(2009) us7491841 process for producing acrylic ester

8/13/2019 (2009) US7491841 Process for Producing Acrylic Ester

http://slidepdf.com/reader/full/2009-us7491841-process-for-producing-acrylic-ester 1/12

1 2 ) United S t a t e s PatentHaramaki e t a 1 .

US007491841B2

US 7 , 4 9 1 , 8 4 1 B2F e b . 1 7 , 2 0 0 9

1 0 ) Patent N 0 . :

4 5 ) Date o f P a t e n t :

( 5 4 ) PROCESS FOR PRODUCINGACRYLIC

ESTER

7 5 ) I n v e n t o r s : H i d e f u m i H a r a m a k i , H i m e j i J P ) ;Manabu a t s u i , H i m e j i J P )

7 3 ) A s s i g n e e : N i p p o n S h o k u b a i C o . , L t d . , O s a k a J P )

* ) N o t i c e : S u b j e c t t o a n y d i s c l a i m e r , t h e t e r m o f h i sp a t e n t i s e x t e n d e d o r a d j u s t e d u n d e r 3 5

U . S . C . 1 5 4 ( b ) b y 1 2 d a y s .

2 1 ) A p p 1 . N o . : 1 1 / s 2 2 , 5 2 1

( 2 2 ) F i l e d : J u l . 6 , 2 0 0 7

( 6 5 ) P r i o r P u b l i c a t i o n Data

US 2008/0015384 A1 J a n . 1 7 , 2008

3 0 ) F o r e i g n A p p l i c a t i o n P r i o r i t y D a t a

J u l . 1 1 , 2006 (JP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2006-190889

( 5 1 ) I n t . C l .

C07C 6 7 / 4 8 ( 2 0 0 6 . 01 )

( 5 2) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 560/218

( 58 ) Field of Classi?cation Search . . . . . . . . . . . . . . . . . . . . . . . None

S e e a p p l i c a ti o n ? l e f o r c o m p l e t e s e a r c h h i s t o r y .

( 5 6 ) R e f e r e n c e s C i t e d

U . S . PATENT DOCUMENTS

3,882,167 5/1975 Lohmar t a 1 . . . . . . . . . . . . . . . 56 0 /2 0 5

4 , 2 8 0 , 0 0 9 A 7 / 1 9 8 1 E r p e n b a c h e t a l .

4,956,493 * 9 /1 9 9 0 Ueokaet 1 . . . . . . . . . . . . . . . . . 56 0 /2 0 8

6,649,787 B1* 11/2003 Nakahara e t a 1 . . . . . . . . . . . . . 560/205

6 , 9 7 7 , 3 1 0 B2 1 2 / 2 0 0 5 Ackermann t a 1 .

FOREIGN PATENT DOCUMENTS

JP 52-57116 5 / 1 9 7 7

JP 58-159442 9 / 1 9 8 3

JP 63-275544 1 1 / 1 9 8 8

JP 2-279655 1 1 / 1 9 9 0

JP 3-34956 2 / 1 9 9 1JP 3-52842 3 / 1 9 9 1

JP 3-52843 3 / 1 9 9 1

JP 3-151347 6 / 1 9 9 1

JP 2003-171347 6 / 2 0 0 3

JP 2003-226669 8 / 2 0 0 3

JP 2006-503795 2/2006

OTHER PUBLICATIONS

N o t i c e o f R e a s o n s f o r R e j e c t i o n i s su e d o n May 8 , 2 0 0 8 , i n J a p a n e s e

P a t e n t A p p l i c a t i o n N o . 2 0 0 6 - 1 9 0 8 8 9 , a n d E n g l i s h t r a n s l a t i o nt h e r e o f .

* c i t e d by examiner

P r i m a r y ExamineriPaul A u c k e r

7 4 ) A t t o r n e y , A g e n t , o r F i r m i W e n d e r o t h , L i n d & o n a c k ,

LLP.

5 7 ) ABSTRACT

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

an a l i p h a t i c o r a l i c y c l i c a l c o h o l h a v i n g from 5 t o 8 c a r b o n

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

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

an a c r y l i c e s t e r , a c r u d e a c r y l i c e s t e r Withdrawn from t h e

bottom o f a l o w - b o i l i n g s e p a r a t i o n column i s s u p p l i e d t o a

r e c t i f y i n g c o l u m n , a r e c t i ? e d a c r y l i c e s t er i s t a k e n o u t from

t h e t o p o f t h e r e c t i f y i n g c o l u m n , W h i l e a h i g h - b o i l i n g s u b

s t a n c e c o n t a i n i n g a n a c r y l i c e s t e r , Which s W i t h d r a w n from

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

b o i l i n g s e p a r a t i o n column a n d / o r a t h i n - ? l m e v a p o r a t o r t o

s e p a r a t e t i n t o a n a c r y l i c e s t er component and a h i g h - b o i l i n g

s u b s t a n c e , a n d t h e s e p a r a t e d a c r y l i c e s t e r c o m p o n e n t s t a k e no u t a s a d i s t i l l a t e and s u p p l i e d t o t h e l o w - b o i l i n g s e p a r a t i o n

column f o r i t s r e c o v e r y .

8 C l a i m s , 3 Drawing S h e e t s



US 7 , 4 9 1 , 8 4 1 B2

1

PROCESS FOR PRODUCING ACRYLIC

ESTER

BACKGROUND OFTHE INVENTION

1 . F i e l d o f t h e I n v e n t i o n

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 a p r o c e s s f o r producing an

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

an a c r y l i c e s t e r from a c r y l i c a c i d and an a l i p h a t i c o r a l i c y c l i c

a l c o h o l h a v i n g from 5 t o 8 c a r b o n a t o m s u s i n g a s t r o n g l y

a c i d i c c a t i o n e x c h a n g e r e s i n .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

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

o u s a l c o h o l s , f o r e x a m p l e , a s d i s c l o s e d i n J a p a n e s e P a t e n t

P u b l i c a t i o n N o . Shou 5 2 - 5 7 1 1 6 , by an e s t e r i ? c a t i o n r e a c t i o n

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

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

J a p a n e s e P a t e n t L a i d - o p e n P u b l i c a t i o n s N o s . H e i 2 - 2 7 9 6 5 5

and H e i 3 - 5 2 8 4 3 , by a n e s t e r i ? c a t i o n r e a c t i o n u s i n g a h e t e r o

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

r e s i n .

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

h e r e t o f o r e b e e n c a r r i e d o u t o p e r a t i o n s i n Which a c r y l i c a c i dand an a l c o h o l a r e e s t e r i ? e d i n a r e a c t o r using a c a t a l y s t such

a s an i n o r g a n i c a c i d , e . g . , s u l f u r i c a c i d o r p h o s p h o r i c a c i d , o r

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

l i q u i d i s s u p p l i e d o a l o W - b o i l i n g s e p a r a t i o n column o s e p a

r a t e i t i n t o a h i g h - b o i l i n g s u b s t a n c e composed m a i n l y o f a

g e n e r a t e d a c r y l i c e s t e r a n d a l o W - b o i l i n g component com

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

e r a t e d W a t e r , and an a c r y l i c e s t e r s c o l l e c t e d from h e f o r m e r

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

I n a p r o c e s s u s i n g an i n o r g a n i c a c i d such s s u l f u r i c a c i d o r

p h o s p h o r i c a c i d a s a n e s t e r i ? c a t i o n c a t a l y s t e . g . , s e e J a p a

n e s e P a t e n t L a i d - o p e n P u b l i c a t i o n N o . Shou 5 2 - 5 7 1 1 6 ) , t h e

u s e of h i g h l y c o r r o s i ve i n o r g a n i c a c i d h a s no o t h e r c h o i c e t o

s e l e c t an a n t i - c o r r o s i v e m a t e r i a l f o r a p p a r a t u s , Which c a u s e s

p r o b l e m s h a t t h e a p p a r a t u s b e c o m e s e x p e n s i v e a n d t h e W a s t el i q u i d t r e a t m e n t t o make a n i n o r g a n i c a c i d c o n t a i n e d i n t h e

W a s t e l i q u i d h a r m l e s s b e c o m e s h i g h l y c o s t l y .I n a n e s t e r i ? c a t i o n r e a c t i o n u s i n g a n i o n e x c h a n g e r e s i n ,

t h e r e i s no drawback t h a t W i l l be i n v o l v e d When an i n o r g a n i c

a c i d i s used a s an e s t e r i ? c a t i o n c a t a l y s t . As f o r a c r y l i c a c i d t o

be used a s a raW m a t e r i a l , a c r y l i c a c i d puri?ed t o remove

l o W - b o i l i n g i m p u r i t i e s a n d h i g h - b o i l i n g i m p u r i t i e s i s u s e d ,t h e p r o d u c t i o n c o s t o f a c r y l i c a c i d r i s e s d u e o t h e r e m o v a l o f

h i g h - b o i l i n g i m p u r i t i e s , a n d t h e r e f o r e , t h e u s e o f u n p u r i ? e d

a c r y l i c a c i d W o u l d become a d v a n t a g e o u s . H o W e v e r , Whena c r y l i c a c i d c o n t a i n i n g a h i g h - b o i l i n g a c i d c o m p o n e n t s u s e d

a s a raW m a t e r i a l , u n f a v o r a b l e p o l y m e r i Z a t i o n r e a c t i o n and

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

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

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

r a t e d . T h u s , i n J a p a n e s e P a t e n t L a i d - o p e n P u b l i c a t i o n N o .

2 0 0 3 - 1 7 1 3 4 7 , t h e r e i s p r o p o s e d a c o u n t e r m e a s u r e t h a t t h e

c o n c e n t r a t i o n o f i m p u r i t i e s s u c h a s m a l e i c a c i d , [ 3 - a c r y l o x

y p r o p i o n i c a c i d i . e . , a d i m e r o f a c r y l i c a c i d ) , f u r f u r a l , a n d

benZaldehyde i s r e s t r i c t e d t o a s p e c i ? c c o n c e n t r a t i o n o r

l o W e r .

Of h e s e h i g h - b o i l i n g i m p u r i t i e s , i n p a r t i c u l a r , h i g h - b o i li n g a c i d c o m p o n e n t s s u c h a s m a l e i c a c i d a n d [ 3 - a c r y l o x y p r o

p i o n i c a c i d c a n e a s i l y b e removed from W a s t e o i l i n t h e

p r o d u c t i o n o f a n e s t e r u s i n g a l o W - b o i l i n g a l c o h o l h a v i n g 4 o r

l e s s carbon atoms a s a raW m a t e r i a l , t h e r e b y c a u s i n g no p a r

t i c u l a r p r o b l e m . H o W e v e r , i n t h e p r o d u c t i o n o f a n e s t e r u s i n g


atoms a s a raW a t e r i a l , i t i s d i f ? c u l t t o s e p a r a t e h i g h - b o i l i n g

20

25

30

35

40

45

50

55

60

6 5

2

a c i d components, Which h a s r e m a r k a b l e i n ? u e n c e s on t h e

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

c o n s u m p t i o n o f t h e main r a W m a t e r i a l , a n d Which r e q u i r e s

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

I n p a r t i c u l a r , [ 3 - a c r y l o x y p r o p i o n i c a c i d i s g e n e r a t e d d u r i n g

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

t h e r e f o r e , t h e c o n t r o l o f t e m p e r a t u r e a n d t h e l i k e d u r i n g t h e

s t o r a g e a r e sometimes r e q u i r e d , Which makes t d i ? i c u l t t o

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

raW m a t e r i a l s i n t h e p r o d u c t i o n of an a c r y l i c e s t e r .

SUMMARY OFTHE INVENTION

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

W i t h e x c e l l e n t economic e f ? c i e n c y , Which c a n e l i m i n a t e t h e

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

loW u n i t c o n s u m p t i o n o f raW m a t e r i a l s , i n t h e p r o c e s s f o r

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

b o i l i n g a c i d c o m p o n e n t s s u c h a s m a l e i c a c i d a n d [ 3 - a c r y l o x

y p r o p i o n i c a c i d i n ? u e n c i n g t h e l o s s i n q u a l i t y a n d t h e u n i tc o n s u m p t i o n o f raW m a t e r i a l s , and a n a l i p h a t i c o r a l i c y c l i c

a l c o h o l having from t o 8 carbon atoms a s raW a t e r i a l s , andu s i n g a s tr o n g l y a c i d i c c a t i o n e x c h a n g e r e s i n a s a c a t a l y s t .

The p r e s e n t i n v e n t o r s have made v a r i o u s s t u d i e s , and a s a

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

p r e s e n t i n v e n t i o n : i n t h e p r o d u c t i o n o f a n a c r y l i c e s t er from

a c r y l i c a c i d a n d a n a l i p h a t i c o r a l i c y c l i c a l c o h o l h a v i n g f r o m

5 t o 8 c a r b o n a t o m s u s i n g a s t r o n g l y a c i d i c c a t i o n e x c h a n g e

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

W i t h o u t l o W e r i n g t h e q u a l i t y o f a p r o d u c t a n d t h e amount o f

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

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

a c r u d e a c r y l i c e s t e r i s r e c t i ? e d , t o a h i g h - b o i l i n g s e p a r at i o n

column a n d / o r a t h i n - ? l m e v a po r a t o r t o s e p a r a t e i t i n t o an

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

t a k i n g o u t t h e s e p a r a t e d a c r y l i c e s t e r component s a i s t i l l a t e

a n d s u p p l y i n g i t t o t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n f o r i t sr e c o v e r y ; and f u r t h e r , an a c r y l i c e s t er c a n b e produced t t h e

l o W e r u n i t c o n s u m p t i o n o f r a W m a t e r i a l s , W h i l e m a i n t a i n i n g

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

d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r a ti o n c o l u m n a n d / o r t h e

t h i n - ? l m e v a p o r a t o r With Water t o c a r r y o u t t h e e x t r a c t i o n

t r e a t m e n t o f h i g h - b o i l i n g a c i d c o m p o n e n t s . I n p a r t i c u l a r , t h e

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

r e d u c i n g t h e b u r d e n s on t h e p u r i ? c a t i o n o f raW m a t e r i a l

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

s i b l e t o e x p a n d t h e W i d t h o f h i g h - b o i l i n g a c i d c o m p o n e n t

c o n t e n t i n a c r y l i c a c i d Which a n be u s e d i n t h e p r o d u c t i o n o f

a n a c r y l i c e s t e r f r o m a c r y l i c a c i d i n ? u e n c e d m a r k e d l y b y

h i g h - b o i l i n g a c i d components s u c h a s m a l e i c a c i d and

[ 3 - a c r y l o x y p r o p i o n i c a c i d , a n d a n a l i p h a t i c o r a l i c y c l i c a l c o

h o l h a v i n g from 5 t o 8 c a r b o n a t o m s .

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

d u c i n g a n a c r y l i c e s t e r b y s u p p l y i n g a c r y l i c a c i d a n d a n

a l i p h a t i c o r a l i c y c l i c a l c o h o l h a v i n g from t o 8 c a r b o n a t o m s

t o an esteri?cation reactor t o cause an esteri?cation reaction

u s i n g a s tr o n g l y a c i d i c c a t i o n e x c h a n g e r e s i n a s a c a t a l y s t i n

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

r e a c t i o n p r o d u c t t o a l o W - b o i l i n g s e p a r a t i o n column o d i s t i l l

an a l c o h o l , a c r y l i c a c i d , and W a t e r from a t o p o f t h e loW

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

p h a s e a n d a n o r g a n i c p h a s e c o n t a i n i n g t h e a l c o h o l a n d c r y l i ca c i d , t h e o r g a n i c p h a s e b e i n g c i r c u l a t e d a s a c i r c u l a t e d l i q u i dt o t h e r e a c t o r , s u p p l y i n g a c r u d e a c r y l i c e s t e r , Which s W i t h

draWn from b o t t o m o f h e l o W - b o i l i n g s e p a r a ti o n c o l u m n , t o

a r e c t i f y i n g c o l u m n , t a k i n g o u t a r e c t i ? e d a c r y l i c e s t er from a



US 7 , 4 9 1 , 8 4 1 B2

3

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

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

from a bottom o f t h e r e c t i f y i n g c o l u m n , t o a h i g h - b o i l i n g

s e p a r a t i o n column a n d / o r a t h i n - ? l m e v a p o r a t o r t o s e p a r a t e t

i n t o a n a c r y l i c e s t e r component and a h i g h - b o i l i n g s u b s ta n c e ,

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

d i s t i l l a t e a n d s u p p l i e d t o t h e l o W - b o i l i n g s e p a r a t i o n c o l u m nf o r i t s r e c o v e r y .

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

d i s t i l l a t e t a k e n o u t f r o m t h e h i g h - b o i l i n g s e p a r a ti o n column

a n d / r t h e t h i n - ? l m e v a p o r a t o r i s s u p p l i e d t o t h e l o W - b o i l i n g

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

d i s t i l l a t e With Water o e x t r a c t and remove a h i g h - b o i l i n g a c i d

component c o n t a i n e d i n t h e d i s t i l l a t e i n t o a W a t e r p h a s e , and

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

r a t i o n column o r t s r e c o v e r y . F o r t h e e x t r a c t i o n and e m o v a l

o f t h e h i g h - b o i l i n g a c i d component, a p r o c e s s W a s t e W a t e r

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

a b l y b e u s e d . The p r o c e s s W a s t e W a t e r may i n c l u d e r e a c t i o n

W a t e r g e n e r a t e d i n t h e e s t e r i ? c a t i o n r e a c t i o n a n d / o r s t e a m

d r a i n e x h a u s t e d When a s t e a m e j e c t o r i s u s e d f o r r e d u c i n g

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

p r o d u c i n g an a c r y l i c e s t e r . The r a t i o o f W a t e r to be used t o

e x t r a c t and remove t h e h i g h - b o i l i n g a c i d c o m p o n e n t , r e l a t i v e

t o t h e d i s t i l l a t e t a k e n f r o m t h e h i g h - b o i l i n g s e p a r a t i o n c o l

umn a n d / o r t h e t h i n - ? l m e v a p o r a t o r , may p r e f e r a b l y be

W i t h i n a r a n g e of from 0 . 5 : 1 t o 2 0 1 1 , more p r e f e r a b l y from

081 o 1 . 5 1 1 , by mass a t i o .

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

t h e p r e s e n t i n v e n t i o n , t h e a c r y l i c a c i d t o be used a s a raW

m a t e r i a l i s a c r y l i c a c i d c o n t a i n i ng h i g h - b o il i n g a c i d compo

n e n t s s u c h a s m a l e i c a c i d and [ 3 - a c r y l o x y p r o p i o n i c a c i d , f o r

e x a m p l e , a c r y l i c a c i d c o n t a i n i n g f r o m 1 0 t o 5 , 0 0 0 ppm o f

m a l e i c a c i d a n d / o r f r o m 1 0 t o 5 , 0 0 0 ppm o f [ 3 - a c r y l o x y p r o

p i o n i c a c i d , p r e f e r a b l y a c r y l i c a c i d c o n t a i n i n g f r o m 1 0 o 5 0 0

p p m o f m a l e i c a c i d a n d / o r from 1 0 t o 3 , 6 0 0 p p m o f [ 3 - a c r y

l o x y p r o p i o n i c a c i d .

A c c o r d i n g o t h e p r e s e n t i n v e n t i o n , i n t h e p r o d u c t i o n o f a n

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

a l c o h o l having from 5 t o 8 carbon atoms a s raW a t e r i a l s and

u s i n g a s t r on g l y a c i d i c c a t i o n e x c h a n g e r e s i n a s a c a t a l y s t , t h e

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

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

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

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

a l s . I n t h e e x t r a c t i o n t r e a t m e n t o f h i g h - b o i l i n g a c i d compo

n e n t s , p r o c e s s W a s t e W a t e r g e n e r a t e d i n a s t e p o f r o d u c i n g an

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

a s e x t r a c t i o n W a t e r , and t h e r e f o r e , t h e r e i s no need t o i n t r od u c e f r e s h W a t e r , from h e o u t s i d e o f h e s y s t e m , l e a d i n g t o an

i n c r e a s e i n t h e amount o f a s t e W a t e r . F u r t h e r , t h e a p p l i c a t i o n

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

makes t p o s s i b l e t o s e p a r a t e a n d r e m o v e , by a n i n e x p e n s i v e

m e t h o d , h i g h - b o i l i n g a c i d c o m p o n e n t s d i f ? c u l t t o b e s e p a

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

g r e a t amounts of h i g h - b o i l i n g a c i d components, a s W e l l a s

makes t e a s y t o c a r r y o u t t h e s t o r a g e management o f a c r y l i c

a c i d a s a raW m a t e r i a l , t h e r e b y making t p o s s i b l e t o broaden

t h e a c c e p t e d r a n g e o f raW m a t e r i a l a c r y l i c a c i d Which can be

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


atoms.

20

25

30

35

40

45

50

60

6 5

4

For t h e s e r e a s o n s , t h e p r e s e n t i n v e n t i o n can p r o v i d e a p r o

c e s s f o r producing an a c r y l i c e s t er With v e r y e x c e l l e n t eco

n o m i c e f ? c i e n c y .

BRIEF DESCRIPTION OFTHE DRAWINGS

F I G . 1 i s a s c h e m a t i c d i a g r a m s h o W i n g one example o f t h e

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

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

t i o n p r o c e s s u s e d i n E x a m p l e s 1 , 2 , a n d 5 .

F I G . 2 i s a s c h e m a t i c d i a g r a m s h o W i n g a n o t h e r e x a m p l e o f

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

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

t i o n p r o c e s s u s e d i n E x a m p l e s 3 , 4 , a n d 6 .

F I G . 3 i s a s c h e m a t i c d i a g r a m s h o W i n g t h e p r o d u c t i o n

p r o c e s s u s e d i n C o m p a r a t i v e E x a m p l e s 1 , 2 , a n d 3 .

DETAILED DESCRIPTION OFTHE INVENTION

The r o c e s s f o r p r o d u c i n g a n a c r y l i c e s t e r 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 ( h e r e i n a f t e r r e f e r r e d t o s i m p l y as “ t h e p r o

d u c t i o n 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 ” i n some c a s e s ) i s a

p r o c e s s f o r p r o d u c i n g a n a c r y l i c e s t e r b y s u p p l y i n g a c r y l i ca c i d and an a l i p h a t i c o r a l i c y c l i c a l c o h o l h a v i n g from 5 t o 8

carbon atoms t o an esteri?cation reactor t o cause an e s t e r i ?

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

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

an o b t a i n e d r e a c t i o n p r o d u c t t o a l o W - b o i l i n g s e p a r a t i o n c o l

umn o d i s t i l l an a l c o h o l , a c r y l i c a c i d , and W a t e r from t h e t o p

o f t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n , a n d s e p a r a t i n g t h e m

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

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

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

e s t e r , Which s W i t h d r a W n from h e b o t t o m o f t h e l o W - b o i l i n g

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

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

s u p p l y i n g a h i g h - b o i l i n g s u b s t a n c e c o n t a i n i n g a n a c r y l i c

e s t e r , Which s W i t h d r a W n fromt h e

b o t t o m o ft h e

r e c t i f y i n gc o l u m n , to a h i g h - b o i l i n g s e p a r a t i o n column a n d / o r a t h i n

?lm e v a p o r a t o r t o s e p a r a t e t i n t o a n a c r y l i c e s t er component

a n d a h i g h - b o i l i n g s u b s t a n c e , t h e s e p a r a t e d a c r y l i c e s t e r com

p o n e n t b e i n g t a k e n o u t a s a d i s t i l l a t e and s u p p l i e d t o t h e

l o W - b o i l i n g s e p a r a t i o n c o l u m n f o r i t s r e c o v e r y .

I n h i s c a s e , a l l o r p a r t o f h e d i s t i l l a t e from h e h i g h - b o i l i n g

s e p a r a t i o n column a n d / r t h e t h i n - ? l m e v a p o r a t o r may p r e f

e r a b l y be mixed With Water t o e x t r a c t and remove a high

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

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

b o i l i n g s e p a r at i o n c o l u m n f o r i t s r e c o v e r y .

I n t h e p r o d u c t i o n 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 , a c r y l i ca c i d c o n t a i n i n g h i g h - b o i l i n g a c i d c o m p o n e n t s s u c h a s m a l e i c

a c i d a n d [ 3 - a c r y l o x y p r o p i o n i c a c i d , e v e n i f i t i s , f o r e x a m p l e ,

a c r y l i c a c i d c o n t a i n i n g f r o m 1 0 t o 5 , 0 0 0 ppm o f m a l e i c a c i d

a n d / o r f r o m 1 0 t o 5 , 0 0 0 p pm o f [ 3 - a c r y l o x y p r o p i o n i c a c i d ,a n d e v e n i f i t may r e f e r a b l y b e a c r y l i c a c i d c o n t a i n i n g f r o m

1 0 t o 500 ppm of a l e i c a c i d and from 1 0 t o 3 , 6 0 0 ppm of

[ 3 - a c r y l o x y p r o p i o n i c a c i d a s shoWn i n Examples d e s c r i b e d

b e l o W , can be used a s a raW m a t e r i a l . I n c i d e n t a l l y , high

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

a n a l y Z e d b y , f o r e x a m p l e , g a s c h r o m a t o g r a p h y .

As a n a l i p h a t i c o r a l i c y c l i c a l c o h o l h a v i n g from 5 t o 8

c a r b o n a t o m s ( h e r e i n a f t e r r e f e r r e d to s i m p l y a s “ t h e a l c o h o l ”

i n some a s e s ) , t h e r e c a n b e m e n t i o n e d , a l t h o u g h n o t p a r t i c u

l a r l y l i m i t e d t h e r e t o , s o l o n g a s an a c r y l i c e s t e r can be formed

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

2 - e t h y l h e x a n o l a n d c y c l o h e x a n o l . Such a n a l c o h o l may b e

l i n e a r o r b r a n c h e d . F u r t h e r , an u n r e a c t e d a l c o h o l r e c o v e r e d



US 7 , 4 9 1 , 8 4 1 B2

5

f r o m t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n a f t e r t h e e s t e r i ? c a

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

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

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

e s t e r i ? c a t i o n r e a c t i o n . I n t h e c a s e of s t r o n g l y a c i d i c c a t i o n

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

p o r o u s t y p e r e s i n may r e f e r a b l y b e u s e d . I n a r t i c u l a r , When

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

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

b e u s e d . As a p o r o u s t y p e s t r o n g l y a c i d i c c a t i o n e x c h a n g e

r e s i n , f o r e x a m p l e , t h e r e may r e f e r a b l y b e u s e d t h o s e W h i c h

h a v e a d e g r e e o f c r o s s - l i n k i n g o f from 2 o 16 , a p o r o s i t y

of from . 1 t o 1 . 0 m L / , and an v e r a g e pore d i a m e t e r of from

1 0 t o 6 0 nm, s p e c i ? c e x a m p l e s o f Which r e C-26C a v a i l a b l e

f r o m D u o l i t e I n t e r n a t i o n a l C o . ) , P K - 2 0 8 , P K - 2 1 6 , PK-228

a v a i l a b l e f r o m M i t s u b i s h i C h e m i c a l C o r p o r a t i o n ) , M S C - l ,

8 8 a v a i l a b l e f r o m The D o W C h e m i c a l C o m p a n y ) ,

A m b e r l y s t - 1 6 a v a i l a b l e f r o m Rohm a n d H a as C o m p a n y ) ,

S P C - 1 0 8 , a n d S P C - 1 1 2 a v a i l a b l e f r o m B a y e r A G ) .The e s t e r i ? c 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 by o n i t o r i n g t h e

c o n v e r s i on o f a c r y l i c a c i d t h r o u g h a n a l y Z i n g t h e c o m p o s i

t i o n s o f an n l e t l i q u i d and a n o u t l e t l i q u i d i n t h e r e a c t o r , and

a d j u s t i n g t h e r e a c t i on t e m p e r a t u r e s o t h a t t h e c o n v e r s i o n o fa c r y l i c a c i d becomes s u b s t a n t i a l l y c o n s t a n t . The c o n v e r s i o n

o f a c r y l i c a c i d may r e f e r a b l y b e W i t h i n a r a n g e o f from —5

to +5 , more p r e f e r a b l y from —3 o +3 , based on t h e

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

s t a r t o f o p e r a t i o n .

The e s t e r i ? c a t i o n r e a c t i o n may p r e f e r a b l y b e c a r r i e d o u t

W i t h i n a r a n g e of from 5 0 ° C . to 1 0 0 0 C . , more p r e f e r a b l y

from 7 0 0 C . t o 1 0 0 0 C . , a l t h o u g h d e p e n d i n g on t h e i n t e n d e d

e s t e r i ? c a t i o n r e a c t i o n . F u r t h e r , t h e e s t e r i ? c 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 a l i q u i d p h a s e , and t h e t y p e o f r e a c t i o n may e

on a ?uid or ?xed ed.

I n t h e e s t e r i ? c a t i o n r e a c t i o n , a p o l y m e r i Z a t i o n i n h i b i t o r

c a n be used a s a p p l i e d i n o r d i n a r y c a s e s . Examples o f t h e

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

o x y h y d r o q u i n o n e , p h e n o t h i a Z i n e , h y d r o x y l a m i n e , a n d p h en y l e n e d i a m i n e . I n c i d e n t a l l y , t h e e f f e c t o f a p o l y m e r i Z a t i o n

i n h i b i t o r can f u r t h e r be enhanced When t h e e s t e r i ? c 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 p r e s e n c e of o l e c u l a r o x y g e n .

The t h u s o b t a i n e d e s t e r i ? c a t i o n r e a c t i o n p r o d u c t i s s u p

p l i e d t o a l o W - b o i l i n g column o r t s d i s t i l l a t i o n , and s u b s t a n

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

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

b o t t o m o f t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n a n d s u p p l i e d t oa r e c t i f y i n g column f o r i t s d i s t i l l a t i o n , t h e r e b y o b t a i n i ng a

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

f y i n g c o l u m n .

O n h e o t h e r h a n d , f r o m t h e t o p o f t h e l o W - b o i l i n g s e p a r a

t i o n c o l u m n , l o W - b o i l i n g c o m p o n e n t s c o m p o s e d m a i n l y o f a n

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

Water a r e d i s t i l l e d and condensed t o s e p a r a t e them i n t o a

W a t e r p h a s e a n d a n o r g a n i c p h a s e composed m a i n l y o f a n

a l c o h o l a n d a c r y l i c a c i d . The o r g a n i c p h a s e i s c i r c u l a t e d a s a

c i r c u l a t e d l i q u i d t o t h e r e a c t o r . On h e o t h e r h a n d , t h e W a t e r

phase may e d i s c a r d e d a s WasteWater o r may e r e c y c l e d a s

process W a s t e W a t e r .

T o a l l o W t h e e s t e r i ? c a t i o n r e a c t i o n t o p r o c e e d s m o o t h l y , i t

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

W a t e r and o i n c r e a s e t h e amounts o f a l c o h o l and a c r y l i c a c i d

i n t h e c o m p o s i t i o n o f a c i r c u l a t e d l i q u i d . T h e r e f o r e , a s f o r t h e

c i r c u l a t e d l i q u i d , a l t h o u g h d e p e n d i n g o n t h e i n t e n d e d a c r y l i ce s t e r and e a c t i o n c o n d i t i o n s , t h e t o t a l amount o f a l c o h o l and

a c r y l i c a c i d may r e f e r a b l y b e 5 0 by mass o r h i g h e r , more

p r e f e r a b l y 60 by mass o r h i g h e r , and t h e c o n c e n t r a t i o n o f

W a t e r may p r e f e r a b l y b e 5 by mass o r l o W e r , more p r e f e r

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6

a b l y 2 y mass o r l o W e r . F u r t h e r , t h e amount o f c i r c u l a t e d

l i q u i d t o be c i r c u l a t e d t o t h e r e a c t o r i s n o t p r e f e r r e d When t i s

t o o high o r t o o loW because of an i n c r e a s e i n t h e amount of

c a t a l y s t n e c e s s a r y f o r t h e e s t e r i ? c a t i o n r e a c t i o n . The a mount

o f i r c u l a t e d l i q u i d may s u i t a b l y b e from t o 5 t i m e s t h e t o t a l

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

A o l y m e r i z a t i o n i n h i b i t o r c a n a l s o b e used i n t h e loWb o i l i n g s e p a r a t i o n c o l u m n . E x a m p l e s o f h e p o l y m e r i z a t i o n

i n h i b i t o r may i n c l u d e t h e same a s exempli?ed r e g a r d i n g t h e

e s t e r i ? c a t i o n r e a c t i o n . In the same manner a s described

a b o v e , t h e e f f e c t o f a p o l y m e r i Z a t i o n i n h i b i t o r can be

e n h a n c e d When t h e o p e r a t i o n o f t h e l o W - b o i l i n g s e p a r a t i on

column 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 o l e c u l a r o x y g e n .

A i g h - b o i l i n g s u b s t a n c e c o n t a i n i n g a n a c r y l i c e s t e r i s

W i t h d r a W n from t h e b o t t o m o f t h e r e c t i f y i n g column a n d

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

e s t e r component s r e c o v e r e d f r o m t h e t o p o f t h e h i g h - b o i l i n g

s e p a r a t i o n c o l u m n . T h e h i g h - b o i l i n g s u b s t a n c e W i t h d r a W n

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

be d i s c h a r g e d a s Waste i l , o r may be f u r t h e r i n t r o d u c e d i n t o

a thin-?lm e v a p o r a t o r t o r e c o v e r an a c r y l i c e s t e r , a f t e r Which

i t may be d i s c h a r g e d a s Waste o i l . On h e o t h e r h a n d , an

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

column a n d / r t h e t h i n - ? l m e v a p o r a t o r i s s u p p l i e d t o t h e


A l l o r p a r t o f t h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r a ti o n

column a n d / r t h e t h i n - ? l m e v a p o r a t o r s mixed i t h Water o

e x t r a c t and remove h i g h - b o i l i n g a c i d components such a s

m a l e i c a c i d a n d [ 3 - a c r y l o x y p r o p i o n i c a c i d c o n t a i n e d t o g e t h e r

W i t h an c r y l i c e s t er i n t h e i s t i l l a t e i n t o a W a t e r p h a s e , and h e

o r g a n i c p h a s e i s s u p p l i e d t o t h e l o W - b o i l i n g s e p a r a t i o n c o lumn o r e c o v e r t h e a c r y l i c e s t e r . At t h i s t i m e , t h e d i s t i l l a t e

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

W i t h o u t a n y t r e a t m e n t t o t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n ,

and l l o r p a r t o f t h e d i s t i l l a t e from t h e t h i n - ? l m e v a p o r a t o r

may e mixed With Water o c a r r y o u t an e x t r a c t i o n t r e a t m e n t .

I n t h i s W a y , t h e e x t r a c t i o n t r e a t m e n t o f h i g h - b o i l i n g a c i d

components can reduce t h e amount of Waste o i l W i t h o u t

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

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

r a n g e o f raW m a t e r i a l a c r y l i c a c i d . I n t h i s c a s e , l o W - p u r i t y

a c r y l i c a c i d c o n t a i n i n g r e l a t i v e l y g r e a t a m o u n t s o f i g h - b o i li n g a c i d c o m p o n e n t s , f o r e x a m p l e , e v e n a c r y l i c a c i d c o n t a i n

i n g from 1 0 t o 5 , 0 0 0 p p m o f m a l e i c a c i d a n d / o r from 1 0 t o

5 , 0 0 0 ppm f 3 - a c r y l o x y p r o p i o n i c a c i d , can be used a s a raW

m a t e r i a l , a n d a s shoWn i n t h e f o l l o W i n g E x a m p l e s , a c r y l i ca c i d c o n t a i n i n g from 1 0 t o 500 p pm o f m a l e i c a c i d and from

1 0 t o 3 , 6 0 0 ppm o f [ 3 - a c r y l o x y p r o p i o n i c a c i d c a n p r e f e r a b l y

b e used a s a raW material.

I n c i d e n t a l l y , a s Water t o be mixed With a l l o r p a r t of t h e

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

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

p r o c e s s W a s t e W a t e r may i n c l u d e r e a c t i o n W a t e r g e n e r a t e d i n

t h e e s t e r i ? c a t i o n r e a c t i o n and s t e a m d r a i n e x h a u s t e d i n t h e

c a s e of using a steam e j e c t o r t o reduce p r e s s u r e i n a p r e s s u r e

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

I n t h i s Way, t h e c o s t f o r WasteWater t r e a t m e n t i s n o t i n c r e a s e d

because of no i n c r e a s e i n t h e amount of a s t e W a t e r by mak

i n g u s e o f W a s t e W at e r d i s c h a r g e d from a s t e p o f p r od u c i n g a n

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

s y s t e m .

F u r t h e r , t h e r a t i o of ater to be used o e x t r a c t and remove

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

f r o m t h e h i g h - b o i l i n g s e p a r a ti o n column a n d / o r t h e t h i n - ? l m

e v a p o r a t o r may p r e f e r a b l y b e W i t h i n a r a n g e o f from 0 . 5 t o

2 . 0 , more p r e f e r a b l y from 0 . 8 t o 1 . 5 , by mass a t i o .



US 7 , 4 9 1 , 8 4 1 B2

7

The p r o d u c t i o n 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 W i l l b e

d e s c r i b e d below i n more e t a i l by e f e r e n c e t o FIGS. 1 and .

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

s u p p l y i n g a h i g h - b o i l i n g s u b s t a n c e c o n t a i n i n g a n a c r y l i ce s t e r , Which i s WithdraWn from t h e bottom o f a r e c t i f y i n g

c o l u m n , to a h i g h - b o i l i n g s e p a r a t i o n column a n d / o r a t h i n

?lm e v a p o r a t o r t o s e p a r a t e t i n t o a n a c r y l i c e s t er component

a n d a h i g h - b o i l i n g s u b s t a n c e , t h e s e p a r a t e d a c r y l i c e s t e r com

ponent being t a k e n o u t a s a d i s t i l l a t e and s u p p l i e d t o a loW

b o i l i n g s e p a r a t i o n column o r i t s r e c o v e r y . At h i s t i m e , a l l o r

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

a n d / r t h e thin-?lm e v a p o r a t o r i s mixed With Water o e x t r a c t

and remove h i g h - b o i l i n g i m p u r i t i e s i n t h e d i s t i l l a t e i n t o a

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

l o W - b o i l i n g s e p a r a t i o n c o l u m n o r i t s r e c o v e r y . T h e r e f o r e , t h e

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

t h e p r o d u c t i o n p r o c e s s e s shoWn n FIGS. 1 and , and c a n be

c a r r i e d o u t b y a d d i n g a p p r o p r i a t e m o d i ? c a t i o n s a n d / o r

c h a n g e s t o t h e s e p r o d u c t i o n p r o c e s s e s u n l e s s s u c h modi?ca

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

i n v e n t i o n .

F I G . 1 i s a s c h e m a t i c d i a g r a m s h o W i n g one example o f t h e

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

a c t e r i Z e d i n t h a t h i g h - b o i l i n g a c i d components a r e d e c r e a s e d

from t h e bottom l i q u i d o f a r e c t i f y i n g column 6 0 0 u s i n g a

h i g h - b o i l i n g s e p a r at i o n column 7 0 0 a n d a t h i n - ? l m e v a p o r a

t o r 800 i n a p o r t i o n d e s i g n a t e d a s “ A ” , and t h e n a l l o r p a r t of

t h e d i s t i l l a t e c o n t a i n i n g an a c r y l i c e s t e r s e p a r a t e d and r e c o v

e r e d i s c i r c u l a t e d t o a l o W - b o i l i n g s e p a r a t i on column 5 0 0 .

A c r y l i c a c i d i s s u p p l i e d t h r o u g h a l i n e 1 t o a n e s t e r i ? c a t i o n

r e a c t o r 1 0 0 ? l l e d W i t h a s t r o n g l y a c i d i c c a t i o n e x c h a n g e e s i n .An l c o h o l i s a l s o s u p p l i e d t h r o u g h a l i n e 2 and a d i s t i l l a t i o n

column 200 t o t h e r e a c t o r 1 0 0 . An l c o h o l and r e a c t i o n Water

a r e d i s t i l l e d o u t and i n t r o d u c e d through a l i n e 4 i n t o t h e

d e c a n t e r 3 0 0 . I n t h e d e c a n t e r 3 0 0 , a W a t e r phase and an

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

T h e n , p a r t o f t h e o r g a n i c p h a s e i s s u p p l i e d t h r o u g h a l i n e 5 t ot h e e s t e r i ? c a t i o n r e a c t o r 1 0 0 , a n d t h e r e s i d u e o f t h e o r g a n i c

phase i s s e n t through a l i n e 6 a s Waste o i l t o a W a s t e - o i l

t r e a t m e n t s t e p . O n t h e o t h e r h a n d , t h e W a t e r p h a s e i s s t o r e d

through a l i n e 7 i n a p r o c e s s WasteWater t a n k 4 0 0 , and s e n t

through a l i n e 8 a s WasteWater t o an a l c o h o l recovery s t e p or

a WasteWater treatment s t e p .

An e s t e r i ? c a t i o n p r o d u c t c o n t a i n i n g a g e n e r a t e d e s t e r ,

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

W a t e r i s s u p p l i e d t h r o u g h a l i n e 9 from t h e r e a c t o r 100 t o t h e

l o W - b o i l i n g s e p a r a t i o n column 5 0 0 f o r i t s d i s t i l l a t i o n . The

b o t t o m l i q u i d o f t h e l o W - b o i l i n g s e p a r a t i o n column 0 0 c o n

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

p l i e d t h r o u g h a l i n e 1 0 t o t h e r e c t i f y i n g column 6 0 0 . The t o p

l i q u i d o f t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n 5 0 0 c o n t a i n s

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

W a t e r , and d i s c h a r g e d t h r o u g h a l i n e 1 1 t o s e p a r a t e i n t o a

W a t e r p h a s e a n d a n o r g a n i c p h a s e c o m p o s e d m a i n l y o f c r y l i ca c i d a n d a n a l c o h o l . T h e n , p a r t o f t h e o r g a n i c p h a s e i s c i r c u

l a t e d a s a c i r c u l a t e d l i q u i d through a l i n e 12 to t h e e s t e r i ? c a

t i o n r e a c t o r 1 0 0 , a n d t h e r e s i d u e o f t h e o r g a n i c p h a s e i s

c i r c u l a t e d a s re?ux t h r o u g h a l i n e 1 3 t o t h e l o W - b o i l i n g s e p a

r a t i o n column 0 0 . O n h e o t h e r h a n d , t h e W a t e r p h a s e i s s e n t

through a l i n e n o t shoWn i n t h e ?gure a s WasteWater t o an

a l c o h o l recovery s t e p o r a WasteWater t r e a t m e n t s t e p .

T h e a c r y l i c e s t e r s u p p l i e d t o t h e r e c t i f y i n g c o l u m n 6 0 0 ,

a f t e r r e c t i ? e d , i s d i s c h a r g e d f r o m t h e t o p o f t h e r e c t i f y i n gcolumn 600 t h r o u g h a l i n e 1 4 ; p a r t t h e r e o f becomes a ? n i s h e d

p r o d u c t t h r o u g h a l i n e 1 5 , and h e r e s i d u a l p a r t s c i r c u l a t e d a s

re?ux t h r o u g h a l i n e 1 6 t o t h e r e c t i f y i n g column 6 0 0 . The

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35

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45

50

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60

6 5

8

b o t t o m l i q u i d o f t h e r e c t i f y i n g column s a h i g h - b o i l i n g s u b

s t an c e c o n t a i n i n g h i g h - b o i l i n g a c i d c o m p o n e n t s s u c h a s

m a l e i c a c i d a n d [ 3 - a c r y l o x y p r o p i o n i c a c i d t o g e t h e r W i t h a

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

1 7 t o t h e h i g h - b o i l i n g s e p a r a ti o n column 7 0 0 .

T h e t o p l i q u i d o f t h e h i g h - b o i l i n g s e p a r at i o n c o l u m n 7 0 0

( r e f e r r e d t o a s “ d i s t i l l a t e ” i n some c a s e s ) c o n t a i n s t h e a c r y l i ce s t e r s e p a r a t e d a n d r e c o v e r e d , a n d a l l o r p a r t o f t h e t o p l i q u i d

i s c i r c u l a t e d t h r o u g h a l i n e 1 8 and h e l i n e 9 to t h e l o W - b o i l i n g

s e p a r a t i o n c o l u m n 5 0 0 . T h e h i g h - b o i l i n g s u b s t a n c e c o n t a i n

i n g h i g h - b o i l i n g a c i d c o m p o n e n t s s u c h a s m a l e i c a c i d a n d

[ 3 - a c r y l o x y pr o p i o n i c a c i d i s s e n t from t h e bottom o f t h e t h i n

?lm e v a p o r a t o r 800 through a l i n e 21 t o a W a s t e - o i l t r e a t m e n t

s t e p .

I n t h e p r o d u c t i o n p r o c e s s shoWn n F I G . 1 , t h e h i g h - b o i l i n g

s e p a r a t i o n column 700 and t h e t h i n - ? l m e v a p o r a t o r 800 a r e

used o s e p a r a t e and e c o v e r t h e a c r y l i c e s t e r c o n t a i n e d i n t h e

b o t t o m l i q u i d o f t h e r e c t i f y i n g c o l u m n 6 0 0 ; h o W e v e r , i t i s n o t

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

t h a t , u s i n g o n l y t h e h i g h - b o i l i n g s e p a r a t i o n c o l u m n 7 0 0 , t h et o p l i q u i d o f t h e h i g h - b o i l i n g s e p a r a t i o n c o l u m n 7 0 0 , c o n

t a i n i n g t h e a c r y l i c e s t e r s e p a r a t e d a n d r e c o v e r e d , i s c i r c u l a t e dt o t h e l o W - b o i l i n g s e p a r a t i o n column 5 0 0 , a n d t h e b o t t o m

l i q u i d o f h e h i g h - b o i l i n g s e p a r a t i o n c o l u m n 7 0 0 , c o n t a i n i n gh i g h - b o i l i ng a c i d components s u c h a s m a l e i c a c i d and

[ 3 - a c r y l o x y p r o p i o n i c a c i d , i s s e n t a s Waste o i l t o a W a s t e - o i l

t r e a t m e n t s t e p ; o r u s i n g o n l y t h e t h i n - ? l m e v a p o r a to r 8 0 0 , a

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

i s WithdraWn f r o m t h e t o p o f t h e t h i n - ? l m e v a p o r a t o r 8 0 0 a n d

c i r c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i o n column 5 0 0 , a n d a

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

a s m a l e i c a c i d a n d [ 3 - a c r y l o x y p r o p i o n i c a c i d i s d i s c h a r g e d

from t h e bottom of h e t h i n - ? l m e v a p o r a t o r 800 and s e n t a s

Waste o i l t o a W a s t e - o il t r e a t m e n t s t e p .

I n such a p r o d u c t i o n of an a c r y l i c e s t e r , e s t e r i ? c 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 s o t h a t t h e c o n v e r s i o n o f a c r y l i c a c i d i s

a l W a y s k e p t c o n s t a n t , a n d t h e r e f o r e ,t h e

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

t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n 5 0 0 a r e a l s o k e p t s t a b l y .

T h a t s , t h e o p e r a t i o n t e m p e r a t u r e o f t h e l o W - b o i l i n g s e p a r a

t i o n column 500 s c o n s t a n t , and h e c o m p o s i t i o n and amount

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

t h e e s t e r i ? c a t i o n r e a c t o r 100 a r e both c o n s t a n t .

F I G . 2 i s a s c h e m a t i c d i a g r a m s h o W i n g a n o t h e r e x a m p l e o f

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

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 . T h i s p r o d u c t i o n p r o c e s s i s

c h a r a c t e r i z e d i n h a t a h i g h - b o i l i n g a c i d s u b s t a n c e c o n t a i n i n g

an a c r y l i c e s t e r , Which s WithdraWn from t h e bottom o f t h e

r e c t i f y i n g column 6 0 0 , i s s u p p l i e d t o a h i g h - b o i l i n g s e p a r a

t i o n column 700 and a t h i n - ? l m e v a p o r a t o r 800 i n a p o r t i o n

d e s i g n a t e d a s “A” t o s e p a r a t e i t i n t o an a c r y l i c e s t er compo

n e n t a n d a h i g h - b o i l i n g s u b s t a n c e , t h e s e p a r a t ed a c r y l i c e s t e rcomponent e i n g t a k e n o u t a s a d i s t i l l a t e , and l l o r p a r t of h e

d i s t i l l a t e i s mixed With a t e r i n a p o r t i o n d e s i g n a t e d a s “B” o

e x t r a c t and remove h i g h - b o i l i n g a c i d components i n t h e d i s

t i l l a t e i n t o a W a t e r p h a s e , t h e o b t a i n e d o r g a n i c p h a s e b e i n g

s u p p l i e d t o t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n 5 0 0 f o r i t s

r e c o v e r y . F u r t h e r , t h i s p r o d u c t i o n p r o c e s s i s t h e same a s t h e

p r o d u c t i o n p r o c e s s shoWn i n F I G . 1 u p t o t h e s t a g e o f r e d u c

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

t h e r e c t i f y i n g c o l u m n 6 0 0 u s i n g t h e h i g h - b o i l i n g s e p a r a t i o nc o l u m n 7 0 0 a n d t h e t h i n - ? l m e v a p o r a t o r 8 0 0 , t h a t i s , e x c e p t

f o r a p o r t i o n d e s i g n a t e d a s “ B ” . T h e r e f o r e , t h e r e W i l l b e

d e s c r i b e d h e r e i n a s t e p o f e x t r a c t i n g a n d r e m o v i n g h i g h

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

h i g h - b o i l i n g s e p a r a t i o n column 7 0 0 ( r e f e r r e d t o a s “ W a t e r



US 7 , 4 9 1 , 8 4 1 B2

e x t r a c t i o n s t e p ” i n some t i m e s ) I n F I G . 2 , t h e same e q u i p

ments a s i n FIG. 1 a r e d e s i g n a t e d by t h e same numbers.

A l l o r p a r t o f t h e t o p l i q u i d o f t h e h i g h - b o i l i n g s e p a r a t i o n

column 700 i s s u p p l i e d through a l i n e 22 and a l i n e 23 t o an

e x t r a c t i o n t a n k 9 0 0 . At h i s t i m e , i t i s s u p p l i e d t o t h e e x t r a c

t i o n t a n k 900 a f t e r b e i n g mixed n t h e l i n e 2 3 W i t h W a s t e W a t e r

from t h e p r o c e s s W a s t e W a t e r t a n k 4 0 0 . I n t h e e x t r a c t i o n t a n k

9 0 0 , h i g h - b o i l i n g a c i d c o m p o n e n t s s u c h a s m a l e i c a c i d and

[ 3 - a c r y l o x y p r o p i o n i c a c i d a r e e x t r a c t e d and removed i n t o a

W a t e r p h a s e . T h e n , a n o r g a n i c p h a s e c o n t a i n i n g a n a c r y l i ce s t e r i s c i r c u l a t e d t h r o u g h t h e l i n e 24 and t h e l i n e 9 t o t h e

l o W - b o i l i n g s e p a r a t i o n c o l u m n 5 0 0 . O n t h e o t h e r h a n d , t h e

W a t e r p h a s e c o n t a i n i n g h i g h - b o i l i n g a c i d c o m p o n e n t s s u c h as

m a l e i c a c i d and [ 3 - a c r y l o x yp r o p i on i c a c i d i s s e n t t h r o u g h a

l i n e 25 a s WasteWater o a WasteWater treatment s t e p . As ater

to be used t o e x t r a c t and remove h i g h - b o i l i n g a c i d compo

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

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

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

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

I n t h e p r o d u c t i o n p r o c e s s shoWn i n F I G . 2 , t h e s t e p o f

e x t r a c t i n g , W i t h W a t e r , a l l o r p a r t o f t h e t o p l i q u i d o f t h e

h i g h - b o i l i n g s e p a r a t i on column 700 s c a r r i e d o u t i n a p o r t i o n

d e s i g n a t e d a s “ B ” ; h o W e v e r , a l l o r p a r t o f t h e t o p l i q u i d o f t h e

h i g h - b o i l i n g s e p a r a t i o n column 7 0 0 may b e c i r c u l a t e d W i t h

o u t a n y t r e a t m e n t t o t h e l o W - b o i l i n g s e p a r a t i o n column 5 0 0 ,

a n d o n l y f o r t h e d i s t i l l a t e f r o m t h e t h i n - ? l m e v a p o r a t o r 8 0 0 ,

t h e s t e p o f e x t r a c t i n g , W i t h W a t e r , a l l o r p a r t o f t h e d i s t i l l a t e

may be c a r r i e d o u t i n a p o r t i o n d e s i g n a t e d a s “ B ” .

I n F I G S . 1 and , t h e m i x i n g r a t i o o f W a s t e W a t e r from t h e

process WasteWater tank 400 t o be used o e x t r a c t and remove

h i g h - b o i l i n g a c i d c o m p o n e n t s , r e l a t i v e t o t h e d i s t i l l a t e f r o m

t h e h i g h - b o i l i n g s e p a r a t i o n column 700 o r t h e t h i n - ? l m

e v a p o r a t o r 8 0 0 , i . e . , t h e d i s t i l l a t e c o n t a i n i n g a n a c r y l i c e s t e rs e p a r a t e d a n d r e c o v e r e d , may r e f e r a b l y b e W i t h i n a r a n g e o f

from . 5 t o 2 . 0 , more r e f e r a b l y from . 8 t o 1 . 5 , by mass a t i o .

When h e m i x i n g r a t i o i s W i t h i n t h i s r a n g e, h i g h - b o i l i n g a c i d

components can e ? i c i e n t l y be e x t r a c t e d and removed i n t o aW a t e r p h a s e , a n d a n a c r y l i c e s t e r f r o m Which h i g h - b o i l i n g

a c i d components h a v e s u f ? c i e n t l y been removed c a n b e c i r

c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i o n column 5 0 0 .

EXAMPLES

The p r e s e n t i n v e n t i o n W i l l be d e s c r i b e d beloW i n more

d e t a i l b y Way o f E x a m p l e s , b u t t h e p r e s e n t i n v e n t i o n i s n o t

l i m i t e d t o t h e f o l l o W i n g E x a m p l e s . The r e s e n t i n v e n t i o n c a n

b e p u t i n t o p r a c t i c e a f t e r a p p r o p r i a t e m o d i ? c a t i o n s o r v a r i a

t i o n s W i t h i n a r a n g e m e e t i n g t h e g i s t s d e s c r i b e d a b o v e and

l a t e r , a l l o f Which a r e i n c l u d e d i n t h e t e c h n i c a l 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 .

E x a m p l e 1

To t h e e s t e r i ? c a t i o n r e a c t o r 100 shoWn i n FIG. 1 Were

s u p p l i e d 4 0 0 k g / h o f a c r y l i c a c i d c o n t a i n i n g f r o m 1 0 t o 5 0

ppm f m a l e i c a c i d and from 100 to 500 p p m o f [ 3 - a c r y l o x

y p r o p i o n i c a c i d , 7 4 0 k g / h o f - e t h y l h e x a n o l , a n d 1 , 5 9 0 k g / h

o f a r e c o v e r e d a l c o h o l l i q u i d , a n d a f t e r 2 0 d a y s o f o p e r a t i o n ,

t h e r e a c t i o n Was a r r i e d out a t a r e a c t i o n temperature of 85 C.

a n d a c o n v e r s i o n o f a c r y l i c a c i d o f 50 , t h e r e b y g i v i n g a

p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 9 9 0 k g / h f r o m t h e t o p o f t h e

r e c t i f y i n g column 6 0 0 . At h i s t i m e , 2 5 k g / h o f W a s t e o i l Was

d i s c h a r g e d f r o m t h e b o t t o m o f t h e t h i n - ? l m e v a p o r a t o r 8 0 0 ,

a n d 1 5 k g / h o f h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r a t i o n

column 700 Was c i r c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i o n c o l

umn 0 0 . The a c i d components c o n t a i n e d i n t h e o b t a i n e d

20

25

30

35

40

45

50

55

60

6 5

1 0

p r o d u c t a c r y l i c e s t e r Were i n an amount of from 25 t o 35 ppm

i n t e r m s o f a c r y l i c a c i d ) . The m e a s u r e m e n t o f a c i d compo

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

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

t e r ) . The r e s u l t s a r e shoWn i n T a b l e 1 .

E x a m p l e 2



p p m o f m a l e i c a c i d and from 100 to 500 p p m o f [ 3 - a c r y l o x


o f a r e c o v e r e d a l c o h o l l i q u i d , a n d f t e r 230 a y s o f o p e r a t i o n ,

t h e r e a c t i o n Was c a r r i e d o u t a t a r e a c t i o n temperature of 1000

C . a n d a c o n v e r s i o n o f a c r y l i c a c i d o f 50 , t h e r e b y g i v i n g a

p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 9 6 5 k g / h f r o m t h e t o p o f h e

r e c t i f y i n g column 6 0 0 . At h i s t i m e , 5 0 k g / h o f W as t e o i l Was


a n d 9 0 k g / h o f t h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r at i o n

column 700 Was c i r c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i on c o l


p r o d u c t a c r y l i c e s t e r Were i n an amount of from 25 t o 35 ppm

i n t e r m s o f a c r y l i c a c i d ) . The r e s u l t s a r e shoWn i n T a b l e 1 .

E x a m p l e 3






t h e r e a c t i o n Was a r r i e d o u t t a r e a c t i o n t e m p e r a t u r e of 5 0 C .


p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 1 , 0 0 0 k g / h f r o m t h e t o p o f

t h e r e c t i f y i n g column 6 0 0 . At h i s t i m e , 1 5 k g / h o f W a s t e o i l

Was d i s c h a r g e d from t h e bottom o f t h e t h i n - ? l m e v a p o r a t o r

8 0 0 , a n d 1 2 5 k g / h o f t h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g

s e p a r a t i o n column 700 a n d 1 4 0 k g / h o f W a s t e W a t e r from t h eWasteWater t a n k 400 Were mixed and s u p p l i e d t o t h e e x t r a c

t i o n t a n k 900 shoWn i n F I G . 2 . The W a t e r phase Was removed

a s W a s t e W a t e r , a n d t h e o r g a n i c p h a s e c o n t a i n i n g a n a c r y l i ce s t e r Was c i r c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i o n column

5 0 0 . The a c i d c o m p o n e n t s c o n t a i n e d i n t h e o b t a i n e d p r o d u c t

a c r y l i c e s t e r Were n an amount of from 25 t o 35 ppm i n terms

o f a c r y l i c a c i d ) . The r e s u l t s a r e shoWn i n T a b l e 1 .

E x a m p l e 4





o f a r e c o v e r e d a l c o h o l l i q u i d , a n d f t e r 230 a y s o f o p e r a t i o n ,


C . a n d a c o n v e r s i o n o f a c r y l i c a c i d o f 50 , t h e r e b y g i v i n g a

p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 9 9 7 k g / h f r o m t h e t o p o f h e

r e c t i f y i n g column 6 0 0 . At h i s t i m e , 1 8 k g / h o f W as t e o i l Was


a n d 1 2 5 k g / h o f h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r at i o n

column 700 and 1 4 0 k g / h o f W a s t e W a t e r from t h e W a s t e W a t e r

t a n k 400 Were mixed and s u p p l i e d t o t h e e x t r a c t i o n t a n k 900

shoWn i n FIG. 2 . The Water phase Was removed a s WasteWa

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

c i r c u l a t e d o t h e l o W - b o i l i n g s e p a r a ti o n column 0 0 . The c i d

c o m p o n e n t s c o n t a i n e d i n t h e o b t a i n e d p r o d u c t a c r y l i c e s t e rWere i n an amount of from 25 t o 3 5 ppm i n t e r m s of c r y l i c

a c i d ) . The r e s u l t s a r e shoWn i n T a b l e 1 .



US 7 , 4 9 1 , 8 4 1 B2

1 1

C o m p a r a t i v e E x a m p l e 1

To t h e e s t e r i ? c a t i o n r e a c t o r 100 shown i n FIG. 3 Were


ppm f m a l e i c a c i d and from 100 to 500 p p m o f [ 3 - a c r y l o x



t h e r e a c t i o n Was a r r i e d o u t a t a r e a c t i o n temperature of 850 .


1 2

p r o d u c t a c r y l i c e s t er Were i n an amount of from 220 t o 280

p p m i n t e r m s o f a c r y l i c a c i d ) . The e s u l t s a r e shoWn n T a b l e

1 .

E x a m p l e 6


s u p p l i e d 4 0 0 k g / h o f c r y l i c a c i d c o n t a i n i n g f r o m 1 0 0 t o 5 0 0

pm f m a l e i c a c i d and from 500 o 3 , 6 0 0 ppm o f [ 3 - a c r y l o x

p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 8 1 5 k g / h f r o m t h e t o p o f t h e 1 0 y p r o p i o n i c a c i d , 7 4 0 k g / h 0 f 2 - e t h y l h e x a n o l , a n d 1 , 5 9 0 k g / h

r e c t i f y i n g Column ) ) _ Ar h i s t i m e , 2 0 0 k g / h e f w a s r e 1 1 was o f a r e c o v e r e d a l c o h o l l i q u i d , a n d f t e r 230 a y s o f o p e r a t i o n ,

d i s c h a r g e d from h e bottom f t h e r e c t i f y i n g Column 0 0 _ The t h e r e a c t i o n Was c a r r i e d o u t a t a r e a c t i o n t e m p e r a t u r e o f 1 0 0 0

a c i d c o m p o n e n t s c o n t a i n e d i n t h e o b t a i n e d p r o d u c t a c r y l i c C - a n d 8 C o n v e r s i o n o f a c r y l i c a c i d o f 5 0 , t h e r e b y g i v i n g a

e s t e r were i n a n amount o f from 2 5 t o 3 5 ppm i n t e r m s o f p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 997 k g / h from t h e t o p o f h e

a c r y l i c a c i d ) , The r e s u l t s a r e shown i n T a b l e 1 _ 1 5 r e c t i f y i n g column 6 0 0 . At h i s t i m e , 1 8 k g / h o f W a s t e o i l Was


C o m p a r a t i v e E x a m p l e 2 a n d 1 2 5 k g / h o f h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r at i o n

column 700 and 1 4 0 k g / h o f W a s t e W a t e r from t h e p r o c e s s

To t h e e s t e r i ? c a t i o n r e a c t o r 100 shoWn i n FIG. 3 Were WasteWater t a n k 400 Were mixed and s u p p l i e d t o t h e e x t r a c

s u p p l i e d 400 k g / h o f a c r y l i c a c i d c o n t a i n i n g from 1 0 t o 5 0 2 0 t i o n t a n k 900 shoWn i n F I G . 2 . The W a t e r p h a s e Was removed

p p m o f m a l e i c a c i d a n d from 1 0 0 t o 500 p p m o f [ 3 - a c r y l o x - a s W a s t e W a t e r , a n d t h e o r g a n i c p h a s e c o n t a i n i n g a n a c r y l i c

y p r o p i o n i c a c i d , 7 4 0 k g / h o f 2 - e t h y l h e x a n o l , a n d 1 , 5 9 0 k g / h e s t e r W a s c i r c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n

o f a r e c o v e r e d a l c o h o l l i q u i d , a n d f t e r 230 a y s o f o p e r a t i o n , 5 0 0 . The a c i d c o m p o n e n t s c o n t a i n e d i n t h e o b t a i n e d p r o d u c tt h e r e a c t i o n Was c a r r i e d o u t at a r e a c t i o n temperature of 1000 a c r y l i c e s t e r Were n an amount of from 35 t o 50 ppm i n terms

C . and a c o n v e r s i o n o f a c r y l i c a c i d o f 50 , t h e r e b y g i v i n g a 2 5 o f a c r y l i c a c i d ) . The r e s u l t s a r e shoWn i n T a b l e 1 .


r e c t i f y i n g column 0 0 . At h i s t i m e , 4 0 0 k g / h o f W a s t e i l Was C o m p a r a t i v e Example 3

d i s c h a r g e d f r o m t h e b o t t o m o f h e r e c t i f y i n g column 0 0 . The

a c i d components c o n t a i n e d i n t h e o b t a i n e d p r o d u c t a c r y l i c T0 t h e e S I e r i ? C a I i O n r e aC I O r 100 ShOWn i n F I G . 3 Were

e s t e r were i n a n amount O f from 2 5 t o 3 5 p pm i n t e n n s O f 3 0 s u p p l i e d 400 k g / h O f a c r y l i c a c i d c o n t a i n i n g from 10010 500

a c r y l i c a c i d ) , The r e s u l t s a r e shown i n T a b l e 1 _ p p m f m a l e i c a c i d and from 5 0 0 t o 3 , 6 0 0 ppm f [ 3 - a c r y l o x


Example o f a r e c o v e r e d a l c o h o l l i q u i d , a n d f t e r 2 3 0 d a y s o f o p e r a t i o n ,


To t h e e s t e r i ? c a t i o n r e a c t o r 100 shoWn i n F I G . 1 Were 3 5 C . and a c o n v e r s i o n o f a c r y l i c a c i d of 50 , t h e r e b y g i v i n g a

s u p p l i e d 4 0 0 k g / h o f c r y l i c a c i d c o n t a i n i n g f r o m 1 0 0 t o 5 0 0 p r o d u c t a c r y l i c e s t e r a t a y i e l d o f 8 4 5 k g / h f r o m t h e t o p o f h e

p p m f m a l e i c a c i d and from 500 o 3 , 6 0 0 p p m f [ 3 - a c r y l o x - r e c t i f y i n g column 0 0 . At h i s t i m e , 1 7 0 k g / h o f W a s t e i l Was

y p r o p i o n i c a c i d , 7 4 0 k g / h o f 2 - e t h y l h e x a n o l , a n d 1 , 5 9 0 k g / h d i s c h a r g e d f r o m t h e b o t t o m o f h e e c t i f y i n g c o l u m n 6 0 0 . T h e

o f a r e c o v e r e d a l c o h o l l i q u i d , a n d f t e r 2 3 0 d a y s o f o p e r a t i o n , a c i d c o m p o n e n t s c o n t a i n e d i n t h e o b t a i n e d p r o d u c t a c r y l i ct h e r e a c t i o n Was c a r r i e d o u t at a r e a c t i o n temperature of 1000 e s t e r Were i n an amount of from 150 t o 170 ppm i n terms of

C . a n d a c o n v e r s i o n o f a c r y l i c a c i d o f 50 , t h e r e b y g i v i n g a a c r y l i c a c i d ) . The e s u l t s a r e shoWn i n T a b l e 1 .

TABLE

Amount o f i m p u r i t i e s Amount o f

Number o f c o n t a i n e d i n raW m a t e r i a l Y i e l d of a c i d components

? g u r e a c r y l i c a c i d p r o d u c t c o n t a i n e d i ns h o w i n g ppm a c r y l i c p r o d u c t a c r y l i c Amount o f

p r o d u c t i o n [ 5 - A c r y l o x y - e s t e r e s t e r W a s t e o i l

p r o c e s s M a l e i c a c i d p r o p i o n i c a c i d k g / h ) ( p p m ) ( k g h )

Example 1 F I G . 1 from 1 0 to 50 from 100 to 500 990 from 25 to 3 5 2 5

Example 2 F I G . 1 from 1 0 to 50 from 100 to 500 965 from 25 to 3 5 50

Example 3 F I G . 2 from 1 0 to 50 from 100 to 500 1 , 0 0 0 from 25 to 3 5 1 5

Example 4 F I G . 2 from 1 0 to 50 from 100 to 500 997 from 25 to 3 5 1 8

Comp. E x . 1 F I G . 3 from 1 0 to 50 from 100 to 500 815 from 25 to 3 5 200

Comp. E x . 2 F I G . 3 from 1 0 to 50 from 100 to 500 615 from 25 to 3 5 400

Example 5 F I G . 1 from 100 to 500 from 500 to 3 , 6 0 0 975 from 220 t o 280 40

Example 6 F I G . 2 from 100 to 500 from 500 to 3 , 6 0 0 997 from 35 to 50 1 8

Comp. E x . 3 F I G . 3 from 100 to 500 from 500 to 3 , 6 0 0 845 from 150 t o 170 170


r e c t i f y i n g column 6 0 0 . At h i s t i m e , 40 k g / h o f W a s t e o i l Was


a n d 9 0 k g / h o f t h e d i s t i l l a t e f r o m t h e h i g h - b o i l i n g s e p a r a t i o n

column 700 Was c i r c u l a t e d t o t h e l o W - b o i l i n g s e p a r a t i o n c o l


60

6 5

As a n b e s e e n from a b l e 1 , i n Examples and , t h e y i e l d

o f a p r o d u c t a c r y l i c e s t er Was a b l e t o be k e p t h i g h i n s u c h a

manner t h a t When an a c r y l i c e s t er Was produced u s i n g t h e

p r o d u c t i o n p r o c e s s shoWn n F I G . 1 , a h i g h - b o i l i n g s u b s t a n c e

c o n t a i n i n g an a c r y l i c e s t e r , Which Was WithdraWn from t h e

bottom o f a r e c t i f y i n g c o l u m n , Was s u p p l i e d to a h i g h - b o i l i n g

s e p a r a t i o n column a n d / o r a t h i n - ? l m e v a p o r a t o r t o s e p a r a t e t



US 7 , 4 9 1 , 8 4 1 B2

1 3

i n t o a n a c r y l i c e s t e r component and a h i g h - b o i l i n g s u b s t a n c e ,

and t h e s e p a r a t e d a c r y l i c e s t er component Was t a k e n o u t a s a

d i s t i l l a t e a n d s u p p l i e d t o a l o W - b o i l i n g s e p a r a t i o n column o r

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

from Waste o i l . At t h i s t i m e , no problem Was caused on t h e

q u a l i t y o f a p r o d u c t .

F u r t h e r , i n Examples 3 and , When a n a c r y l i c e s t e r Was

p r o d u c e d u s i n g t h e p r o d u c t i o n p r o c e s s shoWn i n F I G . 2 , a

h i g h - b o i l i n g s u b s t a n c e c o n t a i n i n g a n a c r y l i c e s t e r , Which Was

WithdraWn from t h e bottom of r e c t i f y i n g column, Was s u p

p l i e d t o a h i g h - b o i l i n g s e p a r at i o n column a n d / o r a t h i n - ? l m

e v a p o r a t o r t o s e p a r a t e i t i n t o a n a c r y l i c e s t e r component and

a h i g h - b o i l i n g p r o d uc t , a n d t h e s e p a r a t e d a c r y l i c e s t e r com

ponent Was taken o u t a s a d i s t i l l a t e , a l l o r p a r t of Which W as

mixed With Water to e x t r a c t and remove h i g h - b o i l i n g a c i d

components s u c h a s m a l e i c a c i d and [ 3 - a c r y l o x y p r o p i o n i c

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

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

W a t e r , a n d t h e o r g a n i c p h a s e b e i n g s u p p l i e d t o a l o W - b o i l i n g

s e p a r a t i o n column t o r e c o v e r a n a c r y l i c e s t e r . I n Examples 3

a n d 4 i n c l u d i n g a s t e p o f W a t e r e x t r a c t i o n , i t became p o s s i b l e

to f u r t h e r d e c r e a s e t h e l o s s o f an a c r y l i c e s t e r from Waste i l

a n d i m p r o v e t h e y i e l d o f a p r o d u c t a c r y l i c e s t e r , c o m p a r e dW i t h t h o s e o f E x a m p l e s 1 a n d 2 , W i t h o u t d e t e r i or a t i n g t h e

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

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

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

a s t r o n g l y a c i d i c c a t i o n e x c h a n g e r e si n a c c o r d i n g l y , i n W h i c h

c a s e t h e amount of h i g h - b o i l i n g a c i d components such a s

[ 3 - a c r y l o x y p r o p i o n i c a c i d i n ? u e n c i n g t h e q u a l i t y o f a p r o d u c t

i n c r e a s e s , and t h e r e f o r e , i t becomes n e c e s s a r y t o make a

r e s p o n s e b y i n c r e a s i n g t h e amount f a s t e i l t o m a i n t a i n t h e

q u a l i t y o f a p r o d u c t a c r y l i c e s t e r . H o W e v e r , a c c o r d i n g t o t h e

c o n d i t i o n s o f Example i n t o Which s t e p o f W a t e r e x t r a c t i o n

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

and t h e s t a b l e y i e l d of a p r o d u c t Were a b l e t o be o b t a i n e d

W i t h o u t r e m a r k a b l y i n c r e a s i n g t h e amount o f W a s t e o i l f r o m

t h e e a r l y p e r i o d o f r e a c t i o n i n Example 3 . The y i e l d o f ap r o d u c t u n d e r c o n d i t i o n s o f a h i g h r e a c t i o n t e m p e r a t u r e Was

q u i t e n o t i c e a b l e a s c o m p a r e d W i t h E x a m p l e 2 a n d Compara

t i v e E x a m p l e 2 .

I n c o n t r a s t , i n C o m p a r a t i v e E x a m p l e s 1 a n d 2 , When a n

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

shoWn n F I G . 3 , t h e bottom i q u i d o f a r e c t i f y i n g column Was

s u b j e c t e d a s Waste i l Without any r e a t m e n t t o a s t e p of aste

t r e a t m e n t , a n d h e r e f o r e , a l t h o u g h t h e a m o u n t o f i g h - b o i l i n g

a c i d c o m p o n e n t s c o n t a i n e d i n t h e p r o d u c t a c r y l i c e s t e ro b t a i n e d a s p a r t o f t h e t o p l i q u i d o f t h e r e c t i f y i n g column i d

n o t c h a n g e a s compared W i t h Examples t o 4 , t h e y i e l d o f a

p r o d u c t a c r y l i c e s t e r Was r e m a r k a b l y d e c r e a s e d a s compared

W i t h Examples 1 t o 4 , and t h e amount of W a s t e o i l Was

r e m a r k a b l y i n c r e a s e d a s compared W i t h Examples t o 4 .

From t h e s e f a c t s , i t can be u n d e r s t o o d t h a t t h e l o s s o f an

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

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

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

l i q u i d o f a r e c t i f y i n g column t o a h i g h - b o i l i n g s e p a r a t i o n

column a n d / r a t h i n - ? l m e v a p o r a t o r , s e p a r a t i n g and t a k i n g

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

l i q u i d o f h e r e c t i f y i n g c o l u m n f r o m a i g h - b o i l i n g s u b s ta n c e ,

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

umn o r t s r e c o v e r y ; and u r t h e r , t h a t a d e c r e a s e i n t h e l o s s of

an a c r y l i c e s t e r from Waste i l can more s t a b l y be achieved o

i m p r o v e p r o d u c t i o n e f ? c i e n c y , b y i n t r o d u c i n g a s t e p o f W a t e r

e x t r a c t i o n i n Which l l o r p a r t o f t h e d i s t i l l a t e from t h e h i g h

b o i l i n g s e p a r a ti o n c o l u m n a n d / o r t h e t h i n - ? l m e v a p o r a t o r i s

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

20

25

30

35

40

45

50

55

60

6 5

1 4

e x t r a c t and remove i h - b o i l i n g a c i d components n t o a Water

p h a s e , Which s d i s c h a r g e d s W a s t e W a t e r , a n d a o r g a n i c p h a s e

i s s u p p l i e d t o t h e l o W - b o i l i n g s e p a r a t i o n column o r e c o v e r a n

a c r y l i c e s t e r .

F u r t h e r , i n Example 5 , a n a c r y l i c e s t e r Was p r o d u c e d i nalmost t h e same manner a s d e s c r i b e d i n Examples 1 and 2

u s i n g t h e p r o d u c t i o n p r o c e s s shoWn n F I G . 1 , e x c e p t t h a t al o W - p u r i t y a c r y l i c a c i d Was used a s a raW m a t e r i a l . Although

t h e amount o f i g h - b o i l i n g a c i d c o m p o n e n t s c o n t a i n e d i n t h e

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

a c r y l i c a c i d a s a raW m a t e r ia l , t h e y i e l d o f a p r o d u c t a c r y l i c

e s t e r and h e amount of aste i l Were t about t h e same e v e l

a s t h o s e i n Examples 1 and .

F u r t h e r , i n Example 6 , a n a c r y l i c e s t e r Was p r o d u c e d i nalmost t h e same manner a s d e s c r i b e d i n Examples 3 and 4

u s i n g t h e p r o d u c t i o n p r o c e s s shoWn n F I G . 2 , e x c e p t t h a t a

l o W - p u r i t y a c r y l i c a c i d Was used a s a raW m a t e r i a l . I n s p i t e of

u s i n g a l o W - p u r i t y a c r y l i c a c i d a s a raW m a t e r i a l , t h e y i e l d o f

a p r o d u c t a c r y l i c e s t e r Was i n c r e a s e d a s compared W i t h

Example 5 , and t h e amount o f W a s t e o i l Was r e m a r k a b l y

d e c r e a s e d a s compared W i t h Example , b o t h o f Which Were

by no means i n f e r i o r to Examples 3 and 4 u s i n g a r e l a t i v e l y

h i g h - p u r i t y a c r y l i c a c i d a s a raW m a t e r i a l .

I n o n t r a s t , i n C o m p a r a t i v e Example , a n a c r y l i c e s t e r Was

produced i n almost t h e same manner a s d e s c r i b e d i n Com

p a r a t i v e E x a m p l e s 1 a n d 2 u s i n g t h e p r o d u c t i o n p r o c e s s

shoWn i n F I G . 3 , e x c e p t t h a t a l o W - p u r i t y a c r y l i c a c i d Was

used s a raW a t e r i a l . The i e l d of product c r y l i c e s t e r Was

r e m a r k a b l y d e c r e a s e d a s c o m p a r e d W i t h E x a m p l e s 5 a n d 6 ,a n d a l t h o u g h t h e a m o u n t o f h i g h - b o i l i n g a c i d c o m p o n e n t s

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

Example 5 , i t Was v e r y g r e a t a s c o m p a r e d W i t h Example 6 ,and t h e amount of Waste o i l Was remarkably i n c r e a s e d a s

c o m p a r e d W i t h E x a m p l e s 5 a n d 6 .

From t h e s e f a c t s , i t can be u n d e r s t o o d t h a t t h e l o s s o f an

a c r y l i c e s t e r form Waste i l can be s u p p r e s s e d on a loW l e v e l ,

W i t h o u t d e t e r i o r a t i n g t h e q u a l i t y o f a p r o d u c t a c r y l i c e s t e r , t oi m p r o v e p r o d u c t i o n e f ? c i e n c y a n d a c h i e v e h e s t a b l e p r o d u c

t i o n , e v e n When l o W - p u r i t y a c r y l i c a c i d c o n t a i n i n g g r e a ta m o u n t s o f h i g h b o i l i n g a c i d components s u c h a s m a l e i c a c i d

and [ 3 - a c r y l o x y p r o p i o n i c a c i d i s used a s a raW m a t e r i a l , o r

even When e l a t i v e l y h i g h - p u r i t y a c r y l i c a c i d i s used a s a raW

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

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

h i g h - b o i l i n g s e p a ra t i o n column n d / r a t h i n - ? l m e v a p o r a t o r ,

a n a c r y l i c e s t e r r e m a i n i n g i n t h e b o t t o m l i q u i d o f t h e r e c t i f yi n g column i s t a k e n o u t a s a d i s t i l l a t e t h r o u g h s e p a r a t i n g a

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

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

remove h i g h - b o i l i n g a c i d components i n t o a W a t e r p h a s e ,

Which s d i s c h a r g e d a s W a s t e W a t e r , a n d a n o r g a n i c p h a s e i s

s u p p l i e d t o a l o W - b o i l i n g s e p a r a t i o n column t o r e c o v e r an

a c r y l i c e s t e r .As d e s c r i b e d a b o v e , t h e p r o d u c t i o n 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 makes t p o s s i b l e t o s t a b l y a c h i e v e a l a r g e r e d u c t i o n

i n t h e p r o d u c t i o n c o s t o f an a c r y l i c e s t e r .

The p r e s e n t i n v e n t i o n p r o v i d e s a p r o c e s s f o r p r o d u c i n g a n

a c r y l i c e s t e r u s i n g a c r y l i c a c i d c o n t a i n i n g h i g h - b o i l i n g a c i dc o m p o n e n t s , s u c h a s m a l e i c a c i d and [ 3 - a c r y l o x y p r o p i o n i c

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

u n i t consumption o f raW m a t e r i a l s , and a n a l i p h a t i c o r a l i c y

c l i c a l c o h o l having from 5 t o 8 carbon a t o m s , a s raW m a t e r i

a l s , and a s t r on g l y a c i d i c c a t i o n e x c h a n g e r e s i n a s a c a t a l y s t ,

Which r o c e s s i s e x c e l l e n t from an e c o n o m i c a l p o i n t o f vieW

b e c a u s e i t can e l i m i n a t e t h e c o n v e n t i o n a l problems t o main

t a i n t h e s t a b l e q u a l i t y a n d t h e l o W u n i t c o n s u m p t i o n o f raW



US 7 , 4 9 1 , 8 4 1 B2

1 5

m a t e r i a l s , and Which p r o c e s s makes a g r e a t c o n t r i b u t i o n t o

t h e ? l e d o f c r y l i c e s t e r p r o d u c t i o n .

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

1 . A r o c e s s f o r p r o d u c i n g a n a c r y l i c e s t e r by s u p p l y i n g

a c r y l i c a c i d a n d a n a l i p h a t i c o r a l i c y c l i c a l c o h o l h a v i n g f r o m

5 t o 8 carbon atoms t o an esteri?cation reactor t o cause an

e s t e r i ? c a t i o n r e a c t i o n u s i n g a s t r o n g l y a c i d i c c a t i o n e x c h a n g e

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

s u p p l y i n g an b t a i n e d r e a c t i o n p r o d u c t t o a l o W - b o i l i n g s e p a

r a t i o n column t o d i s t i l l a n a l c o h o l , a c r y l i c a c i d , and W a t e r

f r o m t h e t o p o f t h e l o W - b o i l i n g s e p a r a t i o n c o l u m n , a n d s e p a

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

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

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

c r u d e a c r y l i c e s t e r , Which s W i t h d r a W n from h e b o t t o m o f h e

l o W - b o i l i n g s e p a r a t i o n c o l u m n , t o a r e c t i f y i n g c o l u m n , t a k i n g

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

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

an a c r y l i c e s t e r , Which s WithdraWn from t h e bottom o f t h e

r e c t i f y i n g c o l u m n , t o a h i g h - b o i l i n g s e p a r at i o n c o l u m n a n d /

o r a thin-?lm e v a p o r a t o r t o s e p a r a t e i t i n t o an a c r y l i c e s t e r

c o m p o n e n t a n d a h i g h - b o i l i n g s u b s ta n c e , t h e s e p a r a t e d

a c r y l i c e s t er component e i n g t a k e n o u t a s a d i s t i l l a t e , m i x i n ga l l o r p a r t of h e d i s t i l l a t e With Water t o e x t r a c t and remove a

h i g h - b o i l i n g a c i d component c o n t a i n e d i n t h e d i s t i l l a t e i n t o a

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


2 . The p r o c e s s a c c o r d i n g t o c l a i m 1 , Wherein W a t e r t o be

used t o e x t r a c t and remove t h e h i g h - b o i l i n g a c i d component

i s a p r o c e s s WasteWater g e n e r a t e d i n a s t e p of producing an

a c r y l i c e s t e r .

20

25

30

1 6

3 . The p r o c e s s a c c o r d i n g t o c l a i m 1 , Wherein a r a t i o o f

Water to be used t o e x t r a c t and remove t h e h i g h - b o i l i n g a c i d

c o m p o n e n t , r e l a t i v e t o t h e d i s t i l l a t e t a k e n from t h e h i g h

b o i l i n g s e p a r at i o n c o l u m n a n d / o r t h e t h i n - ? l m e v a p o r a t o r , i s

W i t h i n a range of from 0 . 5 : 1 t o 20:1 by mass a t i o .

4 . The r o c e s s a c c o r d i n g to c l a i m , W h e r e i n a c r y l i c a c i d o

be used a s a raW m a t e r i a l i n t h e process f o r producing an

a c r y l i c e s t er c o m p r i s e s from 1 0 t o 5 , 0 0 0 p pm o f m a l e i c a c i d

a n d / o r from 1 0 t o 5 , 0 0 0 p p m o f [ 3 - a c r y l o x y p r o p i o n i c a c i d .

5 . The p r o c e s s a c c o r d i n g t o c l a i m 2 , Wherein a r a t i o o f

Water to be used t o e x t r a c t and remove t h e h i g h - b o i l i n g a c i d

c o m p o n e n t , r e l a t i v e t o t h e d i s t i l l a t e t a k e n from t h e h i g h

b o i l i n g s e p a r at i o n c o l u m n a n d / o r t h e t h i n - ? l m e v a p o r a t o r , i s

W i t h i n a range of from 0 . 5 : 1 t o 20:1 by mass a t i o .











a c r y l i c e s t e r c o m p r i s e s from 1 0 t o 5 , 0 0 0 p pm o f m a l e i c a c i d


(2009) us7491841 process for producing acrylic ester

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