o l e i n - r i c h

s t r e a m i n t h e

p r o c e s s a c c o r d i n g

t o

t h e i n v e n t i o n

can

be s p e c i ? c a l l y t h e p r o d u c t s t r e a m

of

a

p r o p y l e n e ( o r

o t h e r

n o n - p e t r o l e u m b a s e d s o u r c e s o f h y d r o

c a r b o n s )

c a t a l y t i c

o x i d a t i o n

p r o c e s s ,

o r

t h e p r o d u c t s t r e a m o f

g l y c e r o l d e h y d r a t i o n

i n

l i q u i d p h a s e o r

i n

g a s p h a s e ,

p r e f e r

a b l y i n g a s p h a s e o r i n a s t r e a m o f hy d r o x y p r o p a n a l d e h y d r a

t i o n . G e n e r a l l y , t h e a c r o l e i n - r i c h s t r e a m r e s u l t s

a s

a g a s

mix

t u r e

t h a t

i s

s u b m i t t e d

d i r e c tl y f o r

t h e

p r o c e s s

a c c o r d i n g

t o t h e

i n v e n t i o n

[ 0 0 7 6 ] E x a m p l e s

o f

o p e r a t i n g

c o n d i t i o n s f o r

d e h y d r a t i n g

g l y c e r o l

i n t o

a c r o l e i n

a r e

d e s c r i b e d

i n

t h e

i n t e r n a t i o n a l

p a t e n t

a p p l i c a t i o n s

WO 6 / 0 8 7 0 8 3 , WO 6 / 0 8 7 0 8 4 , WO 9 / 1 2 8 ,

5 5 5

o r

WO 1 0 / 0 4 6 , 2 2 7 o f t h e

A p p l i c a n t .

S p e c i ? c a l l y , t h e

c a t a l y s t u s e d f o r t h e

r e a c t i o n

o f

d e h y d r a t i o n i s

a c a t a l y s t

h a v i n g Hammett

c i d i t y l o W e r t h a n

+ 2 . S p e c i ? c a l l y , t h e c a t a

l y s t

u s e d f o r

t h e

r e a c t i o n o f d e h y d r a t i o n i s a

c a t a l y s t c o n t a i n

i n g

n o

m o l y b d e n u m .

[ 0 0 7 7 ]

E x a m p l e s o f

o p e r a t i n g c o n d i t i o n s

f o r o x i d a t i o n o f

p r o p y l e n e

i n t o a c r o l e i n a r e d e s c r i b e d

i n

P r o c e s s Economic

Program

6D

f r o m S R 1 c o n s u l t i n g a n d t h e r e f e r e n c e

c i t e d

t h e r e i n .

[ 0 0 7 8 ] The amount o f p r o p a n a l

i n t h e a c r o l e i n - r i c h

s t r e a m

i s g e n e r a l l y

l e s s

t h a n

0 . 2 ,

e x p r e s s e d b y h e m o l e s o f r o p a n a l

r e l a t i v e

t o t h e moles

of

c r o l e i n p r e s e n t i n t h e s t r e a m . I t may


6/13

US 2013/0324758

A 1

r a n g e f r o m

1 / 4 0 0 0

t o

1 /

e x p r e s s e d b y t h e m o l e s o f r o p a n a l

r e l a t i v e t o

t h e

m o l e s

o f a c r o l e i n

p r e s e n t

i n

t h e

s t r e a m ,

p r e f

e r a b l y from 1 / 1 0 0 0 to 1 / 1 0 .

The


s t r e a m i n t h e p r o c e s s a c c o r d i n g to t h e

i n v e n t i o n c o n t a i n s W a t e r ,

o x y g e n , a n d

e v e n t u a l l y

b y - p r o d u c t s

s u c h

a s h y d r o x y p r o p a n o n e , a c e t a l d e h y d e , a c e to n e , a d d i t i o n

p r o d u c t s o f c r o l e i n t o g l y c e r o l , p o l y c o n d e n s a t i o n p r o d u c t s

o f l y c e r o l , c y c l i c g l y c e r o l

e t h e r s ,

h y d r o x y p r o p a n a l ,

p h e n o l

a n d p o l y a r o m a t i c c o m p o u n d s ,

p r o p y l e n e ,

a c r y l i c

a c i d ,

a n d

i n e r t g a s e s s u c h as c a r b o n o x i d e , c a r b o n d i o x i d e , n i t r o g e n ,

h e l i u m ,

a r g o n ,

p r o p a n e .

The a t u r e o f h e


and h e

c o m p o s i t i o n of

h e


s t r e a m

depend of

o u r s e

on

t h e raW

a t e r i a l

used

o produce a c r o l e i n .

[ 0 0 7 9 ]

T h u s ,

i n

t h e

c a s e

Where r o p y l e n e i s t h e

main

raW

m a t e r i a l i n

a n

o x i d a t i o n

r e a c t i o n t o p r o d u c e a c r o l e i n , t h e

a c r o l e i n - r i c h stream may o n t a i n propane

a s

thermal a l l a s t .

[ 0 0 8 0 ] I n t h e

c a s e

Where l y c e r o l i s t h e main raW a t e r i a l

i n a


p r o c e s s t o p r o d u c e a c r o l e i n ,

t h e

m i x t u r e

o f

a c r o l e i n and r o p a n a l may

c o n t a i n

a

l a r g e

amount o f W a t e r

d e p e n d i n g o f

t h e

c o n c e n t r a t i o n

o f

g l y c e r o l i n t h e

f e e d .

[ 0 0 8 1 ] I n t h e p r o c e s s

a c c o r d i n g

t o t h e i n v e n t i o n , t h e con

c e n t r a t i o n o f a c r o l e i n i n t h e g a s m i x t u r e h a t i s p a s s e d t hr o u g h

t h e c a t a l y s t

r a n g e s

from t o 1 2 mole

,

r e f e r a b l y from to

1 0 mole .

[ 0 0 8 2 ]

The r o c e s s a c c o r d i n g

o t h e i n v e n 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

of oxygen,

o r

an x y g e n - c o n t a i n i n g g a s such

a s

i r . G e n e r a l l y , oxygen s a l r e a d y p r e s e n t

i n t h e g a s

m i x t u r e ,

b u t

f u r t h e r

oxygen may be i n j e c t e d i f t h e oxygen c o n c e n t r a

t i o n i s

t o o

l o W . Oxygen c o n t e n t i s c o m p r i s e d b e t W e e n 1

a n d

10 m o l )

a n d

p r e f e r a b l y

b e t W e e n

3

a n d

7

m o l ) .

[ 0 0 8 3 ]

The


o f

W a t e r

o f

t h e


s t r e a m may

a r y

l a r g e l y .

W a t e r c o n t e n t

i s

c o m p r i s e d

betWeen

3 a n d 9 0 m o l ) a n d

p r e f e r a b l y

b e t W e e n 8 a n d 80 m o l ) .

[ 0 0 8 4 ]

The

s e l e c t i v e e l i m i n a t i o n

o f p r o p a n a l

o p e r a t e s

a t

a

t e m p e r a t u r e

b e t W e e n

2 5 0

C . a n d

4 0 0

C . ,

p r e f e r a b l y

betWeen 280 and 350 C . , and t a

p r e s s u r e

betWeen and 5

b a r a b s o l u t e

and

r e f e r a b l y

betWeen

a n d 2 b a r .

[ 0 0 8 5 ] A e e d r a t e o f

t h e

g a s r e a c t a n t

i s

a d v a n t a g e o u s l y

1 0 0 0

o

4 0 , 0 0 0 h ' 1 i n t e r m o f GHSV g a s h o u r l y s p a c e v e l oc

i t y

i n n o r m a l m 3 / h /v o l u m e o f a t a l y s t i n m 3 ) , p r e f e r a b l y 3 0 0 0

to 30000 h _ 1 , more p r e f e r a b l y 5000 to 20000 h _ l . I f t h e

GHSV e c o m e s

l o W e r t h an 1 0 0 0 h _ l ,

t h e

s e l e c t i v i t y W i l l b e

l o W e r e d . On h e

c o n t r a r y , i f

t h e GHSV

x c e e d s

4 0 , 0 0 0

h _ 1 ,

t h e c o n v e r s i o n W i l l

be

l o W e r e d .

[ 0 0 8 6 ] F o r e a c h a t a l y s t t h e r e i s a n optimum f t e m p e r a t u r e

a n d GHSV f o r Which

a

h i g h c o n v e r s i o n o f p r o p a n a l i s

o b t a i n e d a t

a

loW conversion of

c r o l e i n .

[ 0 0 8 7 ] The

e l e c t i v e

e l i m i n a t i o n o f

r o p a n a l

i n

a n

a c r o l e i n

r i c h

s t r e a m a c c o r d i n g t h e i n v e n t i o n can be

c a r r i e d o u t

i n

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moving

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h e m ,

t h e

?xed

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? u i d

bed a r e

p r e f e r a b l e .

[ 0 0 8 8 ]

When ?uid bed o r c i r c u l a t i n g ?uid

bed

e a c t o r i s

used a s a ? r s t r e a c t o r

f o r

t h e

p r o d u c t i o n

of

h e a c r o l e i n - r i c h

s t r e a m , t h e

p r o p a n a l e l i m i n a t i o n

c a t a l y s t can be used a s a

?xedbed doWnstream f

h e

s a i d ? r s t r e a c t o r , o r t canbe

used

a s

a compartmentalized ?uid bed

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can be made by

s i n g

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k e e p

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t h e

l o W e r p a r t

o f h e ? u i d b e d a n d t h e

p r o p a n a l

e l i m i n a t i o n c a t a l y s t i n t h e

u p p e r

p a r t

o f

t h e

? u i d

b e d .

[ 0 0 8 9 ] I n

a

? r s t embodiment o f

t h e i n v e n t i o n , t h e p r o d u c

t i o n o f

t h e


s t r e a m and h e s e l e c t i v e e l i m i n a t i o n

o f r o p a n a l a r e c a r r i e d o u t i n a

t a n d e m - t y p e

r e a c t o r

c o m p r i s

D e c .

5 , 2 0 1 3

i n g tWo e a c t o r s l i n k e d t o each t h e r ,

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tWo e a c t o r s

a r e ? l l e d W i t h a c a t a l y s t f o r t h e p r o d u c t i o n of c r o l e i n and a

c a t a l y s t f o r t h e s e l e c t i v e e l i m i n a t i o n o f r o p a n a l r e s p e c t i v e l y ,

a n d Where t h e p r o d u c t i o n o f a c r o l e i n a n d t h e e l i m i n a t i o n o f

p r o p a n a l

a r e s e p a r a t e l y

c o n d u c t e d

i n

h e i r

r e s p e c t i v e

e a c t o r s .

[ 0 0 9 0 ]

I n a s e c o n d embodiment o f

t h e

i n v e n t i o n , t h e p r o

d u c t i o n

o f t h e a c r o l e i n - r i c h s t r e a m

and h e

s e l e c t i v e

e l i m i n a

t i o n of r o p a n a l a r e c a r r i e d o u t i n

a

s i n g l e - r e a c t o r - t y p e , Where

t h e r e a c t o r ? l l e d

W i t h

a c a t a l y s t f o r t h e s e l e c t i v e e l i m i n a t i o n

o f r o p a n a l

on

h e r e a c t i o n

g a s

o u t l e t s i d e

and

i t h a c a t a l y s t

f o r t h e

p r o d u c t i o n o f

a c r o l e i n on t h e r e a c t i o n

g a s

i n l e t s i d e ,

t h u s

c o n d u c t i n g

i n t h e s i n g l e r e a c t o r t h e p r o d u c t i o n o f

a c r o l e i n f o l l o W e d b y t h e s e l e c t i v e e l i m i n a t i o n

o f

r o p a n a l .

I t

i s p r e f e r a b l e t h a t t h e r e a c t o r h a s d i f f e r e n t Z o n e o f e m p e r a t u r e

c o n t r o l s o t h a t


of

r o p a n a l

can

be

o p e r a t e d a t a

d i f f e r e n t t e m p e r a t u r e from h e p r o d u c t i o n o f a c r o l e i n . I n c a s e

o f a ?xed bed

e a c t o r ,

a

p r e f e r r e d

c o n ? g u r a t i o n

i s

When h e

g a s i s

m o v i n g

u p W a r d t h r o u g h t h e

b e d

a n d t h e p r o p a n a l

e l i m i n a t i o n c a t a l y s t i s

p l a c e d

on

t o p

o f t h e

c a t a l y s t

f o r

t h e

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o f c r o l e i n .

[ 0 0 9 1] I n

t h e

c a s e

of

xed

e d s , When

m u l t i t u b u l a r

e a c t o r

i s

u s e d

f o r t h e a c r o l e i n

p r o d u c t i o n

a p r e f e r r e d c o n ? g u r a t i o n

f o r t h e

s e l e c t i v e


o f r o p a n a l i s a l a y e r o f

c a t a l y s t

on o p

o f

t h e t u b u l a r l a t e , a b o v e t h e

r e a c t o r

t u b e s c o n t a i n i n g

t h e a c r o l e i n

p r o d u c i n g

c a t a l y s t .

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f e r r e d o r e p l a c e

more a s i l y

t h e

p r o p a n a l

e l i m i n a t i o n a t a l y s t

b y vacuum

n l o a d i n g .

[ 0 0 9 2 ] A c r o l e i n t h u s

o b t a i n e d

b y t h e p r o c e s s

a c c o r d i n g

t o

t h e

i n v e n t i o n

c o n t a i n s l e s s

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5000

ppm,

even l e s s t h a n

1 0 0 0

ppm f p r o p a n a l .

[ 0 0 9 3 ]

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s u b j e c t o f t h e i n v e n t i o n i s t h e u s e

o f

a

c a t a l y s t c o m p r i s i n g a t l e a s t molybdenum a n d a t l e a s t o n e

e l e m e n t s e l e c t e d f r o m , S i ,

W , T i ,

Z r , V , N b , T a , C r ,

M n ,

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A s ,

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C e ,

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c h o s e n

n

t h e g r o u p f o r m e d b y t h e

mixed

e t a l o x i d e s

c o n t a i n i n g a t l e a s t molybdenum a n d h e t e r o p o l y a c i d s c o n

t a i n i n g

a t

l e a s t molybdenum,

t o r e d u c e

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o f p r o p a

n a l l o W e r

t h a n

5000 ppm, r e f e r a b l y l o W e r

t h a n

1 0 0 0 ppm,

n

an

acrolein-rich

stream.

[ 0 0 9 4 ] A c r o l e i n

o b t a i n e d

b y t h e p r o c e s s a c c o r d i n g t o t h e

i n v e n t i o n

c a n

b e


f u r t h e r s u b j e c t e d t o

knoWn

o x i d a t i o n

methods o p r o d u c e a c r y l i c

a c i d

W i t h a loW

c o n t e n t

o f p r o p i o n i c a c i d , t y p i c a l l y c o n t a i n i n g

l e s s

t h a n 5 0 0 0 p p m ,

e v e n l e s s

t h a n

1000 ppm f r o p i o n i c a c i d , Which

s

a t y p i c a l

s p e c i ? c a t i o n

l e v e l f o r a b r o a d

r a n g e

o f a p p l i c a t i o n s .

[ 0 0 9 5 ]

T h u s , a n o th e r s u b j e c t

o f

t h e i n v e n t i o n i s t h e u s e o f a

c a t a l y s t c o m p r i s i n g

a t

l e a s t molybdenum a n d a t l e a s t o n e

e l e m e n t s e l e c t e d f r o m , S i ,

W , T i , Z r , V , N b ,

T a , C r ,

M n , F e ,

C o , N i , C u , Z n , G a ,

I n ,

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c h o s e n

n t h e g r o u p f o r m e d b y t h e

mixed

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p r o d u c e a c r y l i c

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l o W c o n t e n t o f p r o p i o n i c a c i d ,

t y p i c a l l y

c o n t a i n i n g

l e s s

t h a n

5000 ppm, even ess t h a n 1000 ppm f

r o p i o n i c

a c i d .

[ 0 0 9 6 ]

G e n e r a l l y , t h e

o x i d a t i o n

e a c t i o n

s

c a r r i e d

o u t

i n

t h e

p r e s e n c e of

molecular

oxygen o r of a

mixture comprising

m o l e c u l a r o x y g e n , at a t e m p e r a t u r e r a n g i n g from 200 C . t o

3 5 0 C . ,

p r e f e r a b l y

from 2 5 0 C . t o 3 2 0 C . , and u n d e r a

p r e s s u r e

r a n g i n g from t o 5 b a r , i n t h e p r e s e n c e o f an x i d a

t i o n c a t a l y s t c o m p r i s i n g a t

l e a s t

o n e e l e m e n t c h o s e n from

h e

l i s t M o ,

, W ,

R e , C r , M n , F e ,

C o ,

N i ,

C u ,

Z n ,

S n ,

T e , S b , B i ,

P t , P d , Ru n d R h , p r e s e n t i n t h e m e t a l l i c f o r m

o r

i n t h e o x i d e ,

s u l f a t e

o r

p h o s p h a t e f o r m . Use s made

i n p a r t i c u l a r

o f

t h e

f o r m u l a t i o n s c o m p r i s i n g Mo n d / o r V n d / o r

W

n d / o r Cu


7/13

US 2013/0324758

A 1

a n d / r Sb a n d / o r Fe s main o n s t i t u e n t s . The x i d a t i o n

c a t a

l y s t may be s u p p o r t e d

on

a c a r r i e r

s u c h

a s

Z i r c o n i a , s i l i c a ,

a l u m i n a ,

s t e a t i t e

a n d

c o m b i n a t i o n

t h e r e o f a n d s i l i c o n c a r b i d e .

Acrolein

a s

stream o n t a i n s

t h e

same

kind

of

components

s

t h e

s e l e c t i v e


s t e p

o f

p r o p a n a l ,

s u c h

a s W a t er ,

o r

i n e r t g a s e s

s u c h

as

c a r b o n o x i d e ,

c a r b o n

d i o x i d e , n i t r o g e n ,

h e l i u m , a r g o n ,

p r o p a n e

o r o r g a n i c i m p u r i t i e s .

[ 0 0 9 7 ] A c r o l e i n o b t a i n e d b y

t h e p r o c e s s

a c c o r d i n g t o

t h e

i n v e n t i o n c a n b e a d v a n t a g e o u s l y f u r t h e r s u b j e c t e d

t o

knoWn

ammoxidation methods t o p r o d u c e a c r y l o n i t r i l e W i t h

a

loW

c o n t e n t o f

r o p i o n i t r i l e ,

t y p i c a l l y c o n t a i n i n g l e s s

t h a n

5 0 0 0

ppm, even l e s s

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1000

ppm

of r o p i o n i t r i l e , Which s a

t y p i c a l s p e c i ? c a t i o n l e v e l f o r a

b r o a d r a n g e

o f

a p p l i c a t i o n s .

[ 0 0 9 8 ] A c r o l e i n

o b t a i n e d

b y t h e p r o c e s s a c c o r d i n g t o t h e

i n v e n t i o n c a n b e


f u r t h e r s u b j e c t e d t o knoWn

c o n d e n s a t i o n r e a c t i o n t o

p r o d u c e g l u t a r a l d e h y d e , f o r

e x a m p l e a c c o r d i n g

t o

t h e p r o c e s s d e s c r i b e d i n t h e document

WO 011/055051.

[ 0 0 9 9 ] A c r o l e i n o b t a i n e d b y

t h e

p r o c e s s a c c o r d i n g t o

t h e

i n v e n t i o n

c a n

b e


f u r t h e r

s u b j e c t e d

t o

knoWn

a d d i t i o n W i t h

m e t h y l

m e r c a p t a n o p r o d u c e m e t h y l m e r c a p t o

p r o p i o n a l d e h y d e

u s e d

f o r m a n u f a c t u r i n g

m e t h i o n i n e

o r i t s

s a l t o r i t s

h y d r o x y l

a n a l o g u e ,

2 - h y d r o x y - 4 - m e t h y l t h i o - b u

t y r i c a c i d . A d v a n t a g e o u s l y ,

a c r o l e i n

i s p u r i ? e d b y b s o r p t i o n

i n W a t e r and f u r t h e r d i s t i l l a t i o n b e f o r e b e i n g r e a c t e d W i t h

m e t h y l m e r c a p t a n

t o

y i e l d m e t h y l m e r c a p t o p r o p i o n a l d e h y d e .

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reduced

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m e t h y l m e r c a p t o p r o p i o n a l d e h y d e c a n

b e

u s e d W i t h o u t p u r i ?

c a t i o n

f o r t h e p r o d u c t i o n of m e t h i o n i n e o r

i t s

s a l t o r

i t s

h y d r o x y a n a l o g u e .

[ 0 1 0 0 ]

A n o t h e r

o b j e c t o f t h e p r e s e n t i n v e n t i o n i s a

p r o c e s s

f o r m a n u f a c t u r i n g a c r y l i c

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n

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i t

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s t e p s :

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a )


o f g l y c e r o l t o

g i v e

a n a c r o l e i n - r i c h

s t r e a m

c o n t a i n i n g p r o p a n a l ,

[ 0 1 0 2 ] b )

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o f p r o p a n a l

b y

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t h e

s a i d

s t r e a m

i n g a s p h a s e i n t h e

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oxygen h r o u g h

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c a t a l y s t

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l e a s t molybdenum a n d

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o n e

e l e m e n t

s e l e c t e d f r o m , S i ,

W , T i ,

Z r ,

V , N b ,

T a , C r ,

M n , F e ,

C o ,

N i ,

C u ,

Z n ,

G a , I n , T l ,

S n ,

A g , A s , G e ,

B ,

B i ,

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S b

T e , C e , P b ;

[ 0 1 0 3 ]

c ) o x i d a t i o n o f t h e a c r o l e i n t o g i v e a c r y l i c a c i d .

[ 0 1 0 4 ] The

r s t

s t e p a )

may

e c a r r i e d o u t i n t h e g a s p h a s e

o r i n t h e l i q u i d p h a s e, p r e f e r a b l y i n t h e g a s p h a s e . When h e

d e h y d r a t i o n 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

g a s

p h a s e ,

v a r i o u s

p r o c e s s t e c h n o lo g i e s may e u s e d , namely

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?xed

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o r s e v e r a l r e a c t o r s i n p a r a l l e l , a ?uid bed

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u s e

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[ 0 1 0 5 ] The e x p e r i m e n t a l c o n d i t i o n s

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g l y c e r o l , o r a

m i x t u r e o f

g l y c e r o l and W a t e r h a v i n g a W e i g h t r a t i o

Which

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0 . 1 t o

1 0 0 ,

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,

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g l y c e r o l and

W a t e r may e u s e d i n

l i q u i d f o r m o r i n g a s e o u s f o r m ,

p r e f e r a b l y

i n t h e g a s

p h a s e

f o r m .

[ 0 1 0 8 ] A c c o r d i n g t o o n e

embodiment

f t h e

i n v e n t i o n , i t i s

p o s s i b l e t o u s e > 95 u r e g l y c e r o l , t h a t i s t o

s a y

W i t h


8/13

US 2013/0324758

A 1

i n g a c r y l i c a c i d b y u s i n g f o r e x a m p l e a d i s t i l l a t i o n s t e p f o r

removing o W - and i

h - b o i l i n g p o i n t m a t e r i a l s

a n d /

r a

c r y s

t a l l i Z a t i o n s t e p f o r

p u r i f y i n g

a c r y l i c

a c i d b y

c r y s t a l l i Z i n g

i t .

[ 0 1 2 0 ]

The a c r y l i c

a c i d t h u s

o b t a i n e d can b e u s e d t o p r o

duce

f o r

example

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s a l t s

a s

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p o l y m e r s

o r W a t e r - a b s o r b e n t

r e s i n s ,

b y

knoWn e t h o d s .

[ 0 1 2 1 ]

A c c o r d i n g

t o o n e

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embodiment o f t h e

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i s

made of an n t e r m e d i a t e s t e p o f

p a r t i a l

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f o r

e x a m p l e

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a p p l i c a t i o n

WO 8 / 0 8 7 , 3 1 5 .

[ 0 1 2 2 ]

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t h e

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r e m o v i n g

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damage

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o x i d a t i o n

o f a c r o l e i n to

g i v e

a c r y l i c a c i d a n d t o a v o i d , d u r i n g t h e

s u b s e q u e n t s t a g e s ,

t h e

r e m o v a l

o f

l a r g e

amounts

o f

W a t e r ,

Which

c o u l d

W e l l

b e

e x p e n s i v e

a n d

r e s u l t i n l o s s e s o f c r y l i c

a c i d .

I n a d d i t i o n ,

i t

makes t

p o s s i b l e

t o remove

a

p o r t i o n

o f t h e h e a v y i m p u r i

t i e s f o r m e d

d u r i n g

t h e


t h e g l y c e r o l a n d

t o

f a c i l i t a t e

p u r i ? c a t i o n

o p e r a t i o n s .

[ 0 1 2 3 ]

T h i s

i n t e r m e d i a t e

s t e p i s c a r r i e d o u t

on

s e p a r a t i n g

u n i t

Which

s

a

c o n d e n s a t i o n

p l a n t

c o m p r i s i n g a n a b s o r p t i o n

column

coupled

or

not coupled

o an

e v a p o r a t o r ,

one or

more

h e a t e x c h a n g e r s , one

o r more

c o n d e n s e r s ,

a

d e p h l e g m a t o r ,

and any

i t e m

o f equipment

e l l

knoWn

o a

p e r s o n

s k i l l e d

i n

t h e a r t Which

makes t

p o s s i b l e

t o

c a r r y o u t a

p a r t i a l conden

s a t i o n

of

an

aqueous

s t r e a m .

[ 0 1 2 4 ]

I t i s c a r r i e d o u t u n d e r

c o n d i t i o n s

s u c h t h a t t h e


s t r e a m i s

s e p a r a t e d i n t o an a c r o l e i n - r i c h g a s

e o u s

p h a s e

a n d a n a c r o l e i n - p o o r

a q u e o u s p h a s e .

[ 0 1 2 5 ] From 2 0 to 95 , r e f e r a b l y f r o m 4 0 t o 90 , o f t h e

W a t e r

r e s e n t i n t h e s t r e a m s removed n t h e l i q u i d s t r e a m and

t h e a c r o l e i n - r i c h p h a s e g e n e r a l l y c o m p r i s e s more t h a n 8 0

a n d

p r e f e r a b l y more h a n

9 0 f h e a c r o l e i n n i t i a l l y

p r e s e n t

i n t h e s t r e a m T h i s r e s u l t i s g e n er a l l y o b t a i n e d b y l o W e r i n g t h e

t e m p e r a t u r e t o a t e m p e r a t u r e of

60 t o

1200

C .

[ 0 1 2 6 ] I n o n e em b o d i m e n t , t h e s t e p o f a r t i a l c o n d e n s a t i o n

o f

a t e r a n d o f t h e h e a v y


d e r i v e d f r o m t h e d e h y

d r a t i o n s t e p a )

i s

c a r r i e d o u t b e f o r e

o p e r a t i n g

t h e s t e p b ) o f

s e l e c t i v e e l i m i n a t i o n

o f

p r o p a n a l . I n

t h i s e m b o d i m e n t , i t

i s

p r e f e r r e d

t h a t t h e c a t a l y s t

f o r

p r o p a n a l e l i m i n a t i o n

a n d

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c a t a l y s t f o r t h e

o x i d a t i o n

o f a c r o l e i n

i n t o

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i n s t a l l e d i n

t h e same e a c t o r . G e n e r a l l y tWo s e p a r a t e r e a c t i o n

Z o n e s W i t h

tWo

s e p a r a t e c o o l i n g s y s t e m s a r e

used

f o r t h e 2

c a t a l y s t s .

I t

i s a l s o

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a r e

o p e r a t e d

i n

2

s e p a r a t e r e a c t o r s .

[ 0 1 2 7 ] I n

a n

a l t e r n a t i v e

f o r m , t h e

s t e p

o f

a r t i a l

c o n d e n s a

t i o n

o f W a t e r

a n d

o f t h e

h e a v y

b y - p r o d u c t s d e r i v e d f r o m t h e

d e h y d r a t i o n s t e p a ) i s c a r r i e d o u t f t e r o p e r a t i n g t h e s t e p b ) o f

s e l e c t i v e e l i m i n a t i o n o f

r o p a n a l .

I n h i s

e m b o d i m e n t ,

p r o p i

o n i c a c i d d e r i v e d f r o m t h e


r e a c t i o n and h e

p r o

p a n a l e l i m i n a t i o n r e a c t i o n may b e e a s i l y

r e m o v e d b y

t h e

p a r t i a l c o n d e n s a t i o n o f

W a t e r

from t h e


s t r e a m

b e f o r e t h e o x i d a t i o n s t a g e . As most

a r t

o f a c r y l i c a c i d i s

a l s o

removed by

t h e

p a r t i a l

c o n d e n s a t i o n o f W a t e r , r e a c t i o n c o n

d i t i o n s

a r e chosen o

l i m i t a s

f a r

a s

p o s s i b l e t h e conversion of

a c r o l e i n i n t h e

p r o p a n a l

e l i m i n a t i o n s t e p .

[ 0 1 2 8 ]

A c c o r d i n g

t o

t h e p r o c e s s o f t h e i n v e n t i o n ,

i t i s

p o s

s i b l e

t o o b t a i n a c r y l i c a c i d

h a v i n g

a

c o n t e n t o f r o p i o n i c

a c i d

l o W e r

t h a n

500 ppm.

D e c .

5 , 2 0 1 3

[ 0 1 2 9 ] NoW, t h e

p r e s e n t

i n v e n t i o n

W i l l

b e e x p l a i n e d

i n

much e t a i l W i t h r e f e r r i n g s e v e r a l e x a m p l e s , b u t

t h i s i n v e n

t i o n

s h o u l d

n o t b e l i m i t e d

t o

t h o s e d e s c r i b e d i n f o l l o W i n g

e x a m p l e s .

I n

t h e

f o l l o W i n g

E x a m p l e s a n d C o m p a r a t i v e

Examples,

eans mole .

EXAMPLES

P r e p a r a t i o n o f

a t a l y s t

E x a m p l e 1

CsPMo

[ 0 1 3 0 ] 1 0 0

g o f phosphomolybdic

a c i d

Was d i s s o l v e d i n

200

mL f e i o n i Z e d Water t o o b t a i n an aqueous

s o l u t i o n

of

pho p h o m o l y b d i c a c i d , and h e n Was mixed t room e m p e r a

t u r e f o r 2 h o u r s .

3 2 . 7

g of 8 . 5 Wt sOH queous

s o l u t i o n Was i l u t e d

With

20

mL

f d e i o n i Z e d W a t e r . The e s u l t i n g CsOH q u e o u s s o l u

t i o n Was d r o p p e d i n

t h e a b o v e a q u e o u s s o l u t i o n

o f phospho

molybdic c i d , and h e n Was mixed

t

room e m p e r a t u r e f o r 2

h o u r s .

The e s u l t i n g y e l l o W s l u r r y Was v a p o r a t e d t 6 0 0

C . by s e

o f

r o t a r y - e v a p o r a t o r .

The b t a i n e d poWder Was d r i e d a t 1 2 0 0 C . f o r 1 0

h o u r s .

The

o m p o s i t i o n o f

t h e

r e s u l t a n t d r i e d s l u r r y i s :

C S 2 . 5 P 1 . 0 M O 2

S u b s e q u e n t l y , t h e r e s u l t a n t p r o d u c t Was

a l c i n e d i n

i r a t 2 5 0

C . f o r 3 h o u r s .

E x a m p l e 2

CsPWMo

[ 0 1 3 1 ] 5 0 g o f h o s p h o t u n g s t o m o l y b d i c a c i d Was i s s o l v e d

i n 20

mL f e i o n i Z e d Water o o b t a i n an aqueous

s o l u t i o n

of

phosphotungstomolybdic a c i d ,

and t h e n Was mixed t room

t e m p e r a t u r e f o r

2

h o u r s .

1 3 . 4 g of

8 . 5 Wt sOH

queous

s o l u t i o n Was i l u t e d With

50 mL

f d e i o n i Z e d W a t e r . The e s u l t i n g

CsOH

q u e o u s s o l u

t i o n Was d r o p p e d i n t h e a b o v e

a q u e o u s s o l u t i o n

o f phospho

t u n g s t o m o l y b d i c a c i d , and h e n Was mixed t room

tempera

t u r e

f o r

2 h o u r s .

The

e s u l t i n g y e l l o W

s l u r r y Was v a p o r a t e d

t

6 0 0 C . by s e o f

r o t a r y - e v a p o r a t o r .

The

b t a i n e d

poWder Was

d r i e d

a t 1 2 0 0

C .

f o r 1 0

h o u r s .

The

o m p o s i t i o n o f

t h e

r e s u l t a n t

d r i e d s l u r r y

i s :

C S 2 . 5 P 1 . O W 6 M O 6

S u b s e q u e n t l y ,

t h e r e s u l t a n t p r o d u c t Was

a l c i n e d i n i r a t

2 5 0

C . f o r 3 h o u r s .

E x a m p l e 3

MoVPCuAs

[ 0 1 3 2 ]

1 0 0

g o f molybdenum r i o x i d e ,

6 . 3

g o f v a n a d i u m

p e n t o x i d e ,

1 . 1 g o f

c o p p e r

o x i d e

and

8 . 0 g o f 8 5 Wt r t h o

p h o s p h o r i c a c i d and 1 . 8 g of 60 Wt r s e n i c a c i d

Were

d i s p e r s e d

i n

1000 mL f d e i o n i Z e d W a t e r .

The

m i x t u r e

Was

r e ? u x e d

f o r

6

h o u r s W h i l e a d d i n g

h y d r o g e n

p e r o x i d e t o

y i e l d

a r e d d i s h - b r o W n , t r a n s p a r e n t s o l u t i o n . A f t e r a

l i t t l e

i n s o l u b l e


9/13

US 2013/0324758

A 1

compound Was removed

from h e

o b t a i n e d

s o l u t i o n , t h e s o l u

t i o n

t h u s formed

Was evaporated t o d r y n e s s

on a

Water

a t h .

The


o f t h e d r i e d p r o d u c t

i s :


t h e r e s u l t a n t p r o d u c t

Was a l c i n e d

under

? o W

of i r a t 310

C .

f o r 5 h o u r s .

E x a m p l e

4

MoVPCuAsSb

[ 0 1 3 3 ] 3 0 0

g o f molybdenum r i o x i d e , 1 1 . 3 7 g o f

a n a d i u m

p e n t o x i d e , 3 . 3 1 g o f c o p p e r o x i d e , 8 . 3 2 g o f c o p p e r

a c e t a t e ,

2 8 . 8 2 g

of85

Wt r t h o p h o s p h o r i c a c i d and 4 . 6 4 g o f 6 0 Wt

r s e n i c

a c i d

Were

i s p e r s e d i n 1900 mL

f

e i o n i Z e d W a t e r

and

h e a t e d a t re?ux

t

95 t o 1 0 0

C . f o r s i x

h o u r s

t o y i e l d a

r e d d i s h - b r o W n , t r a n s p a r e n t s o l u t i o n . S u b s e q u e n t l y , t o t h e

s o l u t i o n

Was

added

1 . 5 2

g o f

antimony r i o x i d e and h e r e s u l t

a n t s o l u t i o n Was

f u r t h e r

heated at

re?ux

at 95 t o

100

C .

f o r

t h r e e h o u r s .

T h e n ,

t h e r e s u l t a nt s l u r r y

Was h e a t e d

i n a

Water

b a t h t o be

e v a p o r a t e d

a n d

d r i e d .

The


o f t h e d r i e d p r o d u c t

i s :


t h e r e s u l t a n t p r o d u c t

Was a l c i n e d

under ? o W

of i r a t 310

C .

f o r 5 h o u r s .

E x a m p l e

5

MoVPCuSbCs

[ 0 1 3 4 ]

To

1200 mL f p u r i ? e d W a t e r

Were

added

200

g o f

molybdenum r i o x i d e , 8 . 8 4 g o f v a n a d i u m

p e n t a o x i d e

a n d

1 7 . 6 1

g o f

8 5 Wt r t h o p h o s p h o r i c

a c i d ,

and h e s o l u t i o n Was

h e a t e d a t re?ux

a t

90

t o

1 0 0

C . f o r ?ve

hours

t o

y i e l d a

r e d d i s h - b r o W n , t r a n s p a r e n t

s o l u t i o n .


t o

t h e s o l u t i o n Was added

6 . 0 7

g o f antimony

t r i o x i d e

and h e

r e s u l t a n t

s o l u t i o n

Was u r t h e r

h e a t e d a t

re?ux

a t 90

o

1 0 0 C . f o r

tWo

hours o o b t a i n an antimony r i o x i d e

d i s s o l v e d ,

h i g h l y

d a r k b l u e

s o l u t i o n .

T h e n ,

t h e r e s u l t i n g s o l u t i o n

Was

c o o l e d t o

from

1 5 to

2 0

C .

To t h e s o l u t i o n Were r a d u a l l y

added

s o l u t i o n of 3 . 3 3 g of

cesium

a c e t a t e d i s s o l v e d i n 150 mL f p u r i ? e d W a t e r and a

s o l u t i o n

o f 1 6 . 0 6

g

f

ammonium c e t a t e

d i s s o l v e d

i n 150

mL

o f u r i ? e d W a t e r

t

t h e

same

i m e

W i t h a g i t a t i o n .

T h e n , t o t h e

s l u r r y Was f u r t h e r

a d d e d a s o l u t i o n

p r e p a r e d

by d i s s o l v i n g

1 1 . 0 9

g o f c u p r i c

a c e t a t e m o n o h y d r a t e

i n

1 7 0

mL f

u r i ? e d

Water and h e r e s u l t a n t s o l u t i o n Was aged a t

1 5

t o

2 0 C .

f o r

o n e h o u r o y i e l d a g r e e n b l u e s l u r r y . T h e n , t h e r e s u l t a n t s lu r r y

Was heated i n

a Water

b a t h t o be

e v a p o r a t e d

and d r i e d .

The

c o m p o s i t i o n o f

t h e

r e s u l t a n t

d r i e d

s l u r r y

i s :

M 9 1 0 V 0 . 7 P 1 . 1 C u 0 . 4 S b 0 . 3 C S o . 5 ( N H 4 ) 1 . 5

S u b s e q u e n t l y , t h e

r e s u l t a n t

p r o d u c t Was a l c i n e d under ? o W

of i r a t 310 C .

f o r

5 h o u r s .

E v a l u a t i o n and e s u l t s

E x a m p l e 6

S e l e c t i v e E l i m i n a t i o n o f

P r o p a n a l i n

a n

A c r o l e i n

FloW

[ 0 1 3 5 ] A a m p l e

o f

CsPMo a t a l y s t f r o m e x a m p l e 1 Was

c o m p a c t e d a n d c r u s h e d a n d

s i e v e d t o o b t a i n p a r t i c l e

s i Z e

o f

D e c .

5 , 2 0 1 3

3 5 to 4 8 m e s h .

A t a i n l e s s s t e e l

t u b e

( i n t e r n a l

d i a m e t e r 1 3

mm) Was l o a d e d W i t h 2 . 0 ml o f c a t a l y s t t o

form

a ?xed

c a t a l y t i c

b e d .

An queous s o l u t i o n

of

c r o l e i n and r o p a n a l Was

f e d

t o

an

e v a p o r a t o r

t o g e t h e r

W i t h

n i t r o g e n

a n d

W i t h

o x y g e n

t

2 7 0

C .

i n

o r d e r

t o

form

f e e d g a s

Which Was a s s e d t h r o u g h t h e ?xed

c a t a l y t i c b e d t a t m o s p h e r i c

p r e s s u r e .

The x e d c a t a l y t i c b e d

W a s

heated

With an e l e c t r i c oven at a temperature of 270

C.

Feed

g a s

had a

f o l l o W i n g c o m p o s i t i o n

i n

mol

: a c r o l e i n :

p r o p a n a l : o x y g e n : n i t r o g e n : W a t e r : 6 . 0 : 0 . 0 6 0 : 3 . 8 : 1 4 : 7 6 . T o t a l

f e e d g a s ? o W Was 1 normal

i t e r

p e r h o u r . Gas

H o u r l y S p a c e

V e l o c i t y

(GHSV) Was

1 5 , 0 0 0 h _ l . GHSV s

t h e

r a t i o

o f

t h e

?oW

o f f e e d g a s ( e x p r e s s ed

i n

n o r m a l

l i t e r p e r

h o u r ) b y

t h e

volume o f

c a t a l y s t

( e x p r e s s e d i n l i t e r ) . F i x e d b e d

Was

o p e r

a t e d f o r

5

h o u r s W i t h o u t p r e s s u r e i n c r e a s e

i n

t h e r e a c t o r .

I n o r d e r

to

c h a r a c t e r i z e t h e


o f h e g a s ? o W

u t

t h e

r e a c t o r , p r o d u c t s Were

condensed

n a

c o n d e n s er c h a r g e d W i t h

d e m i n e r a l i Z e d W a t e r . L i q u i d a q u e o u s p h a s e a n d g a s e o u s

v e n t s

W e r e q u a n t i t a t i v e l y

a n a l y Z e d

b y

g a s

c h r o m a t o g r a p h s

( H P

6 8 9 0

A g i l e n t ,

FFAP

c o l u m n ,

FID

d e t e c t o r ,

CP4900

V a r i a n ,

S i l i c a p l o t

a n d

M o l e c u l a r

S i e v e

5 A ,

TCD

e t e c t o r s ) .

P r o p o r t i o n s

o f

p r o d u c t s

Were c o r r e c t e d i n f a c t o r s from t h e

r e s u l t s o f

t h e

g a s

c h r o m a t o g r a p h t o

d e t e r m i n e

a b s o l u t e

a m o u n t s o f p r o d u c t s .

The o n v e r s i o n

( ) o f

a t e r i a l

( a c r o l e i n

o r p r o p a n al ) ,

a n d

t h e

y i e l d o f o b j e c t i v e

s u b s t a n c e

( ) a n d t h e

r e l a t i v e

r a t e

o f

c o n

v e r s i o n a r e d e t e r m i n e d b y f o l l o W i n g e q u a t i o n s :

The c o n v e r s i o n ( ) o f m a t e r i a l : ( m o l e number f a t e

r i a l r e a c t e d / m o l e

number

f

a t e r i a l

s u p p l i e d ) > < 1 0 0

T h e y i e l d ( ) o f p r o p i o n i c a c i d : ( m o l e n u m b e r

o f p r o

p i o n i c

a c i d o b t a i n e d / m o l e

n u m b e r o f p r o p a n a l

s u p p l i e d ) > < 1 0 0

The e l a t i v e r a t e

o f

r o p a n a l

e l i m i n a t i o n : c o n v e r s i o n

o f p r o p a n a l / c o n v e r s i o n o f a c r o l e i n

R e s u l t s

a r e shoWn n

t a b l e

1 .

E x a m p l e 7

[ 0 1 3 6 ]

The

same e x p e r i m e n t a s i n example 6 Was r e p r o

d u c e d , W i t h a g a s

h o u r l y

s p a c e v e l o c i t y

o f

1 4 , 0 0 0 h ' 1 a n d

v a p o r i Z e r and oven t e m p e r a t u r e s

of 300

C .

Fixed

bed

Was

o p e r a t e d

f o r

5 h o u r s W i t h o u t

p r e s s u r e i n c r e a s e i n

t h e

r e a c t o r .

R e s u l t s

a r e shoWn n

t a b l e

1 .

E x a m p l e

8

[ 0 1 3 7 ] The same e x p e r i m e n t

a s i n example 6

Was r e p r o

d u c e d , W i t h a g a s h o u r l y s p a c e v e l o c i t y

o f

4 , 4 0 0 h - 1 a n d

v a p o r i Z e r and oven

t e m p e r a t u r e s

of 270 C . Fixed

bed

Was

o p e r a t e d

f o r



t h e

r e a c t o r .

R e s u l t s a r e shoWn n t a b l e 1 .

E x a m p l e 9


a s i n example 6

Was r e p r o

d u c e d , W i t h a

g a s h o u r l y s p a c e

v e l o c i t y

o f 4 , 4 0 0 h ' 1 a n d


10/13

US 2013/0324758

A 1

v a p o r i Z e r and oven


of 300 C . Fixed bed Was

o p e r a t e d

f o r



t h e

r e a c t o r .


E x a m p l e

1 0

[ 0 1 3 9 ] The

same e x p e r i m e n t

a s i n

example 6

Was r e p r o

d u c e d ,

W i t h CsPWMo a t a l y s t o f e x a m p l e

2

a n d

W i t h

a

g a s

h o u r l y s p a c e v e l o c i t y o f 5 , 5 0 0 h - 1 a n d v a p o r i s e r a n d o v e n

t e m p e r a t u r e s o f 2 5 0

C .

F i x e d bed Was o p e r a t e d f o r 5 h o u r s

W i t h o u t p r e s s u r e i n c r e a s e

i n t h e r e a c t o r .

R e s u l t s a r e shoWn

n

t a b l e 1 .

E x a m p l e

1 1

[ 0 1 4 0 ] The

same e x p e r i m e n t a s i n example 6 Was

r e p r o

d u c e d , W i t h M oVPCuAs

a t a l y s t o f e x a m p l e 3 and

i t h

a

g a s

h o u r l y s p a c e v e l o c i t y o f 5 , 0 0 0 h - 1 a n d v a p o r i s e r a n d o v e n

t e m p e r a t u r e s o f 3 5 0 C . F i x e d bed Was o p e r a t e d f o r 5

h o u r s

W i t h o u t p r e s s u r e i n c r e a s e i n t h e r e a c t o r .

R e s u l t s a r e

shoWn n

t a b l e

1 .

D e c .

5 , 2 0 1 3

TABLE

Example

1 2 1 3

1 4

C a t a l y s t MoVPCuAs

MoVPCuAsSb

MoVPCuSbCs

GHSV

' l

4 , 7 0 0 4 , 4 0 0 5 , 5 0 0

V a p o r i s e r and oven 385 345

250

t e m p e r a t u r e C . )

P r o p a n a l c o n v e r s i on

( ) 9 7 1 4 9 8

P r o p i o n i c

a c i d y i e l d

( ) 1 4 1 4

13

A c r o l e i n

c o n v e r s i o n

( ) 2 3 3 3 . 4


E x a m p l e 15

[ 0 1 4 4 ] The

same e x p e r i m e n t a s i n example 6

Was r e p r o

d u c e d , W i t h

FeMo a t a l y s t f r o m

M APCO,

e f e r e n c e MFM3

MS, a n d W i t h a g a s h o u r l y s p a c e v e l o c i t y

o f 1 0 , 0 0 0

h - 1

a n d

TABLE

Example 6 7 8 9

1 0

11

C a t a l y s t C sP M o C sP M o C sP M o C sP M o

CsPWMo MoVPCuAs

GHSV

1 5 1 1 5 , 0 0 0

1 4 , 0 0 0 4 , 4 0 0 4 , 4 0 0 5 , 5 0 0

5 , 0 0 0

V a p o r i s e r and oven 270 300 270 300 250 350


C . )

P r o p a n a l c o n v e r s i o n

( ) 9 0 8 2

9 9

1 0 0 9 2

6 5

P r o p i o n i c

a c i d y i e l d

( ) 1 0 1 2

1 1

9

13 15

A c r o l e i n

c o n v e r s i o n

( ) 11 2 5 28 6 5

5 3

1 3

Example

1 2 v a p o r i s e r

and oven t e m p e r a t u r e s o f 3 0 5

C .

F i x e d

bed Was

o p e r a t e d f o r 5

h o u r s W i t h o u t

p r e s s u r e

i n c r e a s e


[ 0 1 4 1 ] The same experiment

a s i n

example 6 Was r e p r o - R e s u l t s a r e shown n

t a b l e

3 ,

d u c e d , W i t h M oVPCuAs

a t a l y s t o f e x a m p l e 3 and

i t h

a g a s

h o u r l y s p a c e v e l o c i t y o f

4 , 7 0 0

h ' 1 a n d v a p o r i s e r a n d o v e n


C . F i x e d

bed

Was

o p e r a t e d

f o r

5 h o u r s




E x a m p l e 1 3

[ 0 1 4 2 ] The


a s i n

example 6 Was

r e p r o

d u c e d ,

W i t h

MoVPCuAsSb

a t a l y s t

o f

e x a m p l e

4

a n d

W i t h

a

g a s

h o u r l y s p a ce

v e l o c i t y o f

4 , 4 0 0



C .

F i x e d bed

Was

o p e r a t e d

f o r

5 h o u r s

W i t h o u t

p r e s s u r e

i n c r e a s e



E x a m p l e 14

[ 0 1 4 3 ] The


a s i n

example 6 Was

r e p r o

d u c e d , W i t h MoVPCuSbCs o f example 5 and

W i t h

a

g a s

h o u r l y s p a c e v e l o c i t y o f

5 , 5 0 0


t e m p e r a t u r e s o f 2 5 0 C . F i x e d bed Was o p e r a t e d f o r 5 h o u r s


i n

t h e

r e a c t o r .

R e s u l t s a r e shoWn

n

t a b l e

2 .

E x a m p l e

1 6

[ 0 1 4 5 ]

The


a s i n

example 1 5

Was

e p r o

d u c e d , W i t h a g a s

h o u r l y

s p a c e v e l o c i t y

o f 2 0 , 0 0 0

h ' 1 a n d

v a p o r i s e r

and

oven t e m p e r a t u r e s

of 330

C .

Fixed

bed

Was

o p e r a t e d

f o r



t h e

r e a c t o r .

R e s u l t s

a r e shoWn n

t a b l e

3 .

E x a m p l e

1 7

[ 0 1 4 6 ]

The

same

e x p e r i m e n t

a s i n

example

1 6

Was

e p r o

d u c e d , W i t h

a f e e d

g a s c o m p o s i t i o n i n

mol

: a c r o l e i n : p r o

p a n a l : o x y g e n : n i t r o g e n : W a t e r : 6 . 2 : 0 . 0 6 2 : 6 . 7 : 6 9 : 1 8 . I n

t h i s

experiment a

much

loWer


of Water

Was

used

compared o

e x a m p l e

1 6 . F i x e d bed Was

o p e r a t e d

f o r 5 h o u r s


i n t h e

r e a c t o r .


E x a m p l e 1 8


a s i n example 6

Was r e p r o

d u c e d ,

W i t h p r o p y l e n e o x i d a t i o n c a t a l y s t b a s e d

on

BiMoFe

t h a t Was r e p a r e d

a c c o r d i n g

t o e x a m p l e 1 o f E u r o p e a n

P a t e n t

EP

0 7 4 6 5 B 1 . Gas h o u r l y s p a c e

v e l o c i t y

Was 5 , 8 0 0 h - 1 a n d

v a p o r i s e r and oven


Were

s e t

t o

325

C .

Fixed


11/13

US 2013/0324758

A 1

bed Was p e r a t e d f o r 5 h o u r s W i t h o u t p r e s s u r e

i n c r e a s e

i n t h e

r e a c t o r .

R e s u l t s a r e

shown n

t a b l e

3 .

E x a m p l e

19

C o m p a r a t i v e

[ 0 1 4 8 ] The

same

e x p e r i m e n t a s i n

example 6

Was r e p r o

d u c e d W i t h T i O 2 c a t a l y s t

( S T 3 1 1 1 9

f r o m N o r p r o

s a i n t

G o b a i n ) . F i x e d

bed

Was p e r a t e d f o r

5

h o u r s W i t h o u t p r e s s u r e

i n c r e a s e i n

t h e

r e a c t o r .

The

same e x p e r i m e n t Was

a l s o

r e p r o d u c e d W i t h

a g a s h o u r l y

s p a c e

v e l o c i t y

o f 3 , 7 0 0 h ' 1 a n d v a p o r i s e r a n d o v e n t e m p e r a

t u r e s

of 300

C . F i x e d bed Was o p e r a t e d f o r

5

h o u r s W i t h o u t

p r e s s u r e i n c r e a s e i n t h e

r e a c t o r .

R e s u l t s

a r e shoWn n

t a b l e

3 .

We b s e r v e d

t h a t p r o p a n a l i s

n o t

s e l e c t i v e l y

e l i m i n a t e d a s

a c r o l e i n i s more c o n v e r t e d t h a n p r o p a n a l .

TABLE

Fxamnle

1 9

15 1 6 1 7

1 8 ( C o m p a r a t i v e )

C a t a l y s t

FeMo

BiMoFe

T i O 2

GHSV l

1 0 , 0 0 0

2 0 , 0 0 0 2 0 , 0 0 0

5 , 8 0 0

1 5 , 0 0 0 , 7 0 0

V a p o r i s e r and oven 305 330 330 325 270 300


C . )

P r o p a n a l c o n v e r s i o n

98

9 9

99 96


12/13

US 2013/0324758

A 1

TABLE - c o n t i n u e d

E x a m p l e

2 1 2 2 c o m p a r a t i v e )

A c e t a l d e h y d e y i e l d ( ) 2 . 3 1 . 6

H y d r o x y p r o p a n o n e

y i e l d

( )

0

0 . 2

P r o p a n a l / a c r o l e i n

m o l a r a t i o ( )

0 . 0 4 0 . 9 2

E x a m p l e

2 3

A c r y l i c

A c i d

P r o d u c t i o n f r o m G l y c e r o l W i t h

a

S t e p

o f S e l e c t i v e

E l i m i n a t i o n o f

P r o p a n a l

[ 0 1 5 2 ] A i m u l a t i o n u s i n g t h e ASPEN PLUS s o f t w a r e

Was used

o

i l l u s t r a t e t h e method

a c c o r d i n g

t o t h e i n v e n t i o n .

I n h i s

e x a m p l e ,

t means y e i g h t and ppmWt means

p a r t

p e r m i l l i o n b y W e i g h t .

We

entioned

n l y t h e

components

t

a c o n c e n t r a t i o n

above

1 t .

A

a s s t r e a m a t

3 2 0

C . under

2 . 8

b a r

( 8 2 . 5 t / h ,

20.8

Wt

g l y c e r o l , 51.7 Wt a t e r ,

21.8

Wt

a r b o n d i o x i d e , 5.3

Wt

oxygen) s s e n t t o a m u l t i t u b e ?xed bed e a c t o r c o n t a i n i n g a

h e t e r o g e n e o u s d e h y d r a t i o n

c a t a l y s t c o u p l e d W i t h a

m o l t e n

s a l t b a t h .

A a s

s t r e a m l e a v e s

t h i s r e a c t o r t 320 C . under 1 . 8

b a r

( 8 2 . 5

t / h ,

59.8 Wt W a t e r , 4.2 Wt

o x y g e n ,

10.2 Wt a c r o l e i n ,

22.4

Wt

C O 2 ) . T h i s

g a s

s t r e a m

c o n t a i n s 650 ppmWt

o f

p r o p a n a l .

T h i s

s t r e a m i s c o o l e d

t o

1 0 2

C . i n a

s e r i e s

o f h e a t

e x c h a n g e r s . A

i q u i d

p h a s e ( 2 6 . 7 t / h , 9 7

W t W a t e r ) i s

removed and t h e g a s

p h a s e i s

s e n t t o t h e

l o W e r

p a r t

o f

con

d e n s a t i o n c o l u m n , t h a t

c o m p r i s e s

a c o n d e n s e r a t i t s

t o p

to

g e n e r a t e

a

l i q u i d

r e ? u x

i n

t h e

c o l u m n . Another

g a s e o u s

How

i s

i n j e c t e d

a t

t h e

b o t t o m o f

t h e

c o l u m n

( 3 5 . 9

t / h ,

1 2 3

C . ,

76.3 Wt CO2,

16.5

Wt a t e r , 3.0 Wt CO, 1.9 Wt

2 ) .

The g a s

p h a s e

t h a t g o e s

o u t t h e

c o n d e n s e r ( 6 9 . 5 t / h , 7 4 C . ,

1 . 7 b a r , 65.9 Wt CO2, 12.1 Wt a c r o l e i n , 10.8 Wt a t e r ,

6.0 Wt 2 , 2.4 Wt

CO,

1.3 Wt c e t a l d e h y d e ,

770

ppmWt

p r o p a n a l )

i s h e a t e d to 2 4 0

C .

i n a

h e a t e x c h a n g e r .

T h i s s t r e a m

i s

s e n t

t o

t h e t o p of a m u l t i t u b u l a r ?xed bed

r e a c t o r

t h a t

c o m p r i s e s 2

s e c t i o n s Each

s e c t i o n

i s

c o u p l e d

With a s p e c i ? c

molten a l t b a t h .

The upper s e c t i o n

c o n t a i n s

a

c a t a l y s t f o r s e l e c t i v e e l i m i n a t i o n o f

r o p a n a l a n d t h e

s a l t b a t h

of h i s

s e c t i o n

i s

k e p t

a t 300 C .

The

o W e r s e c t i o n

c o n t a i n s a

c a t a l y s t f o r t h e

o x i d a t i o n o f

a c r o l e i n

t o

a c r y l i c a c i d a n d t h e

s a l t

b a t h

of h i s s e c t i o n

i s h e a t e d

t o 260 C .

A f t e r

t h e ? r s t s e c t i o n , t h e

g a s

?oW c o n t a i n s 66.6 Wt CO2,

11.8 Wt c r o l e i n , 11.0 t W a t e r , 5.4 Wt

2 , 2.4

Wt

CO,

1 . 3 W t a c e t a l d e h y d e , 1 2 0

ppmWt

r o p a n a l .

At h e

o u t l e t of h e

r e a c t o r ,

t h e

g a s s t r e a m c o n t a i n s 67.2 Wt

CO2, 14.4 Wt

a c r y

Documents

(2013) US20130324758 Process for Manufacturing Acrolein-Acrylic Acid