Production of acetylene from hydrocarbons by submerged combustion

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PRODUCTION OP ACETYLENE PROM HYDROCARBONS BY SUBMERGED COMBUSTION

A T h e s is P r e s e n te d t o th e F a c u lty o f th e D ep artm en t o f C hem ical E n g in e e rin g The U n i v e r s i t y o f S o u th e rn C a l i f o r n i a

In P a r t i a l F u l f i l l m e n t o f th e R e q u irem e n ts f o r th e D egree M aster o f S c ie n c e

James E rw in S u m m e rv ille , J r . A p r i l , 1950

UMI Number: EP41733

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3 t, 5276 , (19U0)

b . U .S . 2 , 235, 74.9 , Nov. 18, 191*1* C .A ., v 35, 1*183, (191*1) 1 5 . a . B r i t . 265,2 3 ^ , J a n . 2 9 , 1926; C .A ., v 22, 2I4.3 ( 1928 )

b* B r i t . 2 8 2 ,6 9 0 , D ec. 2 1 , 1926; C .JU , v 2 2 , 3667, (1928) c . French 7 1 9 ,0 3 5 , Jan. 23, 1931; C .A ., v 26, 3261, (1932) d . U .S . 2,31*9,007, May 1 6 , C .A ., v 3 9 , 656, ( I 9I4.5)

10 p r i n c i p l e ones o f th e s e u s e flam e co m b u stio n b u t m a in ta in th e l i n e a r v e l o c i t y o f th e g a s e s above th e flam e sp eed even 16 i n th e co m b u stio n z o n e . The p r o c e s s u s i n g subm erged com­ b u s t i o n o n ly s p e c i f i e s t h a t a flam e i s p ro d u c e d w ith a c o m b u s tib le g a s an d oxygen below th e s u r f a c e o f a h y d ro ­ c a rb o n l i q u i d an d th e c o m b u s tib le gas i s s h u t o f f a s soon a s th e te m p e ra tu re o f t h e l i q u i d aro u n d th e flam e i s h ig h enough t o e n a b le th e l i q u i d to b u rn w ith oxygen a l o n e .

17‘

: 1&. "a. U .S . 1 , 965 ,7 7 0 J u ly 10, 193 I+J C .A ., v 28, 5I4.7I4., (193W b . U .S . 1 , 965 , 771 , J u l y 10, 1931+; C .A ., v 28, (193U) e . U .S . 2 , 179 , 578 , Nov. 8 , 1959; C .A ., v 5I4., 1211*, (1940 )

5ktk,

17# Herrman, l o c . c i t .

II.

FORMATION OF ACETYLENE BY PYROLYSIS

S in c e l 866 when B e r t h e l o t p u b lis h e d h i s p o s t u l a t e t h a t a c e ty le n e I s a n e c e s s a r y in te r m e d ia te p ro d u c t in th e d e c o m p o sitio n o f h y d ro c a rb o n s , many i n v e s t i g a t o r s have w ork­ ed on th e pro b lem of p ro d u c in g a c e ty le n e b y th e p y r o ly s is o f h y d ro c a rb o n s .

B ecause o f th e abundance o f n a t u r a l gas and *■

th e demand f o r a ro m a tic s an d a c e t y l e n i c compounds much s tu d y h as b e e n done on m ethods o f p ro d u c in g b o th a c e ty le n e and a r o m a tic s b y th e p y r o l y s i s o f m ethane and n a t u r a l g a s e s co n ­ t a i n i n g h ig h p e r c e n ta g e s o f m eth an e.

In th e p r o d u c tio n o f

c a rb o n b la c k b y th e p y r o l y s i s o f n a t u r a l gas some a c e ty le n e can b e o b ta in e d , ru n n in g s e v e r a l p e r c e n t o f th e e f f l u e n t g ases.

A t te m p e ra tu re s i n th e ra n g e o f 800 to 1100°C

u n s a t u r a t e s and a ro m a tic s a re form ed b y th e p y r o l y s i s o f m ethane o r n a t u r a l g a s . R e a c tio n s .

M ethane can b e made to decompose t o c a r ­

bon an d h y d rogen o r to fo rm h ig h e r h y d ro carb o n s on h e a t i n g . E g lo f f in a n ACS monograph d is c u s s e s th e t h e o r i e s t h a t have b een p ro p o se d f o r th e m echanism o f th e d e c o m p o sitio n r e ­ a c tio n s .

The f i r s t was B e r t h e lo t * s p o s t u l a t e t h a t a c e ty le n e

was th e in te r m e d ia te s te p i n th e d e c o m p o s itio n .

T h is mech­

a n ism was s u p p o rte d by th e f a c t t h a t a ro m a tic h y d ro c a rb o n s can be o b ta in e d i n th e p y r o ly s is o f low er a l i p h a t i c h y d ro ­ c a rb o n s an d t h a t a ro m a tic s can a l s o be o b ta in e d by p a s s in g

12 a c e ty le n e through a h ot tu b e. L ater workers have tended to d is a g r e e w ith th e mech­ anism o f B e r t h e lo t ,

S e v e r a l p ro p o sa ls have been g iven fo r

h ig h er hydrocarbons, but methane seems to be a s p e c ia l c a s e . In p a ssin g methane through a carbon fila m e n t lamp immersed in l iq u id n itr o g e n , a t a p ressu r e below 8 cm H* S to rch obta in e d ethane a s the c h ie f d ecom p osition p ro d u c t.

18

E th ylen e

and hydrogen were formed in in c r e a s in g amounts a t h ig h er p ressu res.

When a hot tube i s u sed e t h y le n e , a c e ty le n e ,

carbon, and hydrogen are o b ta in e d .

On th e b a s is o f the se

and s im ila r r e a c t io n s , two prim ary t h e o r ie s on the decom­ p o s it io n o f methane have been p rop osed .

One assumes the

form ation o f f r e e m ethyl r a d ic a ls w ith t h e ir

subsequent r e ­

a c t io n s ; th e other assumes the s p l i t t i n g o f f o f a m olecu le o f hydrogen w ith the form ation o f a m ethylene r a d ic a l. W hile i t does n o t co m p letely e x p la in the o b s e r v a tio n s , the b e s t e x p la n a tio n seems to be th a t of K a ssel through the u se 19 o f m ethylene r a d i c a l s . The fo llo w in g r e a c tio n s are in v o lv e d i n the th eo ry : CH,

= CH2 /

CH2 / CH

H2 - I|.7,000 c a l .

: C2 H6 / 5 5 ,0 0 0 caX.

XfcJ. E gX off, G ustav, "The R ea ctio n s o f Pure Hydro­ carb on s," ACS Monograph 73»-P 33> (1937) 1 9 . I b i d ., p 51).

15

Qz \

* H2

C2H6

=

° 2\

~ ° 2 H2

^ H2 " W ’ 000 c a l *

C2H2

= 2C /

H2 / 7I4. , 250 c a l .

-

5 0 ' 000 c a l *

In th e fo rm a tio n of a c e ty le n e th e o v e r a l l r e a c t i o n i s : 2 CH.

= C2H2 / 3 H2 - 8 9 ,0 0 0 c a l .

T h is r e a c t i o n i s g e n e r a lly accom panied to some e x t e n t b y th e d e c o m p o sitio n i n t o "the e lem e n ts#

The d e c o m p o s itio n r e a c t i o n

r e l e a s e s 7U*230 c a l / g mol o f a c e t y l e n e . C o n d itio n s o f th e r e a c t i o n # & w ide v a r i a t i o n o f co n ­ d i t i o n s have b e e n s t u d i e d , h u t th e most s u c c e s s f u l e x p e r i ­ m ents seem t o have b e e n th o s e u s in g p o r c e l a i n o r s i l i c a tu b e s w ith te m p e r a tu r e s b etw een 1000°C a n d 2000°C, p r e s s u r e s aro u n d 0 .1 a t m ., and c o n t a c t tim e s b etw een 0 .2 and 0 .0 0 1 se c o n d . T e m p e ra tu re :

M ethane w i l l b eg in to decompose i n t o c a rb o n and

hyd ro g en a t ab o u t 850°C.

However lo n g h e a tin g tim e s a r e r e ­

q u ir e d a t "the lo w er te m p e r a tu r e s .

I n 1929 C h am b erlain an d

Bloom s tu d i e d th e p r o d u c tio n o f a ro m a tic s from n a t u r a l g a s e s . They fo u n d t h a t v a r y in g y i e l d s o f o i l s and t a r s c o u ld be o b ­ t a i n e d w ith te m p e r a tu r e s of 500°C to 90 °oC*^° F is c h e r o b ta in ­ ed s a t i s f a c t o r y y i e l d s o f t a r and l i g h t o i l s from m ethane a t 20. C h a m b e rla in , D .S ., an d E .B . Bloom, "Therm al T re a tm e n t o f N a tu r a l G as, 11 I n d . and Eng. Cham #. v 21 p 9^4-5* (1929)

1k te m p e ra tu re s from 9°0°C

1200° C . ^ In 191+2 H asche p u b l i s h ­

ed th e r e s u l t s o f s t u d i e s on th e p r o d u c tio n o f a c e ty le n e b y th e p y r o l y s i s o f h y d ro c a rb o n s •

However h i s s t u d i e s w ere

made on h y d ro c a rb o n s i n th e ra n g e o f p ro p an e to n a t u r a l g a s o lin e o v er a te m p e ra tu re ra n g e o f 800°C to 1500°C r a t h e r th a n on m ethane*

Ihe m ethane i n th e p ro d u c ts re m a in e d

c o n s ta n t up t o lijXX^C.

Some ben zen e was form ed in i n c r e a s ­

in g am ounts up t o a b o u t 1250°C.

The amount o f a c e ty le n e

in c r e a s e d up to 1500°C, th e n begem t o d e c re a s e w ith i n c r e a s in g c a rb o n f o r m a tio n .

22

I n t h e i r s tu d y o f th e p y r o ly s is o f

m ethane deRudder and B iederm ann fo u n d o n ly sm a ll t r a c e s o f a c e ty le n e below 900°C .

A t 1000°C s m a ll am ounts o f e th y le n e

w ere i n th e o f f g a se s a t a tm o sp h e ric p r e s s u r e .

The maximum o amount o f a c e ty le n e in th e o f f g a se s was o b ta in e d a t 1500 C

and low p r e s s u r e s .

The b e s t c o n v e rs io n o f m ethane to o 23 a c e ty le n e was a t a b o u t li^OO C. F r o s t r e p o r t e d a 95$ c o n p)

v e r s io n o f m ethane to a c e ty le n e a t 760mm Hg an d 1527°C . 2 1 . Cliem. A b s t. , v 23 , 269J+, (1 9 2 9 ), - F i s c h e r , F . , " S y n th e s is of A ro m atic H yd ro carb o n s from Methane a t A tm os­ p h e r ic P r e s s u r e and W ith o u t C a t a l y s t s . " B r e n n s to f f Chem ., v 9 , PP 509- 1 6 , (1928) . 2 2 . H asch e, R. L eo n a rd , ^ P ro d u c tio n of A c e ty le n e by Therm al C rack in g o f H y d ro c a rb o n s," Chem & M et, v I4.9 . n 7 . p 7 9 , ( J u ly , 1 * 2 ) . ----------2 3 . E g lo f f , "Pure H y d ro c a rb o n s," p 60, deR u d d er, F . , an d H. B ied erm an n , B u l l , s o c . chem. (IV ), lj.7,70l+> (1 9 5 °) 2U. I b i d . , p 62 , F r o s t , A .V ., K h im te o re t (L e n in g ra d ) 2 , pp 98- 106, (1 9 5 5 ); Qkem. A b s t ., 29, 5625, (1955)*

15 P re ssu re :

The am ount o f a c e ty le n e p ro d u c e d in c r e a s e s w ith

d im in is h in g p r e s s u r e s *

The b e s t r e s u l t s have b een r e p o r t e d

u s i n g p r e s s u r e s a ro u n d 0 ,1 atm*

The re d u c e d p r e s s u r e o f th e

m ethane may be o b ta in e d b y r e d u c in g th e t o t a l p r e s s u r e o r b y u s in g a d i l u e n t t o re d u c e th e p a r t i a l p re s s u re *

deR udder

and B iederm ann o b ta in e d th e maximum am ount of a c e ty le n e i n th e o f f g a se s a t p r e s s u r e s b etw een I4.5 a n d 75mm a *» 1500°C* The maximum co n v er sio n was o b ta in ed a t 82mm.

V arious o th e r s

have rep o r te d maximum y ie ld s in t h i s range o f p r e s s u r e s * ^ A t 1120°C F r o l i c h , W h ite, an d B ay to n r e p o r t e d no n o tic e a b le 26 e f f e c t o f p r e s s u r e s from 25 to 760mm u s in g a q u a r tz tu b e* S to r c h and G olden u s e d c a rb o n d io x id e and steam a s d i l u e n t s t o re d u c e th e p a r t i a l p r e s s u r e o f th e m eth an e.

At

a te m p e ra tu re o f 1500°C t h e i r b e s t r e s u l t s w ere ab o u t 10$ a c e ty le n e i n th e p r o d u c ts u s i n g c a rb o n d io x id e a s th e d i l ­ u e n t.

The C0p h ad th e a d v a n ta g e t h a t t h e r e was no c a rb o n 27 fo rm a tio n ; steam f a i l e d to p r e v e n t t h i s *

C a ta ly s ts :

A number o f m a t e r i a l s in f lu e n c e the decom posi­

t i o n o f m ethane, b u t m ost a l l o f them c a u se th e r e a c t i o n t o go t o th e elem en ts*

S in c e s i l i c a , p o r c e l a i n , and c a rb o ru n ­

dum do n o t have an y a p p r e c ia b le c a t a l y t i c e f f e c t on th e ----------- 3 3 . PP 59-61 2 6 . I b id . . p 59 2 7 . S to r c h , H .H ., and P. L. G olden, " S y n th esis o f A ce ty le n e by the P y r o ly s is o f M ethane," In d . and Eng. Chem. . v 25, p 768, (J u ly , 1 9 5 5 ). --------------

16 d e c o m p o sitio n a t te m p e r a tu r e s below t h a t w here th e m ethane w ould o th e rw is e be s t a b l e . I r o n , n i c k e l , an d p a lla d iu m have 28 th e g r e a t e s t e f f e c t . I n th e p r o d u c tio n o f l i g h t o i l s and t a r from n a t u r a l g a s , i t was fo u n d b y C h am b erlain and Bloom t h a t a f ilm o f c a rb o n h ad to be form ed b e f o r e an y o f th e o i l s a p p e a re d .

Even i n u s in g o th e r k in d s o f c a rb o n the same

f i l m had t o be form ed from th e m ethane b e f o r e th e o i l s w ere o b ta in e d .

They fo u n d t h a t ir o n and co p p er tu b e s gave a

y i e l d o f c a rb o n and h y d ro g en w ith o u t any h ig h e r h y d r o c a r ­ b o n s . ^ I n g e n e r a l c o n t a c t w ith s o l i d s te n d s to d e c r e a s e th e y ie ld s of a c e ty le n e . D ilu e n ts :

D ilu e n ts have b ee n u s e d f o r two p u rp o s e s i n th e

p y r o l y s i s o f m eth an e.

S in c e g r e a t e r y i e l d s a r e o b ta in e d a t

low er p r e s s u r e s , d i l u e n t s w hich can be r e a d i l y removed,rsuschi a s ste a m o r c a rb o n d io x id e , a r e u s e d to re d u c e th e p a r t i a l p ressu re.

H ydrogen and c h l o r in e m ix tu re s and HC1 have a l s o

b een u s e d a s d i l u e n t s .

The r e a c t i o n o f th e H and C l f u r n 50 is h e s p a r t o f th e h e a t t h a t i s n e e d e d . The o th e r p u rp o se o f d i l u e n t i s t o s e rv e a s an in d u c to r i n th e r e a c t i o n .

Waterman an d h is a s s o c i a t e s s t u d ­

i e d th e e f f e c t o f v a r io u s in d u c to r s i n th e p y r o l y s i s o f £8 . E g l o f f , ,fP ure H y d ro c a rb o n s ,” p 73* 2 9 . C h am b erlain and Bloom, o £ . c i t . . p 91+5 • 3 0 . Cham. A b s t . , v 27 . 53i+0, (1 9 3 3 ); v 29. 1*028, (1935)*

m ethane.

They found th a t c e r t a in m a te r ia ls cau se the r e a c ­

t io n s a t tem peratures where methane a lo n e would p ass unchanged*

These m a te r ia ls are a lip h a t ic hydrocarbons,

h a lo g e n s, and h a logen compounds.

A rom aties had no e f f e c t .

In u s in g th e h a lo g en s the hydrogen h a lid e was formed le a v ­ in g the hydrocarbons f r e e o f the h a lo g e n .

The in d u cto r had

more e f f e c t w ith g r e a te r r a t io s o f methane to in d u c to r . 31 Good y ie ld s o f o i l s , ta r and a c e ty le n e were r e p o r te d . Time o f C o n ta c t:

S in c e the a c e ty le n e formed tends to

decompose in t o the e le m e n ts, i t i s n e c e ssa r y to u se o n ly v ery sh o r t h e a tin g p e r io d s .

Nieuwland s t a t e s th a t some o f

th e e a r l i e r workers d id not o b ta in a c e ty le n e in t h e ir 32 r e a c t io n s b eca u se o f th e lo n g tim e u s e d . The sh o rt h e a tin g i s accom p lish ed by q u ic k ly c o o lin g or quenching th e g a ses to a tem perature where th e a c e ty le n e i s s t a b l e . The e f f e c t o f tim e o f c o n ta c t a t v a rio u s p ressu r es and tem peratures has been s tu d ie d b y a number o f p e o p le . These s t u d ie s show th a t a s the tem perature Is In crea sed the tim e o f c o n ta c t must be d e c r e a se d . U sing a quartz tube a t 1120°C w ith a c o n ta c t tim e o f 0 .0 6 s e c . , F r o lic h , W hite and Dayton were able to co n v ert 'J l. Waterman, e t . a l . , flInduced P y r o ly s is o f M ethane,” Journal o f th e S o c ie t y o f Chem. I n d u s tr y . T r a n s a c tio n s, v 5 8 . p p 5 2 3 -2 ? , t n o v .7 193971 5 2 . N ieuw land, J u liu s A ., and B ich ard H. V ogt, ”The C hem istry o f A c e t y le n e ,” ACS Monograph 99# P 20, (1945)*

18 a b o u t 11 p e r c e n t o f methane i n t o a c e ty le n e w ith th e s im u l­ ta n e o u s fo rm a tio n o f o n ly s m a ll am ounts o f o th e r h y d r o c a r ­ bons and c a rb o n .

W ith an e x p o su re o f 0*6 s e c . t h e r e was

c o n s id e r a b le fo rm a tio n o f c a rb o n and p o ly m e r iz a tio n w ith a 35 y i e l d o f o n ly 5 P e r c e n t a c e t y l e n e . H t te m p e r a tu r e s above 10G0°C an d a t a tm o s p h e ric p r e s s u r e deR udder and B iederm ann fo u n d t h a t d e c o m p o s itio n t o c a rb o n and hydrogen was a lm o st c o m p le te .

However a t lo w e r p r e s s u r e s b o th a c e ty l e n e and

e th y le n e c o u ld be o b ta in e d by c h a n g in g th e tim e o f c o n t a c t . They o b ta in e d a maximum o f a c e ty le n e i n th e p r o d u c ts a t a b o u t 1500°C u s i n g c o n ta c t tim e s b etw een 0 .0 1 an d 0 . 2 s e c . The in c r e a s e i n th e tim e o f c o n ta c t d id n o t i n c r e a s e th e p e r c e n t o f a c e ty le n e i n th e o f f g a se s b u t d id in c r e a s e th e am ount o f c a rb o n w ith a d e c re a s e i n th e amount o f undecom ­ p o se d m e th an e .

E g lo f f e x p la in s t h i s b y s a y in g i t c l e a r l y

i n d i c a t e s t h a t th e d e c o m p o s itio n o f m ethane t o th e e le m e n ts a t t h i s te m p e r a tu r e i s more r a p i d th a n th e d e c o m p o sitio n o f th e a c e ty le n e .5 U The maximum y i e l d o f a c e ty le n e a s p e r c e n t m ethane decom posed was I4J4. p e r c e n t o b ta in e d w ith a c o n ta c t 35 tim e o f 0 .1 s e c . a n d a p r e s s u r e o f 82mm. T ro p sch and E g l­ o f f p y ro ly z e d m ethane a t a te m p e ra tu re o f llj.00oC and a p r e s ­ s u r e o f 50mm.

The maximum y i e l d o f a c e ty le n e (12 l i t e r s / 1 0 0

33* E g l o f f , "P u re H y d ro c a rb o n s," p 59 3I4.. I b i d . , p ~60 3 5 . I b i d . . p 60

l i t e r s o f m ethane e n t e r i n g ) was a t a c o n ta c t tim e o f 0*0ll* sec*

The maximum y i e l d o f e th y le n e (3 *1 /1 0 0 ) was fo u n d a t 36 a tim e o f 0*005 sec* W aterm ants d a t a show t h a t i n a p y r o l y s i s in d u c e d w ith p ro p an e th e a c e ty le n e fo rm ed in c r e a s e d w ith s h o r te n e d tim e a t a te m p e ra tu re o f 1190°C .

The amount o f t a r d e c r e a s e d an d

th e amount o f o i l s in c r e a s e d to a maximum*

F o r n o n -in d u c e d

ru n s th e amount o f a c e ty le n e v a r ie d i r r e g u l a r l y .

The amount

o f cru d e ben zen e was a maximum w ith a c o n ta c t tim e of 0 .0 6 2 37 seconds* A c c o rd in g t o N ieu w lan d , e x c e p t a t s h o r t h e a tin g p e r i o d s , c o n s id e r a b le am ounts o f c ru d e b e n z en e an d t a r a r e form ed a t te m p e r a tu r e s b etw een 800 an d 1 0 0 0 ° C .in th e ; , 38 p y r o l y s i s o f h y d ro c a rb o n s . P ro d u c ts and Y i e l d s *

From h e th a n e a t a te m p e ra tu re

o f 1500°C c a rb o n , h y d ro g en , and a c e t y l e n e . a r e .v a ry in g am ounts d e p e n d in g on the p r e s s u r e and the tim e o f c o n ta c t* W ith f a i r l y lo n g tim e a lm o s t co m p lete d e c o m p o s itio n t o th e e le m e n ts i s o b ta in e d .

U sin g te m p e r a tu r e s b etw een 500 an(*

1100°C b en zen e an d h ig h e r a ro m a tic s c a n be p ro d u ced *

W ith

n a t u r a l gas c o n s i s t i n g p r i m a r i l y o f m eth an e, C h am b erlain and Bloom o b ta in e d y i e l d s o f fro m I4. t o I4O l i t e r s o f b en zen e p e r 3b. 'Ibid'*, p 6 l ; T ropsch, H ., and G. E g l o f f , f,High Temperature P y r o ly s is o f Gaseous H ydrocarbons,w In d .~ and Eng. Chem. . v 2 7 , p IO63, ( S e p t ., 1935) 37* W aterm an, dp* c i t * , p 3^5 3 8 . N ieu w lan d , 0£* c i t ** p 20

20 1000 c u b ic m e te rs o f g a s . tu b e s .

They u s e d a number o f d i f f e r e n t

T h is i s a p p r ix ir a a te ly a n 8 p e r c e n t c o n v e rs io n t o

th e o i l s on th e b a s i s o f th e e n t e r i n g gas a t th e maximum fig u re . W ith b u ta n e H asche o b ta in e d 27*5 P0 r C0nb a c e ty le n e fro m th e f e e d .

W ith th e e th y le n e an d m ethane r e c y c l e d , a

5 2 .3 p e r c e n t c o n v e rs io n t o a c e ty le n e was o b ta in e d b a s e d on th e Cj^ f e e d .

W ith o u t th e r e c y c le th e e f f e c t was the fo rm a ­

t i o n o f b e n z e n e , h y d ro g e n , e th y le n e an d m e th an e .

W ith th e

r e c y c le a c e ty le n e was form ed r a t h e r th a n b o th a c e ty l e n e and 1+0 e th y le n e . U sin g c a rb o n d io x id e an d steam a s d i l u e n t s , S to r c h a n d G olden o b ta in e d a c e ty le n e and a m ix tu re o f CO an d H ^.

T h e ir maximum y i e l d o f a c e ty l e n e i n th e e x i t g a s e s was

w ith 90 P0** c e n t d io x id e i n th e f e e d an d a c o n t a c t tim e o f 0 .0 3 s e c .

T hese g a s e s c o n ta in e d 10 p er cen t a c e ty l e n e on a

CO^ f r e e b a s i s .

T hese c o n d itio n s a l s o gave th e g r e a t e s t p e r

c e n t c o n v e rs io n o f 70—75 P0 r c e n t o f ihe m ethane decom posed to a c e ty le n e a t 0 .1 a tm , l6 0 0 °C , an d 0.001+ s e c .

They a l s o

o b ta in e d th e s e r e s u l t s w ith a p a r t i a l p r e s s u r e o f O.2 5 atm . P i c h l e r s a i d t h a t th e c o n t a c t tim e c o u ld v a ry fro m 0 .0 0 1 t o 0 .0 0 5 s e c /* 2 39* C h a m b e rla in , o p . c i t . , p 9l±5 1+0. H asch e, 0£ . c i t . , p 82 1+1. S to r c h an d G olden, 0£ . c i t . , p 768 1+2, E g l o f f , ^Pure H y d ro c a rb o n s ,n p 62

21 E q u ip m e n t.

The ty p e o f eq uipm ent t h a t has g e n e r a lly

b e e n u s e d f o r s t u d i e s o f th e p y r o l y s i s o f m ethane an d h y d ro ­ c a rb o n s has b e e n h e a te d t u b e s *

C h am b erlain and Bloom u s e d

s i l i c a an d m e ta l tu b e s o f v a r y in g le n g th s an d d ia m e te rs * A l l w ere above one h a l f in c h i n d ia m e te r*

H e a tin g was done

w ith a n e l e c t r i c a l e le m e n t wound a ro u n d th e tu b e*

S to r c h

and Golden u s e d a q u a r tz tu b e w ith a 3* 2mm i n s i d e d ia m e te r an d a le n g th o f 20cm*

The m id d le te n c e n tim e te r s w ere a t a

te m p e ra tu re b etw een lJOO an d

T ro p se h and E g lo f f

u s e d a p o r c e l a i n P y th a g o ra s tu b e w ith a c o n s ta n t te m p e ra tu re f o r 15cm. th e i n s i d e d ia m e te r was $rm , th e o u ts i d e d ia m e te r 1+5 ]+6 5mm. W aterman u s e d a q u a r tz tu b e* Hasche u s e d e l e c t r i ­ c a l l y h e a te d carborundum tu b e s i n th e l a b o r a t o r y .

They h ad

a n i n s i d e d ia m e te r o f one h a l f in c h , o u ts id e d ia m e te r of 2 i n c h e s , an d w ere 6 f t * lo n g .

He u s e d a c o r e b u s te r t o re d u c e

th e a r e a an d in c r e a s e th e v e l o c i t i e s *

I n th e sem i-w orks h i s

tu b e s had th e f o llo w in g d im e n s io n s : ID 1+ i n . , 0D 5 3A- in * , le n g th 8 f t .

The c o r e b u s te r had a d ia m e te r o f 3 i i n . ^

1+3# tfham berlain, 0£ . c i t *, pp 9U5-9 ijl+. S to r ch and G olden, o £ . c i t ** p 7^9 1j5 • Tropseh and E g l o f f , o £ . c i t * t p 1 0 6 j 1+6. Waterman, op * c i t . , p 32I+ 1+7* H asch e, o£* c i t . , p 79

CHAPTER I I I

METHODS OF APPROACH TO THE PROBLEM A c e ty le n e I s form ed d u r in g th e d e c o m p o sitio n o f h y d ro c a rb o n s o f a lo w e r c a rb o n to hy d ro g en r a t i o , an d i t i s t h i s phenomenom t h a t i s u s e d a s th e b a s i s o f p r o d u c tio n o f th e gas fro m th e o th e r h y d ro carb o n s*

In o rd e r to o b ta in the

h ig h e r am ounts o f a c e ty le n e i n th e p r o d u c ts , i t i s n e c e s s a r y to o b ta in v e ry h ig h te m p e r a tu r e s f o r a s h o r t tim e an d to th e n r a p i d l y c o o l th e g a s e s b e f o r e th e a c e ty le n e decom poses i n t o th e e le m e n ts*

I n m ost c r a c k in g o p e r a tio n s th e h e a t i s

s u p p lie d e x te r m a lly th r o u g h a h e a te d tube*

M a te r ia ls w h ich

w i l l w ith s ta n d th e c o n d itio n s n e c e s s a r y f o r a c e ty le n e p r o ­ d u c tio n have low th e rm a l c o n d u c t i v i t i e s and t h e r e f o r e l i m i t th e p ro c e s s*

By s u p p ly in g th e h e a t i n t e r n a l l y th ro u g h p a r ­

t i a l l y o x id iz in g th e h y d ro c a rb o n t h i s l i m i t a t i o n may b e overcom e.

The pro b lem th e n becomes one o f e f f e c t i n g th e

r e q u ir e d v e ry r a p i d r e d u c t io n i n te m p e ra tu re *

T his h as b ee n

done by u s in g a w a te r s p r a y o r p a s s in g th e g ases a g a i n s t a 8 o ld s u r f a c e , By s u p p ly in g s u f f i c i e n t p r e s s u r e and a sh ro u d to p r o t e c t th e b a s e o f th e flam e fro m th e w a te r a flam e may be b u rn e d u n d e rn e a th the s u r f a c e o f th e l i q u i d .

W ith a f a i r l y

h ig h c o n c e n tr a t io n o f oxygen and a l a r g e enough c o n t a in e r a lm o st any o r d in a r y o x y - a c e ty le n e b lo w p ip e may be s u c c e s s -

23 f u l l y b u rn e d u n d e r w a te r w ith o u t a s h ro u d .

W ith a p ro p e r

sh ro u d o r b u rn e r o th e r g a se s may be b u rn e d in subm erged com­ b u s t i o n , t h a t i s w ith th e mouth of the b u r n e r b e n e a th th e s u r f a c e of th e l i q u i d .

S uch b u r n e r s a re a t p r e s e n t commer­

c i a l l y u s e d f o r h e a t i n g and e v a p o r a tio n .

S in c e th e p ro d u c ts

o f com bu stio n m ust p a s s o u t th ro u g h the l i q u i d , th e method o f subm erged co m b u stio n w ould seem t o p ro v id e a good means o f e f f e c t i n g th e r a p i d quench n e c e s s a r y to p r e v e n t the d e c o m p o sitio n o f th e a c e ty le n e *

I t was t h i s means t h a t t h i s

s tu d y i n v e s t i g a t e d . S in c e i t i s th e r a p i d quench w hich i s d e s i r e d , and s in c e h y d ro c a rb o n s may b e c ra c k e d to l i g h t e r p r o d u c ts , i t was a l s o d e c id e d t o s tu d y th e u s e o f k e ro s e n e a s th e f l u i d w ith th e p o s s i b i l i t y o f o b ta in in g th e d e s i r e d a c e ty le n e fro m th e c r a c k in g a s w e ll as th e p a r t i a l o x id a tio n o f th e n a t u r a l gas • B ecause o f th e la c k o f in f o r m a tio n on th e sy stem s tu d i e d and i t s p o s s i b i l i t i e s , th e w ork done was o f an e x p lo r a to r y n a t u r e .

CHAPTER IV

APPARATUS AND MATERIAIS TJSED The a p p a r a tu s u s e d i n th e s tu d y i s d iv id e d i n t o t h a t u s e d w ith th e r e a c t i o n and t h a t u s e d t o a n a ly z e th e sam ples ta k e n d u r in g th e r e a c tio n s *

B oth g ro u p s a r e d e s c r ib e d an d

s p e c i f i c a t i o n s and a n a ly s e s o f th e m a t e r i a l s u s e d i n ea ch a r e g iv e n i n t h i s c h a p te r* I.

REACTION APPARATUS

B u rn e r an d r e a c t i o n cham ber♦

The m ain p a r t o f th e

a p p a r a tu s u s e d f o r th e r e a c t i o n was th e chamber v h ic h co n ­ ta in e d th e l i q u i d an d th e b u rn e r*

The cham ber was made o f

m ild s t e e l tu b in g o f 6 in c h o u ts id e d ia m e te r and l / 8t h in c h w a ll t h i c k n e s s .

I t was te n In c h e s i n l e n g t h .

The to p an d

b o tto m were c lo s e d b y w e ld in g i n q u a r t e r in c h p l a t e .

T here

w ere f o u r o p en in g s i n th e to p , one i n th e s i d e , and one i n th e bottom *

I n th e c e n te r o f th e to p one h a l f o f an in c h

an d a q u a r te r s ta n d a r d i r o n p ip e c o u p lin g was w eld ed f o r th e b u rn er p a r t .

T hree one in c h p ip e s tu b s t h r e e in c h e s i n

l e n g th w ere w eld ed to th e to p a t an a n g le f o r gas o u t l e t s . These w ere th r e a d e d .

A one-^half in c h p ip e c o u p lin g was c u t

i n t o and one h a l f was w elded to th e b o tto m f o r one l i q u i d o u t l e t and th e o th e r to th e s id e a t th e b o tto m a s a n o th e r o u t l e t and means o f d e te rm in in g th e l i q u i d l e v e l .

25 The b u r n e r was c o n s tr u c te d from a n Oxweld O xyacetyle n e B low pipe W-7 an& some p ip e f i t t i n g s .

A o n e - e ig h t t o a

q u a r t e r b u s h in g was th r e a d e d o n to v a r io u s t i p s f o r th e blow ­ p ip e and sh ro u d s w ere form ed fro m o th e r b u s h in g s , c o u p lin g s , and n ip p le s #

Numerous c o m b in a tio n s o f t i p s sh ro u d d i a ­

m e te r s , and le n g th s w ere t r i e d i n a b u c k e t o f w a te r u n t i l one was fo u n d t h a t w ould b u rn s a t i s f a c t o r i l y w ith an e x c e ss of gas.

T h is was d e te rm in e d by c h e c k in g th e s u r f a c e o f th e

l i q u i d a t i n t e r v a l s f o r f l a s h i n g o f u n b u rn e d g a se s o r c o m b u stib le p r o d u c ts .

The c o m b in a tio n t h a t was f i n a l l y

d e c id e d upon was made from a No. 15 t i p , an e i g t h t o q u a r t e r b u s h in g , a q u a r t e r t o t h r e e - q u a r t e r b u s h in g , a t h r e e - q u a r t e r c o u p lin g , and a s h o r t p ie c e on one in c h b la c k ir o n p i p e . The p ip e was ta c k w eld ed to th e c o u p lin g an d th e r e s t were screw ed t o g e t h e r . The l i q u i d l e v e l i n th e chamber was d e te rm in e d b y a g la s s tu b e b e n t to form a s e a l .

The lo w er end o f t h i s tu b e

was i n s e r t e d i n a c o rk i n a s id e - o p e n in g e l l a t t a c h e d to th e s id e o p e n in g o f th e chamber by a c lo s e n i p p l e . end was open t o th e a tm o s p h e re . a f f e c t e d th e r e a d i n g .

The u p p e r

There w ere two th in g s w hich

B ecau se o f th e open end th e p r e s s u r e

te n d e d t o make i t h ig h , b u t p r e s s u r e i n th e chamber was u s u a l l y s m a ll.

The o th e r o p en in g o f th e e l l was th e o u t l e t

f o r c i r c u l a t i o n of th e l i q u i d and the flo w te n d e d to make th e r e a d in g low .

N e ith e r was s i g n i f i c a n t how ever a s a

26

O xw eld O x y a e e t y l e n e .B low pipe vV-Y \ Yip ‘h e rm o c o up 1 e No . 30 1 / 4 - 1 /8 . r u s h i n g 3 /4 - 1 /4 B u sh in

Y in .

3 td . 8 a lv

1 in . P ip e

FIGURE I BURNER DETAIL,

r e l a t i v e p o s i t i o n was e s t a b l i s h e d and marked on th e tu b e . Thus th e l i q u i d l e v e l was e s s e n t i a l l y c o n s ta n t th ro u g h o u t th e r u n s . b u rn er.

F ig u re I shows tiie shape and d im e n sio n s o f th e F ig u re I I i s a d ia g ra m o f th e e n t i r e r e a c t i o n

a p p a ra tu s • C o n d en ser and c o o lin g s y ste m . th e sy stem i n two w ays.

H eat was rem oved from

T here was a r e f l u x c o n d e n se r to

r e t u r n a l l c o n d e n sa b le m a t e r i a l s to th e r e a c t i o n chamber and a c i r c u l a t i o n o f l i q u i d o v e r a c o o lin g c o i l . A lth o u g h p r o v is io n was made f o r th r e e c o n d e n s e rs , o n ly one was u s e d .

T h is was c o n s tr u c te d fro m a f i v e f o o t

l e n g th o f one in c h s ta n d a r d i r o n p ip e ja c k e t e d w ith a f o u r and o n e - h a lf f o o t le n g t h o f two in c h p ip e .

W ater i n l e t a t

th e b o tto m and o u t l e t a t th e to p w ere h a l f in c h p i p e .

The

c o n d e n se r was c o n n e c te d to th e r e a c t i o n chamber an d th e w a te r l i n e s w ith u n io n s t o a llo w i t to be r e a d i l y rem oved f o r c le a n in g .

A t th e to p o f th e co n d e n se r t h e r e was a coup­

l i n g and b u s h in g to re d u c e th e o p en in g so t h a t a r u b b e r hose c o u ld be c o n n e c te d .

T h is h o se was n o t c o n n e c te d a t th e open

end e x c e p t when r a t e m easurem ents o r sam p les w ere ta k e n b e c a u s e o f th e c a rb o n b la c k i n th e p ro d u c t g a s e s . m e te r w e lls were p la c e d i n th e w a te r l i n e s .

Thermo­

W ater r a t e was

m easu red b y w e ig h in g th e d is c h a r g e . I n o r d e r t o make xuns w ith c o n s ta n t l i q u i d te m p e ra ­ t u r e s a sy stem was p ro v id e d t o c i r c u l a t e th e l i q u i d o v e r a

28

C ooling W a ter NATURAL GAS OXiGK-M.

Th e r m o -

A ir

C ooling W ater

■ O pen

CHARGE TANK

cooling

tank

FIGURE I I DI&GRAT-i OK rFACTION AFPa I^TUS

29 c o o lin g c o il*

The c o i l was made fro m s i x t e e n f e e t o f o n e -

e i g h th in c h co p p e r tu b in g .

I t was w rapped w ith a f i v e in c h

c e n te r t o c e n te r d ia m e te r an d was s p re a d to a le n g th o f f i v e an d o n e - h a lf in c h e s .

The c o l l ..was s e t i n a s t a i n l e s s s t e e l

c o n t a in e r w hich h ad a d e p th o f e i g h t and one h a l f in c h e s an d a d ia m e te r - o f sev en an d o n e - q u a r te r in c h e s .

The c o n ta in e r

was c o v e re d b y a n in e in c h sq u a re o f t h r e e - e i g h t s in c h p l y ­ wood.

T h is was f a s t e n e d t o th e c o n t a in e r by b o l t s w hich

w ere b e n t so t h a t th e h e a d s f i t t e d u n d e r th e l i p o f th e co n ­ ta in e r.

A s h o r t p ie c e o f ru b b e r tu b in g was s p l i t t o form

th e g a s k e t.

T here w ere f o u r o p en in g s i n th e to p o f th e

c o o lin g ta n k - - two f o r th e c o o lin g c o l l an d two f o r l i q u i d i n l e t an d o u t l e t . R ubber h o se was u s e d t o c o n n e c t th e c o o lin g c o i l t o th e w a te r l i n e an d t o th e d r a i n .

W ater r a t e was m easu red b y

w e ig h in g , an d th e te m p e ra tu re was m easured by a th erm o m eter i n a c o n ta in e r in w hich th e w a te r was d is c h a r g e d .

The flo w

o f l i q u i d was by g r a v i t y fro m th e s id e o u t l e t o f th e chamber to th e ta n k fro m w here i t was pumped b ac k t o th e chamber th ro u g h th e b o tto m .

The pump i n l e t was a sip h o n fro m th e

b o tto m o f th e ta n k .

Pump s u c t i o n was o b ta in e d by s h u t t i n g

o f f th e pump and a llo w in g l i q u i d t o flo w t o th e ta n k th ro u g h th e pump u n t i l th e s e c t i o n l i n e was f i l l e d . was an E a s t e r n C e n t r i f u g a l Pump Model B -l* p ip e s w ere o n e - q u a r te r in c h .

The pump u s e d C irc u la tio n

Plow was c o n t r o l l e d b y g a te

v a lv e s i n th e g r a v i t y l i n e an d th e pump d is c h a r g e l i n e .

30 L iq u id c h a r R ing s y s te m *

I n th o s e ru n s made u s in g

w a te r th e l i q u i d was a l r e a d y i n th e r e a c t i o n cham ber when th e ru n was s t a r t e d *

B ecause o f s a f e t y how ever i t was n e c ­

e s s a r y t o b r i n g th e o r g a n ic l i q u i d s i n t o th e cham ber a f t e r th e b u r n e r was i n p la c e *

The sy stem u s e d was a p r e s s u r e

ta n k c o n n e c te d t o th e b o tto m o p e n in g of. th e r e a c t i o n cham ber b y a one h a l f in c h p ip e lin e *

T h is ta n k was f i t t e d w ith a

v a lv e t o a llo w a i r t o be pumpfcd i n t o i t by means o f a hand pump*

V alv e s an d a u n io n a llo w e d th e ta n k to be rem oved

fro m th e sy ste m f o r c le a n in g *

The l i q u i d was r e t u r n e d t o

th e ta n k from th e r e a c t i o n cham ber b y g r a v i t y flow * Flow an d te m p e r a tu r e m easu rem en t*

Flow r a t e s o f th e

g a s e s w ere made u s i n g a P r e c i s i o n S c i e n t i f i c Company Wet T e s t M e te r.

The tu b in g fro m th e to p o f th e co n d e n ser was

c o n n e c te d t o th e m e te r when m easurem ents o f th e p r o d u c ts gas r a t e w ere made.

A T im e -It e l e c t r i c tim e r w hich r e a d i n

m in u te s and h u n d re th s o f a m in u te was u s e d to m easure th e tim e .

D u rin g th e w ater, ru n s th e oxygen an d n a t u r a l gas f e e d

r a t e s w ere m easu red i n th e same manner a s th e p ro d u c t g a se s b y a llo w in g them t o p a s s th ro u g h th e e q u ip m e n t.

However

d u rin g th e o r g a n ic l i q u i d ru n s a p ie c e o f in c h and a q u a r t e r p ip e was f i t t e d to h o ld th e b u r n e r and a llo w th e g a se s t o be ru n th ro u g h a r u b b e r tu b in g to th e m e te r .

W ith t h i s th e

f e e d r a t e an d oxygen r a t i o was s e t b e f o r e th e run*

W ater

r a t e s w ere m easured b y c o l l e c t i n g and w e ig h in g sam ples*

L iq u id te m p e ra tu re s i n th e r e a c t i o n cham ber w ere m easured w ith a th erm o co u p le i n th e b o tto m o f th e chamber* A C ole In s tru m e n t Co. # 8P6 W all M ounting O-JOOC P y ro m eter w ith a c o ld ju n c tio n co m p en satio n was u s e d .

T h is p y ro m e te r

was c a l i b r a t e d f o r s i x f e e t o f Mo. JO I r o n - C o n s ta n tin w ire w ith a w elded j u n c t i o n .

T h is same p y ro m ete r was u s e d w ith a

th e rm o co u p le i n s i d e th e b u r n e r sh ro u d to d e te rm in e w h e th e r th e flam e h ad e x t in g u is h e d .

A th r e e p o s i t i o n s w itc h a llo w e d

r a p i d ch eck s o f t h i s te m p e r a tu r e .

C o o lin g w a te r tem peravu

t u r e s w ere m easured w ith -1 0 t o HOC m ercu ry th e rm o m e te rs. The d is c h a r g e w a te r fro m th e c o o lin g c o i l was p a s s e d th ro u g h a b e a k e r in w hich th e th erm o m eter was p la c e d a t th e o u t l e t o f th e r u b b e r tu b e .

G o o lin g w a te r i n l e t te m p e r a tu r e s were

m easured a t th e th erm o m eter w e ll a t th e e n tr a n c e to th e c o n d e n s e r. II. Gas A n a l y s i s .

ANALYTICAL APPARATUS Sam ples o f th e co m b u stio n p ro d u c ts

w ere c a u g h t a f t e r th e g a s e s h ad b e e n m e te re d i n th e c a s e o f w a te r ru n s and w ith o u t th e m e te r i n th e sy ste m i n th e c a s e o f th e o r g a n ic l i q u i d s b e c a u s e o f th e carb o n in th e g a s e s . G lass g as sam ple b o t t l e s w ith a c a p a c ity o f 300 ml and JOO ml w ere u s e d .

T hese w ere c o n n e c te d t o th e c o n d e n se r

o u t l e t th ro u g h a Y c o n n e c tio n so t h a t o n ly a p a r t o f th e p ro d u c t gas was c a u g h t t o p r e v e n t a b u i l d u p o f p r e s s u r e i n

32 th e chamber w h ile o b ta in in g th e sa m p le .

W ater was d is p la c e d

fro m th e sam ple b o t t l e s b y th e g a s e s d u r in g th e sa m p lin g . The g a s e s w ere a n a ly z e d w ith a B u r r e l l Gas A n a ly s is s e t.

The s e t u s e d had a g as r e s e r v o i r w hich w ould h o ld a

100 ml sam p le, one c o n ta c t p i p e t t e , an d f o u r b u b b le r p ip e tte s .

T here was a co p p e r o x id e tu b e f o r th e o x id a tio n

o f hyd ro g en an d c a rb o n monoxide an d a c a t a l y s t tu b e f o r h y d ro carb o n d e t e r m in a t io n s . L iq u id a n a l y s e s .

Sam ples o f th e o r g a n ic l i q u i d s were

o b ta in e d d u r in g th e r u n s .

The API g r a v i t y an d ASTM

d i s t i l l a t i o n s w ere r u n on t h e s e .

S ta n d a rd eq u ip m en t a s

s p e c i f i e d i n th e ASTM Manual f o r p e tro le u m p r o d u c ts f o r th e d i s t a l l a t i o n o f k e ro s e n e was u s e d .

S m a ll API h y d ro m e te rs

and 100 ml g r a d u a te s w ere u s e d t o d e te rm in e th e g r a v i t y . The te m p e ra tu re o f th e sam p les f o r th e g r a v i t y .

The tem p­

e r a t u r e o f t h e sam p les f a r th e g r a v i t y d e te r m in a tio n s were m easured w ith a 0 -1 5 0 °F m ercu ry th e rm o m e te r. III.

SPECIFICATIONS AND ANALYSES OP MATERIALS USED

R e a c tio n m a t e r i a l s .

T here w ere two g ro u p s o f m a te r­

i a l in v o lv e d i n th e r e a c t i o n — th e gas f e e d an d th e quench liq u id s .

The gas f e e d c o n s i s t e d o f two co m p o n en ts.

N a tu r a l

gas a s f u r n is h e d to th e U n i v e r s i t y fro m th e m ains o f th e S o u th e rn C a l i f o r n i a Gas Company was th e c o m b u s tib le m a te r­ i a l i n th e f e e d .

The o th e r was t h e r a p e u t i c q u a l i t y

33 oxygen o b ta in e d i n s i z e ’’K*1 c y l in d e r s from th e Id n d e A ir P ro d u c ts Company.

The a n a l y s i s o f th e gas i n th e v i c i n i t y

o f th e U n iv e r s it y a s f u r n is h e d b y th e Gas Company was a s f o llo w s : C arbon D i o x i d e ........................................................l.O/o Oxygen ............................................. 0*1 M e t h a n e ................................................................... 83*5 E t h a n e ................................................................ . 14*7 N i t r o g e n ............................................................ 0 .7 100.0

N et H e a tin g V alue p e r s t d . c u . f t .

9^5

(c a lc .)

W ater, k e r o s e n e , an d E d e le a n u e x t r a c t w ere u s e d i n th e r e a c t i o n cham ber a s th e q u e n c h in g medium.

The k e ro s e n e

was p u rc h a s e d a t a l o c a l s e r v ic e s t a t i o n , so i t h ad h ad th e a ro m a tic m a te r ia l s rem oved.

The E d e le a n u e x t r a c t was a m ix­

t u r e o f e q u a l p a r t s from sam ples from R i c h f i e l d O il Company and S h e ll O il Company.

T h is e x t r a c t i s th e a ro m a tic p o r t i o n

o f th e p e tro le u m f r a c t i o n o f th e k e ro s e n e b o i l i n g r a n g e . was e x t r a c t e d w ith SO2 w hich was l a t e r b o i l e d o f f . r a f f i n a t e from t t i s p ro c e s s i s k e r o s e n e . k e ro s e n e were u s e d .

The

Two s o u rc e s o f the

Runs 28 th ro u g h 53 were k e ro s e n e W AW

and ru n s 56 and 57 were w ith nBw. i n ru n s 5l+ a nd 5 5 •

It

E d e le a n u e x t r a c t was u s e d

P r o p e r t i e s o f th e l i q u i d s u s e d a r e g iv e n

i n T able I . R e a g e n ts .

The gas a n a l y s i s was done by p a s s in g th e

sam ple th ro u g h s u c c e s s iv e a b s o r b e n ts .

S u f f i c i e n t s to c k s o f

th e v a r io u s a b s o r b e n ts were made up i n th e la b o r a t o r y b e f o r e

TABLE I PROPERTIES OP' QfJENCH L IP ID S

L iq u id ASTM D i s t i l l a t i o n I n i t i a l B »P• 5 10 20 iO

K erosene . "A" 325 °p 552 368 3% I+1 I4.

>0

I

90 95 End P o in t R ecovery C o lo r API G ra v ity H ydrogen#

hbo

m 501 98# C le a r

K ero sen e f,B"

m 1)00 1)10

\a 9 U29 m k55 1+9T 518 91% C le a r 1& .0 13 >55

E d ele an u E x tr a c t 314-2 378 387 398 £+10 1*2 1+28

g

1+80 14-98

9 Red 2 6 .7 1 0 .6 5

#The w eig jit p e r c e n t o f h y drogen was com puted fro m a n e m p ir ic a l e q u a tio n u s in g the API g r a v i t y an d th e mean a v e ra g e h o i l i n g p o i n t . See "Sample C a lc u l a ti o n s " page lq.1#

55 th e e x p e rim e n ta l ru n s w ere b e g a n .

The r e a g e n ts u s e d f o r th e

com ponents o f th e g a s e s a r e shown i n T able IX . T6BIE I I GAS ANALYSIS REAGENTS

Component_________________________R eag en t_______ COo C^ 2 C|H6

55# KOH Hg(CN)? 87# H2S0h

H2 CO

I^ P y to g a lla te C opper Oxide C opper Oxide

T able I I l i s t s th e g a se s i n th e o rd e r in w b ich th e y w ere d e te rm in e d .

The h y d ro g en was b y d i f f e r e n c e a f t e r

p a s s in g o v er th e co p p er o x id e a t 300°C.

The carbon m onoxide

was oxiditedL to th e d io x id e w h ich was a b so rb e d i n th e KOH, The re m a in d e r was l i s t e d a s R e sid u e i n th e c l a t z .

CHAPTER V

EXPERIMENTAL PROCEDURE AND DATA T h is c h a p te r c o n ta in s d e s c r i p t i o n s o f th e p ro c e d u re s u s e d to o b ta in th e e x p e rim e n ta l d a ta ta k e n i n th e s tu d y and a d is c u s s io n o f the d a t a , ~.

PROCEDURES

P ro c ed u re w ith w a te r . i n t o two g ro u p s .

The w a te r ru n s w ere d iv id e d

Those ru n s up th ro u g h No. 16 were made

w ith no c o o lin g o f th e l i q u i d i n th e r e a c t i o n cham ber.

The

re m a in d e r o f th e ru n s w ere made w ith th e te m p e r a tu r e h e ld c o n s ta n t i n s t e p s . In b o th c a s e s th e m ethod o f s t a r t i n g th e r u n was th e sam e.

The b u rn e r was i g n i t e d o u ts id e th e cham ber.

s e t t i n g was made on th e oxygen and was n o t c h a n g ed .

A v a lv e The

amount o f n a t u r a l g as was v a r i e d w h ile th e b u r n e r was t r i e d i n a b u c k e t o f w a te r .

The gas was i n c r e a s e d u n t i l f l a s h i n g

c o u ld b e o b ta in e d a t th e s u r f a c e of th e b u c k e t w ith the flam e u n d e r th e s u r f a c e . th e flam e e x tin g u is h e d .

The gas was th e n in c r e a s e d u n t i l I t was r e l i g h t e d and a g a in t r i e d .

I f i t b u rn e d s a t i s f a c t o r i l y , th e b u r n e r was p la c e d i n th e cham ber.

I f n o t th e gas was s lo w ly re d u c e d u n t i l the m axi­

mum amount t h a t w ould p e rm it c o n tin u e d b u r n in g i n a c o n t a in e r a p p ro x im a te ly th e s i z e o f th e chamber was o b t a i n ­

37 ed.

The l e v e l o f th e w a te r I n th e cham ber on s t a r t i n g was

th e same a s t h a t u s e d i n th e ru n s*

The b u r n e r s h o u ld b e

c a r e f u l l y and s lo w ly lo w ered i n t o the l i q u i d t o p r e v e n t e x ­ tin g u is h in g •

When th e flam e d id become e x tin g u is h e d i n

s t a r t i n g , th e .o x y g e n was s h u t o f f a t th e cock b etw een the b lo w p ip e v a lv e an d th e r e g u l a t o r on th e c y lin d e r to a llo w th e e x p o s iv e m ix tu re t o be sw ept o u t b y th e g a s . was th e n rem oved and r e t r i e d a t the same s e t t i r g .

The b u r n e r I f i t d id

n o t work a f t e r s e v e r a l t r i a l s , th e r a t i o was r e s e t i n th e b u c k e t* W ith the flam e b u r n in g in th e cham ber th e co n d e n se r w a te r was tu r n e d on an d th e to p o f th e chamber was s e a le d w ith a m ag n esia mud and che eked f o r f l a s h i n g to d eterm in e th e p re s e n c e o f l e a k s .

D ata was th e n ta k e n on th e l i q u i d

te m p e r a tu r e , the p r o d u c t r a t e , an d th e tim e u n t i l the flam e was e x tin g u is h e d *

The p ro d u c t r a t e was m easu red by the tim e

r e q u i r e d f o r a g iv e n q u a n t i t y o f gas t o p a s s th ro u g h th e m eter*

S am ples o f th e g as w ere ta k e n a t r e g u l a r I n t e r v a l s

o f l i q u i d te m p e r a tu r e .

The te m p e ra tu re i n d i c a t e d by the

therm ocouple- I n the b u r n e r was a l s o ch eck ed a t i n t e r v a l s f o r e x tin g u is h m e n t • The p ro c e d u re w ith c i r c u l a t i o n o f th e w a te r to m ain­ t a i n a c o n s ta n t te m p e ra tu re i n th e chamber was th e same a s t h a t w ith r i s i n g te m p e ra tu re e x c e p t f o r th e c o o lin g .

In

t h i s c a s e a s soon a s th e flam e was b u r n in g s u c c e s s f u l l y i n

38 th e cham ber, th e v a lv e betw een th e cham ber and the c o o lin g ta n k was opened s l i g h t l y .

As th e l e v e l b egan t o f a l l th e

v a lv e on the pump d is c h a r g e was opened t o a llo w l i q u i d to flo w b ack th ro u g h th e pump t o p rim e i t *

Then th e pump was

s t a r t e d and th e v a lv e s a d j u s t e d t o m a in ta in th e l e v e l i n th e chamber*

W ater was tu r n e d on i n th e c o o lin g c o i l an d th e

r a t e g r a d u a lly a d j u s t e d t o k eep th e l i q u i d te m p e ra tu re a s i n d i c a t e d by th e p y ro m e te r c o n s t a n t . P ro c e d u re wl t h o r g a n ic l i q u i d s *

The m ethod u s e d w ith

o r g a n ic l i q u i d s d i f f e r e d i n s e v e r a l r e s p e c t s fro m t h a t i n th e w a te r r u n s .

The r u n was s t a r t e d w ith the l i q u i d i n th e

c h a rg in g ta n k i n s t e a d o f th e cham ber, th e oxygen t o gas r a t i o was s e t i n a d i f f e r e n t m anner, and th e e x i t tu b in g was n o t c o n n e c te d t o the m e te r and sam pling a p p a r a tu s th ro u g h o u t th e run* The l i q u i d was c h a rg e d t o th e c o o lin g ta n k u n t i l th e c o l l was c o v e re d a n d th e n to th e chamber u n t i l th e d e s i r e d d e p th was o b ta in e d .

T h at i n th e chamber was r u n i n t o th e

c h a rg in g ta n k an d en ough more ad d ed t o p r e v e n t a i r from r e a c h in g t h e o u t l e t o f th e c h a rg in g ta n k .

The c o o lin g w a te r

was th e n tu r n e d on i n th e co n d e n se r and th e c o i l . The r a t i o o f oxygen t o n a t u r a l gas and th e r a t e of f e e d g a se s was s e t i n th e a p p a r a tu s p r e p a r e d f o r th a t*

The

oxygen was th e n tu r n e d o f f w ith th e cock an d th e cham ber and c o n d e n s e r f lu s h e d o u t w ith gas to p r e v e n t an e x p lo s iv e m ix-

59 t u r e o f a i r and gas o r v a p o r s .

The fla m e was th e n i g n i t e d

a n d th e b u r n e r p la c e d i n th e cham ber.

B ecause o f some fla m ­

in g a t th e to p o f th e chamber a s th e b u r n e r was i n s e r t e d , a