proceso de hidrogenacion new
TRANSCRIPT
8/8/2019 Proceso de Hidrogenacion New
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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
Lev e l in p lan t e f f lu en tN o n i o n i c I n f l u e nt : 5 m g / L I n f l u e n t : 2 5 m g / L
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 )
No n io n ic % No n io n ic o n d r ied so l id s
7 EO 0 .2 81 1 EO 0 .2 91 5 EO 0 .2 42 0 EO 0 .2 5
Co n t ro l p lan t 0 ,2 9
T A B L E V I
Po ly e th y len e Gly co l Lev e ls in P lan t E f f l u e n t s
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 .
Manufacture of Fat ty Alcohols
Based on Natural Fa ts and Oi ls
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
Natura l Synthe t ic
(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
T o t a l 4 1 0 5 8 0
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 ~
C R U D R A T F ~A C , ~ S
; §ES]ERIFICATION FRACTIONATIONOISTILLAIN
lCRUDE E] HYL STERS
;
I RACTIONArION]DISTILLATION
I
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I HYDROGENATION
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