CEH Acetic Acid
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December 1988- Acetic Acid602 . 5 0 2 0 A
C E H M a r k e t i n g R e s e a r c h R e p o r t
ACETIC ACIDBy
Kevin Wheeler
CEH Marketing Research Reports are comprehensive
studies prepared fr om information in the CEH Data
Center and from extensive personal interviews with
s o u r c e s i n t h e c h e m i c a l i n d u s t r y . A d i s t i n c t i v e f e a t u r e o f
t h e s e r e p or t s i s t h e a n al y s i s o f f u t u r e s u p p l y / d e m a n d
relationships .
O 1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t io n a l
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December 1988 ACETIC ACIDA c e t i t c A c i d
602 .5020 B
TABLE OF CONTENTSSummary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . 602 . 5 0 2 0 CM a n u f a c t u r i n g P r o c e s s e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 D
S y n t h e t ic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 DM e t h a n o l C a r b o n y l a t i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 E
O x i d a t i o n o f n - B u t a n e o r N a p h t h a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 F
O x i d a t i o n o f A c e t a l d e h y d e 602 . 5 0 2 0 GT e r e p h t h a l i c A c i d Co p r o d u c t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 G
B y - P r o d u c t A c e t i c A c i d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 G
N a t u r a 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 HProduction Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 H
Supply and Demand by Region . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602.50201U n i t e d S t a t e s 602. 50201
Producing Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602.5 0201P r o d u c t i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 RConsumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 T
Vinyl Acetate Monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 UA c e t i c A n h y d r i d e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 U
C e l l u l o s e a c e t a t e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 V
A c e t i c a n h y d r i d e ( d e r i v a t i v e s o t h e r t h a n c e l l u l o s e a c e t a t e ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 VE s t e r s o f A c e t i c A c i d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602.5020 W
B u t y l a c e t a t e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602. 5020 W
P r o p y l a c e t a t e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 XE t h y l a c e t a t e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 X
G l y c o l m o n o e t h e r a c e t a t e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 XA m y l a c e t a t e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 YO t h e r a c e t i c a c i d e s t e r s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 Y
T e r e p h t h a l i c A c i d / D i m e t h y l T e r e p h t h a l a t e ( T P A / D M T ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 YM o n o c h l o r o a c e t i c A c i d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 ZT e x t i l e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 0 ZOther . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 A
P r i c e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 ATrade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 C
Canada and Mexico . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 E
Producing Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 ES a l i e n t S t a t i s t i c s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 EC o n s u m p t i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 FTrade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 5021 F. . .
W e s t e r n E u r o p e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . .
. . .
.
602 . 5 0 2 1 F
Producing Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 FS a l i e n t S t a t i s t i c s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 HConsumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602.50211P r i c e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602.50211
Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 JProducing Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 JP r o d u c t i o n . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602. 5 0 2 1 JConsumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 KP r i c e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 LTrade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 . 5 0 2 1 L
B i b l i o g r a p h y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602 5021 M. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i on a l
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t December 1988 ACETIC ACID Acetic Acid602. 5 0 2 0 C
SUMMARYA c e t i c a c i d i s s y n t h e t i c a l l y p r o d u c e d b y s e v e r a l p r o c e s s e s a n d f e e d s t o c k s . I t i s a l so re c ov e r ed as a b y -
p r o d u c t o f m a n y r e a c t i o n s . A s s h o w n b e l o w , t h e m a j o r i t y o f v i r g i n a c e t i c a c i d i s p r o d u c e d b y m e t h a n o l
c a r b o n y l a t i o n . T h e a p p r o x i m a t e w o r l d c a p a c i t y f o r a c e t i c a c i d b y p r o c e s s / f e e d s t o c k i n 1 9 8 7 w a s a s
f o l l o w s :
Methanol Carbonylation 47%A c e t a l d e h y d e O x i d a t i o n 27%
E t h y l A l c o h o l 5 .5%
Butane/Naphtha Oxidation 6 .5%
C o a l - B a s e d S y n t h e s i s G a s 3%P r o c e s s / F e e d s t o c k N o t I d e n t i f i e d 11%
T h e f o l l o w i n g t a b l e s h o w s w o r l d s u p p l y a n d d e m a n d f o r a c e t i c a c i d i n 1 9 8 7 , w i t h f o r e c a s t s f o r 1 9 9 2 :
World Supply/Demand for Acetic Acid
(millions of pounds)
United
S t a t e s
Western
I 3 u r o p e Japan Other$ T o t a l
C a p a c i t y
P r o d u c t i o n
I m p o r t s
E x p o r t s
Consumption
1987
3 , 3 9 1
3 , 2 2 8
35
102
3 , 2 6 6
1992
3 , 6 1 6
3 , 5 8 2
20
100,
3 , 6 1 0
1987
2 , 5 8 4
2 , 4 1 0
n e t 7 0
2 , 3 5 4
1992 19873,183 1,2192,590 809
110net 154 862,560 831
1992
1 , 2 9 6
783
1 1 0
44
851
1987
3 , 0 9 7
2 , 8 7 3
n e t 8 2
2 , 9 3 9
1992
3 , 9 1 3
3 , 4 1 9
n e t 1 6 5
3 , 4 6 1
1987 199210,291 12,008
9,3 19 10,375974 1,093999 1,1689,390 10,482
( t h o u s a n d s o f m e t r i c t o n s )
United
States
We s tern
Europe Japan Other' T o t a l
1987 1992 1987 1992 1987 1992 1987 1992 1987 19,92C a p a c i t y 1 , 5 3 8 1 , 6 4 0 1 , 1 7 2 1,444 553 588 1 , 4 0 5 1 , 7 7 5 4 , 6 6 8 5 , 4 4 7P r o d u c t i o n 1 , 4 6 4 1 , 6 2 5 1 , 0 9 3 1,175 367 355 1 , 3 0 3 1 , 5 5 1 4 , 2 2 7 4 , 7 0 6I m p o r t s 1 6 9 5 0 50 n e t 3 7 n e t 7 5 442 496
E x p o r t s 146 45 n e t 3 2 net 70 39 20 453 530Consumption 1 , 4 8 1 1 , 6 3 7 1 , 0 6 8 1,161 377 386 1 , 3 3 3 1 , 5 7 1 4 , 2 5 9 4 , 7 5 5a. O t h e r i n c l u d e s A n d e a n c o u n t r i e s , A r g e n t i n a , S o u t h e a s t A s i a , A u s t r a l i a , B r a z i l , B u l g a r i a , C a n a d a , C h i l e , P e o p l e ' s R e p u b l i c : o f
China, Czechoslova kia, Egypt, German Democratic Republic, Hungary, India, Iran, Israel, Republic of Korea, Mexico, New
Zealand, Poland, Rumania, Saudi Arabia, South Africa, Taiwan, USSR, and Yugoslavia .
SOURCE: CEH estimates in conjunction with World Petrochemicals Program, SRI International .
I n 1 9 8 7 , N o r t h A m e r i c a ( U n i t e d S t a t e s , C a n a d a , a n d M e x i c o ) , W e s t e r n E u r o p e , a n d J a p a n a c c o u n t e d i : o r
m o r e t h a n 7 0 % o f t h e t o t a l w o r l d c a p a c i t y f o r a c e t i c a c i d . W i t h f e w e x c e p t i o n s , n e w f a c i l i t i e s w i l l b e
b a s e d o n m e t h a n o l c a r b o n y l a t i o n t e c h n o l o g y . F a c i l i t i e s b a s e d o n t h i s p r o c e s s w i l l b e b u i l t i n I n d i a , t h e
U S S R , B u l g a r i a , a n d t h e P e o p l e ' s R e p u b l i c o f C h i n a b y 1 9 9 2 . N o n e w f a c i l i t i e s a r e p l a n n e d e l s e w h e r e i n
t h e w o r l d o v e r t h e n e x t f i v e y e a r s . G r o w i n g d e m a n d i n d e v e l o p i n g c o u n t r i e s , o t h e r t h a n E a s t e r n E u r o p e ,
w i l l b e m e t p r i m a r i l y b y e x p o r t s f r o m t h e U n i t e d S t a t e s a n d W e s t e r n E u r o p e .
1988 by the Chemical Economics Handbook-SRI International
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Deeember 19&& ACETIC ACID Acetic Acid602 . 5 0 2 0 D
W o r l d p r o d u c t i o n a n d c o n s u m p t i o n o f a c e t i c a c i d w i l l i n c r e a s e a t a n a v e r a g e a n n u a l r a t e o f 2 .2% per year
between 1987 and 1992 . The strongest demand growth for a cetic acid will occur in the developing
regions of the Far Eas t, Eastern Europe and South America, where consumption is projected to grow at
3 . 0 - 3 . 5% . The fastest growing end uses will be in vinyl acetate monomer and as a solvent in the
production of TPA/DMT .
U. S. a c e t i c a c i d p r o d u c t i o n a n d c o n s u m p t i o n w i l l i n c r e a s e a t a r a t e s l i g h t l y g r e a t e r t h a n 2 % p e r y e a r
between 1987 and 1992 . Impor ts, whichh were u p in 1988, will decrea se to 1987 levels by 1989 as
H o e c h s t C e l a n e s e r e s t a r t s i t s P a m p a , T e x a s f a c i l i t y i n D e c e m b e r 1 9 8 8 . I m p o r t s a r e e x p e c t e d t o d e c l i n e
some what through 1992. Exports will remain level over the next five years as new capacity comes on
stream in Western Europe and the Far East . V i n y l a c e t a t e m o n o m e r , t h e l a r g e s t e n d u s e f o r a c e t i c a c i d ,
w i l l g r o w s l i g h t l y f a s t e r t h a n G N P a n d e x p o r t s w i l l c o n t i n u e t o a c c o u n t f o r a b o u t 3 0 % o f v i n y l a c e t a t e
monomer p roduction . S t r o n g d e m a n d f o r T P A , u s e d i n p o l y e s t e r t e r e p h t h a l i c a c i d r e s i n s , w i l l i n c r e a s e t h e
c o n s u m p t i o n o f a c e t i c a c i d u s e d a s a p r o c e s s s o l v e n t . O t h e r m a j o r m a r k e t s f o r a c e t i c a c i d , s u c h a s a c e t i c
a n h y d r i d e a n d e s t e r s , a r e m a t u r e w i t h l i t t l e g r o w t h e x p e c t e d , w h i l e s o m e n e w e r , s m a l l e r m a r k e t s ( e . g . ,
r o a d m a i n t e n a n c e a n d m e d i c a l ) h a v e g o o d g r o w t h p o t e n t i a l s .
A c e t i c a c i d p r o d u c t i o n w i l l i n c r e a s e i n W e s t e r n E u r o p e a s B P I n t e r n a t i o n a l b r i n g s n e w c a p a c i t y o n s t r e a m
in the United Kingdom and Industrias Qui micas As ociadas res tarts its plant in Spain . Consumption in
Western Europe is expe cted to grow at about 1 . 4 - 1 . 9 % a n n u a l l y , s l i g h t l y l e s s t h a n i n t h e U n i t e d S t a t e s .
Net expo rts are ex pected to double by 1992 . Use in vinyl acetate monomer and solvent application in
TPA production will grow most strongly .
I n J a p a n , p r o d u c t i o n o f a c e t i c a c i d i s p r o j e c t e d t o d e c l i n e b y 0 .5% pe r ye ar betwee n 1987 and 1992 .
D u r i n g t h e s a m e p e r i o d , c o n s u m p t i o n i s e x p e c t e d t o i n c r e a s e 0 .5% per y ear with demand met by recy cled
a c e t i c a c i d f r o m i m p o r t e d v i n y l a c e t a t e m o n o m e r u s e d t o p r o d u c e p o l y v i n y l a l c o h o l .
Acetic acid consumption in the rest of the world is forecas t to increase mo re rap idly-about 3 . 3 %
annually-during this peri od . A s w i t h t h e U n i t e d S t a t e s a n d W e s t e r n E u r o p e , a c e t i c a c i d u s e d t o p r o d u c e
vinyl acetate monome r and acetic acid used as a solve nt in new TPA facilitie s will have good growth
p r o s p e c t s .
MANUFACTURING PROCESSESSYNTHETICAcetic acid can be produced synthetically or from natural sour ces . Synthetic production includes
m e t h a n o l c a r b o n y l a t i o n , a c e t a l d e h y d e o x i d a t i o n , b u t a n e / n a p h t h a o x i d a t i o n , a n d c o a l - b a s e d s y n t h e s i s g a s .
I t i s a l s o p r o d u c e d a s a b y - p r o d u c t o f m a n y r e a c t i o n s f r o m w h i c h i t i s t h e n r e c o v e r e d a n d r e c y c l e d .
The most drama tic change in ace tic acid production technology has been the advent and growth in
popular ity of methanol carbonylation . F o r i l l u s t r a t i o n , i n t h e U n i t e d S t a t e s , c a p a c i t y b a s e d o n m e t h a n o l
c a r b o n y l a t i o n g r e w f r o m o n l y 4 % o f t o t a l c a p a c i t y i n 1 9 7 0 t o 8 1% o f t o t a l o p e r a t i o n a l c a p a c i t y i n 1 9 8 8 .
In comparison, ac etic acid from ace taldehyde has steadily declined from 41% in 1978 to only 12% in
1988 . Acetic a cid production from n-butane was temporarily s uspended following Hoechst Celanese's
Pampa facility ex plosion in November 1987 . H o w e v e r , t h i s f a c i l i t y i s s c h e d u l e d f o r s t a r t - u p i n D e c e m b e r
1988 and will regain about 15% of domestic ca paci ty . T h e f o l l o w i n g t a b l e i l l u s t r a t e s t h e t r e n d t o w a r d
m e t h a n o l - b a s e d a c e t i c a c i d o v e r o t h e r p r o c e s s e s d u r i n g t h e 1 9 7 8 - 1 9 8 8 p e r i o d :
O 1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l .
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December 1988 ACETIC ACID Acetic Acid602.5020 EU . S . C a p a c i t y f o r A c e t i c A c i d b y M a j o r P r o c e s s
Methanol
Carbonylation Acetaldehyde'
n-Butane Liqu id-
Phase Oxidation O t h e r t ' Total
M i l l i o n s
o f
Pounds Percent
M i l l i o n s
o f
Pounds P e r c e n t
M i l l i o n s
o f
Pounds Percent
M i l l i o n
of
Pound
s
s PercentM i l l i o n
o f
Pound
s
s Percentc
1978 515 17 1 , 2 1 0 4 1 1 , 1 5 0 39 80 3 2 , 9 5 5 100
1980 1 , 7 0 0 42 1 , 1 2 5 2 8 1 , 1 5 0 2 8 80 2 4 , 0 5 5 100
1982 1 , 8 0 0 44 925 23 1 , 2 5 0 3 1 60 2 4 , 0 3 5 100
1985 1 , 8 9 0 59 550 1 7 550 1 7 1 9 5 6 3 , 1 8 5 100
1988 2 , 3 9 0 8 1 350 1 2 0d 0 200 7 2 , 9 4 0 100
a . Acetic acid derived from TPA production prior to 1988 is included under the acetaldehyde process . I n 1 9 8 8 , n o a c e t i c a c i d
was derived from TPA production.
b. Coproduct acetic acid from coal gas acetic anhydride operations is included under OTHER beginning in 1 98 5 . Also
i n c l u d e d i n t h i s c a t e g o r y i s p r o d u c t i o n f r o m p e r a c e t i c a c i d m a n u f a c t ur e .
c . May not equal 100% because of rounding .
d . Hoechst Celanese's 550 m illion pounds of acetic acid from n-butane liquid-phase oxidation will resume production in
January 19 89 .
SOURCE: CEH estim ates .
Methanol Carbonylation
I n 1 9 8 8 , n e a r l y 5 0 % o f t h e t o t a l w o r l d c a p a c i t y f o r a c e t i c a c i d i s b a s e d o n m e t h a n o l c a r b o n y l a t i o n . T h i s
route has lower overall production costs than other synthetic routes when compared on a newly
c o n s t r uc t e d p l a nt b a s i s . T w o t e c h n o l o g i e s f o r m e t h a n o l c a r b o n y l a t i o n a r e a v a i l a b l e . A c e t i c a c i d c a n b e
s y n t h e s i z e d f r o m c a r b o n m o n o x i d e a n d m e t h a n o l , u s i n g h i g h p r e s s u r e a n d a c o b a l t c a t a l y s t i n t h e p r e s e n c e
of iodine (B ASF ) or low pressure and a rhodium-halide catalyst ( Monsanto) . Yields range from 9 0% for
high-pressure carbonylation to 99 .5% for low-p ressu re carbonylation, based on methanol . The high-
p r e s s u r e p r o c e s s i s m o r e c o s t l y t h a n t h e l o w - p r e s s u r e p r o c e s s a n d i s u s e d o n l y i n i s o l a t e d c a s e s . B P
C h e m i c a l s I n t e r n a t i o n a l h a s p u r c h a s e d t h e r i g h t s t o t h e l o w - p r e s s u r e p r o c e s s ( M o n s a n t o ) a n d i s t h e o n l ; y
l i c e n s o r . U s i n g M t o s y m b o l i z e e i t h e r r h o d i u m o r c o b a l t , t h e r e a c t i o n s t e p s i n v o l v e d a r e a s f o l l o w s :
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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December 1988 ACETIC ACID A c e t i c A c i d602 . 5 0 2 ( ) F
(1) CH0H + HI - 0H1 + H2~
"'3(2) CH31 + [M complex] -1M comple
I I
x
( 3 ) CH3
M complex
I
+ CO --p- ~3C-OM complex
i
I
(4 ) CH3!C-0i
M complex
I
I
+ H20 ---opCH3COOH + HI + [M complex]
M o s t n e w pl a n t s w i l l u t i l i z e t h e l o w - pr e s s u re m e t h a n o l c a rb o n yl a t i o n t e c h n o l og y . L i c e n s e s h a v e b e e n
i s s u e d r e c e n t l y i n I n d i a a n d t h e P e o p l e ' s R e p u b li c o f C h i n a .
O x i d a t i o n o f n - B u t a n e o r N a p h t h a
T h e p r o c e s s i n v o l v e s a l a r g e n u m b e r o f r e a c t i o n s w h e r e b y h y d r o p e r o x i d e r a d i c a l s a r e f o r m e d , f o l l o w e d
b y r e a c t i o n o f t h e r a d i c a l s t o f o r m a v a ri e t y o f o x yg e n a t e d p r o d u c t s . T h e o v e r a l l r e a c t i o n c o n s i s t s o f t h e
f o l l o w i n g s t e p s :
I n i t i a t i o n: Radical source -#o R-
Propagation: R' + 02 -r ROOROO- + RH -----1 ROOH + RT e r m i n a t i o n: 2R --1 stable productsR + RQO -10 stable products
2R00 ~ stable productsT h e o x i d a t i o n i s c a r r i e d o u t a t 1 6 0 - 1 80 C a n d 5 0 - 5 7 k i l o g ra m s p e r s q u a r e c e n t i m e t e r ( 7 0 0 -8 0 0 p s i g ) ,
u s u a l l y i n t h e p r e s e n c e o f c o b a l t o r m a n g a n e s e . The principal products are acetic acid and methyl et
ketone; h o w e v e r , p r o d u c t s s u c h a s e t h a n o l , f o r m i c a c i d , m e t h a n o l , a n d o t h e r o r g a n i c s a r e a l s o p r o d u c e d.T h e p r o d u c t r a t i o c a n b e v a r i e d t o o b t a i n m o r e o f a d e s i r e d p r o d u c t . Naphtha feedstock can be oxidi zed i
a similar process to yield acetic acid . Naphtha oxidation is used exclusively by BP Chemicals
Internati onal, Ltd, in the Uni ted Kingdom and butane oxidation is used exclusively by Hoechst Celane
1988 by the Chemical Economics Handbook-SRI International- tr-//legacy.library.ucsf.edu/tid/hhj82e00/pdf
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December 1988 ACETIC ACID Acetic Acids o 2 . 5 o 2 0 < s
i n t h e U n i t e d S t a t e s . T h e s e o x i d a t i o n p r o c e s s e s a r e n o t c o s t c o m p e t i t i v e w i t h m e t h a n o l t e c h n o l o g y i f o n l y
a c e t i c a c i d p r o d u c t i s c o n s i d e r e d ; h o w e v e r , b y - p r o d u c t c r e d i t s a t c u r r e n t m a r k e t p r i c e s a l l o w e x i s t i n g
p l a n t s t o c o m p e t e e f f e c t i v e l y . ( F o r m o r e i n f o r m a t i o n , s e e t h e C E H m a r k e t i n g r e s e a r c h r e p o r t o n B u t a n e s )
O x i d a t i o n o f A c e t a l d e h y d e
By January 1, 1989 only 10% of U . S . acetic acid capacity will be based on Wacker-acetaldehyde
o x i d a t i o n . Hoech st C elanese d iscontinued operation of its acetaldehyde-based unit in 1982 . Eastman
o p e r a t e d o n l y e n o u g h a c e t a l d e h y d e o x i d a t i o n c a p a c i t y t o m a k e u p t h e a m o u n t o f a c e t i c a c i d r e q u i r e d o v e r
a n d a b o v e i t s o t h e r r o u t e s o f a c e t i c a c i d p r o d u c t i o n ; however, an explosion at the Hoechst Celanese
butane-based plant (Pampa, Texas) in late 1987 made it desirable for Eastman to utilize all its
a c e t a l d e h y d e u n i t i n 1 9 8 7 . Concurrently, Eastman was in the p rocess of decoupling TPA /DMT and acetic
a c i d p r o d u c t i o n , a n d i n 1 9 8 8 a c e t a l d e h y d e o x i d a t i o n c a p a c i t y w a s i n c r e a s e d f u r t h e r . Much of Europe's
a c e t i c a c i d c a p a c i t y i s s t i l l b a s e d o n a c e t a l d e h y d e . This met hod consists of the direct oxidation of
ethylene to acetaldehyde via the Wacker process, followed by the oxidation of acetaldehyde in the
p r e s e n c e o f m a n g a n e s e a c e t a t e , f o r m i n g a c e t i c a c i d .
(1) 2C2H4 + 02 PdC12, CuCl2, H20 110 2CH3CHOethylene acetaldehydem o l w t: 28.05 440 5
(2) 2CH3CHO + 02 -10 2CH3COOHa c e t i c a c i d
m o i w t:600 5A t t h e c u r r e n t m a r k e t p r i c e o f 3 5 - 4 0 c e n t s p e r p o u n d f o r a c e t a l d e h y d e , a p r o d u c e r r e q u i r e s a c a p t i v e
s o u r c e o f a c e t a l d e h y d e . T h e p r o c e s s y i e l d o n a c e t a l d e h y d e i s t y p i c a l l y 95 % . ( S e e t h e C E H m a r k e t i n g
r e s e a r c h r e p o r t o n E t h y l e n e a n d t h e C E H p r o d u c t r e v i e w o n A c e t a l d e h y d e f o r m o r e i n f o r m a t i o n . )
Terephthalic Acid C oproduct
U n t i l t h e f o u r t h q u a r t e r o f 1 98 7 , E a s t m a n u s e d a T P A /D M T p r o c e s s a t K i n g s p o r t , T e n n e s s e e t h a t
c o p r o d u c e d a c e t i c a c i d . T h e q u a n t i t y o f a c i d p r o d u c e d b y t h e o x i d a t i o n o f t h e a c e t a l d e h y d e r e a c t a n t
varied depending on TPA/DM T production . E a s t m a n h a s n o w d e c o u p l e d a c e t i c a c i d p r o d u c t i o n f r o m
TPA p roduction. T h e i r p r o c e s s n o l o n g e r r e qu i r e s a c e t a l d e h y d e a s a c o r e a c t a n t a n d n o w u s e s a h a l o g e n
p r o m o t e r , a l s o , t h e T P A p r o c e s s u s e s n o a c e t i c a c i d a s s o l v e n t , u n l i k e t h e A m o c o p r o c e s s .
BY-PRODUCT ACETIC ACIDA c e t i c a c i d i s p r o d u c e d a s a b y - p r o d u c t o f m a n y r e a c t i o n s . I t i s o f t e n r e c o v e r e d a n d r e c y c l e d i n s o m e
f a s h i o n , u s u a l ly a s a n e s t e r o r s a l t , o r u s e d i n a p p l i c a t i o n s w h e r e a d i l u t e a c i d i s a c c e p t a b l e . Some may be
r e c o n c e n t r a t e d t o g l a c i a l a c e t i c a c i d a n d r e u s e d .
A c e t i c a n h y d r i d e r e a c t i o n s a r e n e a r l y a l w a y s a c c o m p a n i e d b y t h e p r o d u c t i o n o f a m o l e e q u i v a l e n t o f
a c e t i c a c i d . T h e l a r g e s t u s e f o r a c e t i c a n h y d r i d e i s i n p r o d u c t i o n o f c e l l u l o s e a c e t a t e . S i n c e t h e a c i d
p r o d u c e d i n t h i s r e a c t i o n i s r e c o v e r e d a n d r e c y c l e d t o p r o d u c e m o r e c e l l u l o se a c e t a t e , t h e a c i d g e n e r a t e d
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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December 1988 ACETIC ACID Acetic Acid602. 5 0 2 0 H
i n t h i s r e a c t i o n h a s h i s t o r i c a l l y n o t b e e n t r e a t e d a s a b y - p r o d u c t . T h i s a r e a i s d i s c u s s e d m o r e f u l l y i n t h e
CONSUMPITON sections of this report .
P o l y v i n y l a c e t a t e i s c o n v e r t e d t o p o l y v i n y l a l c o h o l b y s t e a m i n g o r e s t e r i n t e r c h a n g e w i t h m e t h a n o l o r
e t h a n o l . T h e b y - p r o d u c t s o f t h e s e r e a c t i o n s a r e a c e t i c a c i d , m e t h y l a c e t a t e , o r e t h y l a c e t a t e .
A c e t i c a c i d i s a b y - p r o d u c t o f t h e a l l y l a l c o h o l - p e r a c e t ic a c i d r o u t e t o g l y c e r i n ( w h i c h , u n t i l 1 9 8 3 , w a s
u s e d b y F M C ) a n d i s a l s o t h e m a j o r b y - p r o d u c t i n t h e l i q u i d - p h a s e o x i d a t i o n o f a c e t a l d e h y d e t o p e r a c e t i c
acid employed by Union Carbide . Rhone-Poulen c recovers small volumes of acetic acid from various
acetylations, including coumarin manufacture, and Dow and Monsanto recover some acetic acid from
a s p i r i n p r o d u c t i o n .
NATURALHistorica lly, small amounts of acetic acid were produced as a result of destructive distilla tion (or
carbonization) of hardwoods . When wood is subjected to temperatures above 100C, thermal
decomposition occurs . I n d u s t r i a l c a r b o n i z a t i o n e m p l o y s t e m p e r a t u r e s u p t o 5 0 0 C . A s a r e s u l t o f t h e r m a l
d e c o m p o s i t i o n , t h e l a r g e c o m p l e x p o l y m e r i c m o l e c u l e s o f t h e w o o d t i s s u e a r e b r o k e n d o w n t o c a r b o n a n d
a wide variety of simple molecules . These products separate naturally into four groups : charcoal,
p y r o l i g n e o u s a c i d l i q u o r , t a r , a n d n o n c o n d e n s a b l e g a s e s . T h e p y ro l i g n e ou s a c i d l i qu o r i s t h e n r ef i n e d a n d
f r a c t i o n a t e d i n t o w a t e r , t a r , w o o d o i l s , a n d p u r e c h e m i c a l s .
D i l u t e a c e t i c a c i d ( 5 - 1 8 % ) i s p r o d u c e d b y f e r m e n t a t i o n f o r p i c k l i n g o r c o n d i m e n t u s e .
PRODUCTION COSTST h e f o l l o w i n g t a b l e s u m m a r i z e s t h e m a j o r p r o d u c t i o n c o s t c o m p o n e n t s f o r a c e t i c a c i d b y t w o o f t h e t h r e e
major synthetic processes . Major cost components are based on new construction and may not be
r e p r e s e n t a t i v e o f a c t u a l c o s t s a n d v a l u e s o f e x i s t i n g o p e r a t i o n s . F o r e x a m p l e , r a w m a t e r i a l c o s t s w i l l v a r y ,
w i t h l o w e r p r o d u c t i o n c o s t s f a v o r i n g p r o d u c e r s w i t h c a p t i v e r a w m a t e r i a l s u p p l i e s .
Major Cost Components of Synthetic Acetic Acid Manufacture-1987'
A c e t a l d e h y d e b y O x i d a t i o n
w i t h A i r
Low-Pressure Carbonylation
of Methanol
C e n t s p e r
Pound
C e n t s p e r
Kilogram
C e n t s p e r
Pound
Cents per
Kilogram
N e t V a r i a b l e C o s t s b 30 . 6 67 . 5 6 . 5 14 .4
R a w M a t e r i a l s 2 8 . 9 6 3 . 7 5 . 2 1 1 . 5
U t i l i t i e s 2 . 6 5 . 7 1 . 3 2 . 9
B y - P r o d u c t C r e d i t s / D e b i t s -0 . 9 - - - - - -
Labor 03 0 . 7 0 . 4 0 . 9O t h e r P r o d u c t i o n C o s t s 4 . 3 9 . 4 3 . 6 8 .0
T o t a l P r o d u c t i o n C o s t s 3 5 .2 77 . 5 1 0 .6 23 . 3
(
a - C o s t s a r e f o r a 6 0 0 m i l l i o n p o u n d - p e r - y e a r a c e t i c a c i d p l a n t , U . S . G u l f C o a s t , o v e n u g h t c o n s t r u c t i o n ,
m i d - 1 9 8 7 , o p e r a t i n g a t f u l l c a p a c i t y , a n d a t t a i n i n g f u l l v a l u e f o r b y - p r o d u c t s .
b . M a y n o t e q u a l t h e s u m s o f t h e c o m p o n e n t s b e c a u s e o f r o u n d i n g .
SOURCE: 1 9 8 7 P E P Y e a r b o o k , P r o c e s s E c o n o m i c s P r o g r a m , , S R I I n t e r n a t i o n a l .
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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December 1988ACETCACDAceticAcid602 .5020 1
Comparable data are not available for the n-butane oxidation process . Although production costs are highin this process, coproduct credits allow existing facilities to be competitive .*
SUPPLY AND DEMAND BY REGIO NUNITED STATE SPRODUCING COMPANIESAcetic acid produced from raw materials, such as methanol or acetaldehdye, is identified as virgin aceticacid, while acid obtained as a reaction by-product or regenerated from spent solvents is identified asrecovered acetic acid . For example, the acid used to make polyvinyl acetate is recovered when thepolyvinyl acetate is converted to polyvinyl alcohol . The distinction is made to prevent the double-counting of acetic acid production . Capacity data for recovered as well as virgin acetic acid are presentedin the next series of tables. The first two tabulations are for virgin acid . They are followed by a tabulationof recovered acid capacities. The first table of this series lists U .S . producers and capacities for virginacetic acid in 1988 .
U .S . Producers of Virgin Acetic Acid
Company andPlant Location
Annual Capacityas of
January 1, 1988(millions of
pounds) ProcessBorden Inc.
Borden Chemical DivisionGeismar, LAa40Mthano carbonyation(high pressure)
Eastman Kodak CompanyEastman Chemical Divisio n
Tennessee Eastman CompanyKngsport, TN160Coal gas coproduct350 Acetaldehyde oxidatioHoechst Celanese Corp .
Hoechst Celanese ChemicalGroup, Inc .
Clear Lake, TXbPampa, TX c
*
Quantum Chemical Corp .Chemicals Division
USI Chemicals Company,division
Deer Park, TXd
1,040(550)
Methanol carbonylation(low pressure)
n-Butane LPO
820 Methanol carbonylation(low pressure)
For additional information on the process economics for acetic acid manufacture, see Acetic Acid and AceticAnhydride, Report No. 37A, March 1973, and Acetic Acid by Low Pressure Carbonylation of Methanol, Review78-3-4, January 1980, Process Economics Program, SRI International .
1988 by the Chemical Economics Handbook-SRI International
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D e c e m b e r 1 9 8 8 ACETIC ACID Acetic Acid602.5020 JU. S . P r o d u c e r s o f V i r g i n A c e t i c A c i d ( c o n t i n u e d )
ompany and
P l a n t L o c a t i o n
S t e r l i n g C h e m i c a l s , I n c .
Texas City, TX
Annual Capacity
a s o f
J a n u a r y 1 , 1 9 8 8
( m i l l i o n s o f
pounds)
49 0
r o c e s s
Methanol c a r b o n y l a t i o n
( l o w p r e s s u r e )
Union Carbide Corporation
Chemicals and Plastics Business
Group
Solvents and Coatings
Materials Division
Brownsville, TXf 7 0 0 ) -Butane LPO
Taft, LA 40 Peracetic acid coproduct
T o t a l 2 , 9 4 0
a. B o r d e n r e s t a r t e d i t s p l a n t a t G e i s m a r , L o u i s i a n a in J a n u a r y 1 9 8 8 t o s u p p l e m e n t t h e U . S . s u p p l y o f a c e t i c
a c i d , a n d i s e x p e c t e d t o s h u t d o w n i n A p r i l 1 9 8 9 . A n e s t i m a t e d 3 5 - 4 0 m i l l i o n p o u n d s o f c a p a c i t y i s i n
o p e r a t i o n .
b. P l a n t d e b o t t l e n e c k e d t o 1 , 1 0 0 m i l l i o n p o u n d s p e r y e a r i n t h e s e c o n d q u a r t e r o f 1 9 8 8 .
c . I n N o v e m b e r 1 9 8 7 t h i s p l a n t e x p e r i e n c e d a n e x p l o s i o n , b u t w i l l b e b a c k o n s t r e a m b y J an u a r y 1 9 8 9 .
d . T h e U S I p l a n t c a m e o n s t r e a m i n t h e f i r s t q u a r t e r o f 1 9 8 0 .
e. Sterling will expand to 600 million pounds per year in January 1989 .
f . U n i o n C a r b i d e e x p a n d e d a c e t i c a c i d c a p a c i t y b y 1 0 0 m i l l i o n p o u n d s a t B r o w n s v i l l e , T e x a s d u r i n g t h e
s e c o n d h a l f o f 1 9 8 1 . T h e p l a n t w a s s h u t d o w n i n A p r i 1 1 9 8 3 .
SOURCE: CEH estimates .
A history of capacity changes for producers of vi rgin acetic acid from 1979 to 1988 is shown in the
f o l l o w i n g t a b l e :
U. S . C a p a c i t y f o r V i r g i n A c e t i c A c i dCompany and
t L t il
A n n u a l C a p a c i t y a s o f J a n u a r y 1
( m i l l i o n s o f p o u n d s )
ocaan on P r o c e s s
Borden
Geismar, LA 1979 100 1986 - - Methanol/CO
1980 100 1987 -1981 ] . 0 0 1988 40'
1982 - -
1983 - -
1984 -1985 - .
O 1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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Decernber 1988 ACETIC ACID Acetic Acid5 0 2 0 K
U . S . C a p a c i t y f o r V i r g i n A c e t i c A c i d ( c o n t i n u e d )Company and
A n n u a l C a p a c i t y a s o f J a n u a r y 1
( m i l l i o n s o f p o u n d s )
P l a n t L o c a t i o n P r o c e s s
Eastman
K i n g s p o r t , T N 1979 - - 1986 1 6 0 C o a l - b a s e d
1980- -
1987 1 6 0 s y n t h e s i s g a s
1981 - - 1988 1 6 0
1982 - -
1983 - -
1984 - -
1985 150
1979 450 1986 250 A c e t a l d e h y d e
1980 4 5 0 1987 250 oxidation
1981 400 1988 350
1982 400
1983 4 0 0
1984 40 0
1985 250
1979 - - 1986 300 TPA/coproduct
1980 - 1987 3001981 - - 1988 -
1982 -1983 300
1984 300
1985 300
FMCBayport, TX 1979 40 1986 - - G l y c e r i n
1980 40 1987 - - c o p r o d u c t
1981 40 1988 - -
1982 20
1983 - -
1984 - -
1985
H o e c h s t C e l a n e s e
B a y C i t y , T X 1979 1 7 5 1986 - - Acetaldehyde
1980 1 7 5 1987 - - o x i d a t i o n
1981 1 7 5 1988 - -
1982 - -
1983 - -
1984 -
1985 - -
C l e a r L a k e , T X 1979 50 0 1986 - - Acetaldehyde
1980 50 0 1987 - o x i d a t i o n
1981
1982
500 --- - 19881983 - -
1984 - -
1985 - -
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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D e c e m b e r 1 9 8 8 ACETIC ACID A c e t i c A c i d
602 . 5 0 2 0 L
U. S . C a p a c i t y f o r V i r g i n A c e t i c A c i d ( c o n t i n u e d )Company and
A n n u a l C a p a c i t y a s o f J a n u a r y 1
( m i l l i o n s o f p o u n d s )
P l a n t L o c a t i o n P r o c e s s
H o e c h s t C e l a n e s e
( c o n t i n u e d ) 1979 600 1986 800 Methanol/CO
1980 600 1987 800
1981 600 1988 1 , 0 4 0
1982 800
1983 800
1984 800
1985 800
Pampa, TX 1979 550 1986 550 n-Butane LPO
1980 550 1987 55 0
1981 550 1988 - b
1982 550
1983 550
1984 550
1985 550
Monsanto
T e x a s C i t y , T X 1979 400 1986 490 Methanol/CO
1980 400 1987 -
1981 400 1988 -
1982 40 0
1983 40 0
1984 49 0
1985 49 0
S t e r l i n g
T e x a s C i t y , T X 1979 - - 1986 - Methanol/CO1980 - - 1987 49 0
1981 - - 1988 490
1982 - -
1983 - -
1984 - -
1985 - -
U n i o n C a r b i d e
B r o w n s v i l l e , T X 1979 600 1986 - - n-Butane LPO
1980 600 1987 - -
1981 600 1988 -
1982 700
1983 - -
1984 - -
1985 - -
T a f t , L A 1979 40 198640 P e r a c e t i c a c i d
1980 40 1987 40
1981 40 1988 40
1982 40
1983 40
1984 40
1985 40
1988 by the Chemical Economics Handbook-SRI International
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December 1988 ACETIC ACID Acetic Acid602.5020 M
U. S . C a p a c i t y f o r V i r g i n A c e t i c A c i d ( c o n t i n u e d )Company and
Annual Capacity as of January 1
(millions of pounds)
P l a n t L o c a t i o n Process
USI
D e e r P a r k , T X 1979 300 1986 600 MethanoI/CO
1980 600 1987 800
1981 600 _ 1988 8201982 600
1983 6 0 0
1984 600
1985 600
T o t a l 1979 3 , 7 5 5 1986 3 , 1 9 0
1980 4 , 0 5 5 1987 3 , 3 9 0
1981 4 , 2 0 5 1988 2 , 9 4 0
1982 3 , 8 1 0
1983 3 , 0 9 0
1984 3 , 1 8 0
1985 3 , 0 8 0
a. Shut down in 1 9 8 2 . About 40 million pounds of capacity were brought back on stream in 1988 to
supplement U . S . s u p p l ie s . Plant is expe cted to shut down in April 1989 following Hoechst Celanese s
P a m p a , T e x a s f a c i l i t y r e s t a r t .
b . P l a n t e x p l o s i o n i n N o v e m b e r 1 9 8 7 .
SOURCE: CEH estimates .
As shown in the previous table, capacity reached a peak in 198 1, at a time of worldwide economic
r e c e s s i o n , r e s u l t i n g i n o p e r a t i n g r a t e s o f a b o u t 6 5 % . Rationalization in 1982 and 1983 brought capacity
u t i l i z a t i o n t o b e t t e r t h a n 9 0 % i n 1 9 8 3 . The operating rate slumped again in 1984 as a result of weak
demand, but increased to about 94% in 1985 as the e conomy rebounded . Plant problems and scheduled
t u r n a r o u n d s l i m i t e d e f f e c t i v e c a p a c i t y i n 1 9 8 6 . In 1987, d ue primarily to increased de mand for vinyl
acetate monome r, plants were running at around 95 % of capacity . In 1988, with the temporary loss of
c a p a c i t y a t H o e c h s t C e l a n e s e ' s f a c i l i t y a t P a m p a , T e x a s , p l a n t s r a n a t n e a r 1 0 0 % o f c a p a c i t y . The Hoechst
C e l a n e s e f a c i l i t y r e p r e s e n t s a p p r o x i m a t e l y 1 5 % o f U . S . c a p a c i t y a n d 5 % o f t o t a l w o r l d c a p a c i t y . I n 1 9 8 8 ,
Hoechst Celanese increased acetic acid capacity by 60 million pounds at Clear Lake, Tex as, and USI
C h e m i c a l s i n c r e a s e d c a p a c i t y b y 2 0 m i l l i o n p o u n d s a t D e e r P a r k , T e x a s . I n 1 9 8 9, S t e r l i n g C h e m i c a l w i l l
i n c r e a s e c a p a c i t y a t T e x a s C i t y , T e x a s b y 1 1 0 m i l l i o n p o u n d s . T h e s e c a p a c i t y i n c r e a s e s a n d t h e r e s t a r t o f
the Hoe chst Celanese Pam pa facility will bring U . S . c a p a c i t y b a c k i n l i n e w i t h d e m a n d i n 1 9 8 9 , a n d t h e
U n i t e d S t a t e s w i l l n o t r e q u i r e a d d i t i o n a l c a p a c i t y t h r o u g h 1 9 9 2 .
T h e n e x t t a b l e p r o v i d e s h i s t o r i c a l c a p a c i t y f o r r e c o v e r e d a c e t i c a c i d f r o m 1 9 7 9 t o 1 9 8 8 . N o t i n c l u d e d i n
t h e t a b l e i s a c e t i c a c i d r e c o v e r e d f r o m t h e a c e t y l a t i o n o f c e l l u l o s e a c e t a t e , w h i c h i s u s u a l l y r e c y c l e d w i t h i n
t h e p l a n t t o p r o d u c e m o r e a c e t i c a n h y d r i d e .
1 9 8 8 by t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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602.5020 N
U. S . C a p a c i t y f o r R e c o v e r e d A c e t i c A c i d aCompany and
t L t il
A n n u a l C a p a c i t y a s o f J a n u a r y 1
( m i l l i o n s o f p o u n d s )
ocaan on Source
A i r P r o d u c t s
C a l v e r t C i t y , K Y 1979 50 1986 125 P o l y v i n y l a l c o h o l
1980 68 1987 125 p r o d u c t i o n
1981 6 8 1988 125
1982 7 5
1983 7 5
1984 7 5
1985 125
Dow Chemical
Midland, MI 1979 n a 1986 4 - 6 A s p i r i n p r o d u c t i o n
1980 na 1987 4 - 6
1981 na 1988 4-6
1982 na
1983 na
1984 na
1985 n a
Du Pont
L a P o r t e , T X 1979 154 1986 154 P o l y v i n y l a l c o h o l
1980 154 1987 154 p r o d u c t i o n
1981 154 1988 154
1982 154
1983 154
1984 154
1985 154
Monsanto
S t . L o u i s , M O 1979 6 1986 6 A s p i r i n p r o d u c t i o n
1980 6 1987 6
1981 6 1988 6
1982 6
1983 6
1984 6
1985 6
S p r i n g f i e l d , M A b 1979
1980
5 6
5 6
1986
1987
2 - 4
2 - 4
P o l Y v ~ 1 b u t y r a lmYp r o d u c t i o n
1981 5 6 1988 2 - 4
1982 5 6
1983 56
1984 56
1985 56
Rhone-Poulenc
New Brunswick, N J 1979 na 1986 < 1 A c e t y l a t i o n
1980 na 1987 < 1
1981 na 1988 < 1
1982 na
1983 na
1984 na
1985 n a
0 1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k- S R I I n t e r n a t i o n a l
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December 1988 ACETIC ACIDU. S . C a p a c i t y f o r R e c o v e r e d A c e t i c A c i d t ( c o n t i n u e d )
A c e t i c A c i d
602.50200
Company and
A n n u a l C a p a c i t y a s o f J a n u a r y 1
( m i l l i o n s o f p o u n d s )
P l a n t L o c a t i o n Source
S t e r l i n g D r u g
T r e n t o n , N J 1979 na 1986 1 A s p i r i n p r o d u c t i o n
1980 na 1987 1
1981 na 1988 1
1982 na
1983 na
1984 na
1985 na
U n i o n C a r b i d e
T a f t , L A 1979 na 1986 na P e r a c e t i c a c i d
1980 na 1987 na e p o x i d a t i o n
1981 na 1988 na
1982 na
1983 na
1984 na
1985 na
T o t a l 1979 >266 1986 >293-297
1980 >284 1987 >293-297
1981 >284 1988 >293-297
1982 >291
1983 >291
1984 >291
1985 >341
a . D o e s n o t i n c l u d e b y - p r o d u c t a c e t i c a c i d f r o m t h e p r o d u c t i o n o f c e l l u l o s e a c e t a t e , a s t h i s p r o d u c t i s
u s u a l l y r e c y c l e d . H o e c h s t C e l a n e s e a n d E a s t m a n a r e t h e o n l y p r o d u c e r s o f c e l l u l o s e a c e t a t e .
b. P r i o r t o 1 9 8 6 , M o n s a n t o p r o d u c e d . p o l y v i n y l a i c o h o l .
SOURCE: CEH estimates .
T h e f o l l o w i n g t a b l e s h o w s t h e n e t s u p p l y b a l a n c e f o r U . S . a c e t i c a c i d p r o d u c e r s a n d m a j o r c o n s u m e r s :
1988 by the Chemical Economics Handbook-SRI Internationa
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N e t S u p p l y B a l a n c e f o r U . S . Acetic Acid Producers and Major Consumers-September 1,1988'
A c e t i c A c i d R e q u i r e m e n t s f o r C h e m i c a l D e r i v a t i v e s
( b a s e d o n 1 0 0 % o f d e r i v a t i v e n a m e p l a t e c a p a c i t y )
Name . A c e t i c A n h y d r i d e S o l v e n t M o n o - T o t a l Apparentplate V i n y l for TPA/ chloro- A c e t i c Net Supply
A c e t i c A c i d
Producers
A c e t i c
Acid
A c e t a t e
M o n o m e r b
Cellulose
Acetatec Otherd E s t e r s
D M T P r o -
d u c t i o n
Acetic
Acid Textile Other
Acid
Required S u r p l u s D e f i c i t
4 Borden 40 0 40~~ Eastman 51 0 2 7 3 1 0 0 70 443 6 70 00 0 H oe ch st Ce la ne s e 1 , 1 0 0 785 312 50 5 1 1 ,1 98 98
~~ Qu antu m 820 438 438 382E I r Sterlin g 49 0 na na 49 0~n U n i o n C a r b i d e 40 402 7 3 475 435~B
Total 3 00 0 1 625 5 8 5 1 5 0 19 4 0 0 0 0 2 554 4 4 1 bw~ , , ,M0
A c e t i c A c i d
~0 C o n s u m e r s
B
y Air Products 1 2 5 0 1 2 5~A m o c o 1 8 5 18 5 1 8 5
. .7
~Aqualon
( H ercules/ H enk el) 1 6 1 6 1 6ARCO 10 1 0 1 0~ BASF 1 3 1 3 1 3~ Cape Industries 90 9 0 90~ Chevron 30 30 30~ E I . d u P o n t
de Nemours 154 365 140 505 3 5 1~ Dow 6 1 9 1 9 1 3~~ Monsanto 10 3 5 35 25
Total 29 5 36 5 0 0 23 415 3 5 0 6 5 903
Total 3 , 2 9 5 1 ,9 9 0 585 150 217 415 3 5 0 65 3 , 4 5 7 16 2
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a. N o t e t h e d i f f e r e n c e i n t h e e f f e c t i v e d a t e o f t h i s t a b l e i n c o m p a r i s o n t o t h e p r e v i o u s v i r g i n a c e t i c a c i d c a p a c i t y . Total virgin acid includes Hoechst Celanese's 60 mi
p o u n d - p e r - y e a r e x p a n s i o n a t C l e a r L a k e , T e x a s.~b . F a c t o r o f 0.73 unit of acetic acid per unit of vinyl acetate monomer.~. F a c t o r o f 0 . 3 9 u n i t o f a c e t i c a c i d p e r u n i t o f c e l l u l o s e a c e t a t e .
d . O t h e r a c e t i c a c i d a n h y d r i d e i n c l u d e s e x p o r t s .
SOURCE: CEH estimates .
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December 1988 ACETIC ACIDPRODUCTIONT h e f o l l o w i n g t a b l e a n d g r a p h p r e s e n t d a t a o n p r o d u c t i o n a n d s a l e s o f a c e t i c a c i d s i n c e 1 9 5 5 .
U. S . P r o d u c t i o n a n d S a t e s f o r A c e t i c A c i d( m i l l i o n s o f p o u n d s )
Production' S a l e s
1955 547 7 3
1956 573 7 9
1957 544 1 0 4
1958 584 9 5
1959 672 1 0 8
1960 76 5 1 4 1
1 9 6 1 784 160
1962 985 1 7 8
1963 1 , 1 0 0 20 5
1964 1 , 1 2 0 234
1965 1 , 3 6 5 29 5
1966 1 , 4 0 9 335
1967 1 , 5 6 0 342
1968 1 , 7 3 8 379
1969 1 , 7 7 0 42 5
1970 1 , 9 3 2 390
1971 1 , 9 5 6 368
1972 2 , 2 3 5 570
1973 2 , 4 2 9 60 8
1974 2 , 5 8 4 66 6
1975 2 , 1 9 8 60 0
1976 2 , 4 6 2 544
1977 2 , 5 7 0 60 0
1978 2 , 7 7 6 823
1979 3 , 2 6 5 574
1980 2 , 9 7 7 51 5
1 9 8 1 2 , 7 0 5 450
1982 2 , 7 4 8 522
1983 2 , 8 0 7 83 6
1984 2 , 6 1 9 8 1 1
1985 2 , 8 9 8 1 , 0 2 8
1986 2 , 7 2 8 8 6 5
1987 3 , 2 4 6 1 , 1 0 3
See MANUAL OF CURRENT INDICATORS for addition al information .
a. From 1955 to 1 965, about 18-24 million pounds of acetic acid
were produced by the destructive disti llation of wood and are
i n c l u d e d i n p r o d u c t i o n .
SOURCE: S y n t h e t i c O rg a n i c C h e m i c a l s , U . S . Production andSales, U . S . International Trade Commission .
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
A c e t i c A c i d
6 0 2 .5020 R
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December 1988 ACETIC ACID Acetic Acid602 .5020 T
A c e t i c a c i d p r o d u c t i o n p e a k e d i n 1 9 8 7 a t 3 . 2 b i l l i o n p o u n d s a f t e r f l u c t u a t i n g b e t w e e n 2 . 6 b i l l i o n a n d 2 . 9
billion pounds from 19 80 to 1986 . I n 1 9 8 6 , p r o d u c t i o n l e v e l s w e r e e x p e c t e d t o b e h i g h e r , b u t s e v e r a l
p l a n t s e x p e r i e n c e d o p e r a t i n g p r o b l e m s : I n 1 9 8 8 , w i t h r e d u c e d c a pa c i t y , p r o d u c t i on i s e x p e c t e d t o d r o p to
t h e 1 9 8 6 l e v e l o f a b o u t 2 . 7 - 2 . 8 b i l l i o n p o u n d s . W i t h t h e r e s t a r t o f t h e H o e c h s t C e l a n e s e f a c i l i t y i n 1 9 8 9 ,
p r o d u c t i o n i s e x p e c t e d t o g r o w a t a r a t e o f a b o u t 2 % t o r e a c h m o r e t h a n 3 . 6 b i l l i o n p o u n d s i n 1 9 9 2 .
A b o u t 1 0 0 m i l l i o n p o u nd s o f a c e t i c ac i d ( v i n e g a r ) i s p r od u c e d b y f e r m e n ta t i o n a n n ua l l y . A c e t i c a ci d
c o n t e n t o f v i n e g a r r a n g e s f r o m 5 - 1 8 % w e i g h t b y v o l u m e a n d i s u s e d p r i m a r i l y i n t h e p r e s e r v a t i o n
(pickling) of foods .
CONSUMPTIONAcetic acid is a mature commodity chemical, but has shown some renewed growth in the last few years .
A l t h o u g h a c e t i c a c i d h a s a w i d e v a r i e t y o f a p p l i c a t i o n s , a b o u t 5 6 % o f d o m e s t i c a c i d c o n s u m p t i o n i n 1 9 8 7
w a s u s e d f o r t h e m a n u f a c t u r e o f v i n y l a c e t a t e m o n o m e r , a n o t h e r 8 - 9 % a s a s o l v e n t f o r t e r e p h t h a l i c a c i d
p r o d u c t i o n , a n d 8 % i n a c e t i c a n h y d r i d e u s e d t o m a k e c e l l u l o s e a c e t a t e . The remaining 27% goes into the
manufacture of esters of acetic acid, acetic anhydride (other than that used for cellulose acetate
p r o d u c t i o n ) , a n d a n u m b e r o f m i s c e l l a n e o u s s m a l l e r u s e s.
U. S . consumption of acetic acid increas ed about 4% annually between 1984 and 1987, primarily as ar e s u l t o f i n c r e a s e d r e q u i r e m e n t s f o r v i n y l a c e t a t e m o n o m e r p r o d u c t i o n . A c e t i c a ci d r e q u i r e m e n t s f o r o t h e r
d e r i v a t i v e s h e l d f a i r l y s t e a d y d u r i n g t h a t p e r i o d o r g r e w s l o w l y , e x c e p t f o r m o n o c h l o r o a c e t i c a c i d , w h i c h
d e c l i n e d .
T h e f o l l o w i n g t a b l e p r o v i d e s h i s t o r i c a l c o n s u m p t i o n o f a c e t i c a c i d w i t h f o r e c a s t s f o r 1 9 9 2 :
U. S . C o n s u m p t i o n o f A c e t i c A c i d( m i l l i o n s o f p o u n d s )
A c e t i c A n h y d r i d e
Vin l Ch l o -
A c e t a t e
Mo n o m e r '
C e l l u l o s e
A c e t a t e
OtherUses Esters DMT/TPAo r
a c e t i c
Acid T e x t i l e s Other T o t a 1 6
1979 1 , 3 1 3 570 150 329 325 5 5 65 140 2 , 9 4 71980 1 , 2 7 8 590 135 316 300 5 1 60 110 2 , 8 4 01 9 8 1 1 , 2 8 1 586 140 328 270 6 0 70 125 2 , 8 6 01982 1 , 2 4 9 516 145 314 215 5 5 65 128 2 , 6 8 71983 1 , 2 8 8 483 150 309 250 60 70 130 2 , 7 4 01984 1 , 3 4 4 274 150 302 260 6 0 70 130 2 , 5 9 01985 1 , 5 4 2 235 161 316 250 5 0 70 132 2 , 7 5 61986 1 , 6 1 0 235 190 331 250 3 1 75 166 2 , 8 8 81987 1 , 8 2 9 300 234 343 275 22 75 168 3 , 2 6 61992 2 , 1 2 0 - 2 , 1 4 0 3 0 8 - 3 1 5 240-246 360-37 0 300 2 1 - 4 4 70 195-200 3 , 5 7 0 -
3 , 6 4 0
Average Annual Growth Rate
(percent)
1 9 8 7 -
1992 3 . 0 - 3 .2% 0 . 5 - 1 .0% 1 . 0 - 1 .5% 1 . 0 - 2.0% 1.7% (-1. 0 ) -4 .0% ( - 1 . 0 ) - 0.0% 3 . 0 - 3 .5% 2 . 0 - 2.4%
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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a. Data include vinyl acetate monomer used to produce polyvinyl alcohol . Estimates based on data published by the U . S .
I n t e r n a t i o n a l T r a d e C o m m i s s i o n u s i n g a f a c t o r o f 0 . 7 3 ( a c t u a l r a n g e 0 . 7 1 - 0 . 7 3 ) . I n d u s t r y s o u r c e s i n d i c a t e d a t a f o r a c e t i c a c i d
consumed in the production of vinyl acetate monom er are understated by 130-150 million pounds in 1983 and 130 -240
million pounds in 1984 .
b . T o t a l s m a y n o t e q u a l t h e s u m s o f t h e c a t e g o r i e s b e c a u s e o f r o u n d i n g .
SOURCE: CEH estimate s .
The outlook for acetic acid consump tion between 1987 and 1992 is for a modest increase of 2 . 0 - 2 .4%
a n n u a l l y . C o n s u m p t i o n f o r v i n y l a c e t a t e m o n o m e r w i l l c o n t i n u e t o b e t h e f a s t e s t g r o w i n g o u t l e t a n d w i l l
i n c r ea s e 3 . 0 - 3 .2% per year . M i s c e l l a n e o u s n e w u s es w i l l p r o v i d e m o d e s t g r o w t h f o r a c e t i c a c i d .
Vinyl Acetate Monomer
V i n y l a c e t a t e i s t h e l a r g e s t e n d u s e f o r a c e t i c a c i d , a c c o u n t i n g f o r a b o u t 5 6 % o f d o m e s t i c c o n s u m p t i o n i n
1987 . I n t h e U n i t e d S t a t e s , v i n y l a c e t a t e i s p r o d u c e d b y r e a c t i n g e t h y l e n e a n d a c e t i c a c i d i n t h e v a p o r
phase. The producers of vinyl acetate are Hoechst Celanese, Du Pont, Quantum Chemical, and Union
Carbide. Both Hoechst Celanese and Du P ont have increased vinyl acetate monomer capacity since
midyear 1987 by 150 million pounds and 75 million pounds, respectively . I n t h e f i r s t q u a r t e r o f 1 9 8 1 3 ,
Union Carbide and BP Chemicals America, which markets Ste rling's acetic acid, ha ve formed American
A c e t y ls ( a f i n a n c i a l a n d m ar k e t i n g j o i n t v en t u r e) . T h i s a s s u r e s U n i o n C a r b i d e a s o u r c e o f a c e t i c a c i d f o r
v i n y l a c e t a t e m o n o m e r p r o d u c t i o n a n d a s s u r e s B P a m a r k e t f o r S t e r l i n g ' s a c e t i c a c i d .
Vinyl acetate monomer is used in making polyvinyl acetate emulsions and resins, polyviny l alcohol,
p o l y v i n y l b u t y r a l , v i n y l c h l o r i d e c o p o l y m e r s , a n d e t h y l e n e v i n y l a c e t a t e r e s i n s , a n d i n o t h e r a p p l i c a t i o n s .
T h e m a j o r u s e s f o r t h e s e c o m p o u n d s a r e i n p a i n t s a n d a d h e s i v e s a n d i n p o l y v i n y l a l c o h o l . I n 1 9 8 7 , v i n y l
a c e t a t e p r o d u c t i o n o f 2 , 5 0 6 m i l l i o n p o u n d s r e q u i r e d a p p r o x i m a t e l y 1 , 8 3 0 m i l l i o n p o u n d s o f a c e t i c a c i d .
An estimated 200-225 million pounds of acetic acid were g enerated from the conversion of polyvinyl
a c e t a t e t o p o l y v i n y l a l c o h o l a n d p o l y v i n y l b u t y r a l . A i r P r o d u c t s ' r e c o v e re d a c i d i s s o l d o n t h e m e r c h a n t
market, while Du Pont and Monsanto captively consume recovered acid .
Export demand accounted for about 30% of vinyl acetate monome r production in 1987 . In 1988, a weakU. S . d o l l a r f u r t h e r i n c r e a s e d f o r e i g n d e m a n d f o r U . S . vinyl acetate monomer . Unfortunately, feedstockd i s r u p t i o n s k e p t p r o d u c e r s f r o m c a p i t a l i z i n g o n a f a v o r a b l e t r a d e s i t u a t i o n a s p r o d u c e r s w e r e f o r c e d t o
allocate vinyl acetate monomer to domestic customers . F e e d s t o c k d i s r u p t i o n s i n c l u d e d t h e e x p l o s i o n a t
Hoechst Celanese's acetic acid plant in Pampa, Te xas in November 1987 and ex plosions at the steam-
c r a c k i n g f a c i l i t i e s a t S h e l l ' s p l a n t ( N o r c o , T e x a s ) a n d T e x a c o ' s p l a n t ( P o r t A r t h u r , T e x a s ) i n 1 9 8 8 .
A cet i c a c i d r e q u i r ements f or v i n y l a cetate p roduct i o n a re p rojected t o g row a t 3 . 0 - 3 . 2 % p e r y e a r b e t w e e n
1 9 8 7 a n d 1 9 9 2 , r e q u i r i n g 2 , 1 2 0 - 2 , 1 4 0 m i l l i o n p o u n ds o f a c e t i c ac i d . D u r i n g t h i s p e r i o d , d o m e s t i c d e m a n d
w i l l r e m a i n s t r o n g a n d e x p o r t s w i l l s u p p l y a t i g h t w o r l d m a r k e t , w i t h n o p l a n n e d v i n y l a c e t a t e p l a n t s
s c h e d u l e d t h r o u g h 1 9 9 2 . ( F o r m o r e i n f o r m a t i o n o n v i n y l a c e t a t e m o n o m e r , s e e t h e C E H m a r k e t i n g
researc h r e p orts o n V i n y l A cetate, P ol y v i n y l A cetate, a nd t h e C E H p roduct r ev i e w o n P ol y v i n y l A lco h ol )
Acetic Anhydride
Acetic acid is used to make acetic anhydride by two major processes . I n t h e f i r s t , a c e t i c a c i d i s r e a c t e d
with ketene, which is generated from acetic acid . About 1 . 2 5 p o u n d s o f a c e ti c a c i d a r e r e q u i r e d t : o
produce a pound of anhydride by this process . T h e s e c o n d p r o c e s s , u s e d o n l y b y E a s t m a n , r e a c t s a c e t i c
0 1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n at i o n a l
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Descmber 2 988 ACETIC ACID Acetic Acid602. 5 0 2 0 V
a c i d w i t h m e t h a n o l t o p r o d u c e m e t h y l a c e t a t e , w h i c h i s c a r b o n y l a t e d t o t h e a n h y d r i d e . T h e t h e o r e t i c a l
c o n v e r s i o n f a c t o r f o r t h i s p r o c e s s i s 0 . 5 9 p o u n d o f a c e t i c a c i d p e r p o u n d o f a c e t i c a n h y d r i d e . Hoechst
C e l a n e s e u s e s o n l y t h e k e t e n e r o u t e t o a c e t i c a n h y d r i d e , w h i l e E a s t m a n h a s b o t h t y p e s o f p r o c e s s e s .
T h e l a r g e s t u s e f o r a c e t i c a n h y d r i d e i s i n t h e p r o d u c t i o n o f c e l l u l o s e a c e t a t e , t h e c o n s u m p t i o n o f w h i c h i s
described in more detail below . A l l o t h e r u s e s f o r a c e t i c a n h y d r i d e a r e t r e a t e d s e p a r a t e l y i n t h e s e c t i o n
f o l l o w i n g C e l l u l o s e a c e t a t e .
C ellulose acetate
Acetic acid is required in several steps during cellu lose acetate manufacture : (1) cellulose may be
p r e p a r e d f o r a c e t y l a t i o n w i t h a n a c e t i c a c i d - - w a t e r m i x t u r e , ( 2 ) d u r i n g a c e t y l a t i o n , a c e t i c a c i d i s u s e d a s a
s o l v e n t f o r a c e t i c a n h y d r i d e , a n d ( 3 ) w h e n c e l l u l o s e a c e t a t e f l a k e i s r e c o v e r e d , t h e h y d r o l y z e d c e l l u l o s e
a c e t a t e s o l u t i o n i s p r e c i p i t a t e d b y m i x i n g w i t h d i l u t e a c e t i c a c i d , t h e p r e c i p i t a t e i s s e p a r a t e d , a n d t h e d i l u t e
a c e t i c a c i d i s r e c o v e r e d . T h e d i l u t e a c i d m a y b e u s e d d i r e c t l y i n o t h e r p a r t s o f t h e p r o c e s s , r e c o v e r e d f o r
r e u s e , o r c o n v e r t e d t o a c e t i c a n h y d r i d e f o r a c e t y l a t i o n . Hoechst Celanese and Eastman Chemical are the
two U . S . p r o d u c e r s o f c e l l u l o se a c e t a t e .
Acetic acid requirements for acetic anhydrid e used for cellulose acetate production dropped f rom 483
million pounds in 1983 to about 300 million pounds in 1987 . T h e l a r g e d r o p i n a c e t i c a c i d r e q u i r e m e n t s
v e r s u s c e l l u l o s e a c e t a t e p r o d u c t i o n w a s d u e t o t h e f u l l p h a s i n g - i n o f E a s t m a n ' s a c e t i c a n h y d r i d e p l a n t i n
1984 . Eastman's pr ocess technology uses coal-b ased synthesis gas to produ ce acetic anhydr ide usin g
a c e t i c a c i d p r o d u c e d i n s i t u .
C e l l u l o s e a c e t a t e f l a k e i s u s e d t o m a n u f a c t u r e c e l l u l o s e a c e t a t e a n d t r i a c e t a t e f i b e r s a n d c e l l u l o s e e s t e r
p l a s t i c s , i n c l u d i n g c e l l u l o s e a c e t a t e , c e l l u l o s e a c e t a t e b u t y r a te ( C A B ) , a n d c e l l u l o s e a c e t a t e p r o p i o n a t e
( C AP ) . These compounds are used for film and sheet and for mold ing and extrusion applications .
P r o d u c t i o n o f c e l l u l o s e a c e t a t e i n 1 9 8 7 w a s e s t i m a t e d t o b e a b o u t 8 1 0 m i l l i o n p o u n d s . About 430 million
p o u n d s w e r e u s e d t o m a k e c i g a r e t t e f i l t e r t o w , w h i l e t e x t i l e f i b e r s r e q u i r e d 1 5 0 m i l l i o n p o u n d s ; plastics
r e q u i r e d a b o u t 8 5 m i l l i o n p o u n d s , p h o t o g r a p h i c f i l m s a b o u t 5 0 - 5 5 m i l l i o n p o u n d s , a n d 9 2 m i l l i o n p o u n d s
were exported . P r o d u c t i o n o f c e l l u l o s e a c e t a t e i s f o r e c a s t t o g r o w s l o w l y a t 0 . 5 -1 .0% per year between
1987 and 1992 . E x p o r t s o f c i g a r e t t e f i l t e r t o w t o d e v e l o p i n g c o u n t r i e s w i l l b e t h e p r i m a r y g r o w t h a r e a .
( F o r m o r e i n f o n n a t i o n o n c e l l u l o s e a c e t a t e f b e r s a n d p l a s t i c s , s e e t h e C E H m a r k e t i n g r e p o r t s o n C e l l u l o s e
A c e t a t e a n d T r i a c e t a t e F i b e r s a n d C e l l u l o s e A c e t a t e a n d C e l l u l o s e E s t e r P l a s t i c s )
Acetic anhydride (derivatives other than cellulose acetate)
T h e r e a r e s e v e r a l s m a l l m a r k e t s f o r a c e t i c a n h y d r i d e t h a t a r e b e l i e v e d t o h a v e r e q u i r e d a n e s t i m a t e d 2 3 0
million pounds of acetic anhydride in 1987 . A weak U . S . d o l l a r i n 1 9 8 7 i n c r e a s e d d e m a n d f o r a c e t i c
a n h y d r i d e e x p o r t s t o o v e r 8 0 m i l l i o n p o u n d s , d o u b l e t h e a n h y d r i d e e x p o r t s i n 1 9 8 6 a n d s e v e n t i m e s t h e
amount shipped in 1985 . T h e m o s t c l e a r l y d e f i n e d d o m e s t i c m a r k e t f o r t h e a n h y d r i d e i s t h e a c e t y l a t i o n o f
salicylic acid to make aspirin a nd the manufa cture of acetaminophen (N-acetyl-para-aminophenol) .
Approxim ately 22-24 milli on pounds of acetic acid were required for these purposes in 1987 . Other
a p p l i c a t i o n s f o r a c e t i c a n h y d r i d e i n c l u d e s t a r c h a c e t y l a t i o n t o m a k e t e x t i l e s i z i n g a g e n t s , e l e c t r o l y t i c
p o l i s h i n g o f m e t a l s , s e m i c o n d u c t o r p r o c e s s i n g , v a r i o u s o x i d a t i o n r e a c t i o n s , a n d u s e i n t h e m a n u f a c t u r e o f
a c e t y l c h l o r i d e . Acetic anhydr ide may al so be used to make acetates of vitam in E (d- , or dl-al pha-
t o c o p h e r o l a c e t a t e ) . (For more infor mation, see the CEH data summa ry on Acetic Anhydr ide--U. S . D a t a ,
Su m m a r y . )
O O 1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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A c e t i c A c i d .
602 .5020 W
T h e m a j o r e s t e r s o f a c e t i c a c i d - e t h y l a c e t a t e , n - b ut y l a n d i s o b u t y l a c e t a t e , a n d n - p r o p y l a n d i s o p r o p y l
a c e t a t e - a r e u s e d m a i n l y a s s o l v e n t s f o r i n k s , p a i n t s , a n d c o a t i n g s . T h e y a r e p r e p a r e d b y e s t e r i f y i n g t h e
c o r r e s p o n d i n g a l c o h o l w i t h a c e t i c a c i d i n t h e p r e s e n c e o f a s u l f u r i c a c i d c a t a l y s t , w i t h m o r e t h a n o n e
e s t e r i f i c a t i o n o f t e n c a r r i e d o u t i n c o m m o n e q u i pm e n t a t t h e s a m e f a c i l i t y . E s t e r s o f a c e t i c a c i d a r e a l s o
p r o d u c e d a s b y - p r o d uc t s o f o t h e r r e a c t i o n s , r e d u c i n g t h e r e q u i r e m e n t s f o r a c e t i c a c i d .
A t o t a l o f 3 4 3 m i l l i o n p o u n d s o f a c e t i c a c i d w e r e r e q u i r e d f o r a l l e s t e r s o f a c e t i c a c i d ( i n c l u d i n g g l y c o l
e t h e r a c e t a t e s ) i n 1 9 8 7 . By 1992, acetic acid requirements for these compounds will be approximately
360-370 million pounds, assuming a projected growt h rate of 1 . 0 - 1 .5% annually . B u t y l a c e t a t e s , t h e
l a r g e s t g r o u p o f a c e t i c a c i d e s t e r s , w i l l s h o w t h e s t r o n g e s t g r o w t h , w i t h a 2 - 3 % a v e r a g e a n nu a l i n c r e a s e .
P r o p y l e n e - s e r i e s g l y c o l e t h e r a c e t a t e s w i l l g r o w b y d i s p l a c i n g e t h y l e n e - s e r i e s g l y c o l e t h e r a c e t a t e s , b u t
f u t u r e c o n s um p t i o n o f a c e t i c a c i d wi l l s t ay a t pr e s e n t l e v e ls . T h e r e m a i n i n g a c e t i c a c i d e s t e r s w i l l s h o w
l i t t l e o r n o g r o w t h .
A s u m m a r y o f ac e t i c a c i d r e q u i r e m e n t s f o r i m p o r t a n t e s t e r s f o l l o w s :
U.S . Consumption of Acetic Acid for MajorEsters and Glycol Ether Acetates-1987
(millions of pounds)
Butyl Acetates 120
Propyl Acetates 72
E t h y l A c e t a t e 76
G l y c o l E t h e r A c e t a t e s 6 5
Amyl Acetates 5
Other 5
T o t a l 343
SOURCE: CEH estima tes .
B u t y l a c e t a t e s
B u t y l a c e t a t e s a r e m a d e b y e s t e r i f y i n g t h e a p p r o p r i a t e a l c o h o l w i t h a c e t i c a c i d . F o u r p r o d u c e r s o f b u t y l
acetates in the United St ates operated in 1987 (BASF, Hoechst Celanese, Tennessee Eastman, and Union
Carbide) . I n 1 9 8 7 , a b o u t 2 9 0 m i l l i o n p o u n d s o f b u t y l a c e t a t e s ( n - b u t y l a n d i s o b u t y l ) w e r e p r o d u c e d i n t h e
United States. This represents an acetic acid requi rement of about 154 million pounds . However, by-
product production is estimated to hav e reduced the acet ic acid consumption in 1987 to 120 million
pounds . By 1992, butyl acetate production will re quire an estimated 132-138 million pounds of acetic
acid, assuming a projected average yearly growth of 2-3% . B u t y l a c e t a t e s a r e u s e d a s s o l v e n t s f o r f a s t -
drying paints and coatings an d account for 80% of domestic consumption . The remainder is used as a
r e a c t i o n m e d i u m a n d f o r o t h e r s o l v e n t a p p l i c a t i o n s t h a t i n c l u d e v i n y l r e s i n s , p r i n t i n g i n k s , a n d c o s m e t i c s .
(For more information, see the CEH data summary on Butyl Acetates- United States . )
1988 by the Chemical Economics Handbook-SRI International
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P r o p y l a c e t a t e s
P r o p y l a c e t a t e s a r e m a d e b y e s t e r i f y i n g t h e c o r r e s p o n d i n g a l c o h o l w i t h a c e t i c a c i d . H o e c h s t C e l a n e s e ,
T e n n e s s e e E a s t m a n , a n d U n i o n C a r b i d e a r e : p r o d u c e r s o f i s o p r o p y l a c e t a t e a n d n - p r o p y l a c e t a t e .
U. S . p r o d u c t i o n o f n - p r o p y l a c e t a t e i n 1 9 8 7 w a s 7 2 m i l l i o n p o u n d s , r e q u i r i n g a b o u t 4 0 m i l l i o n p o u n d s o fa c e t i c a c i d . T h e l a r g e s t u s e f o r n - p r o p y i a c e t a t e i s a s a s o l v e n t f o r p r i n t i n g i n k s , c o n s u m i n g a b o u t 7 0 % o f
t h e d o m e s t i c d e m a n d f o r n - p r o p y l a c e t a t e . I t i s a l s o u s e d a s a s o l v e n t f o r n i t r o c e l l u l o s e l a c q u e r s a n d o t h e r
c e l l u l o s e e s t e r s a n d e t h e r s . I s o p r o p y l a c e t a t e i s a l s o a s o l v e n t f o r a n u m b e r o f s y n t h e t i c a n d n a t u r a l r e s i n s
a n d i s u s e d w h e r e t h e r a t e o f e v a p o r a t i o n o f t h e s o l v e n t n e e d s c r i t i c a l c o n t r o l . P r o d u c t i o n o f t h e i s o p r o p y l
ester requires about 32 million pounds per year . Propyl acetates are projected to grow slowly at an
average annual rate betwe en 0% and 1% for the next five years, requiring between 72 million and 76
m i l l i o n p o u n d s o f a c e t i c a c i d .
E t h y l a c e t a t e
Hoechst Celanese, Texas Eastman, and Monsanto reported ethyl acetate production in 1987 . I n a d d i t i o n
t o t h e d i r e c t e s t e r i f i c a t i o n o f e t h a n o l , w h i c h i s u s e d b y a l l p r o d u c e r s , e t h y l a c e t a t e i s a l s o p r o d u c e d b y
H o e c h s t C e l a n e s e a s a b y - p r o d u c t o f t h e l i q u i d - p h a s e o x i d a t i o n o f b u t a n e t o a c e t i c a c i d a n d b y E a s t m a n
v i a t h e T i s h c h e n k o r e a c t i o n . I n t h i s r e a c t i o n , a c e t a l d e h y d e u n d e r g o e s o x i d a t i o n - r e d u c t i o n t o t h e e s t e r i n
the presence of an aluminum or sodium alkoxide catalyst . Monsanto produces ethyl acetate as a by-
p r o d u c t o f p o l y v i n y l b u t y r a t e p r o d u c t i o n .
I f a l l a c e t a t e p r o d u c t i o n w e r e m a d e b y t h e r e a c t i o n o f a c e t i c a c i d w i t h e t h y l a l c o h o l , 1 4 8 m i l l i o n p o u n d s
o f a c i d w o u l d b e r e q u i r e d . H o w e v e r , i t i s e s t i m a t e d t h a t t h e a c t u a l r e q u i r e m e n t f o r a c e t i c a c i d w a s o n l y 7 6
m i l l i o n p o u n d s i n 1 9 8 7 b e c a u s e a p o r t i o n o f t h e e t h y l a c e t a t e w a s a c c o u n t e d f o r b y o t h e r s o u r c e s . The
m a j o r a p p l i c a t i o n f o r e t h y l a c e t a t e i s a s a s o l v e n t f o r c o a t i n g s , p l a s t i c s , a n d o t h e r u s e s . Production of
e t h y l a c e t a t e i s e x p e c t e d t o g r o w a t a b o u t ; t % p e r y e a r , r e q u i r i n g a b o u t 8 0 m i l l i o n p o u n d s o f a c e t i c a c i d i n
1 9 9 2 . ( F o r a d d i t i o n a l i n f o r m a t i o n , s e e t h e C E H d a t a s u m m a r y o n E t h y l A c e t a t e - U n i t e d S t a t e s . )
Glycol monoether acetates
Glycol monoethers are produced by reacting ethylene oxide or propylene oxide with anhydrous methyl,
e t h y l , o r b u t y l a l c o h o l s . T h e m o n o e t h e r i s t h e n r e a c t e d w i t h a c e t i c a c i d t o f o r m t h e a c e t a t e. The three
largest-volume ether acetates are ethylene glycol monoethyl ether acetate, ethylene glycol mono butyl
e t h e r a c e t a t e , a n d p r o p y l e n e g l y c o l m o n o m e t h y l e t h e r a c e t a t e .
T h e s e a c e t a t e s a r e u s e d a s s o l v e n t s f o r n i t r o c e l l u l o s e a n d a c r y l i c l a c q u e r s , v a r n i s h r e m o v e r s , a n d w o o d
s t a i n s . T h e a c e t a t e o f m o n o b u t y l e t h e r h a s a p p l i c a t i o n s a s a s u r f a c e c o a t i n g s o l v e n t a n d a s a f u g i t i v e
p l a s t i c i z e r i n l a t e x a d h e s i v e f o r m u l a t i o n s . I t i s e s t i m a t e d t h a t 6 5 m i l l i o n p o u n d s o f a c e t i c a c i d w e r e
r e q u i r e d t o p r o d u c e t h e s e a c e t a t e s ( a p p r o x i m a t e l y 1 5 5 - 1 6 0 m i l l i o n p o u n d s t o t a l a c e t a t e s ) i n 1 9 8 7 . The
growth of ethylene series glycol ether s and ether acetates has been adversely affected by a nu mber of
l a b o r a t o r y s t u d i e s t h a t h a v e s h o w n t h e s e s u b s t a n c e s t o c a u s e b i r t h d e f e c t s i n l a b o r a t o r y a n i m a l s. Because
o f t h i s , a n d t h e s u s p i c i o n t h a t t h e y m a y a l s o p o s e h e a l t h h a z a r d s t o h u m a n s , s e v e r a l p r o d u c e r s h a v e l e f t
t h e b u s i n e s s a n d m a n y p r o d u c t s h a v e b e e n r e f o r m u l a t e d t o r e d u c e o r e l i m i n a t e g l y c o l m o n o e t h e r a c e t a t e s .
R e s t r i c t i o n s b y t h e E P A o n t h e u s e o f s o m e o f t h e s e p r o d u c t s h a v e b e e n i n e f f e c t s i n c e 1 9 8 5 . Propylene
g l y c o l m o n o e t h e r a c e t a t e s a r e e x p e c t e d t o s u b s t i t u t e f o r t h e e t h y l e n e g l y c o l m o n o e t h e r a c e t a t e s t o s o m e
e x t e n t i n t h e f u t u r e . F o r t h e n e x t f i v e y e a r s , a c e t i c a c i d d e m a n d f o r g l y c o l e t h e r a c e t a t e s w i l l r e m a i n
s t a t i c . (For more information, see the CEH marketing research reports on Glycol Ethers and Propylene
Oxide . )
1 9 8 8 b y t h e C h e m i c a l E c o n o m i c s H a n d b o o k - S R I I n t e r n a t i o n a l
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A m y l a c e t a t e s
Union Carbide was the only producer of amyl acetates in 1987 . These acetates are products of the
e s t e r i f i c a t i o n o f a m y l a l c o h o l s w i t h a c e t i c a c i d . P r o d u c t i o n o f a m y l a c e t a t e s i n 1 9 8 7 i s e s t i m a t e d t o h a v e
been 10-12 million pounds, requiring 4 . 5 -5 . 5 m i l l i o n p o u n d s o f a c e t i c a c i d . Requirements in 1992 will
remain at about 5 million pounds . A m y l a c e t a t e s a r e u s e d m a i n l y a s s o l v e n t s f o r n i t r o c e l l u l o s e l a c q u er s ,
consuming about 50% of the domestic demand . Other solvent applications include production of
p h o t o g r a p h i c f i l m s , l e a t h e r p o l i s h e s , t e x t i l e s i z i n g , a n d p r i n t i n g c o m p o u n d s . (F or more information, see
the CEH data summary on Amyl Acetates-United States . )
O t h e r a c e t i c a c i d e s t e r s
There are a number of other less important esters of acetic acid, most of which are used in solvent
a p p l i c a t i o n s . T h e s e i n c l u d e m e t h y l a c e t a t e u s e d a s a s o l ve n t f o r c e l l u l o s e n i t r a t e a n d c e l l u l o s e a c e t a t e ; 2 -
e t h y l h e x y l a c e t a t e , a s o l v e n t f o r l a c q u e r s , e m u l s i o n s , a n d i n k s ; g l y c e r y l t r i a c e t a t e , w i t h a p p l i c a t i o n s a s a
p l a st i c i ze r f o r c e ll u l o si c r e s i ns a n d c e l l ul o s e a c et a t e t o w ; a n d b e n z y l a c e t a t e ( r e q u i r i n g a b o u t 1 0 0 t h o u s a n d
p o u n d s o f a c e t i c a c i d ) , a f r a g r a n c e c h e m i c a l . A c e t i c a c i d c o n s u m e d f o r t h e s e e s t e r s i s e s t i m a t e d a t n o
m o r e t h a n 5 m i l l i o n p o u n d s a n d i s g r o w i n g v e r y s l o w l y .
Terephthalic Acid/Dimethyl Terephthalate (TPA/DMT)
A c e t i c a c i d m a y e i t h e r b e c o n s u m e d o r p r o d u c e d i n t h e p r o d u c t i o n o f t e r e p h t h a l i c a c i d ( T P A ) , d e p e n d i n g
u p o n t h e p r o c e s s u s e d .
In the United States, purified TPA is made by the Amoco process, which oxidizes 25% para-x ylene in
a c e t i c a c i d w i t h a i r i n t h e l i qu i d p h a s e . G l a c i a l a c e t i c a c i d i s u s e d t o d i l u t e t h e p - x y l e n e a n d i s l a t e r
r e c o v e r e d f o r r e c y c l e . A s m a l l p e r c e n t a g e o f t h e a c e t i c a c i d s o l v e n t i s o x i d i z e d a n d l o s t i n t h e p r o c e s s .
Du Pont produces crude TPA from para-xylene, which is then purified v ia DMT . These processes also
consume small amounts of acetic acid . Continuous improv ements have been made in these processes so
t h a t o n l y b e t w e e n 0 . 0 6 a n d 0 . 1 0 u n i t o f a c e t i c a c i d a r e l o s t p e r u n i t o f T P A p r o d u c e d . About 275 million
p o u n d s o f a c e t i c a c i d w e r e c o n s u m e d f o r t h i s p u r p o s e i n 1 9 8 7 .
Acetic acid was formerly produced by Eastman at K ingsport, Tennessee as a coproduct in the production
o f t e r e p h t h a l i c a c i d . In this process, ace taldehyde was used as a promoter