CEH Acetic Acid

7/28/2019 CEH Acetic Acid

1/39

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

//legacy.library.ucsf.edu/tid/hhj82e00/pdf


2/39

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



3/39

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



4/39

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 .



5/39

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



6/39

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


7/39

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




8/39

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 .




9/39

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 .




10/39

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



11/39

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



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 - -




12/39

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



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




13/39

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


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 .


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



14/39

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



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



15/39

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



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 .


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



16/39

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

/legacy.library.ucsf.edu/tid/hhj82e00/pdf


17/39

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 .


/legacy.library.ucsf.edu/tid/hhj82e00/pdf


18/39

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 .


A c e t i c A c i d

6 0 2 .5020 R



19/39

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%




20/39

December 1988 ACETIC ACID Acetic Acid602. 5 0 2 0 i J

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



21/39

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



22/39

December 1988 ACETIC ACIDE s t e r s o f A c e t i c A c i d

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


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 . )




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December I988 ACETIC ACID Acetic Acid602 . 5 0 2 0 X

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 . )




24/39

December 1988 ACETIC ACID Acetic Acid60 2.5020 Y

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

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