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B I O D E G R A D A T I O N O F N O N I O N IC S U R F A C T A N T S

T A B L E I V

E f f e c t o f I n f l u e n t C o n c e n t r a t i o n o n E f f l u e n t L e v e l

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7 EO 0 .1 4 0 .1 5

11 EO 0.15 0 .1015 EO 0.21 0 .312 0 EO 0 .3 4 0 .6 2

Co n t ro l p lan t ( s ewag e o n ly ) 0 .3 3 0 .1 1

T A B L E V

Lev e ls o f No n lo n ic o n A c t iv a ted Slu d g e( I n f l u e n t C o n c e n t r a t i o n = 2 5 m g / L )

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7 EO 0 .2 81 1 EO 0 .2 91 5 EO 0 .2 42 0 EO 0 .2 5

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T A B L E V I

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I n f lu e n t " P E G " E f f lu e n t " P E G "No n io n ic (n ag /L) (mg /L) % Remo v a l

11 EO 19.8 0 . 7 7 96.015 EO 20.9 2 .61 88.02 0 EO 2 1 .8 2 .4 5 8 9 .0

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

b i o d e g r a d a t i o n s i n ce , t h r o u g h o u t , t h e a n a ly s i s w a s m a d e

u s i ng t h e W i c k b o l d m e t h o d w h i c h o n l y m e a s u r es i n t a c t

n o n i o n i c . T o o b t a i n s o m e i n d i c a t io n o f t h e l ev e l o f u l t i m a t e

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

e f f l u e n ts w e r e d e t e r m i n e d b y t h e H B r f is s io n m e t h o d d e s-

c r i b e d b y T o b i n e t a l. ( 3) . T h i s t e c h n i q u e d e t e r m i n e s t h e

t o t a l - O C H 2 " C H 2 - f u n c t i o n a l g r o u p s p r e s e n t i n t h e s a m p l e .T h e r e s u lt s o b t a i n e d a r e g i v e n in T a b l e V I .

T h e r e s u l t s c l e a r ly d e m o n s t r a t e t h a t a l a r ge p r o p o r t i o n

o f t h e P E G - li k e i n t e r m e d i a t e s a r e r e m o v e d d u r i n g t r e a t m e n t

a n d s h o w t h a t a l c o h o l e t h o x y l a t e s u n d e r g o e x t e n s i v e ul ti -m a t e b i o d e g r a d a t i o n d u r i n g s e w a g e t r e a t m e n t .

I n c o n t r a s t , T o b i n e t a l. ( 3) f o u n d o n l y c a . 25 % ' P E G '

d e g r a d a t i o n w h e n t e s t in g D o b a n o l 9 E 0 in t h e O E C D c o n -

f i r m a t o r y t e st . T h e r a t h e r l o w a c t i v i t y o f s l u d g es g r o w n

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

m a s s p r o d u c e d f r o m d o m e s t i c s e w a g e is t h e m o s t p r o b a b l e

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

A C K N O W L E D G M E N T S

Th e an a ly s i s fo r n o n io n ic s in p lan t s amp le s was d o n e b y J . Wa te r san d J .T . Ga r r ig an. T .R . Wi l l i ams p ro v id ed tech n ica l a s s i s tan ce .

R E F E R E N C E S

1. Wickb old , R. , Tens ide Deterg . 9 :173 (19 72).2 . B i rch , R .R . , Pre sen ta t io n a t th e XI I I Jo rn ad as d e l Co m i te

Esp an o l d e l a De te rg en c ia .3 . To b in , R .S .F . I . On u sk a , B .G . Bro wn lee , D . I [ . I. An th o n y an d

M.E. Co mb a , Wa te r Res . t0 :5 2 9 (1 9 7 6 ) .4 . R ich , L .G . , En v i ro n men ta l Sy s tems E n g in ee rin g , McG raw Hi ll

In c . , New Yo rk .

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UDO R . KREU TZ ER , Henke l KGaA , Pos tfach 1100, D -4000 Dusse ldor f 1 , West Germany

A B S T R A C T

Th e p re sen t wo r ld wid e cap ac i ty o f f a t ty a lco h o ls i s c a . 1 .0 mi l l io nme t r ic to n s p e r y ea r . Ab o u t 6 0 % o f th i s c ap ac i ty i s b a sed o n p e t ro -

ch emica l f eed s to ck s , 4 0 % o n n a tu ra l f a t s an d o i l s . Th ree b as ic d o -min a t in g co mmerc ia l - sca le p ro cesse s a re u sed to man u fac tu re f a t tya lco h o ls : th e Zieg le r p ro cess an d th e Ox o sy n th es i s s ta r t in g f ro mp e t ro ch emica l f eed s to ck s , an d th e h ig h -p re s su re h y d ro g en a t io n o fnatural fa t ty acids and esters . Basically , the h igh-pressure hydro-g en a t io n can b e u sed wi th t r ig ly ce r ide s , f a t ty ac id s o r f a t ty ac ides te r s as f eed s to ck . Th e d i rec t h y d ro g en a t io n o f f a t s an d o i l s ha s n o tb een d ev e lo p ed to a co mmerc ia l - sca le p rocess , ma in ly b ecau se i t wasn o t p o ss ib le to p rev en t d eco mp o s i t io n o f th e v a lu ab le b y p ro d u c tg ly ce ro l . Co n v e rs io n o f f a t ty ac id s in to f a t ty a lco h o ls b y ca ta ly t ich y d ro g en a t io n wi th o u t p ree s te r i f i c a t io n req u i re s co r ro s io n - re s i s tan tma te r ia l s o f co n s t ru c t io n an d ac id - re s i s tan t c a ta ly s t s . Req u i redreac t io n temp era tu re s a re h ig h e r , r e su l t in g in a h ig h e r h y d ro ca rb o nco n ten t . Th e ma jo r i ty o f f a t ty , a lco h o l p lan t s b a sed o n n a tu ra lfa t s an d o i l s u se me th y l e s te r s a s f eed s to ck . Th ese can b e mad ee i th e r b y e s te r i f i c a t io n o f f a t ty ac id s o r b y - t ran se s te r if i c a t io n o ft r ig ly ce r id e s . Fo r ca ta ly t i c h ig h -p re s su re h y d ro g en a t io n o f me th y l

e s te rs to f a t ty a lco h o ls , sev era l p ro cess o p t io n s h av e b een d ev e lo p ed .Th e b awic d i s t in g u ish in g fea tu re i s th e ca ta ly s t ap p l ica t io n e i th e rin a f ix ed b ed a r ran g eme n t o r su sp en d ed in th e me th y l e s te r f eed .

I N T R O D U C T I O N

F a t t y a l c o h o l s , p a r t i c u l a r ly t h e d e t e r g e n t r a n g e C 12 a n d

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

f o r a h o s t o f d e r i v a t iv e s a n d a p p l i c a t i o n s .T o d a y , i n th e W e s t e rn h e m i s p h e r e , t h e c o m m e r c i a l

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

p r o c e s s a l t e r n a t iv e s : t h e h i g h - p re s s u r e h y d r o g e n a t i o n o f

f a t t y a c i d s an d e s t e r s, t h e Z i e g l e r s y n t h e s i s, a n d t h e O x o

s y n t h e s i s .

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

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

n a t u r a l f a t s a n d o i ls a re t h e r a w m a t e r i a l s f o r t h e h y d r o -

g e n a t i o n o f f a t t y a c i d s a n d e s t e rs t o n a t u r a l a l c o h o l s ( 1 ).

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

f a t t y a l c o h o l s is c a . 1 . 0 m i l l i o n m e t r i c t o n s / y e a r ( T a b l e I ).

A r e g i on a l b r e a k d o w n o f t h e w o r l d c a p a c i t y i n t o n a t u r a l

a n d s y n t h e t i c f a t t y a l c o h o l s s h o w s t h a t i n t h e U S A th e

b u l k o f f a t t y a l c o h o l s i s o f p e t r o c h e m i c a l o r ig i n , w h e r e a s

i n E u r o p e m o r e t h a n 6 0 % o f t h e t o t a l v o l u m e i s m a d ef r o m n a t u r a l f a t s a n d o i ls . W o r l d w i d e , c a . 60 % o f t h e f a t t y

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

JAOCS, vol . 61, no. 2 (February 1984)

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U . R. K R E U T Z E R

T A B L E I

W o rld C a p a c i t y 1 9 8 3 - N a t u ra l a n d S y n t h e t i c F a t t y A l c o h o l s

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(1 ,000 met r ic tons )

E u r o p e 2 2 0 1 3 0

U S A 1 3 0 4 0 0A s i a 6 0 5 0

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c a . 4 0 % o n n a t u r a l f a t s a n d o i l s .

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

o r d e r o f 7 0 0 , 0 0 0 m e t r i c t o n s / y e a r , c o r r e s p o n d i n g t o a n

o v e r a l l c a p a c i t y u t i l i z a t i o n o f c a . 7 0 % .

Process Alternative s

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

s t a r t e d a b o u t 5 0 y e a r s a g o , b u t c o n t i n u o u s t e c h n o l o g i c a l

d e v e l o p m e n t i m p r o v e d t h e e c o n o m y o f t h is p r o c e s s s ig n i-

f i c a n t l y .

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

s y s t e m s , t o r e d u c e t h e e n e rg y c o n s u m p t i o n , a n d t o in s t a ll

a u t o m a t i c c o m p u t e r s y s t e m s to r u n a t o p t i m u m e f f ic i e n c y

w i th a m i n i m u m o f m a n p o w e r .

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

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

m a t e r i a l . P r i m a r y f e e d s t o c k s f o r t h e C 1 2- C1 4 r a n g e a r e

c o c o n u t a n d p a l m k e r n e l o i l , a n d f o r C 1 6 -C 1 8 a l c o h o l s

t e c h n i c = l g r a d e s o f t a l l o w a n d p a l m o i l a r e u s e d .A g r e a t v a r i e t y o f s p e c i a l a l c o h o l s is r e a d i l y a v a i l a b l e

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

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

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

a l c o h o l s w i t h i o d i n e v a l u e s u p t o 1 7 0 f r o m l i n s e e d o il .

F i g u r e 1 s h o w s t h e v a r i o u s r o u t e s f r o m n a t u r a l f a t s

a n d o i l s t o f a t t y a l c o h o l s .T h e o r e t i c a l l y , t h e s i m p l e s t w a y t o c o n v e r t f a t s a n d o i l s to

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

T h i s o n e - s t e p p r o c e s s w o u l d s av e t h e m a n u f a c t u r e o f in t e r -

m e d i a t e s l i k e f a t t y a c i d s o r m e t h y l e s te r s. T h e c a t a l y t i c

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

h a s a m a j o r d r a w b a c k . T h e r e a c t i o n c o n d i t i o n s w h i c h h a ve

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

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

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

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

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

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

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

A n o t h e r o p t i o n i s th e s p l i t ti n g o f f a ts a n d o i ls i n t o f a t t y

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

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

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

e s t e r i f ic a t i o n is c o n n e c t e d w i t h s o m e s p e c if i c r e q u i r e m e n t s

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

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

h a s t o b e d e s i g n e d f o r a h ig h e r t e m p e r a t u r e a n d p r e s su r e

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

a c i d - r e s i s t a n t .

T h e h y d r o g e n a t i o n o f f a t t y a c i d s is b a s ic a l l y f e a s ib l e

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

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

c a . 3 0 0 C , i . e ., c a . 5 0 - 1 0 0 C h i g h e r t h a n n e c e s s a r y f o r t h e

h y d r o g e n a t i o n o f m e t h y l e s t e rs . T h e s e m o r e r i g o ro u sr e a c t i o n c o n d i t i o n s l e a d t o a c e rt a i n a m o u n t o f o v e r h y d r o -

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

OIL R FAT

1 0 L Y C E R I N ~~ I I G " C E ~ N ~

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FATTY LCOHOLS

J I RACIIONATIONDISTILLAIION

I YDROGENATION

F I G . 1 . Ma n u f a ct u r in g ro u t es o f f a t t y a lco h o l s f ro m n a t u ra l f a t sa n d o i l s .

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

t h e c a s e w h e n a b r o a d c u t o f f a t t y a c i d s is u s e d a s f e e d -

s t o c k .T h e f o r m a t i o n o f h y d r o c a r b o n s m e a n s a d r o p i n o v e r al l

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

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

r e s i s t a n t s in c e o th e r w i s e s o a p f o r m a t i o n w o u l d t a k e p l a c e ,

e n t a i l i n g a h i g h e r c a t a l y s t c o n s u m p t i o n a n d a d d i t i o n a lp u r i f i c a t i o n a n d r e w o r k s t e p s . T h e a c i d - r e s i s t a n t c o p p e r

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

i n g . T h u s i t h a s a s h o r t u s e f u l l i f e, a n d - a m a j o r d r a w b a c k

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

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

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

L a s t n o t l e a st , t h e r e a r e so m e o p e n q u e s t i o n s r e g a r d in g

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

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

p e r a t u r e o f c a . 3 0 0 C . T o m y k n o w l e d g e , i t i s b e c a u s e o f

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

a c i d s is n o t u s e d o n a l a r g e c o m m e r c i a l s c a l e .

L u r g i ( 2 ) h a s d e v e l o p e d a h y d r o g e n a t i o n p r o c e s s w h i c h

a l l o w s th e u s e o f f a t t y a c i d s a s f e e d s t o c k w i t h o u t p r e v i o u s

e s t e r i f i c a t i o n i n a s e p a r a t e u n i t . L u r g i c h a r a c t e r i z e s t h i s

s u s p e n s i o n p r o c e s s i n t h i s w a y : t h a t b y r e c i r c u l a t in g f a t t y

a l c o h o l i n a f i r s t s t e p , a n " i n s i t u " e s t e r i f i c a t i o n t a k e s

p l a c e t o c o n v e r t t h e f a t t y a c i d i n t o a w a x e s t e r . T h e s e c o n d

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

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

t h e h y d r o g e n o l y s i s o f a n e s te r .

Methyl Ester Preparation

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

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

o f f a t t y a c id s , p r e f e r a b l y m e t h y l e s t e r s, h a v e b e c o m e t h e

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

i s m a n u f a c t u r e d v i a t h e m e t h y l e s t e r r o u t e . M e t h y l e s t er s o ff a t t y a c i d s ca n b e m a d e e i t h e r b y e s t e r if i c a t i o n o f f a t t y

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

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MANUFACTURE OF FATTY ALCOHOLS

The esterification can be done batchwise under pressure

at temper ature s of ca. 200-250 C. Since the esterifica tion is

an equilibrium reaction, the reaction water has to be

removed co ntinuo usly to obtai n a high ester yield.

A favorable process op tion is the con tin uou s esterifica-

tion in a countercurrent reaction column. Henkel has

developed a process technol ogy based on the principle of

an esterification reaction with a simultaneous absorption ofsuperheated methano l vapor and desorption of the reaction

water (Fig. 2) (3). The principle of this process is an esteri-

fication reaction with a simultaneous absorption of super-

heated methanol vapor and desorption of the reaction

wa te r .

Preheated fatt y acid cont aini ng an alkaline catalyst is

fed into a double bubble plate distillation column from the

top, countercurrent to methanol that enters the column

from the bottom. The reaction is carried out at a pressure of

ca. 10 bar and a temperature of 240 C. Excess methanol

can be ke pt significantly lower th an in the batch esteri-

fication. The batch process under pressure requires a

molar ratio of methanol to fatty acid of 3-4:1, whereas

for the con tin uou s process a molar ratio of 1.5:1 is suf-

ficient. The excess methanol leaves the column at the toptogether with water formed during the reaction (methanol /

water = 50:50 weight %), the methyl ester is taken off at

the bot tom and, afte r passing a flash vessel to remove

traces of methanol , enters a distillation unit. The methy l

ester leaving the flash vessel has an acid value of down to

0.5 and does no t require a refining step. The methy l ester

is separated from the catalyst cont aining residue by topping

off u nder vacuum. The metha nol is purified by rectification

and is reused as starting material.

The esterification is a preferential method for esters

from specific fatty acids, which no lo nger repre sent the

original composition of a natural fat, e.g., by separation

into an olein and a stearin fraction. The con tinuou s esteri-

fication process in a reaction column is superior to the

batch process, in that the same high yield can be obtained

in a muc h shorter dwell time and with a substanti ally lower

excess of methanol.

The predominant process for the manufacture of methyl

esters is the transesterification of fats and oils with meth-

anol. The ester intercha nge, i.e., the repl aceme nt of the

alcohol component glycerine by methanol takes place

METHANOL

AQUEOUSMETHANOL

4

I CATA L TETNANO:

VACUUM

METHYL ESTER

, ~

/ ~ FATTYACID

REACTION- FL A SH DISTILLATIONCOLUMN

FIG. 2. Manufacture of fatty acid meth yl esters by esterif ication.

RESIDUE

METHANOL01L CATALYST GLYCERNE

MEHYLESTERi

RESIDUE

, >

TRANSESTERIFICATION METHANOL/GLYCERINESEPARATION

METHYL ESTER

DISTILLATION

FIG. 3. Manufacture of fatty acid methyl esters by transesterification.

JA OCS , vo l . 6 1 , n o . 2 (F e b r u a ry 1 9 8 4 )

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3 4 6

U . R . K R E U T Z E R

q u i t e e a s i l y a t l o w t e m p e r a t u r e s o f c a . 5 0 - 7 0 C a n d u n d e r

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

t h e p r e s e n c e o f a l k a l in e c a t a ly s t . A f t e r t h e r e a c t i o n m i x t u r e

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

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

p r o c e s s e d .T h e s e m i l d r e a c t i o n c o n d i t i o n s , h o w e v e r , r e q u i r e a pr e -

n e u t r a l i z a t i o n o f t h e f a t b y m e a n s o f e .g . , a l k a l i r e f i n i n g ,

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

T h e r e m o v a l o f fr e e f a t t y a c i d s ( F F A ) i s n o t r e q u i r e d i f

t h e t r a n s e s t e r i f i c a t i o n i s c a r r ie d o u t u n d e r p r e s s u r e , e .g . ,a t 9 0 b a r a n d a t a h i g h e r t e m p e r a t u r e , e . g . , a t 2 4 0 C . U n d e r

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

a h ig h F F A c o n t e n t c a n b e c o n v e r t e d i n t o m e t h y l e s t e r s

w i t h o u t p r e n e u t r a l i z a t i o n , s i n c e a s i m u l t a n e o u s e s t e r i f i c a -

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

F i g u r e 3 s h o w s t h e p r o c e s s f l o w d i a g r a m o f a c o n t i n u o u s

t r a n s e s t e r i fi c a t i o n u n i t d e s i g n ed f o r h i g h e r p r e ss u r e a n d

t e m p e r a t u r e . U n r e f i n e d o i l, m e t h a n o l - i n an e x c e ss o f

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

2 4 0 C a n d a r e f e d i n p a r a l le l f l o w i n t o t h e b o t t o m o f th e

r e a c t o r b y m e t e r i n g p u m p s . A f t e r fl a s h in g o f f th e b u l k o f

t h e e x c e s s m e t h a n o l , t h e r e a c t i o n m i x t u r e e n t e r s a se p a r a -t o r , i n w h i c h s e t t l in g in t o a n u p p e r l a y e r c o n t a i n i n g t h e

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

a l l o w e d . I n a b u b b l e t r a y c o l u m n w i t h r e f lu x , p u r e m e t h -

a n o l i s t o p p e d o f f a n d t h e n r e c y c l e d i n t o t h e t r a n s e st e r i -

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

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

T h e g l y c e r i n e w i t h a p u r i t y o f m o r e t h a n 9 0 % is r e m o v e d

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

t o a s u b s e q u e n t v a c u u m d i s t i ll a t i o n . A c c o r d i n g t o f a t t y

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

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

a p p l i e d .

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

p r e s s u r e d o e s n o t r e q u i r e p r e s s u r e v e ss e l s, r e s u l t in g i n lo w e r

c a p i t a l i n v e s tm e n t , a n d t h e e x c e s s o f m e t h a n o l c a n b ek e p t l o w e r t h a n i n t h e p r e s s u r e p r o ce s s .

T h e a m o u n t o f a q ue o u s m e t h a n o l t o b e r e w o r k e d f o r

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

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

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

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

a l l o w s t h e u s e o f i n f e r i o r g r a d e s o f o i l w i t h a h i g h F F Ac o n t e n t w i t h o u t p r e v io u s t r ea t m e n t .

High-Pressure Hyd rogen ation

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

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

g e n e o u s c a t a l y s ts . T h e r e a r e s e v e ra l a p p r o a c h e s t o c l a s s i f y

t h e v a r i o u s p r o c e s s a l te r n a t i v e s, d e p e n d i n g o n w h i c h

f e a t u r e o n e w a n t s t o e m p h a s i z e . D e p e n d i n g o n t h e f o r m

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

c a n b e d i v i d e d i n t o s u s p e n s i o n a n d f i x e d b e d p r o c e s s e s .

F i g u r e 4 s h o w s a s i m p l i f i e d p r o c e s s f l o w d i a g r a m o f a

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

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

f r o m t h e b o t t o m . T h e c a t a l y s t , at l e a s t 2 % c o p p e r c h r o -

m i t e p o w d e r s u s p e n d e d i n m e t h y l e s t er , is a d d e d b y a

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

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

2 5 0 - 3 0 0 b a r a n d 2 5 0 - 3 0 0 C . T h e e s te r t h r o u g h p u t p e r h o u r

i s i n t h e o r d e r o f m a g n i t u d e o f t h e r e a c t o r v o l u m e . C a . 2 0

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

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

a g i t a t io n . T h e i n l e t t e m p e r a t u r e d e p e n d s u p o n t h e d e g re e

o f u n s a t u r a t i o n o f t h e f a t t y c a r b o n c h a in . S in c e t h e h y d r o -

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

e s t e r s i s s t a r t e d a t t h e l o w e r e n d o f t h e a b o v e m e n t i o n e d

t e m p e r a t u r e r a n g e, f o r , w i th i n c r e a s i n g t e m p e r a t u r e , u n -

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

f a v o r e d .

T h e r e a c t i o n m i x t u r e i s c o o l e d a n d s e p a r a t e d in t o l iq u i d

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

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

a m e t h a n o l s t r i p p i n g u n it . A f t e r r e m o v a l o f t h e m e t h a n o l

t h e c a t a l y s t is f i l t e r e d o f f . T h e c r u d e f a t t y a l c o h o l s t i ll

c o n t a i n s 2 - 5 % e s t e r w h i c h c a n b e r e m o v e d b y a d d i t i o n o f

a l k a li t o f o r m s o a p w h i c h r e m a i n s i n t h e b o t t o m o f t h e

s u b s e q u e n t d i s t i ll a t i o n . D u e t o o v e r h y d r o g e n a t i o n o f t h e

f a t t y a l c o h o l , u p t o 2 - 3% h y d r o c a r b o n s a r e f o r m e d , l o w e r -

i n g t h e o v e r a l l y i e l d s i g n i f i c a n t l y . E v e n w i t h r e c y c l i n g , t h ec a t a l y s t c o n s u m p t i o n i s i n t h e r a n g e o f 0 . 5 -0 . 7 % .

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

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

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

e s t e r i s u s e d a s f e e d s t o c k .

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

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

t h a t t h e e q u i p m e n t i n t o u c h w i t h t h e f a t t y a c i d is m a d e

CATALYST~ = ~

FATTYCI DMETHYL STER

FATTYACDMETHYLESTER

i ACTORSEPARATORS

RECYCLEAS

HYDROGEN~ ,

I MET~

METHANOLSEPARATON

R I L T R A T 0 ~ ~

CRUDERATTY LCOHOLS

F I G . 4 . H igh -p ressu re h yd rogen at ion o f f a t t y a c i d m e t h y l e s t e rs - - suspension process.

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M A N U F A C T U RE O F F A T T Y A L C O H O L S

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

s u c h a s t h e A d k i n s - t y p e c o p p e r c h r o m i t e .

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

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

s y s t e m . D e p e n d i n g o n w h e t h e r t h e o r g a n i c fe e d p a s s e s

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

s t a t e , t h e t e r m s v a p o r p h a s e o r t r ic k l e h y d r o g e n a t i o n a r e

i n u s e .S i n c e t h e s t a t e o f a g g r e g a ti o n o f t h e r e a c t i o n m i x t u r e

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

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

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

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

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

o n e d i s t i n g u i s h e s b e tw e e n t h e f i x e d b e d p r o c e s s es b y t h e

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

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

m a s s i v e c a t a l y s t is e m p l o y e d ( F i g . 5 ) , a p a r t o f t h e o r g a n i c

f e e d i s v a p o r i z e d i n a n e x c e s s o f 2 0 - 5 0 m o l e s o f h y d r o g e n ,

a n d p a s s e d o v e r t h e f i x e d b e d c a t a l y s t . T h e h y d r o g e n a t i o n

i s a c c o m p l i s h e d a t a p r e s s u re o f 2 0 0 - 3 0 0 b a r a n d a t e m -

p e r a t u r e o f 2 0 0 - 2 5 0 C . T h e m e t h y l e s t e r i s m i x e d w i t h

f r e sh a n d r e c y c l e d h i g h - p re s s u r e h y d r o g e n a n d h e a t e d u p b yh e a t i n t e rc h a n g e w i t h t h e r e a c t i o n m i x t u r e l e a vi n g t h e

r e a c t o r . T h e f e e d is b r o u g h t u p t o p r o c e s s t e m p e r a t u r e b y a

p e a k h e a t e r a n d e n t e r s o n e o r s e v er a l r e a c t o r s f r o m t h e t o p .

T h e m a i n l y v a p o r i z e d m a t e r i a l p a ss e s o v e r th e f i x e d c a t a l y s t

b e d .

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

t h e c o m p a c t p e l l e t i z e d c a t a l y s t c o n s is t s o f a b l e n d o f m e t a l

o x i d e s c o n t a i n i n g c o p p e r , e . g ., c o p p e r / z i n c o x i d e . S i nc e t h e

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

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

c o p p e r / z i n c c a t a l y s t i s n o t a c i d - r e s is t a n t a n d c o n s e q u e n t l y

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

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

f a t t y a c i d m e t h y l e s t e r s r e m a i n u n c h a n g e d , i . e ., u n s a t u r a t e de s t e rs c a n b e c o n v e r t e d i n t o u n s a t u r a t e d f a t t y a l c o h o l s .

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

u n s a t u r a t e d f a t t y a l c o h o l s w i t h i o d i n e v a l u e s u p t o 1 7 0

c a n b e m a n u f a c t u r e d .

A f t e r l e a v in g t h e r e a c t o r , t h e r e a c t i o n m i x t u r e i s c o o l e d

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

t o r . T h e g a s e o u s p h a s e c o n s i s t i n g m a i n l y o f e x ce s s h y d r o -

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

i n t o a f la s h t a n k i n w h i c h m e t h a n o l i s s t r i p p e d f r o m t h e

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

p u r i f i c a t i o n . I f , h o w e v e r , n a r r o w c u t s a r e d e s ir e d , a n d a

f r a c t i o n a t io n h a s n o t a l r ea d y b e e n m a d e w i t h t h e m e t h y l

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

p r i a t e r e c t i f i c a t i o n u n i t .

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

m i l d . T h e h i g h a m o u n t o f r e c i r c u l a t e d ga s p r o v i d e s f a s t

r e m o v a l o f t h e h e a t o f r e a c t io n , k e e p i n g s i de r e a c t i o n s

s u c h a s h y d r o c a r b o n f o r m a t i o n a t a v e r y lo w l ev e l . T h eo v e r a l l y i e l d o f f a t t y a l c o h o l is c a . 9 9% , w i t h a c o n t e n t o f

h y d r o c a r b o n s a n d n o n h y d r o g e n a t e d e s te r n o t e x c ee d i n g

1 .0 % . T h e c a t a l y s t c o n s u m p t i o n i s b e l o w 0 . 3 % .

T h e f i x e d b e d p r o c e s s in w h i c h a s u p p o r t e d c a t a l y s t is

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

a s u s e d f o r m a s s i v e c a ta l y s t s . A l s o , t h e r e a c t i o n c o n d i t i o n s

a r e si m i l a r t o t h o s e f o r c o m p a c t c a t a l y s t s.

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

t r i c k l e s d o w n o v e r t h e f i x e d c a t a l y s t b e d i n a l i q u i d s ta t e .

T h e m o l a r e x ce s s o f h y d r o g e n a n d t h e r e w i th t h e a m o u n t

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

w i t h c o m p a c t c a t a l y st s . B e c a u s e o f t h e l iq u i d s t a te o f th e

f e e d , t h e c a t a l y s t h as t o b e o f a h ig h m e c h a n i c a l s t a b i l i t y ;

t h e r e f o r e , s u p p o r t e d c a t a l y s t s l i k e 2 0 - 4 0% c o p p e r c h r o m i t e

o n a s i l i c a g e l c a r r i e r a r e u s e d . T h i s h i g h m e c h a n i c a l s t a b i -l i t y o f t h e s u p p o r t e d c a t a l y s t a ll o w s a l so th e h y d r o g e n a t i o n

o f m a t e r i a l s n o t e a s i l y v o l a t i l i z e d , l i k e w a x e s t e r s .

T h e f a t t y a l c o h o l s f r o m t h i s p ro c e s s a r e o f th e s a m e

h i g h q u a l i t y a s a c h i e v e d w i t h m a s s i v e c a t a l y s t s , p a r t i c u l a r l y

w i t h r e g a r d t o t h e l o w h y d r o c a r b o n c o n t e n t . T h e s p e c i fi c

c a t a l y s t c o n s u m p t i o n c a n b e k e p t d o w n t o ca . 0. 3 % .

S i n c e t h e s p e c i f i c t h r o u g h p u t r a t e , i . e ., t h e s p a c e -

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

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

s a m e t h r o u g h p u t . O n t h e o t h e r h a n d , t h e a m o u n t o f

r e c y c l e g a s c a n b e k e p t l o w e r , w h i c h a l l o w s r e d u c t i o n si n o t h e r e q u i p m e n t , s u c h a s g a s r e c i r c u l a t i o n p u m p s , a n dp i p i n g d i m e n s i o n s .

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

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

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

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

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

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

a l c o h o l , a n d r e w o r k o f t h e u n r e a c t e d m e t h y l e s t e r is m o r e

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

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

f i x e d b e d p l a n t .

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

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

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

FATTY ACiD

METHYL ESTER

HYDROGEN, > - -

P R E H E ~ Ir c o J

I

RECYCLINGAS

GASOMETER

F L A S H A N K

F AT T Y LC OH OL

FIG. 5 . High-pressurehydrogenationof fa t ty ac id methy l es te r s - f ixed bed process .

JAOCS, vo l . 61 , no . 2 (February 1984)

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348

U.R. KREUTZER

with a very low formation of hydrocarbons. The catalyst

consumption of the suspension process, which is in the

range of 0.4-0.7%, is considerably higher than in the fixed

bed process (0.2-0.3%). Energy consu mpt ion is estima ted

to be in the same order of magnitude, the suspension pro-

cess requiring higher temperatures, and the fixed bed process

having a larger power insta1Ied for bigger recircuIation

pumps and compressors.The qualit y of the crude fatty alcohols resulting from

the fixed bed process is better, with a lower hydrocarbon

cont ent and lower saponification values. The fatty alcohol

of the suspension process can be brought up to the same

quality level; however, this requires an additional purifica-tion step.

REFERENCES

1. Schdtt, H., UIImanns Encyklopi~die der Techn. Chemic, 4th

edn., Vol. 11, 1976, p. 427.2. Buchold, H., Chem. Eng. 90:42 (1983).3. Jeromin, L ., et al., Fette, Seifen, Anstrichm. 83:493 (1981).

W est European Household D etergent Trends

E. SO LL EV EL D, S hel l International Chem ical Co. Ltd., Shel l Centre, London SE1 7PG,United Kingdom

A B S T R A C T

It is estimated that there wil l continue to be a relatively stronggrowth in demand for alcohol derivatives, ca. 3 times as high asthat for the product sector as a whole. Detergent alkylate growthwill be somewhat lower, but it will remain the staple diet of theindustry and by far the single largest volume detergent intermediate.

Household detergents - both the heavy-duty product s

used for the domestic laundry and the light-duty washing-

up liquids - const itut e the single largest segment of various

detergent market sectors. In terms of active matter, it

represents some 60% of a total annua l West Europ ean

demand currently r unning at ca. 1,200,000 metric tons.

The household market is tending towards maturity and

its growth has now declined to levels below expectedaverage West European GNP growth rates. Although the

future detergent product growth rates may be modest in

comparison with those of the 1950s and 1960s, the growth

in demand for particular types of active matter is expected

to be considerably higher. Within an overall modest growth

rate for the product as sold to the consumer and assuming

no change in average active matter content, a high relative

growth rate for particular types of active matter can be

achieved if products are reformulated.

The driving forces for the expected reformulation -

particularl y of the heavy-du ty produc ts - are provided by

both environmen tal requirements and the need to mainta in

the pro ducts as new and innovative in the consu mer's

mind. Thus, even in depressed economic conditions, one

would expect change to occur, and, particularly if this iscoupled with improved cost performance of the product,

change becomes inevitable.

It is necessary for a company like my own, a major

supplier of detergent intermediates (the chemical deriva-

tives of which find their way into the products sold to the

consumer) to understand these formulatory trends if we

are going to con tin ue to be successful in providing produ cts

in the right volumes at the right times in response to mar ketrequirements.

L I G H T - D U T Y L I Q U I D S

Former growth rates of 7-8% per ann um have declined and

are expected to be of the order of 1-2% per annum until the

end of the decade. The historical usage and expected futuredemand is shown in Table I.

The higher growth rate in the latter part of the decade is

JAOC S, vol. 61, no. 2 (February 1984)

caused by some count ries changing from powd ers to liquids.Formulation of light-duty liquids has changed over the

last 10 years principally as a result of the introduction of

paraffin sulfonates. Further changes are expected as alpha

olefin sulfonate s (AOS) be come increasingly available and

afford the formulator the opportunity to improve the

mildness of the product while mainta ining detergency. The

expected changes in demand for active matter are shown in

Table 1.

H E A V Y - D U T Y S E C T O R

The heaw-duty product sector is by far the largest of the

household product market, as shown in Table lI. It is in

this sector that environmental constraints have, and will

continue for some time to have, a strong influence on theformu lati on of these products. Signific ant parameters inthis context are:

-t re nd towards lower phosphate levels from 30-40%

to ca. 20% backed by legislation in some countrie s;

-energy conservation lowering average wash tempera-

tures from 60 C to 40 C;

-further slight increase of the synthetic component in

the textile mix; and

- product cost/performance.

Although 2-3 years ago we expected the industry res-

ponse to these requirements to be both higher active matter

levels and increased usage of alcohol long-chain etho xylat es

(nonionics), matters developed differently. Currently there

are four separate trend s or comb inat ions of these: high

nonionic based formulations, high bleach levels, use ofbleach activators, and zeolite/phosphate combinations.

The basic expectation that usage of nonionics would

increase was correct. It is relevant to point out th at the

reason for the use of long-chain ethox ylates was their

lower sensitivity to hard water - compared to alkyl benz ene

sulfonat e - and their efficiency in cleaning, particularl y of

synthetic s. The use of these prod ucts also permit ted the

cost/performance of the product to the enhanced: washing

efficiency was improved and the expensive phosphate

compo nent reduced. Additionail y, heavy-duty Iiquids were

introduced into German y and France - two of the major

detergent markets in West Europe -- the majority of these

liquids contain no phosphate; to compensate for this, they

contain nearly 3 times as much active matter as powders

per unit weight of product.Although we expect that, for the reasons already cited,

long-chain ethoxylates will continue to increase it is also