. CHEMICAL
* M E T A L L U R G I C A L
ENGINEERING
E S T A B L I S H E D 1 9 0 î
A P R I L , 1 9 4 0
S. D. K IR K PA TR IC K , Editor
Regularizing Chemical Employment
E
x c e p t f o r th e p r o d u c tio n o f fe rtiliz e rs , c o tto n s e e d o il a n d a few s p e c ia l p r o d u c ts s u c h a s a n ti-fre e z e , th e c h e m ic a l in d u s tr ie s a r e re la tiv e ly fr e e f r o m s e a s o n a l v a r ia tio n s . E m p lo y m e n t h a s sh o w n g r e a te r th a n a v e ra g e s ta b ility even in th e fa c e o f r a t h e r v io le n t f lu c tu a tio n s in g e n e ra l b u s in e s s c o n d itio n s . T h is d e s i r a b le c o n d itio n h a s b e e n d u e n o t o n ly to th e d iv e rs ifie d c h a r a c te r o f c h e m ic a l m a n u f a c tu r e a n d d is t r i
b u tio n , b u t a ls o to c a r e f u l p la n n in g a n d s c h e d u lin g of p r o d u c tio n . A d e lic a te b a la n c e o f m a n y c o m p e titiv e f a c to r s a n d re la tio n s h ip s is n o w th r e a te n e d b y f u r th e r in v a s io n o f G o v e rn m e n t in to th e a ffa irs o f p r iv a te e n te r p ris e .
I n a s tu d y o f e m p lo y m e n t r e g u la r iz a tio n a m o n g 183 m e m b e r c o m p a n ie s re c e n tly c o m p le te d b y a c o m m itte e o f th e N a tio n a l A s s o c ia tio n o f M a n u f a c tu r e r s , it w as fo u n d th a t th e W a g e -H o u r L a w h a d a d d e d a n ew o b s ta c le to s ta b iliz a tio n . W h e re in th e p a s t so m e c o m p a n ie s h a v e f o u n d t h a t th e a v e r a g in g o f w o rk -h o u rs a m o n g e m p lo y e e s m a d e it p o s s ib le to p r o v id e a g re a te r d e g re e o f e m p lo y m e n t r e g u la r iz a tio n th r o u g h o u t th e y e a r, th is m e th o d is n o w r e s tr ic te d b y th e W a g e -H o u r L a w .
B u t m o r e s e r io u s p ro b le m s fo r c h e m ic a l in d u s try a r e in v o lv e d in th e p ro c e s s o f fix in g m in im u m w ag es u n d e r th e p ro v is io n s o f th e W a ls h -H e a ly P u b lic C o n tr a c ts A c t. E v e n th o u g h a firm m a y n o t b e p ro d u c in g g o o d s f o r sa le u n d e r p u b lic c o n tr a c t, it c a n b e affected b y th e s e w a g e d e te r m in a tio n s . T h e y e s ta b lis h p r e c e d e n ts t h a t c a n a n d w ill b e u s e d b y la b o r o rg a n iz e rs . A n d th e y u p s e t c o m p e titiv e r e la tio n s b e tw e e n d iffe re n t d iv is io n s w ith in a n in d u s tr y .
C o n s id e r, f o r e x a m p le , th e w id e r a n g e in m in im u m w a g e s a lr e a d y e s ta b lis h e d w ith in th e p ro c e s s in d u s tr ie s . I n th e c a se o f f e r til iz e r m a n u f a c tu r e r s a r e g io n a l d if fe re n tia tio n p e r m itte d a m in im u m w a g e in th e S o u th
o f 2 5 c e n ts p e r h o u r (w h ic h w a s s u b s e q u e n tly r a is e d b y th e W a g e -H o u r L a w to 3 0 c e n t s ) . In th e e x p lo s iv e s i n d u s tr y a s in g le m u c h h ig h e r m in im u m o f 5 7 ^ c e n ts h a s b e e n fix ed . P r e s u m a b ly h e a v y c h e m ic a l m a n u f a c t u r e r s w ill b e g iv e n a m in im u m so m e p la c e b e tw e e n th e s e tw o e x tre m e s .
N o w su p p o s e th a t th e G o v e rn m e n t is b u y in g s u l
p h u r ic a c id . I t m ig h t w ell o b ta in its re q u ir e m e n ts f r o m a f e r tiliz e r c o m p a n y o r f r o m a h e a v y c h e m ic a l firm o r f r o m a n e x p lo s iv e s m a n u f a c tu r e r . I n th e s e th r e e c a se s th e r e m ig h t b e th r e e d if fe re n t lev els o f m in im u m w a g e s u n d e r th r e e s e p a r a te r u lin g s o f th e S e c r e ta r y o f L a b o r . T h e fe r tiliz e r p la n t c o u ld p a y a m in im u m o f o n ly a b o u t h a l f t h a t r e q u i r e d o f th e c h e m ic a l o r e x p lo s iv e s m a n u f a c tu r e r s p r o d u c in g th e id e n tic a l p r o d u c t. U n le s s th e L a b o r D e p a r tm e n t is a b le to s t r a ig h t e n o u t th e s e u n c e r ta in tie s , th e w h o le sy s te m o f e s ta b lis h in g m in im u m w ag es is g o in g to b r e a k d o w n .
A m e ric a n c h e m ic a l in d u s tr y , a s effectiv ely r e p r e s e n te d b e f o r e th e D e p a r tm e n t o f L a b o r , b y th e C h e m ic a l A llia n c e , I n c ., h a s a s k e d o n ly f o r f a i r a n d e q u it
a b le tr e a tm e n t. I t h a s a n e m p lo y m e n t r e c o r d o f w h ic h it is d u ly p r o u d . I t s h o u r l y r a te s a r e h ig h e r th a n th e a v e ra g e , b u t m o r e im p o r t a n t is th e c o n tin u ity o f e m p lo y m e n t t h a t m e a n s m u c h h ig h e r a n n u a l w ag es f o r its e m p lo y e e s. I t h a s p la c e d a h ig h e r p r o p o r tio n o f its “ k e y p e o p le ” o n a s a la r y b a s is . I t h a s d o n e m o r e th a n a n y o th e r in d u s tr y to d e v e lo p n e w p r o d u c ts a n d p ro c e s se s to o ffset se a s o n a l a n d “ c u s to m -m a d e ” b u s i
n e ss , a n d to p r o v id e n e w jo b s th r o u g h re s e a rc h . A ll th is h a s h e lp e d to b r in g a b o u t a m o r e sta b le lev el in th e v o lu m e o f e m p lo y m e n t in c h e m ic a l in d u s tr y . B u t w e m u s t n o t f o r g e t t h a t th is is r e g u la r iz a tio n th a t h a s re s u lte d f r o m p r iv a te e n te r p r is e r a t h e r th a n fr o m g o v e rn m e n ta l re g u la tio n s .
From an
A TT E N T IO N : SECOND HONEYM O ON ERS
Nia g a r a Fa l l s is n o te d fo r tw o th in g s — e le c tr o c h e m ic a l in d u s tr y a n d h o n e y m o o n in g . W h ic h o f th ese w as th e d e te r m in in g f a c to r in s e le c tin g th e B u ffa lo -N ia g a ra F a lls a re a f o r th e 3 2 n d a n n u a l m e e tin g o f th e A m e ric a n I n s titu te o f C h e m ic a l E n g in e e rs h a s n o t b een a d m itte d officially. B u t w e h a v e o u r su s p ic io n s . T h e L a d ie s ’ p r o g r a m lists a se rie s o f a ffa irs la b e le d “ H o n e y m o o n E v e n t N o . 1,”
“ H o n e y m o o n E v e n t N o . 2 ,” etc. T h e re is an im p lic a tio n th a t h u s b a n d s w o u ld n o t b e u n w elco m e . R e c a ll
in g th e re s u lts o f th e n in e y e a rs o f re s e a rc h in m a r ita l r e la tio n s by D rs. B u rg ess a n d C o ttre ll, w h ic h c o n firm e d o u r view s th a t c h e m ic a l e n g in e e rs m a k e th e b e s t h u s b a n d s (see C h e m . & M e t., D ec. 1939, p. 7 4 9 ) , we w o u ld re s p e c tfu lly s u g g e s t th a t th e lo c a l c o m m itte e lim it its p la n t v is its to u n a tta c h e d a n d d is illu s io n e d m ales.
1IEAT CONGRESS TO T H E DRA W
Co n g r e s s s h o u ld n o t u n d e rta k e to p a ss on te c h n ic a l m a tte r s a ffe c tin g new m a te r ia ls o f w a r. M o re o v e r, C o n g re ss n o r m a lly w o u ld n o t w ish to d o so. B u t o c c a sio n a lly , as d u r in g M a r c h , so m e C o n g ressm en g e t e x c ite d o v er w h a t th e y th in k , o r alleg e to be, g ro s s n e g le c t o f n ew d e fe n s e o p p o r tu n itie s . T h e se s itu a tio n s a re o fte n o f r e a l c o n c e rn to th e c h e m ic a l in d u s try .
T h e re c e n t case r e f e r r e d to is th e p ro p o s a l o f L e ste r B arlo w to p ro v id e a new s o r t o f e x p lo s iv e w ith su c h d e a d ly p o w e r a s to c h a n g e th e w h o le a s p e c t o f w a rfa re . H e c la im e d th a t h e c o u ld n o t get a f a i r te s t o f h is in v e n tio n b u t h e d id su c c e e d in in te re s tin g c e rta in c o n g re s sm e n in it. F in a lly fo u r C o n g re ss io n a l c o m m itte e s h e ld a jo i n t se ssio n to h e a r th e c la im s o f th is in v e n to r. M e lo d ra m a p r e v a ile d . A t th e e n d o f th is se c re t m eetin g , th e c o m m itte e o rd e r e d th e s te n o g r a p h e r to b u r n h is n o te s o n th e c o m m itte e ta b le w h ile th e c o m m itte e w it
n essed th e d e s tru c tio n o f th e re c o r d th a t m ig h t o th e rw ise h a v e p ro v id e d f o r th e im p r o p e r re v e a l
in g o f a tre m e n d o u s m ili ta r y se c re t. T h e re s u lt, th e r e fo re , w as m e re ly a n a g re e m e n t b etw een th e C o n g re ss io n a l g ro u p a n d th e m ilita r y a u th o r itie s to lest M r. B a rlo w ’s in v e n tio n .
F o r th e m o m e n t it is n o t o f a n y c o n c e rn w h e th e r th e in v e n tio n is g o o d o r w o rth le ss. T h e im p o r ta n t m a tte r is th a t C o n g re ss sh o u ld n o t h a v e b u s ie d its e lf w ith th is d e ta il. I t is u n f o r tu n a te th a t s u c h a n in c id e n t s h o u ld ev e r h a v e re c e iv e d s u c h s e n s a tio n a l
p u b lic ity a n d it sh o u ld b e to th e b e s t in te r e s t o f c h e m ic a l in d u s tr y to fin d a w ay to p r e v e n t its r e p e titio n .
T h r e e p o s s ib le re a s o n s a re n o te d f o r th e C o n g re s s io n a l in te r e s t in s u c h a c a se . S o m e C o n g re s s m e n m a y th in k , as h a s b e e n c h a r g e d , th a t th e e x p lo s iv e s in d u s tr y tr ie d to s u p p r e s s n ew d e v e lo p m e n ts lik e th is o n e in o r d e r to p r o te c t th e p re s e n t m a r k e t f o r m i li ta r y p ro d u c ts . O th e r C o n g re ss m e n seem to th in k t h a t th e m ilita r y a u th o r itie s a re m o r e a t f a u lt— th a t th e y p r e f e r to go a lo n g w ith th e e a sy w a y o f r e p e a tin g old p ra c tic e s in d e fin ite ly . B u t in so m e in s ta n c e s , i t lo o k s to th e o u ts id e r as th o u g h th e C o n g re ss m e n w e re p r i n c ip a l ly in te re s te d in g e ttin g th e ir n a m e s on th e f r o n t p a g e s o f th e d a ily p a p e r s as a re s u lt o f th e ir s p e c ta c u la r h a n d lin g of th is n o v e l case.
W h a te v e r th e c a u s e , th e n e e d f o r re m e d y is e v i
d e n t. C o n g re ss h a s a r i g h t to d e c id e p o lic y . Its m e m b e rs a re , th e r e fo re , e n title d to in f o r m a tio n a b o u t new d e v e lo p m e n ts , ev en th o u g h th e y m a y n o t b e c o m p e te n t to m a k e th e te c h n ic a l a p p r a is a ls . P e r h a p s so m e w ise r e p r e s e n ta tiv e o f in d u s tr y w ill b e a b le to w o rk o u t a p la n th a t w ill p r o m o te p r o m p t a d o p tio n o f m e r ito r iu s in v e n tio n s b u t w ill also d is p o se o f c a se s la c k in g m e r it— ju s t as p ro m p tly a n d to th e s a tis f a c tio n o f a n y f a ir - m in d e d le g is la to r.
T h e r e p u ta tio n s o f th e m ilita r y a u th o r itie s a n d o f in d u s tr y w ill th u s b e p ro te c te d .
FO R “ P U R E R ” RESEA RC H
Pr i o r t o t h e Wo r l d Wa r m o s t s c ie n tis ts e x p e r i
m e n te d m e r e ly fo r th e sa k e o f e x p e rim e n tin g . T w e n ty o r th ir ty y e a r s la t e r s o m e o n e else cam e a lo n g a n d fo u n d p r a c t ic a l a p p li c a ti o n s f o r th e re s u lts o f t h e i r e x p e rim e n ts . T o d a y o u r m o d e rn r e s e a rc h e rs u s u a lly ta c k le t h e i r p ro b le m s th e o th e r e n d first. T h e y s t a r t w ith a n a p p lic a tio n in m in d a n d w o rk to w a rd a p a r t ic u la r in v e n tio n .
F o r la c k o f a b e tte r n a m e , th e o ld e r m e th o d h a s been d u b b e d “ p u r e ” re s e a rc h . A p p a r e n tly it is h e ld in r a t h e r lowT e ste e m in in d u s tr y b e c a u se m o s t c o m p a n ie s a r e u n w illin g to s p e n d h u g e s u m s o n a r e s e a r c h p r o g r a m th a t m a y n o t r e s u lt in im m e d ia te d o lla r-a n d -c e n ts d iv id e n d s . T h is th e y r e g a r d , as a lo g ic a l b u s in e ss-lik e p r o c e d u r e in th e u s e o f s to c k h o ld e r s ’ m o n e y . Y e t b y so d o in g th e s e firm s m a y n e g le c t e n tire ly th e m o s t fe r tile fie ld s in sc ie n c e f r o m w h ic h th e re a lly g r e a t n ew in v e n tio n s w ill p r o b a b ly co m e.
218 VOL. <17 • CHEMICAL & METALLURGICAL ENGINEERING • No. 4
A P R I L 1 9 4 0
Editorial Viewpoint
F o r tu n a te ly th e r e a r e c o m p a n ie s th a t h a v e b o th th e m e a n s a n d th e f o r e s ig h t to s p o n s o r lo n g -ra n g e p r o g r a m s in f u n d a m e n ta l r e s e a rc h . A few m a y e m p lo y th e ir o w n sta ff a n d fa c ilitie s f o r s u c h w o rk ; o th e r s h a v e w o rk e d w ith th e co lleg es to s e t u p r e s e a r c h fe llo w s h ip s . A n o u ts ta n d in g e x a m p le o f th e l a t t e r ty p e is th e d u P o n t F e llo w s h ip P la n f o r w h ic h a p p r o x im a te ly § 4 0 0 ,0 0 0 h a s b e e n s p e n t d u r in g th e p a s t 2 0 y e a r s f o r s o -c a lle d “ p u r e ” r e s e a rc h in u n i
v e rs ity la b o r a to r ie s . R e se a rc h s u b je c ts as w ell a s th e fe llo w s a r e se le c te d b y th e c o lle g e p r o f e s s o r s . T h e r e a r e n o w 20 p o s t-g ra d u a te fe llo w s h ip s a n d 6 p o st- d o c to r a te f e llo w s h ip s a n d th e r e h a v e b e e n a lm o st 5 0 0 in d iv id u a l fe llo w sh ip h o ld e r s d u r i n g th e life o f th e p la n .
In c id e n ta lly , i t is in te r e s tin g to n o te t h a t o n ly 15 p e r c e n t o f th e s e m en h a v e la te r jo in e d th e du P o n t s ta ff. I n o th e r w o rd s , th e a c c e p ta n c e o f th e fe llo w s h ip p la n im p lie s n o o b lig a tio n on th e b e n e fic ia ry a s r e g a r d s h is f u t u r e e m p lo y m e n t.
F o r tu n a te , to o , is th e fa c t t h a t th e d u P o n t c o m p a n y h a s n o p a te n t o n th is id e a . I t is o n e th a t can a n d s h o u ld b e a d o p te d m o r e g e n e r a lly th r o u g h o u t th e c h e m ic a l in d u s tr y . T h o s e c o m p a n ie s t h a t h a v e d ra w n h e a v ily o n th e w ell o f f u n d a m e n ta l scien ce c a n w ell a ffo rd to h e lp in r e p le n is h in g th e su p p ly .
W A TC H O U T F O R TANKS!
Ch e m i c a l e n g i n e e r s a n d o p e r a tin g m en h a v e a s e r io u s r e s p o n s ib ility d u r in g p e r io d s o f e m e rg e n c y c a u s e d b y flo o d s. T h is h a s a g a in b e e n e m p h a s iz e d d u r i n g th e re c e n t h ig h w a te r o n th e S u s q u e h a n n a R iv e r in P e n n s y lv a n ia . P e tr o le u m ta n k a g e th e re a d d e d fire h a z a r d to flood. W h e n e v e r flo o d th r e a t
e n s a p la n t, s p e c ia l a tte n tio n s h o u ld b e g iv e n to ta n k a g e a s w ell a s to o p e r a tin g m a c h in e ry a n d m a te r ia ls in p ro c e s s.
M a n y o p e r a tin g m e n seem to o v e rlo o k th e fa c t th a t ta n k s w e ll d e s ig n e d f o r f u ll lo a d a n d o n e x c e l
le n t f o u n d a tio n s f o r n o r m a l o p e r a tio n s m a y b e v e ry v u ln e r a b le w h en a tta c k e d e x te r n a lly b y flood w a te rs . C o n tro l o f e x p lo s iv e , fla m m a b le o r c o r r o siv e c o n te n ts th e n b e c o m e s h ig h ly im p o r t a n t. I t is o fte n n e c e s s a ry to fill s u c h ta n k s w ith w a te r in a n tic ip a tio n o f h ig h w a te r in o r d e r to s e c u r e th e m p r o p e r ly o n th e ir f o u n d a tio n . F o r e x a m p le , in m a n y c a se s w a te r s h o u ld b e f o r c e d in u n d e r th e fla m m a b le p e tr o le u m c o n te n t so th a t th e “ sp e c ific le v ity ” o f th e o il c o n te n t m a y b e o ffset b y th e a d d i tio n a l w e ig h t o f th e w a te r. T h u s th e ta n k a g e is
p r o te c te d , d a n g e r to s u r r o u n d in g p r o p e r tie s m in i
m iz e d a n d o fte n th e c o n te n ts o f th e ta n k its e lf n o t s e r io u s ly h a rm e d .
A n e m p ty ta n k is m u c h less r u g g e d th a n a fu ll o n e. A n o p tio n a l tr e a tm e n t f o r p ro te c tio n o f e m p ty ta n k s , in s te a d o f fillin g th e m w ith w a te r, is to c u t h o le s a t o r th r o u g h th e b o tto m . T h e n th e r is in g flood w a te rs w ill ta k e c a re o f f illin g th e ta n k s a u to m a tic a lly . T o p v e n ts m u s t b e o p e n , o f c o u rs e , a n d th e e m e rg e n c y o p e n in g s m u s t b e at th e b o tto m o f th e e m p ty ta n k , n o t ju s t n e a r th e b o tto m . I t le q u ir e s o n ly a v e ry few in c h e s o f w a te r to flo at a n e m p ty ta n k , a n d w h e n th e flood re c e d e s it is n o t a lw ay s p o s s ib le to g u id e th e ta n k b a c k to its o r ig in a l p o s itio n . T h is is p a r t ic u la r ly tr u e w h en se v e ra l ta n k s m u s t b e g u id e d a t th e sa m e tim e .
A GOOD T O O L W RONGLY U SED
N e w l i m i t m a r k e r s w e re se t u p c le a r ly b y th e S u p re m e C o u rt la t e in M a r c h in its d e c is io n r e g a r d in g th e E th y l G a so lin e C o r p o r a t io n ’s c o n tro l o f m o to r-f u e l p ric e s . T h e C o u rt m a d e e v id e n t th a t r e g a r d le s s o f th e r i g h t to m o n o p o liz e p r o d u c tio n u n d e r a p a te n t, th is c o m p a n y c o u ld n o t b e p e r m itte d to go so f a r in p r ic e r e g u la tio n a n d m e r c h a n d is in g c o n tr o l a s it f o r m e r ly h a d b e e n d o in g . T h is is n o t a n im p o r t a n t n ew p rin c ip le . I t m e r e ly c o n firm s th e c o m m o n ru lin g of th e C o u it th a t a le ^ a l r i g h t to d o c e r ta in th in g s m a y n o t b e e x te n d e d p e r se to th e d o in g o f o th e r a c ts th a t a r e ille g a l.
A ll o f in d u s tr y c o n c e rn e d w ith p a te n ts a n d lic e n s in g w ill stu d y th is d e c is io n c a re fu lly . P e r h a p s th e r e a r e v e ry few c h e m ic a l p a te n ts o f s u c h f u n d a m e n ta l n a tu r e as th o s e g o v e rn in g E th y l flu id . A n d s u r e ly th e r e a r e still fe w e r w h ic h r e la te to c o m m o d i- tie s o f a w id e r g e n e r a l p o p u la r in te re s t. B u t th e s a m e p r in c ip le s r e g a r d in g p a te n t r ig h ts w ill a p p ly to c o m m o d itie s o f le s s e r im p o r ta n c e a n d o f less p o p u la r a p p e a l.
T h e p a te n t sy s te m h a s b e e n s u b je c t to c ritic is m b y m a n y o n th e g r o u n d t h a t it g iv e s u n w a r r a n te d m o n o p o ly r ig h ts , c o n tr a r y to th e p u b lic in te re s t.
I t m a y b e th a t th is d e c is io n , a lth o u g h u n w e lc o m e to so m e o f in d u s tr y , m a y re a lly b e b e n e fic ia l b y p o in t
in g o u t h o w e x c e ssiv e m o n o p o ly a c tio n s h o u ld b e g u a r d e d a g a in s t. T h u s th e d e c is io n , th o u g h r e s tr i c tiv e in n a tu r e , m a y te n d a lso to p ro te c t th e p a te n t sy ste m its e lf. C h e m ic a l e x e c u tiv e s a n d e n g in e e rs w ill w ish to w e ig h th e s e fa c to rs c a re f u lly f o r th e ir o w n s itu a tio n s .
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“Rubber” From Petroleum Gases
Synthetic rubberlike m aterials are a ttra ctin g w orld-wide atten tio n these days as m ore and more com panies intensify their research in this direction. B u tadiene and isobutylene polym ers appear to offer the best possibilities of com peting ivith natui al ru b b er in the not-too-distant fu tu re.
DEXTER NORTH
W ashington Representative A rthur D. Little, Inc.
R
e c e n t a n n o u n c e m e n t by theS ta n d a rd O il Co. of New Jersey th a t it w ill build a p la n t fo r p ro duction of synthetic ru b b e r of the B una type a t B aton R ouge, La., q u ick ens the alread y keen in te re st in syn
thetic ru b b erlik e plastics. W ith r e search being carried on in th is field by m any nations, technological d e velopm ents a re m oving sw iftly. Com
m ercial production in th e U nited S tates, G erm any, an d R ussia h as alread y assum ed p ro p o rtio n s of a m a jo r ind u stry . In E urope, p a rtic u larly in th e to ta lita ria n states, av aila
b ility of synthetic ru b b e rs assum es increasing im p o rtan ce b ecause of the necessity of conserving foreign ex
change, an d to some m ay m ean v ir
tu a l self sufficiency in xubberlike m aterials. In the U nited States, w hich is in the forefro n t of develop
m ent, we are concerned m ore w ith o b tain in g a su p erio r p roduct, a l
though not u n m in d fu l of eventual in dependence of an im p o rted com m odity controlled by a foreign m onopoly.
A lthough th e various synthetic ru b b e rs a re p riced m uch h ig h er th a n n a tu ra l ru b b e r, th e ir p ro p ertie s are su p erio r in m any respects. C om pound
in g w ith th e n a tu ra l p ro d u c t to im prove its c h aracteristics, su b s titu tion in special uses, an d en tirely new a p p licatio n s a re a ll tak in g in creased q u an tities of the synthetics. A s costs becom e low er from p erfection of process an d q u ality an d from in
crease in o u tp u t, com petition w ith n a tu ra l ru b b e r m ay becom e su b sta n tial in th e not d is ta n t fu tu re. On the o th er h an d , however, the fact th a t the
Pressure storage tanks for isobutylene and other raw m aterials used to make Vistanex, a rubber-like m aterial, in Standard Oil Co.’s Bayway, N . J., plant. S. 0 . of La. w ill build a Buna plant at B aton Rouge p rice of c ru d e ru b b e r can be low ered
su b sta n tia lly below w h a t w e n o rm ally pay, re n d e rs its a c tu a l d isp lacem en t rem ote.
T h e accom panying list of tra d e nam es, to g e th e r w ith th e ir chem ical type o r o rigin in clu d es m ost of th e synthetic ru b b e rs now in com m er
c ial pro d u ctio n e ith e r in th e U nited S tates o r abroad.
A ll com m ercial sy n th etic ru b b e rs are p roduced, in p a r t a t le a st, from one or from eith er one of two, of the follow ing u n s a tu ra te d h y d ro carb o n gases— butad ien e, isobutylene, acety
lene, o r ethylene— w hich a re derived
from p etro leu m , coal, o r as w ith b u ta diene in R u ssia, from veg etab le sources. B una ru b b e r is derived from b u tad ien e, o b tain ed in G erm any from acety len e ex c a rb id e o r m ore recen tly from h y d ro carb o n gases of sy n th etic p etro leu m p ro d u ctio n , an d in the U n ite d S tates from p e tro leu m gases.
Iso b u ty len e is o b tain ed from p e tro leu m gases. N eo p ren e is derived from acetylene, T h io k o l from e th y l
ene, an d vinyl c h lo rid e from e ith e r acetylene o r ethylene.
P ro b a b ly the m ost extensive w ork is b ein g done bo th h e re a n d a b ro a d on
“ ru b b e r s ” derived from p etro leu m
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A P R I L 1 9 4 0
gases. T h e ab u n d a n c e an d cheapness of this raw m a te ria l, to g e th e r w ith the versatility of derivatives pro m ises a b rig h t fu tu re n o t only fo r these “ ru b b e rs” b u t also fo r re la te d synthetic resin s fo r rig id p lastics a n d su rface coatings. C onceivably these re la te d d em an d s m ay aid m a te ria lly in p ro viding c h e a p p rim a ry derivatives, m uch as a cetate ray o n h as done for cellulose acetate p lastics a n d viscose rayon fo r tr a n s p a re n t cellulose w ra p ping m aterial.
Im m en se strid e s too have been m ade in “ ru b b e rs ” d erived p rim a rily from m a te ria ls o th er th a n p e tro leu m gases, n o tab ly n eo p ren e, T h io k o l (o n e raw m a te ria l com es from cra c k e d h y d ro c a rb o n s ), a n d the polym erized vinyl c h lo rid es in th e U n ited S tates an d
“ S o v p ren e” in R u ssia. N eoprene is derived by ca ta ly tic synthesis of acety len e to m onovinylacetylene and reactio n o f h y d ro g en c h lo rid e on th e la tte r to form ch lo ro p ren e. Chloro- p re n e is th en polym erized to the r u b b erlik e m a te ria l n eo p ren e. E x cellen t resistan ce to an im al, v eg etab le, an d m in e ra l oils, to su n lig h t, h e a t, ozone, a n d m ost chem icals h as le d to w ide
s p re a d u se of n eo p ren e in gasoline a n d oil hose, protective c lo th in g , foot
w ear, p a c k in g a n d g ask et m a te ria l, protective coverings fo r w ires an d cables, an d m any o th e r uses.
T h io k o l, a polym erization p ro d u c t of th e reactio n of ethylene dich lo rid e a n d sodium p o ly su lp h id e, is c h a ra c te r
ized by extrem ely h ig h resistan ce to a la rg e n u m b e r of o rg an ic solvents, an d h ig h resistan ce to m o istu re ab so rp tio n an d p erm eatio n . P rin c ip a l o u tlets are in th e autom otive in d u stry , th e oil in d u stry , in re frig e ra tin g a n d a ir condi
tioning, an d th e p rin tin g industry'.
T hiokol is also av ailab le in pow der form for p ro d u ctio n o f m olded goods.
W hen polyvinyl ch lo rid e is highly plasticized, ru b b e rlik e p ro p e rtie s are im p a rte d to it. T h e m a te ria l is su p e rio r to n a tu r a l ru b b e r in flexing life, a n d in resistan ce to su n lig h t, w ater, oxidation, an d c e rta in oils. A t le a s t th re e v arieties of th is r u b b e r
like m a te ria l are being p ro d u ced . So v ersatile is th is type of m a te ria l th a t its uses cover a w ide ra n g e , from in su latio n fo r elec tric w ires a n d chem i
c a l a n d oil re s is ta n t hose, tu b in g , an d eq u ip m e n t lin in g , to w ra p p in g m a te ria l a n d fa b ric co atin g .
R esistoflex, o r p lasticized polyvinyl alcohol, one of th e new est of th e ru b b e rlik e plastics, w as developed in G erm an y to m eet the d em an d fo r a m a te ria l unaffected by gasoline, oils, an d solvents, in re sista n c e to w hich it is claim ed to be su p e rio r to o th e r syn
th e tic resin s. T h e m a te ria l possesses
Synthetic Rubbers M anufactured Comm ercially
B u n a S (G erm a n y )
B u n a N ( G e r m a n y ) ; P e r b u n a n (U .S .) I5una N N (G e r m a n y ) ; P e r b u n a n e x tr a N eo p reñ e ( U .S .) ; S o v p re n e (U .S .S .R .) V ls ta n e x ( U . S .) ; O p p a n o l (G e r m a n y ) R e s is to lie x (U .S. a n d G erm a n y ) T h io k o l (U .S .) : P e r d u r e n (G erm a n y ) K o r o se n l (U .S .)
F ia in e n o l (U .S .) K n ig h tw a r e (U .S .) I c e n t e (G erm a n y ) M opolam (G erm a n y ) A X F
B u ta d ien e-sty re n e B u ta d ie n e - a c r y lic n itrite (U .S .) B u ta d ie n e - a c r y lic n itr ite
P o ly e lilo r o p r e n e P o l y is o b u t y le n e P o ly v in y l a lc o h o l P o ly a lk y le n e su lp h id es P la s tic iz e d p o ly v in y l c h lo r id e P la s t ic iz e d p o ly v i n y l c h lo r id e P la s tic iz e d p o ly v in y l c h lo r id e P la s tic iz e d p o ly v i n y l c h lo r id e P la s tic iz e d p o ly v in y l c h lo r id e P o l y x y le n e s
h ig h tensile stre n g th , g re a t resistan ce to im pact, is su itab le fo r e ith e r h ig h p re ssu re or vacuum tu b in g , an d m ay be used over a wide te m p e ra tu re ran g e. I t is n o t h ig h ly re s ista n t to w ater, how ever, a n d th erefo re can n o t satisfacto rily be em ployed for w ater or steam lin es. I t is read ily m olded into sheets, tu b in g , d ia p h ra g m s an d o th e r sh ap es, chiefly for fuel an d b ra k e lin es an d lu b ric a tin g system s of autom otive eq u ip m e n t; in conveying solvents, v egetable oils an d m in erals in th e chem ical a n d p rocess in d u s
trie s ; in h y d rau lic lin e s; an d in fuel a n d oil-h an d lin g eq u ip m en t. P olyvinyl alcohol is m a n u fa c tu re d by deacetyla- tion of polyvinyl a c e ta te w hich in tu rn is m ade by the reactio n of acetylene on acetic acid.
A X F , w hich is m ade by th e c a ta ly tic re a c tio n of benzene an d ethyl ch lo rid e, is a som ew hat elastic, un- v u lcan izab le m a te ria l of d a rk brow n co lo r possessing little ten sile stre n g th , b u t ex cellen t resistan ce to m ost oils a n d solvents, an d to d ilu te alk alies a n d acids. I t is used p rin c ip a lly as a com p o u n d in g m a te ria l to im prove th e w o rk in g a n d o th er p ro p e rtie s of ru b b er, n e o p re n e an d Thiokol.
B u tad ien e “ ru b b e rs,” how ever, are
com m anding the sp o tlig h t of a tte n tion b ecause of S ta n d a rd O il’s re c e n t an n o u n cem en t. T h is com pany has a c q u ire d from the developers, th e G erm an I. G., licenses for m ak in g B una ty p e ru b b e r. P la n s for p ro d u c tion b efore th e en d of th e y e a r in a p la n t of 10,000 lb. daily cap acity a t B aton R ouge, L a., w ere an n o u n ced on A p ril 4, 1940. T he raw m a te ria ls, b u tad ien e an d acry lic n itrile , w ill be recovered or synthesized from refin ery gases. I t w as also an n o u n ced th a t F iresto n e T ire & R u b b e r Co. has tak en out a license to m a n u fa c tu re its own req u ire m e n ts of B una, s ta r t
in g in the im m ediate fu tu re. A n o th er le a d in g ru b b e r com pany h as inform ed S ta n d a rd Oil D evelopm ent Co. th a t it w ill p u rch ase th e synthetic m a te ria l from th e B aton R ouge p la n t.
S everal p etro leu m com panies b e sides S ta n d a rd O il— also chem ical com panies a n d others— have been w orking intensively on m ethods of p ro d u cin g b u tad ien e from p etro leu m gases. Som e of th e processes u n d e r in v estig atio n in clu d e cata ly tic d e h y d ro g en atio n of b u ta n e o r butene, c rack in g the h ex an e c u t from naph- th en ic cru d es, from cyclicized hexanes, h y drogenative c rack in g of benzene,
In this pilot plant U niversal Oil Products Co. worked out its process fo r m ak
ing butadiene from butanes and butenes. At right is the conversion furnace (S)
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221
Left—Still for fractionating isobutylene under pressure and building fo r making polybutene at Standard Oil Co.
R ig h t-S id e view of U.O.P. pilot plant showing the conversion furnace, cooling system and instrum ent-rcceiver house
and c rack in g petroleum u n d er ce r
tain conditions to yield a m ixture of b utadiene an d o th er u n satu rate s.
E ith e r b u tan e or b u ten e (obtained from refinery gases) ap p e a rs to be the m ost likely sta rtin g m aterial. Both the H oudry and Gyro processes of crack in g petroleum are susceptible to m odifications to give ap p reciab le yields of b utadiene.
U niversal O il P ro d u c ts Co. a n nounced la st sum m er a process for p roduction of bu tad ien e, consisting of cataly tic dehydrogenation of bu tan e at 1,000 deg. F. to butylene to b u ta diene. Once th ro u g h y ield s are said to vary from 20 to 30 p er cent, w ith u lti
m ate yields u p to 80 p er cen t. T he novelty of the process seem s to lie in th e catalyst, as d ehydrogenation of b u tan e is n o t new .
New Plant at Chester
P h illip s P etro leu m Co., a la rg e p ro du cer of butane, has been w orking actively on p roduction and recovery of butad ien e. U nited G as Im provem ent Co. is erectin g a p la n t a t C hester, P a., for the p roduction of a series of u n satu rate d and aro m atic hydrocarbons, in clu d in g b u tad ien e and styrene.
T h e Dow C hem ical Co. is pro d u cin g butad ien e in its process for crack in g petroleum to obtain ethylene for its
ra p id expansion in chem icals derived from the la tte r. T h e c ru d e b u tad ien e is now la rg e ly b u rn e d fo r fuel. Dow h as p a te n ts covering m a n u fa c tu re of d e fin e s (in c lu d in g b u ta d ie n e ) from petroleum . W h eth e r th e hig h eth an e gas to be p ip ed 54 m iles from T em ple to the Dow p la n t a t M id lan d , M ich., w ill yield b u tad ien e as w ell as e th y len e is n o t in d icated . I t is rep o rte d th a t Dow has o b tain ed a license for p ro d u cin g b u tad ien e by th e process of U niversal Oil P ro d u cts.
How to Purify B utadiene N one of th ese m ethods give b u ta diene sufficiently p u re for m a n u fa c tu re of b u tad ien e “ ru b b e r.” In fact su ita b le m ethods of p u rifica tio n of the recovered b u tad ien e is one of the p rin c ip a l problem s in com m ercial de
velopm ent of b u tad ien e “ ru b b e r.”
T endency seem s to be to w ard s in itia l recovery of c ru d e b u tad ien e by such m ethods as azeotropic d istilla tio n or modified ex tractio n m ethods, a n d final purification by form ation of te m po rary chem ical com pounds, as w ith cu p ro u s chlo rid e or s u lp h u r dioxide.
Dow C hem ical Co. is the first A m erican com pany to pro d u ce and sell p u re bu tad ien e. T he process con
sists in form ation of th e tem p o rary derivative butad ien e-su lp h o n e from
w hich a re s u lta n t b u tad ien e p ro d u c t of over 99.5 p e r cen t p u rity is ob
tain ed . Its su p e rio rity over G erm an b u tad ien e is in d ic a te d in th a t an a t
m osphere of n itro g e n is u n n ecessary fo r polym erization to sy n th etic r u b ber, as w ith th e G erm an p ro d u ct.
P re s e n t p rice o f th is p u re b u tad ien e is in the n eig h b o rh o o d of 20fi p e r lb., b u t it is hoped th a t la rg e scale p ro duction w ill low er th e cost.
Dow is c o o p eratin g w ith a ru b b e r m a n u fa c tu re r in th e developm ent of b u ta d ie n e “ ru b b e r s ” o f bo th th e acry lic n itrile an d the sty re n e types.
O th er ru b b e r com panies a re also w orking actively on th e co m pounding an d a p p lic a tio n s of B una.
T h e o th e r c o n stitu e n ts of B una ru b b e r a re acry lic n itrile for th e N type, a n d sty re n e for th e S type. T h e fo rm er can be m ade by d eh y d ratio n of eth y lcy an o h y d rin w hich in tu rn is p ro d u ced from eth y len e c h lo ro h y d rin an d sodium cyanide, o r by ca ta ly tic ad d itio n of hyd ro cy an ic a c id to acety
lene. T h e cost of hyd ro cy an ic acid h a s been re d u c e d by a new process of synthesis from am m onia an d m eth ane. S tyrene is now b ein g m ade by Dow C hem ical Co. from benzene an d e th y l c h lo rid e. T h e purified b u tad ien e is c a ta ly tically polym erized e ith e r w ith th e acry lic n itrile o r the styrene, the
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la te x is co ag u la ted w ith acetic acid, w ashed, d ried , an d an tio x id an ts in c o rp o rated .
T h e best g rad es of b u tad ien e “ ru b b e r” are B una N an d NN (in the U nited S tates, P e rb u n a n and P er- b u n an e x tr a ) . T hey are re s ista n t to an im al, vegetable, and m in eral oils, b u t sw ell in aro m atic hy d ro carb o n s, ketones, alcohols a n d esters, and in ch lo rin a te d h y d ro carb o n s and org an ic bases they sw ell m ore th an n a tu ra l ru b b e r. In aging, exposure to su n lig h t, in resistan ce to heat, ozone, m oisture, ab rasio n an d flexing, in p e r
m an e n t set an d creep , an d in hys
teresis loss, they a re su p e rio r to n a t
u ra l ru b b e r. B una N a n d NN also ex
cel the n a tu r a l p ro d u c t in deform ation a t elevated te m p e ra tu re s, a n d a re only slig h tly s u b je c t to cold flow. B ein g in fe rio r to ru b b e r in e lec trical p ro p e r
ties, they are used for in s u la tin g only as oil a n d solvent re s is ta n t covers to p ro tect u n d e rly in g in su latio n .
P rin c ip a l uses of B u n a ru b b e r in clu d e oil re s is ta n t m ech a n ical goods such as gasoline an d oil hose, tr a n s m ission an d conveyor belts, g askets a n d pack in g s, in oil a n d ab rasio n r e sis ta n t w ire a n d hose sh eath in g , as m ach in ery m o u n tin g blocks, p ro tec
tive clo th in g an d footw ear, oil r e sista n t artificial le a th e r an d coated fab rics, steam hose, d ia p h ra g m s, and bellows.
L ast sum m er, p rio r to exhaustion of su p p lies of im p o rted P e rb u n a n , the p ric e in th e U n ited S tates w as 90£
p er lb., com pared w ith 65ji for neo
p ren e an d a b o u t 16fi p e r lb. for c ru d e ru b b e r. I f a ra tio of say 4 to 1 in prices is m ain tain ed , sy n th etic ru b b ers w ill find th e ir m a rk e ts only in sp ecial fields u n d e r sp ecial co n d i
tions, r a th e r th a n in th e gen eral r u b b er goods field.
T h e p o ten tial su p p ly of b u tad ien e is enorm ous an d is estim ated in term s of h u n d re d s of m illions of pounds, even billions, a n n u ally . T h e cost of b u tad ien e “ ru b b e r” w ill no d o u b t be su b s ta n tia lly re d u c e d th ro u g h te c h n o lo g ical im provem ents in processes of p ro d u ctio n o f in te rm e d ia te m ate
ria ls an d finished p ro d u ct, by im provem ent in q u ality of the p ro d u ct, a n d in la r g e r volum e of p ro d u ctio n . I t h as been in d icated th a t th e cost of p u re b u tad ien e, p rin c ip a l c o n stit
u en t of B una ru b b e rs, w ill a p p ro a c h lOjJ p e r lb. Cost of acry lic n itrile w ill p ro b ab ly be som ew hat m ore. R ep o rts from G erm any s ta te th a t a cost o f 20?
p er lb. for B una N in th is co u n try is hoped for. Cost of B una S should be som ew hat less, acco rd in g to the G er
m an ex p erien ce, as the cost of styrene is su b s ta n tia lly less th an th a t of
T op—Side view of stills used in the m anufacture of polybutene-oil solutions or concentrates. Vistanex m ade here was developed in Germ any as Oppanol Bottom —D etail view of m easuring and sam pling tanks and proportioning pum p in U.O.P.’s unit for m aking butadiene, raw m aterial for all form s of Buna
acrylic n itrile. However, p resen t sty
ren e costs in the U nited S tates seem to be relatively high w hen viewed in the lig h t of the hoped-for less th an 20c1 p er lb. B una S.
W ith cru d e ru b b e r selling at a n o r
m al price of say 16«* (p re se n t price is approxim ately 20^) and B una N a t 50<! p e r lb., dem and for the la tte r would still be in special uses and r e l
atively sm all; with, B una at 35^, d e m and w ould be su b sta n tia l; and at 20(i, its su p erio r p ro p ertie s w ould en
ab le it to com pete w ith ru b b er.
Isobutylene, the raw m aterial for V istanex, is form ed in the crack in g of petroleum or of n a tu ra l gas, and can be recovered by relatively sim ple m ethods. A t p re se n t most of it is co n verted to high anti-knock m otor fuel, sold as fuel gas in ad m ix tu re w ith pro p an e or b u tan e, or consum ed in refineries as fuel. Q uantities of iso
butylene used in the m an u factu re of V istanex are relatively sm all b u t in creasing, and the po ten tial su p p ly is im m ense. /
Polyisobutylene w as developed in G erm any by the I. G. F a rb e n in d u strie as “ O ppanol,” an d A m erican m an u facturing rig h ts w ere g ra n te d to S tan d ard Oil Co. of New Jersey , w hich produces it a t Bayway, N. J., u n d er the nam e V istanex. S elling agent except in th e lu b ricatio n field is A dvance Solvents an d Chem ical Corp.
W hen p u re isobutylene is polym er
ized a t low tem p e ra tu re in the p re s
ence of a cata ly st such as boron tri
fluoride, a series of high m olecular w eight lin e a r polym ers is form ed, according to th e e x ten t of polym eriza
tion. T hese polym ers are chem ically
alm ost com pletely s a tu ra te d and therefore in ert to m ost types of d ete
rioration.
V istanex has excellent resistan ce to co n cen trated acids an d m ost comm on chem icals except c h lo rin e and b ro mine. A lthough in e rt to ozone, Vis
tanex, p a rtic u la rly the high m ole
cu la r w eights, depolym erizes u n d er stro n g sunlight. U n d er h e a t it is stab le to 100 deg. C., b u t softens p erm an en tly if exposed for lo n g perio d s above th a t tem p eratu re. I t h as little or no odor, an d is non-toxic.
U nlike ru b b e r V istanex does not com bine read ily w ith su lp h u r, n o r oxi
dize easily. In ten sile stre n g th , r e bound, X -ray stru c tu re , elec trical p ro p ertie s, elastic m em ory, fractio n al solubility, an d m echanical o rien tatio n , V istanex is sim ilar to ru b b e r. P a rtia l su b stitu tio n in the ru b b e r m ix im proves aging, ozone and oxygen resis
tance, elec trical c h a ra c te ristic s, r e sistance to chem icals an d to m oisture absorption, an d decreases sw elling in m any solvents.
T he unvulcanizability of polyisobu
tylene has led to co n sid erab le w ork bo th in this co u n try an d in G erm any on com bining it w ith vulcanizing-type polym ers. S ta n d a rd O il D evelopm ent Co. lias been active in th is field and its com bined exp erien ce in bo th poly
isobutylene an d b u tad ien e “ ru b b e r”
should be p roductive of in te re stin g de
velopm ents. In th is d irectio n wrh a t a p p e a rs to offer an in te re stin g a n d po
ten tially la rg e a p p lic a tio n of V is
tanex is set fo rth in U n ited S tates p a te n t N o. 2,180,082, issued Novem
ber 14, 1939, to the I. G. F a rb e n in d u strie A. G. T h is p a te n t describes th e form ation of a ru b b e rlik e m aterial
of extrem ely good ab rasiv e p ro p e rtie s by in co rp o ratio n of polyisobutylene of from 50,000 to 100,000 m o lecu lar w eight into the m onom er of a sy n th e tic ru b b e r such as ch lo ro p ren e, b u tad ien e-sty ren e, o r b u tad ien e-acry lic n itrile , and th en p olym erizing the com bination. T h is p ro ced u re p resu m ably m akes possible th e re te n tio n of th e v a lu a b le p ro p e rtie s p rovided by th e long, fibrous m olecules of poly
isobutylene w hile in tro d u c in g th e vul
canizing c h a ra c te ristic s of th e copoly
m erized m a te ria ls, a n d should provide su b stan ces w ith u sefu l p ro p e rtie s a t low costs. S hould a satisfacto ry an d p ro p e rly p ric e d m a te ria l th u s be de
veloped for autom obile tires, a h u g e m a rk e t w ould be open to a t le a s t two of the sy n th etic ru b b ers.
T h e four p rin c ip a l o u tlets for V is
tan ex a re in com p o u n d in g of lu b r i
ca tin g oils, in vario u s m odifications of paraffin w ax su ch as P aro iilm , in ru b b e r com pounding, a n d in th e m an u fa c tu re of adhesives such as tin p astes, p a p er-b ack ed m etal foil, facing of b o ttle cap lin ers, an d h e a t sealin g com pounds. O th er uses fo r V istanex a re in su p e ra g in g com pounds, in com pounds for acid re s ista n t articles, in elec trical in su latio n , fa b ric proofing, an d as le a th e r d ressin g s a n d finishes.
V istan ex of h ig h m o lecu lar w eig h t of the o rd e r o f 250,000 is said to possess p o te n tia litie s as a sy n th etic fiber. Its p re s e n t a p p lic a tio n s a re scarcely com petitive w ith ru b b e r. W ith costs of p ro d u c tio n on la rg e volum e b asis said to a p p ro a c h 10fS p e r lb., a n d w ith developm ent of v u lcan izab le “ ru b b e rs ” in co n ju n ctio n w ith o th er m aterials, V istanex m ay becom e an im p o rta n t
facto r in com petition w ith ru b b e r.
Storage tanks for Standard Oil’s finished polyisobutylene-oil products at Bayway, N. J,
224 VOL. 47 • CHEMICAL & METALLURGICAL ENGINEERING • No. 4
A P R I L 1 9 4 0
Neohexane for 100-0ctane Plus
A new synthetic hydrocarbon m ade by therm al alkylation surpasses iso-octane itself as a blending agent in aviation m otor fuels. Its value hinges on two im p o rtan t properties
— h igh lead susceptibility an d high volatility.
MELVIN E. CLARK
Assistant Editor
Chemical & M etallurgical Engineering
W
H A T IS N E O H E X A N E ? A lo t of o rg a n ic chem ists m um bled in th e ir b eard s w hen ask ed th a t q uestion la s t sum m er, b u t now the term h as becom e a byw ord in th e p e tro leu m in d u stry . T h e prefix neo in d icates th e presen ce o£ a c arb o n atom a tta c h e d by a ll fo u r valence bo n d s to o th e r c arb o n atom s, acco rd in g to D r.F. C. W h itm o re’s “ O rg an ic C hem is
try .” T h en neohexane is m erely a h ex ane co n ta in in g a neo lin k a g e and th ere can be b u t one— 2, 2 dim ethylbu- tane.
W hy th is com pound should su d denly becom e so im p o rta n t is an in terestin g story. L ast su m m er th ere w ere fa in t ru m o rs from New Y ork to Los A n g eles th a t the P h illip s P e tro l
eum Co. h a d developed a new s u p e r
fuel— a g asoline in g re d ie n t th a t h ad an o ctan e ra tin g ’w ay off th e scale, p ro b ab ly 125 to 150. T h en followed the re p o r t th a t it w as called neo h ex ane. F in a lly the an n o u n cem en t w as m ade by P h illip s th a t th e sto ry w as p a rtly tru e. T hey did have a new high o ctan e m otor fuel, it w as n eohexane, b u t its octane ra tin g w'as only 94.
H ow ever, b ecau se of its b len d in g p ro p ertie s, fuels w ith as h ig h as 115 o ctan e -ratin g could be m ade w ith it.
Now the new in d u s tria l chem ical—
surely it can be ca lle d an “ in d u s tria l ch em ical” b ecau se i t is m ade in su b sta n tia lly p u re form by a chem ical process— has outgrow n its p ilo t p lan t.
A com m ercial in sta lla tio n s ta rte d o p e ra tin g at B orger, T ex as, in J a n u a ry , 1940.
A t la s t it is econom ically feasi
ble to m ake an aviation gasoline with an o ctane ra tin g over 100. T h is will m ean b e tte r p erfo rm an ce and m ore econom ical op eratio n fo r lo n g d istan ce flying. G ustav Egloff h as said th a t the in crease from 87 to 100 in o ctane n u m b er allow s a p lan e to c a rry 1,200 lb.
less fu el on a 1,400 m ile flight. Seven m ore passen g ers o r an equivalent w eight of m ail or freig h t m ay be ca rrie d instead. T h is m eans §2,000 a
trip for the C hina C lip p er. T h e fu ll benefit of the developm ent of fuels over 100 octane ra tin g can n o t, how ever, be realized u ntil higher-com pres- sion aviation engines are b uilt.
P roperties of Neohexane I f 2.2 d im eth y lb u tan e (n eo h ex an e) h as an o ctane ra tin g of only 94, w hat m akes it the pow erful fuel it is? T h e answ er lies in the two most im p o rta n t p ro p e rtie s of th e h y d ro carb o n — h ig h Blim ps used for storage of liquefied petroleum gas m ade by the Phillips Petroleum Co. at Borger, Texas. This company has m ade petroleum history with the invention of a new process—therm al alkylation—w hereby neohexane is made from ethylene and isobutane
VOL. 47 • CHEMICAL &■ METALLURGICAL ENGINEERING • No. 4 A P R I L 1 9 4 0
225
Panoram a view of part of the Borger, Texas, refinery of the P hillips Petroleum Co. shows fractionating towers and the thermal alkylation unit (in the background) w here a new super octane aviation fuel is m ade from refinery gases
lead susceptibility and high volatility.
L ead susceptibility is a p ro p erty of a hydrocarbon w hich may be m easured by the in crease in octane n u m b e r ob
tained by the add itio n of a given am ount of tetraeth y llead . It is the ability of a fuel to resp o n d to “ le a d ing.”
T he accom panying g rap h shows the effect of adding te tra e th y lle a d to neo hexane, to iso-octane an d to a 50-50 m ixture of the two. T he steep er the curve the g re a te r the lead su scep ti
bility. N ote th a t w ith 3 cc. of T EL , neohexane is equivalent to iso-octane alth o u g h it w as only 94 octane to start com pared w ith 100 for iso-octane.
W ith m ore th an 3 cc. of T E L , neo
hexane is su p e rio r in octane ratin g . A n o th er im p o rtan t p o in t illu s tra te d h ere is th a t n eohexane im p a rts m ore th an its sh are of lead su scep tib ility to the m ixture. In o th er w ords, a 50-50 m ix tu re is more lead su scep tib le th an m ight be expected.
Then T here Is Volatility So m uch for lead su scep tib ility . If th a t and cost w ere the only c o n sid e ra tions in b len d in g gasoline, the task w ould be easy. But u n fo rtu n ate ly th e facto r of v olatility en ters in.
G asolines m u st boil in a c ertain ran g e w hich varies som ew hat w ith th e
g ra d e of gasoline, its use, and the season of the year. C onventional avia
tion gasolines have an average boiling ran g e of 180-210 deg. F. M ost d e sira ble high-octane in g red ien ts have a boiling p o in t m uch h ig h e r th an th a t (iso-octane, 200-240 deg. F .) an d so m ust be d ilu ted w ith m ore volatile, less k n o ck -resistan t hy d ro carb o n s.
T h is red u ces the o ctan e ra tin g o f th e blend.
Now w ith neohexane, th is condition can be co rrected . I t boils a t 121 deg.
F. a n d also h as h ig h o ctan e ra tin g . T h erefo re, n eo h ex an e an d iso-octane can be b len d ed (w ith o th e r h y d ro carb o n s) to yield a blend in th e rig h t
At left are lead susceptibility curves for neohexane, for a 50-50 m ixture of neohexane and iso-octane, and fo r pure iso-octane. The steepness of the curve indicates the better lead susceptibility of neohexane. At right is a flow diagram
showing both the catalytic and therm al alkylation processes. Note the differences in tem perature and pressure
120 118
116 H
114 I *
ł 112
. 2 n o
■X.
at IUÜ a 6 10b
104 102 100
NeK/hexane , /
'<A
octaneJ
¿ s
Iso/
V
À
/ r f
tLL
. . . . 50 Ne-50 rrnohexonxture e and i so-octane
i
i f (C o O from Ob* rf* !| and F r* y lL _
1 2 i 4 5 6
CĆ-of T etraeth y llead
G A S O L IN E BY A L K Y L A T IO N
C a ta ly tic A lk yla tio n Paraffines
rich in Isobutone
H ,S0 .
''Retire, isobutone NaOH
Recycle so^ ProponeJOUt
Water l i s a le r
Recycling
¿Pump Reoctor
Vj
JecYde a;
High octane gasoline
Typical R e a c tio n : CH) fH j
IC H jlj C H -CH j + CKjCHjG U C H ,
CH
Isobutone Butylene—t lso-octane
O Chem.i. Met.
Therm al A lk y la tio n
Isobutone Crocking *
furnacH,4?6*F,?5-ÍK) p.s.i.
H,CH4 o u t
Ft hone propane butane or mixtures
0os containing . >'• o/hylene
T
n-butane,etc Isobutone
a n d ethylene Charging pump
Compressor Propane,
1 f- "ethane 1— L- ' out
Æ Q 1
T ypical Reaction:
(C H j), C H -C H j * CHj- Ç - C ^ C Hj
ĆH
Isobutan? E thylene Neohexane
ÇHj
VOL. 47 • CHEMICAL & METALLURGICAL ENGINEERING • No. 4 A P R I L 1 9 4 0
b oiling ra n g e an d w ith m uch h ig h e r o ctan e n u m b er th an h ereto fo re a tta in able.
Properties of N eohexane
R eiil va p o r p ressu re, l b ... 9.5 A .P .I. g r a v ity ...84.9 A .S .T .M . o c ta n e n u m b e r...94 llo it in g p o in t, (leg. F ...121.5 S p ecific G r a v ity ( 2 0 / 4 (leg. C ) . . . . 0 . G 4 9 4 I te fr a c tiv e in d e x n „ 20 D o g . C 1.30887 F r e e z in g p o in t, (leg . F ... — 144.8
T herm al A lkylation
T h e com m ercial process by w hich neohexane is m ad e is called th erm a l a lkyla tio n . I t w as developed th ro u g h th e p ilo t p la n t stag e by th e research d e p a rtm e n t of P h illip s P etro leu m Co.
T h e reactio n s involved are, as in all petroleum processes, q u ite com plex;
b u t th e m ost im p o rta n t reactio n is th a t in d icated on the flow sheet.
T h is is an a lk y latio n reactio n — the com bination of an d e fin e w ith a parafline. I t is c a rrie d out a t high te m p e ra tu re an d hig h p re s su re in the presen ce of an excess of iso-butane.
O f course th e process as com m er
c ially p ra c tic e d does n o t use C.P.
ethlyene o r isobutane. T he ethylene is derived from a m ix tu re of parafline gases w hich m ay in clu d e m ethane, eth an e , p ro p an e an d b u tan e, by c ra c k ing in a tu b e fu rn ace a t 1,425 deg. F.
and a p re ssu re only a few pounds above atm o sp h eric.
P ro d u c ts of this reactio n are cooled an d com pressed. H eavier fractio n s are d raw n oil a t th is p o in t in th e form
of gasoline. E thylene, th e m ain prod- d u ct of th e c rack in g o p eratio n , is a b sorbed in iso b u tan e an d c h a rg e d to the a lk y latio n furnace. T h is is a n o th e r tu b e coil fu rn ace w ith the ethy- lene-isobutane m ix tu re forced in th ro u g h a n u m b e r of in le ts (n o t show n on flow s h e e t ) . A s e p a ra te stream of p re h e a te d iso b u tan e is also in je c te d into the reactio n space in the furn ace w here the te m p e ra tu re is 950 deg. F.
an d th e p re ssu re is in the ra n g e of 3,000-5,000 lb. p e r sq.in.
T h e re a re a n u m b e r of p ro d u cts of this reactio n w hich a re se p a ra te d in fractio n ato rs. P ro p a n e , eth a n e an d any lig h te r p ro d u cts a re p u rg e d from the system . Is o b u tan e is re c irc u la te d . N eohexane an d heavier p ro d u cts leave the p rocess as c ru d e n eohexane g as
oline to be fu rth e r refined.
F rom th is c ru d e a lk y late c u t it is possible to fractio n ate su b stan tially p u re n eohexane as w ell as o th er hy d ro carb o n s, m ak in g the process v irtu ally a chem ical synthesis. T h e accom pany
ing tab le shows the difference in bo il
ing p oints w hich m akes neohexane easily se p a ra b le from o th er p a rts of th e m ix tu re.
H ydrocarbon Boiling Points
D eg. F.
I s o p e n t a n e ... 82 .3 n -P e n ta n e ... 90. S X eo h ex a n e ... 121.3 2 ,3 -D im e th y lb u ta n e ... 1 3 0 .G 2 -M eth y lp en ta n e ...140.4 3 -M e th y lp en ta n e ... 14 5 .8 n -H ex a n e ... 155.8
In th e acco m p an y in g flow sheet the a u th o r has shown th e step s in the c a ta ly tic a lk y latio n process as w ell as the th e rm a l process so th a t th e lik e nesses a n d differences m ay be o b served. C ataly tic alk y latio n reach ed th e com m ercial stag e ju s t a step ah ead of th erm al, th e first u n its be
g in n in g o p eratio n s la s t sum m er.
Not the Last W ord
S uch a re the m ethods by w hich high-octane gasolines are m ade to day. B ut th e final c h a p te r in th is story h as by no m eans been w ritten . In a ll p ro b ab ility n eohexane, lik e o th e r v a l
uable h y d ro carb o n s w ill eventually be m ade by ca ta ly tic m ethods at, m uch m ore n o rm al te m p e ra tu re s an d p re s sures. W hen the u ltim ate h as been achieved w ith th is com pound, still o th er m ore highly k n o ck -resistan t com pounds w ill m ake th e ir a p p e a r
ance.
Even now p e tro leu m chem ists talk of m aking such h y d ro carb o n s as te tra m e th y lb u ta n e a n d 2,2,3-trim ethyl- b u tan e, com pounds w hose o ctane ra tin g s a re a t le a s t 125. B oth a re often th o u g h t of as the u ltim a te in m otor fuel possibilities. A s y e t th e ir com m ercial m a n u fa c tu re is only a d ream , b u t chem ists an d en g in ee rs do a lot of research on d ream s th ese days.
G . G . O b e r f e l l a n d F . E . F r e y d e s c r i b e t h e r m a l a l k y l a t i o n a n d t h e p r o p e r t i e s o f n e o h e x a n e m i x t u r e in g r e a t e r d e t a i l In OU
& G a s J . , N o v . 2 3 a n d N o v . 3 0 , 1 9 3 9 .
F ractionation of crude neohexane is perform ed in distillation colum ns sim ilar to these in P hillips’ Borger refinery
VOL. 47 • CHEMICAL & METALLURGICAL ENGINEERING • No. 4 A P R I L 1 9 4 0
227
Symposium Considers Drying of Air
Three papers dealing w ith the drying of a ir and gases by dehum idification m ethods, presented at a recent A.S.M.E. m eeting, are briefly sum m arized here. Use of absorptive solutions, silica gel and activated alum ina, are th e subjects considered.
E
v i d e n c e of rap id ly in creasin g in terest in the use of adsorptive and absorptive dehum idifica- tion for air and gases w as presen ted on M arch 19 in New Y ork at a M etropolitan Section m eeting of th e A m eri
can Society of M echanical E ngineers, a rra n g e d by the Society’s P rocess In d u stries Division. T h ree p a p e rs were offered to an interested group of about 100 engineers.
T he first p ap er, p re p a re d by Jam es C. P atterso n , m an ag er of the D eh y d ra
tion Division of the C a rrie r Corp., Syracuse, N. Y., w as a gen eral one, discussing the need fo r d irect deh u m id ification by m eans of solid adsorbents and liquid absorbents, as distinguished from the use of refrig e ra tio n alone.
T he p a p e r pointed out th a t dehum idifi
cation ap p licatio n s for solid a d so rb ents such as silica gel and activated alum ina, and liq u id ab so rb en ts such as lithium chloride an d calcium ch lo ride, are becom ing a n in creasin g ly im p o rta n t facto r in the m olding of a ir conditioning p ractice. A lm ost any percentage of the to tal m oisture con
ten t of a ir o r oth er gases can be r e moved by this m ethod w ithout the use of m ech an ical refrig eratio n , or the need for reh eatin g .
D ehum idifying by physical a d so rp tion or chem ical ab sorption converts the la te n t h e a t of the m oisture r e moved from the a ir to sensible heat, w ith a co rresp o n d in g rise in th e dry b u lb tem p eratu re. If the te m p e ra tu re of av ailab le w ater can n o t accom plish the su b seq u en t cooling, a relatively sm all am ount of m echanical re frig e ra tion can be used, or evaporative cool
ing. O f course, w ith refrig e ra tio n alone, the ex ten t of m oisture reduction is d ep en d en t upon the ex ten t of tem p e ra tu re red u ctio n , w hile w ith dehum idification by ad so rp tio n or absorption, the deg ree of dehum idify
ing is not a function of te m p e ra tu re reduction. T h erefo re d irect d eh u m id i
fication is in d icated p a rtic u la rly w here it is necessary to control the hum idity in d ependently of the d ry bu lb tem
p e ra tu re ; w here a com paratively la rg e p a rt of the total lo ad is la te n t h e a t;
w here econom ies can be obtained th ro u g h th e use of gas fuel or steam in th e dehum idifying p h a se ; o r w here
cold w ater is av ailab le for cooling.
T he a u th o r p o in ted out th a t solid a d so rb en ts a d so rb m o istu re o r oth er condensable v ap o r by su rfa c e a ttra c tion and c a p illa rity a n d condense the v apor u ntil th e v ap o r p re s su re of th e liquid alread y condensed a p p ro ach es th e p a rtia l p ressu re of its v ap o r in the air. A p p licatio n of h e a t read ily re activates the ad so rb en t. In the case of a b so rp tio n , the so lutions used have a low er v ap o r p re s su re of w ater th a n the p a rtia l p re ssu re of w ater in the a ir a n d so when m oist a ir is b ro u g h t into co n tac t w ith such a solution, th e low er v ap o r p re ssu re of th e liq u id tends to ap p ro ach the h ig h e r v ap o r p re ssu re of the a ir w ith a co n seq u en t ex ch an g e of m o istu re from a ir to ab so rb en t. C on
sta n t m oisture rem oving ab ility can be m ain tain ed by c h a n g in g e ith e r the te m p e ra tu re of th e so lution o r its
density, the la tte r by re c o n c e n tra tin g th e re c irc u la te d solution by th e a p p li
cation of h e a t. I f d esired , m o istu re can be added to a ir by ra isin g th e te m p e ra tu re o r low ering th e co n cen tratio n of th e solution.
A s betw een vario u s types of ch em i
cal dehum idification, th e re is no “ b est”
m ethod. T he choice d ep en d s up o n the type of a p p licatio n , d esired p e rfo rm ance, fu el costs an d o th e r factors. G en
e ra lly sp eak in g , solid ad so rb e n ts b e com e m ore d e sira b le as th e e x te n t of dehum idification re q u ire d increases.
F in a l choice am ong re frig e ra tio n an d any of the dehum idification m ethods m ust, in the la s t analysis, be based upon low est overall cost, in clu d in g in itia l and o p e ra tin g costs.
N orm ally, it m ay be considered th a t b oth d eh y d ratio n an d re frig e ra tio n r e q u ire ap p ro x im ately the sam e am ount of cooling w a te r for p ro d u cin g eq u iv a
le n t w ork. W ith w ater av ailab le below 65 deg. F ., th e selection of d e h y d ra tion eq u ip m e n t becom es d esirab le . E ven w ith relativ ely h ig h w ater tem
Lithium chloride system m aintaining air conditions for a dryer 140 i) p.m. 68°
r 4 > ^
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228 VOL. 47 • CHEMICAL & METALLURGICAL ENGINEERING • No. 4
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