Crude Petroleum

88.* Deodorization of Irak Crude by Means of Soda. H . P a sc a l. l i m a Congrès M o n d . P étrole, 1938, 2, 329-333.— T h o prosenco of 1-8% s u lp h u r a n d 0-11% free h y d ro g e n s u lp h id e in I r a k c ru d e in tro d u c e d difficu lties in tr a n s p o r tin g a n d refin in g th e c ru d o duo to th o fu m es ev o lv ed . T h es e difficu lties h av o n o w b e en overcom e b y th e e rec tio n o f sta b iliz in g p la n t, b u t p rio r to t h is t h e y w ore su ccessfu lly d e a lt w ith b y in je c tin g a se a -w ato r so lu tio n of c a u s tic s o d a in to t h e cru d o d u rin g p u m p in g o p e ra tio n s a t th e p o r ts o f lo ad in g . T h is t r e a tm e n t d eo d o rized th o c ru d e, b u t in tro d u c e d f u r th e r d ifficu lties in refining d u o to (1) p e r s is te n t e m u lsio n s, (2) d e p o s its in p ip e s tills d e riv e d fro m w a ter-so lu b le s a lts , (3) d e p o sits in c rac k in g s tills d e riv e d fro m o il-soluble s a lts . T h ese d ifficulties wore overcom e b y b re a k in g t h e e m u lsio n s b y p r e h e a tin g a n d w a sh in g th o c ru d e w ith fres h w a ter.

A m e th o d of e s tim a tio n o f d isso lv e d h y d ro g e n s u lp h id e in c ru d e is g iv en : sw eeping th o c ru d o w ith n itro g e n a n d a b so rb in g h y d ro g e n su lp h id e in zinc o r so d iu m a c e ta te .

W . P . 89.* Petroleum E m ulsions and their Chemical R esolution. L . T . M onson. l i m e Congrès M o n d . Pétrole, 1938, 2, 335-343.— A su rv e y of th e th e o ry a n d p ra c tic e of de- cm u lsifica tio n o f c ru d e oil. T h o a u th o r d iscu sses v a rio u s g e n e ra l th e o rie s o f ém u lsifica ­ tio n in th e lig h t of h is ex p erie n c e w ith cru d e-o il e m u lsio n s. R e c e n t d e v e lo p m e n ts in t h e p ra c tic e of d e-em u lsifieatio n a re in d ic a te d , p la n t d escrib ed , a n d m e th o d s of te s tin g

d iscu ssed . W . P .

Cracking.

90.* Combination Selective Cracking. E . R . Sm oloy, W . M eckler, a n d A. H . S e h u tto . l i m e Congrès M o n d . Pétrole, 1938, 2, 3 5 5-368.— S electio n of s to c k s a cc o rd in g to bo ilin g ran g o a n d a cc o rd in g to r e fr a c tiv ity (w hich d iffe re n tia te s v irg in fro m re-cy cled sto ck s) lo ad s to h ig h e r efficiency in c rac k in g pro cesses.

F lo w -sh eo ts a n d p la n t d a ta a re g iv en in d e ta il fo r a n u m b e r of m o d ern th re e - a n d four-coil c o m b in a tio n c rac k in g u n its . T h e a rra n g e m e n t of e q u ip m e n t is d isc u sse d a n d a n e w ty p e of h e a te r d escrib ed , w h e re b y t h e h e a tin g c u rv e is c o n tro lle d b y th o u se of in d e p e n d e n tly fired h e a tin g a n d so a k in g se c tio n s. W . P . 91.* Selective Cracking and Continuous Coking. J . G ra n t. l i m e Congrès M o m d . Pétrole, 1938, 2, 369-374.— A n a c c o u n t o f a re c o n s tru c tio n p ro g ra m m e u n d e rta k e n b y S hell P o tro lo u m C o rp o ra tio n a t W o o d R iv e r, w h e reb y th o D u b b s fuel-oil crac k in g p la n t w as m o d ern ize d b y in s ta lla tio n o f selectiv e c rac k in g a n d c o n tin u o u s coking e q u ip m e n t. T h e o p e ra tio n o f th e n e w u n it is d e scrib ed . T h o a d v a n ta g e s o f th e n e w u n it a re : (1) re d u c e d o p e ra tin g c o s t, (2) in creased “ on s tr e a m ” efficiency, (3) a b ility to v a r y p ro d u c tio n of gaso lin e a n d in te rm e d ia te d is tilla te s a t w ill, (4) p ro d u c tio n of

g aso lin es of 70-7 2 o c ta n e n u m b e r. W . P .

Hydrogenation.

92.* H ydrogenation of Hydrocarbons in Absence of Catalysts. A . L eopold. l i m e Congrès M o n d . Pétrole, 1937, 2, 217-222.— H y d ro g e n a tio n in ab sen co o f c a ta ly s ts is d isc u sse d a n d th o re s u lts o f th r e e series of e x p e rim e n ts u n d e r d iffere n t c o n d itio n s a ie g iv en in d e ta il. I t is c o n clu d ed t h a t t h e yield of lig h t p ro d u c ts o b ta in e d b y h y d ro g e n a ­ tio n d e p e n d s n o t o n ly o n th e te m p e ra tu re , p re ssu re , a n d d u ra tio n , b u t also on th o re la tiv e p ro p o rtio n s of h y d ro g e n a n d h y d ro c a rb o n s. W . P . 93.* Industrial Production o! Gasoline by Selective H ydrogenation in Absence of Catalysts. A . L eo p o ld . l i m e Congrès M o n d . Pétrole, 1937, 2, 22 3-225.— C o n tin u in g w o rk a lre a d y p u b lis h e d (see p re ce d in g a b s tr a c t) , it is sh o w n t h a t th o n a tu r e a n d q u a n tity of p ro d u c ts p ro d u c e d b y h y d ro g e n a tio n d e p en d o n six m a in fa c to rs : p re s s u re ; te m p e ra tu r e ; d u r a tio n ; sp eed of c irc u la tio n ; th e s te e l su rfa ce s of th e a p p a r a tu s ;

ABSTRACTS.

a n d th e volum o of th e m a te ria l p ro c essed . T h e h y d ro g e n c o n su m p tio n d e p e n d s on th o ty p o of h y d ro c a rb o n p ro c essed a n d o n t h e m e th o d o f s p littin g in v o lv ed . T h e re a c tio n c a n b e e x o th e rm ic o r en d o th e rm ie , a cc o rd in g to th e re la tiv e a m o u n ts of h y d ro g e n a n d h y d ro c a rb o n s p re s e n t, a n d th is ra tio m u s t b e s u ita b ly a d ju s te d to ach iev e econom ic y ield s. A m odified fo rm o f p ip e -s till h a s b e en fo u n d m o re effective a n d c h ea p er t h a n a u to c la v e s fo r c a rry in g o u t h y d ro g e n a tio n . W . P . 94.* H ydrogenation of Roum anian Petroleum . C. C an d ca a n d A. M arsch all. l i m e Congrès M o n d . Pétrole, 1937, 2, 2 2 7-236.— A s tu d y of th e h y d ro g e n a tio n of c ru d e oil a n d o f i ts v a rio u s fra c tio n s u sin g m o ly b d e n u m s u lp h id e a s c a ta ly s t. I t is concluded t h a t th e p ro c ess d e p e n d s n o t o n ly on te m p e ra tu re , p re ssu re , a n d d u ra tio n , b u t also o n t h e ch em ical c o m p o sitio n of th e b asic m a te ria l. I n th e p ro c ess u se d , o p tim u m te m p e ra tu r e o f 300-350° C. a n d o p tim u m p re s s u re o f 200-300 a tm . g a v e y ield s u p to 5 0 % o f g asoline. T h e gaso lin e h a s a re d u c e d p e rc e n ta g e o f u n s a tu r a te d h y d ro c a rb o n s a n d a n in cre as ed p re ce n ta g o of a ro m a tic s a n d n a p h th e n e s . I t s s u lp h u r c o n te n t is low , a n d i t h a s a lo w te n d e n c y to g u m fo rm a tio n . W . P . 95.* Catalytic H ydrogenation of Low-Temperature Tar under H igh Pressure. S. A ndo.

l i m e Congrès M o n d . Pétrole, 1937, 2, 237-248.— L o w -te m p e ra tu re t a r p ro d u c ed from H o k o k u co al b y th e Im p e ria l F u e l R e se a rc h I n s t i tu t e o f J a p a n w as h y d ro g e n a te d u n d e r v a ry in g c o n d itio n s em p lo y in g a 5 -litre rev o lv in g a u to c la v e . H ig h p re ssu re s a n d m o ly b d e n u m c a ta ly s ts w ere u se d . T h e effects o f te m p e ra tu re , tim e , p re ssu re , a n d ta r - h y d r o g e n ra tio w ere s tu d ie d in re la tio n to y ield a n d q u a lity of p ro d u c ts . F u ll d a ta a re g iv en re la tin g to a b o u t t h i r t y te s ts . I n g en eral, h ig h er te m p e ra tu re s g av e g re a te r y ie ld s o f fra c tio n s below 200° C. w ith h ig h e r a ro m a tic c o n te n t ; h ig h er p re ssu re s g a v e g re a te r y ield s o f fra c tio n s b elo w 200° C., b u t slig h tly low er a ro m a tic c o n te n ts . In c re a s e d tim e o f re a c tio n g a v e lo w er y ie ld s a n d h ig h o r h y d ro g e n c o n ­

s u m p tio n . W . P .

96.* H ydrogen of Tars and Tar Oils. J . G. K in g a n d C. M. Caw ley. l i m e Congrès M o n d . P étrole, 1937, 2, 249-262.— W ith a v iew to u tiliz in g t a r s p ro d u c e d b y low- te m p e ra tu r e c a rb o n iz a tio n , h y d ro g e n a tio n o f t a r s a n d t a r d is tilla te s h a s b een s tu d ie d a t t h e F u e l R e se a rc h S ta tio n , E n g la n d . T h e re a c tio n s in v o lv ed a n d th e effects o f th e v a rio u s v a r ia n ts a re d isc u sse d a n d e x p e rim e n ta l d a ta p re s e n te d . T h e effective p r o ­ d u c tio n of g asoline fro m t a r re q u ire s a tw o -sta g e h y d ro g e n a tio n : liq u id -p h a so follow ed b y v a p o u r-p h a so . M o ly b d e n u m c a ta ly s ts a re u se d , th o s e d e p o site d o n a lu m in a being fo u n d s u p e rio r to th o p e lle te d fo rm . L o w -te m p e ra tu re t a r s p ro c ess b e tte r t h a n high- te m p e ra tu r e t a r s ; o f th e la tto r , v e rtic a l r e to r t t a r s a re b e tt e r th a n h o riz o n ta l r e to r t ta r s . H ig h e r te m p e ra tu r e s acc e le rato h y d ro g e n a tio n , b u t d e crease m a x im u m degree o f re a c tio n . T h e effect of p re s s u re is co m p lex , b u t in g e n era l h ig h p re s s u re im p ro v e s th o y ield a n d th e re is less d e te rio ra tio n o f c a ta ly s t. L a b o ra to ry a n d sem i-tech n ical

p la n ts a re d escrib ed . W . P .

97.* M assive Catalysts in H igh-Pressure H ydrogenation. M. P ie r. l i m e Congrès M otid. Pétrole, 1937, 2, 263-270.-—-The u se of so lid c a ta ly s t in m assiv e fo rm is claim ed to be s u p e rio r to th e ir u se in a finely d iv id e d form . T h e l a t t e r fo rm is lim ite d to liq u id - p h a s e re a c tio n a n d is esp ecially c o n v e n ie n t w h ere fres h c a ta ly s t m u s t b e c o n tin u o u sly a d d e d . T h o fo rm e r m e th o d , h ow ever, is a d a p te d to b o th v a p o u r- a n d liq u id -p h a se re ac tio n s.

T h e influence o f te m p e ra tu re , p re ssu re , a n d ty p e of c a ta ly s t is d e m o n s tra te d in th e p ro d u c tio n of gaso lin e fro m c o a l-ta r oils.

T h e h y d ro g e n a tio n of lu b ric a tin g oils to im p ro v e th e ir v is c o s ity -te m p e ra tu re

su s c e p tib ility is d escrib ed . W . P .

98.* H ydrogenation of Cracked Gasoline. K . K u d o a n d H . F u jim o to . l i m e Congrès M ond. Pétrole, 1937, 2, 2 7 1-275.— C rack ed g aso lin es a re n o t s a tis f a c to r y a s a v ia tio n fu els o w ing to t h e ir ch em ical in s ta b ility , b u t s u ita b le fuols c a n b e p re p a re d fro m th e m b y h y d ro g e n a tio n . L a b o ra to ry a n d se m i-tech n ical e x p e rim e n ts a re d e scrib ed in w hich c rac k ed g aso lin e w a s h y d ro g e n a te d in th e p re sen c e o f n ick el o x id e a s c a ta ly s t.

W . P .

ABSTRACTS.

ABSTRACTS.

I t is considered possiblo t h a t p ro d u c tio n of lig h t m o to r fu e ls w ill re ac h 1,800,000 to n s in 1939, callin g fo r a b o u t 8 m illio n to n s o f lig n ite. I n th o c o n s tru c tio n of th es e larg e u n its o f coal-oil p ro d u c tio n co n sid e ra b le q u a n titie s of special ste els a re re q u ire d , w h ich m a y n o t bo re a d ily a v a ila b le to G e rm a n y u n d e r w a r c o n d itio n s. T ho p o ssi­

b ilitie s of p ro d u c tio n of diesel oils a n d h ig h -o c tan e fu els fro m coal-oils a re con sid ered

d o u b tfu l. S. J . A.

102a.* Production of A viation Fuels by H igh-Pressure H ydrogenation. E . Y . M u rp h rce, E . J . G ohr, a n d C. L . B ro w n . In d listr. E n g n g Chem., 1939, 31, (9), 1083-1089.— T ho a p p lic a tio n of h ig h -p ressu ro h y d ro g e n a tio n to th e p ro d u c tio n of a v ia tio n gasolines, b len d in g a g e n ts , a n d 100 o c ta n e fuels is d iscu ssed . T ho h y d ro g e n nocossary for th es e v a rio u s p ro cesses is p ro d u c e d in a tw o -sta g e o p e ra tio n a s follow s. I n th o firs t sta g e a m ix tu re o f s te a m a n d n a tu r a l g as is p a s s e d th ro u g h a b a n k of p a ralle l tu b e s co n ta in in g c a ta ly s t h e a te d to a h ig h te m p e ra tu re . H y d ro g e n a n d c a rb o n m o n o x id e a re fo rm ed in t h is s ta g e. A d d itio n a l s te a m is th e n a d d e d to th e m ix tu re , a n d f u r th e r re d u c tio n is c o n d u c te d in a seco n d sta g e a t a low er te m p e ra tu re . I n t h is seco n d s ta g e th e carb o n m on o x id o a n d s te a m r e a c t to p ro d u c e c a rb o n d io x id e a n d m o re h y d ro g e n .

A ty p ic a l a v ia tio n n a p h th a h y d ro g e n a tio n p la n t a t c o n v ersio n s of 5 0 -7 5 % p e r p a ss y ie ld s 8 0 -9 5 % o f 7 5 -7 8 o c ta n e h y d ro g e n a te d n a p h th a h a v in g ex cellen t s ta b ility , high le a d s u s c o p tib ility , low s u lp h u r c o n te n t, a n d go o d colour.

H y d ro g e n a tio n of iso b u ty le n o d im e r a n d iso -n o rm al b u ty le n o c o d im er in creases th e o c ta n e n u m b e r fro m 8 2-81 to 97-100, b u t th is m a te ria l, on a cc o u n t o f it3 v o la tility , is o n ly s u ita b le a s a b len d in g a g e n t. V a rio u s ta b le s a re g iv e n show ing t h e c h a ra c te ris tic s of th e h y d ro g e n a te d fu e ls a n d p o ly m e rs, a n d v a rio u s h ig h -o ctan e a v ia tio n fuels p r o ­ d u c e d b y b len d in g h y d ro g e n a te d p ro d u c ts . H . E . T.

Polymerization.

103.* Polym erization and A lkylation of isoB u tylene for Production of iso-O ctane Fuels.

G. N a t ta a n d M. B a c c a re d d a , G him . e I n d u s tr ia , 1939, 7 , 3 9 3-418.— T h o c o n tin u o u sly in cre asin g im p o rta n c e of p ro c esses fo r p o ly m e riz a tio n o f d e fin e s fo r p ro d u c tio n of h ig h -o c ta n e gaso lin e is p o in te d o u t, a n d th o n e c e ssity of a m o re c are fu l se g reg atio n of c rac k in g a n d re fin e ry gases is s tre sse d .

I n I ta ly , in p a rtic u la r, whoro th o p ro cessin g of p e tro le u m p ro d u c ts is lim ite d , a se p a ra tio n of th o v a rio u s c o m p o n e n ts of th e g ase o u s b le n d s fro m crac k in g sh o u ld be effected, u sin g , fo r in sta n c e , iso b u ty lo n e a n d is o b u ta n e for t h e s y n th e s is of 100 O .N . fuels, p ro p y le n e fo r th e p ro d u c tio n of iso p ro p y l alco h o l, b u ta d ie n e to g e th e r w ith e th y le n e fo r s y n th e tic ru b b e r.

T h e v a rio u s chem ical p ro c e d u re s p ro p o se d fo r th e p o ly m e riz a tio n an d a lk y la tio n of d e fin e s a re th e n e x am in ed a n d classified acc o rd in g to th o c a ta ly s t em p lo y ed , su lp h u ric a cid , p h o s p h o r a n d arsen ic a c id s, h a lo g e n a te d m e ta ls a n d g aseo u s c a ta ly s ts .

A m e th o d s tu d ie d b y t h e a u th o r s fo r th o p ro d u c tio n of iso -o ctan e th ro u g h dim oriza- tio n of iso b u ty len o is d e sc rib e d : th o m e th o d is a n e m in e n tly selec tiv e p o ly m o rizatio n , w h ich is effected in p resen ce of tw o c a ta ly s ts , g aseo u s (HC1) a n d solid (alu m in iu m oxide in m o s t cases). T h o influence of th o v a rio u s fa c to rs, su ch a s te m p e ra tu ro , c o n ta c t tim e , a n d c o n c e n tra tio n o f th e c a ta ly s t, is d iscu sse d . I t w as fo u n d t h a t by o p e ra tin g a t 200° C. w ith 1 % o f HC1 a n d c o n ta c t tim e s o f a few seco n d s i t wa3 p o ssib le to o b ta in y ield s h ig h er t h a n 8 0 % o f tra n s fo rm e d iso b u ty le n e . D u rin g th is p ro cess is fo rm ed a sm a ll a m o u n t o f is o b u ty l ch lo rid e, w h ich c a n b e easily e lim in a te d b y fra c tio n a te d d is tilla tio n a n d th e n re-cy c le d a s c a ta ly s t, th o u g h less a c tiv e th a n HC1. I t w as n o te d t h a t th e p o ly m e riz a tio n le a d s a lso to th o fo rm a tio n o f triiso b u ty le n e , tra n s fo rm a b le b y m o an s o f a p p ro p ria te c a ta ly s ts , a lm o s t q u a n titiv e ly to diiso- a n d iso -b u ty len e.

I t is p o in te d o u t t h a t t h e so lid c a ta ly s t, a lu m in iu m o xide, c a n e asily bo reg en e rated , a n d t h a t th e se lectiv e p o ly m e riz a tio n w ith h y d ro c h lo ric acid h a s th o a d v a n ta g e of o p e ra tio n a t re la tiv e ly low te m p e ra tu re s , n o rm a l p re ssu re , a n d in p resen ce of o th e r

h y d ro c a rb o n s. F- G.

2 8 a ABSTRACTS.