Catalytic dealkylation of naphthenes and paraffins
by James F Ross
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of IMaster of Science in Chemical Engineering
Montana State University
© Copyright by James F Ross (1950)
Abstract:
Several naphthenes and paraffins were passed over hydrogen fluoride activated alumina catalyst at
temperatures of 500-550° C., liquid space velocities of 0.2/hr., and atmospheric pressure (640 mm.
hg.). Analysis of the gaseous and liquid reactor effluent showed that the sixteen compound a used
(cyclohexane, methylcyclohexane, ethylcyclo-hexane, methylcyclospentane, n-hexane, n-heptane,
n-octane, n-dodecane, n-hexandecane, n-obexane, 3,3,4-trimethylpentane, 2,3,5-trimethylhexane,
2,3-dimethylbutane, 2,4-dimethylpentane, 3-methylpentane, and 3-methyl-heptane) all suffered fairly
random carbon-carbon bond rupture. In every case, however, two of the main reaction products were a
low boil ing liquid, presumably the result of realkylation of dealkylated pro-ducts, and propylene.
Decomposition activation energise were related to the structure of the molecule undergoing reaction.
Normal alkanes required an activation energy of about 40 k-cal/mol. Paraffins possessing at least one
tertiary carbon atom required only 18 k-cal/mol. while neohexane required 35 k-cal/mol. Alkyl
cyclohexanes required an activation energy of 12 k-cal/mol. while methyloyolopentane needed 25
k-cal/mol.
The activation energy for normal paraffins decreased regularly from about 48 k-cal/mol. for n-heptane
to 40 k-cal/mol. for n-hexadecane.
The catalytic decomposition of normal paraffins wae estimated as proceeding about 750 times faster
than the uncatalyzed thermal decomposition, under the conditions of this investigation. CATALYTIC D;;ALKYLATI GK OF N/vjFHTHSNSS AKD PARAFFlKS
by
J J m s F. BOSS
A THSSIS
Subm itted t o th e G raduate F a c u lty
in
p a r t i a l f u l f i l l m o n t o f th e re q u ire m e n ts
f o r th e d ecree o f
M aster o f S cience in Chem ical S n c in e e rin g
at
Montana S ta te C o lleg e
A pproved:
H ead, M ajor D efiartnan
Exam ining Si
a n . G raduate D iv is io n
Boaenan, Montana
Ju n e, 1950
ii3 is
O
^ i
2
TABUS OF COIffiEIfTS
page
A b s t r a c t . ........................ ............................................................................................. 4
5
I n tr o d u c t i o n ..............................................
E quipm ent, IvSothods, M a te r ia ls ............................................. . . 1 4
A.
B.
C.
E quipm ent. . . . I . . . . . . . . . . . . . . . ...............
Ivbthods. . . . » .............
L b t o r i a l s ......... ...............................
...1 4
,17
20
Saiaplo C a lc u la t io n s .................... ..................... ....................... ..............................22
R e s u lts and D is c u s s i o n .......................................
..........................................25
Summary. ......................................................
.....3 4
Acknowledgement........................
L ite n a tu re Ci t e d
35
...........
Appe n d e x ...................................................
............................... . . . 3 6
38
^ 6 ^
F ig u re I , Diagram o f E q u ip ro n t............................ ......................... 38
F ig u re 2 , A c tiv a tio n E n ergy P l o t * .
......... . . . . 3 9
F ig u re 3 , A rrh e n iu s E q u a tio n P l o t . . . ..........................................40
T able V, D e a lk y la tio n o f C yclohexane. ........................ . . . . . . . 4 1
Table T I , D a lk y la tio n o f L ieth y lc y c lo h ex a n e .....................,,4 2
T able T I I , D e a lk y la tio n o f E th y lc y c lo h e x a n e ...........................43
Table T i l l , D e a lk y la tio n o f I b th y lc y c lo p e n tane
Table IX , D e a lk y la tio n o f n -H ex an e.. . . . . . . . . . .
Table X, D e a lk y la tio n o f n -Ifo p tan e........................
Table XT, D e a lk y la tio n o f n -O c ta n o .................... ....................... 47
T able X II, D e a lk y la t io n o f n-Dode carte...................... ..
48
Table X I I I , D e a lk y la tio n o f n -R sxadecano.................................49
Table XJT, D e a lk y la tio n o f Neohexane.............................50
T able XT, D e a lk y la tio n o f 2 , 2 , 4 -T r imd t hylpe a t a n e ...........,.5 1
Table XTI, D e a lk y la tio n o f 2 ,2 ,5 -T rIm sth y lh ex an o . . . . . . . , 5 2
T able XVTIf D e a lk y la tio n o f 2 , 3 -D in e th y lb u ta m ........... .. .,5 3
Table XVTII, D e a lk y la tio n o f 2,4-D iiiiethyluenbane. . . . . . . . 5 4
Table XIX, D eallcy latio n o f 3 - lb th y lp e n ta n e ............................ 55
T able XX, D o a lk y lu tio n o f S - Ib th y lh e p ta n e .. . . . . . . . . . . . . . 5 6
4
;p
83225
C lW
*» 3 —
Page
Table SXI, K in e tic Data f o r th e D e a lk y la tio n o f
H aphthenea and i ^ a r a f f i n a .........................................57
T able XX.II, R e f ra c tiv e In d ic e s o f S e v e ra l Cyclo­
hexane and S th y lcy o lo h ex an e C u ts .. . . . . . . . . . 5 9
Table m il, S q u ilib rim a o f D im ethyl- and S th y l
C yclohexanes......... ........................................................
T able XXIY, Ih ro p e rtie s o f th e C a t a l y s t . .............................61
** 4 “
ABaRLWP
Several naphthene a and paraffins ware passed ovw hydrogen fluor­
ide activated alumina catalyst at temperatures o f 500-530° C., liq uid
space v e lo c itie s o f 0 .3 /h r ., and atmospheric pressure (640 mm. Hg.}•
Analysis o f the gaseous and liq uid reactor efflu en t showed that the
sixteen compounds used (cyclohexane, mothyloyclohexane, ethyloyolohexane, methyloyolopentane, n-hexane, n-'haptane, n-ootane, n-dodeoane,
n-hexadecane, neohexane, 3 ,2 ,d-trimethy!pentane, 2,2,5-trim ethylhexane,
2,3-dimethylbutane, 3 ,4-dimethylpentane, 3~mthylpentane, and 3-methylheptane) a l l suffered fa ir ly random carbon-carbon bond rupture. In
every case, however, two of the main reaction products were a low b o il­
ing liq u id , presumably the resu lt o f realkylation o f dealkylated pro­
ducts, and propylene.
Deemnposition activation energies ware related to the structure o f
the molecule undergoing reaction . Normal alkanes required an activation
energy o f about 40 k-cal/m ol. Paraffins possessing at le a s t one ter­
tia ry carbon atom required only 18 k-cal/mol* while neohexane required
35 k-cal/m ol. Alkyl cyclohexanea required an activation energy o f 13 kc a l/a o l. while methyleyelopentana needed 25 k-cal/m ol.
The activation energy for normal paraffins decreased regularly from
about 48 k-cal/m ol. for n-haptane to 40 k-cal/m ol. for n-hexadecane.
The c a ta ly tic decomposition of normal paraffins was estimated as
proceeding about 750 times fa ster than the uncatalyzed thermal decompo­
s it io n , under the conditions of th is in vestigation .
• 5 «*
IHTRODOCTICN
DeaJUcylat ion, as applied to hydrooarbons, m y be defined as the
rupture o f sp e c ific carbon-carbon bonds in the molecule,
Deaklyla-
tion oan thus be distinguished from the more general term "cracking",
which connotea a more general, random bond rupture.
Thermodynamically, almost every hydrocarbon is unstable with re­
spect to i t s elements, carbon and hydrogen,(I)
In general, also* larger
hydrocarbons are more unstable than smaller homologuos, (I) and these
larger molecules w i l l, under the accelerating influence o f heat, bo con­
verted to smaller hydrocarbons, carbon, and hydrogen.
K in etlcallyf i t
may be shown th at, in general, hydrocarbons possess such a high energy
o f a ctivation of decomposition, that measurable rates for th is reaction
with simple molecules begin only at temperatures occoewhat above 200° 0.
Although the ordinary thermal decomposition of hydrocarbons has
not been proved to proceed through a free radical mechanism, there is
much evidence that the formation o f free rad icals i s the f i r s t step in
the decomposition o f hydrocarbons at more elevated temperatures.
Rice
and coworkers (14) detected free radicals in high temperature hydrocar­
bon decomposition.
Krey (3) was able to in itia te butane decomposition
at temperatures below the normal decomposition range by introducing
methyl ra d ica ls.
Rice and Dooley (12) found that lead mirrors were re­
moved by the products of ethane d isso cia tio n at 850-950° C,
Hobbs and
Hinshelwood (8) demonstrated that n itr ic oxide Inhibited the decomposi­
tio n o f ethane at 600° C,
6
On. th e b a s is o f t h i s and o th e r e v id e n c e (1 8 ), i t i s re a so n a b le
to conclude t h a t a t low p r e s s u r e s , even a t o rd in a ry d eco m p o sitio n
te m p e ra tu re s , hyd ro carb o n s decompose t o form f r e e r a d i c a l s .
Postulating a f r e e radical cBChanism, the f ir s t stop in the
thermal decomposition of a hydrocarbon becomes:
H da. ------------- »
R .+ R.»
R:n
R .+ H.
^
I f th e en erg y o f a c t i v a t i o n o f th e r e v e rs e r e a c tio n s ;
ft.
f t . ' —-----ft:R»
ft.
H,
or
—
7» R :H
i s z e r o , o r a t l e a s t a rtre m e d y sm all (a s ev id en ced by th e e x tre m ely
s h o r t l i f e o f m ost o rg a n ic f r e e r a d i c a l s ) , th e en erg y o f a c t i v a t i o n
o f th e forw ard r e a c t i o n becomes e q u a l to th e bond s tr e n g th and i t
i s p o s s ib le to e s tim a te th e k i n e t i c p r o b a b ility o f th e fo rm a tio n o f
a g iv e n r a d i c a l from a com parison o f e x p e rim e n ta lly d eterm in ed bond
e n e r g ie s .
Table I (18)
Bond E n e rg ie s , k - o a l .
R esidue
R-H
R-CHn1
CH3
IO2
86
83
C2K3
97
83
80
n-Cgiiy
95
82
Iso-C 3IIy
89
78
n~C4ll3
94
81
T e rt C4H9
86
76
R -O im
T able I I n d ic a te s g r e a t e r e a s e o f carb o n -o arb o n ru p tu r e a t a t e r t i a r y
o r q u a te rn a ry ourban, atom .
Becauae o f th e h ig h e r en erg y In v o lv e d , d e -
hyxlrogaaat ion to form an o l e f i n o f th e same carbon s k e le to n should be
a minor s id e r e a c t i o n .
B ut bond e n e r g ie s a lo n e w i l l n o t a llo w p r e d ic tio n o f p ro d u c ts to
be e x p ec te d s in c e th e a c t u a l p ro d u c ts o b ta in e d from th e rm a l c ra c k in g
a re due t o v a rio u s seco n d ary r e a c t i o n s .
The f r e e r a d i c a l s formed may
e i t h e r decompose f u r t h e r o r r e a c t w ith o th e r m o lecu les p ro d u cin g new
r e a c tiv e r a d i c a l s .
By c o n s id e rin g v a rio u s secondary r e a c tio n s which
wotLld a r i s e from a g iv en f r e e r a d i c a l , a th e o ry b ased on a f r e e r a d i ­
c a l mechanism h as b een developed by Rioe and H e rz fe ld (13) to account
f o r many o f th e o b serv ed k i n e t i c phenomena and p ro d u c ts o f th erm al
c ra c k in g .
S
F rey and Hepp (4) co n firm th e p r e d ic tio n s deduced from Table I 1
h av in g o b ta in e d th e v a lu e s f o r s p e c i f i c r a t e c o n s ta n ts a t 475° C.
l i s t e d i n Table I I .
T able I I
T h o r m l D ecom position R ate C o n sta n ts
Substance
k
propane
1 .5 x 10-5
n -b u ta n e
4 .0 X
is o -b u ta n e
4 .8 x
"
n -p e n ta n e
5 .7 x
n
is o -p e n ta n e
6 .5 x
"
n-he xtme
15.
x
”
iso -h e x an e
21.
x
«
Normal hyd ro carb o n s above hexane p o s s e s s a somewhat c o n s ta n t en­
e rg y o f a c t i v a t i o n f o r th e deco m p o sitio n r e a c tio n o f 65 k - c a l (Cf1-C i0 )
t o 60 k - c a l (CiowGss) (1 5 ).
The e x te n t t o w hich a carbon s k e le to n i s branched h a s a d i r e c t
b e a r in g on th e s t a b i l i t y o f th e compound.
Good, Voge, and G re e n fe ld e r
(6 ) , s tu d y in g th e e f f e c t o f c h a in b ra n c h in g , found t h a t f o r s im ila r
c o n d itio n s , th e r e l a t i v e s t a b i l i t y o f th e v a fio u s hexanes w as:
Beohexam *) n-Hexane \
3-'. b th y lp o n ta m \
2 -iie th y lp e n ta n e X 2 ,S -D im th y lb u ta n e
9
Tho p ro d u c ts o b ta in s d f r o z & th e rm a l c ra c k in g r e a c tio n u s u a lly
a h a / t h a t th e h ig h e r ttorm al p a r a f f i n s c le a v e n e a r th e m iddle o f th e
c h a in .
T lleo h o y ev and F e ig in (21) p r e s e n t th e d a ta re c o rd e d in Table
III.
T ab le I I I
F r a c tio n s o b ta in e d from Therm al C racking (21)
H ydrocarbon C ra cte d
P redom inate F r a c tio n s o f
D ecom position P ro d u c ts
n-D eCciiiQ
G asea , B in ta n e a , Fantenes
n-Dodocano
G ases, P e n ta n e s , P s n te n e s ,
H ep tan es, H e p tan e s, Oc­
ta n e s , O ctenes
n-Hezadacane
Gassa, Pontanes , Fantones,
Octanes, Cctenes, Honaneo,
H eaeaes, 130-2000 c .
D o tria c o a a m
G ases, O ctan es, Ce to n e s ,
Honanea , Nonenes , C16 and
G17 f r a c t i o n s
In th e s e r u n s , hydrogen fo rm a tio n was alm ost n e g l i g i b l e , ra n g in g
from 0 .0 0 1 t o G9Ifj0
K aphthones w ith lo n g s id e c h a in s behave s i m i l a r l y , th e s id e c h a in
re s e m b lin g th e c o rre sp o n d in g p a r a f f i n .
B o w v e r, whan th e s id e c h a in s
a re m ethyl o r e t h y l g ro u p s, th e m olecule h e co m a c o m p a ra tiv e ly s t a b l e ,
and sav o rs c o n d itio n s a rc re q u ire d t o r u p tu r e th e m olecule (1 6 ).
,nan-
t i t a t ive d a ta by T ilic h e y e v (2 0 ), l i s t e d in Table 17 i l l u s t r a t e th e r e l ­
a tiv e s t a b i l i t y o f s e v e r a l n ap h th en es and th e c o rre sp o n d in g p a r a f f i n s .
10 Tablo 17
S p e c if ic R ate C o n sta n ts f o r Therm al C rack in g o f
N aiM henes anti C o rresp o n d in g P a r a f f in s a t 500°C.
H ydrocarbon
k
C yclopentane
0 .1 2 x 10
Cyclohexane
0 .1 9 x
If
T e tra lln
3 .2
x
It
D e c a lin
3 .7
x
If
n -p e n ta m
2 .3
x
If
n-hexane
10.
x
If
n-decone
74.
x
H
I t i s a t once a p p aren t t h a t n a p h th e n ic r i n g s p o s se ss a h ig h d e­
g re e o f s t a b i l i t y .
I n th e p re sen c e o f c ra c k in g c a t a l y s t s , how ever,
n a p h th e n ic r i n g s become v e ry u n s ta b l e , th e r a t e o f d e c o m p o sitio n
b e in g 10 t o 20 tim e s g r e a t e r th a n t h a t o f th e norm al p a r a f f i n w ith
th e same nmrfoer o f carbon atom s ( 1 6 ) .
C a ta ly s ts cap ab le o f a c c e le r a ti n g hydrocarbon deco m p o sitio n
may be c l a s s i f i e d in to th r e e ty p e s :
F r i e d e l - C r a f t s , I n te rm e d ia te ,
o r A d so rp tio n .
F r ie d e l- C r o f ta c a t a l y s t s such a s A lC l3 , BF3 , HF, o r II3SO4, are
in v a r ia b ly n u c le o p h ilic r e a g e n ts which i n i t i a t e a r e v e r s e o f F r ie d e lC r a f ts a lk y la tio n by form ing a c o o rd in a tio n complex w ith th e hydro­
carbon m o le c u le .
The mechanism o f a p a r a f f i n d e a lk y la tio n o f t h i s
type b e g in s w ith th e c a t a l y s t c o o rd in a tin g w ith a hydrogen atom o f
1.1
th e h y d ro carb o n .
The co ordinated , hydrogen le av e a tl'is p a r a f i’i a , which
c au se s an e l e c t r o n etiiift and e j e c t i o n o£ a cm -baniou, w hich iz rA d la te ly
u n ite s w ith th e p ro to n p re v io u s ly e j e c t e d .
The r e a c t i o n i s com plete a s
th e c o o rd in a tio n complex s e p a r a te s in to a low er p a r a f f i n and th e c a t a ­
l y s t (1 9 ).
n
r
Hi Cl 0 ; R + H l i l
R H
a . f ”
— -> • S i d i *d: R
% S
B . . H: ? : H +H : 2$ G: H
Vt Vt
B1
S i Cl :C:R + S i'
% %
E7IHiFlH
It
K iH sF iH
S
S:H + HF
F r i s d e l - C r a f t s c a ta ly s ta cause c arb o n -ca rb o n clea v a g e to o ccu r prad o rd a& tely a t c e r t a i n s p e c if ic bonds.
Under th e In flu e n c e o f th e se c n t -
a l y r t s , a r o m t i o s in v a r ia b ly s p l i t o f f s id e c h a in s , y ie ld in g aro m atic
r in g s and o l e f i n s ; p a r a f f in s u s u a lly s p l i t in to iso b u ta n e o r Iso p en tan e
(where p o ssib le) and o l e f i n s (1 6 ).
In p a r a f f i n d e a lk y l a tio n , the p ro ­
d u c ts t o be obtained may so astirn e s be p r e d ic te d on th e b a s is o f th e e Ie c 4-ronic theory (1 1 ).
I n t e r ip d ia te c a t a l y s t s behave m e h th e ease to w ard s hydrocarbons
aa F r is d e l- O r a f t s c a t a l y s t s , b u t a r e u s u a ll y n e ith e r a s a c tiv e n o r a s
s p e c ific .
These c a t a l y s t s , w hich e re u s u a lly a c ti v a te d c la y s o r m e ta l
o x id e s o r s u l f i d e a , p e ase as c o o rd in a te u n s a tu r a ti o n which e n a b le s them
t o form c. lo o se complex w ith h y d ro c a rb o n s, b u t th e y do n o t c a ta ly z e
o th e r "FriedaI - C r a f t s r e a c t i o n s .
Some o f th e s e in te rm e d ia te c a t a l y s t s .
- 18
such a s Or2Cs l a r g e ly b r in g about te r m in a l d eh y d ro g en atio n to form an
o l e f i n o f th e cime carbon s k e le to n , w h ile o t h e r s , such as th e a c ti v a ­
te d c la y s , m ain ly cause c e n t r a l c arb o n -ca rb o n ru p tu r e (1 6 ) .
U n liir StrieSel-Crafts and In te rm e d ia te c a t a l y s t a , whicfcr causa de­
a lk y la tio n by a mechanism t o t a l l y d i f f e r e n t from th e rm a l c ra c k in g , ad­
s o r p tio n c a t a l y s t s ap p ear m ain ly t o a c c e le r a te th e th e rm a l c ra c k in g r e ­
a c ti o n .
ConsoyiU e n tly , th e se c a t a l y s t s b rin g about more random c arb o n -
carbon r u p tu r e th a n th e o th e r ty p e s .
A d so rp tio n , o r s u rfa c e a c tiv e c a t a l y s t s owe t h e I r c a t a l y t i c a c t i v ­
i t y b o th t o a la y e r in g o f th e a c t i v a t i o n en erg y and a la r g e s u rfa c e
a re a .
I t may bo shewn (5) t h a t f o r one sq u are c e n tim e te r o f s u r f a c e ;
—
=
10”13 e dS/RT
whezt? Ic0 i s th e s p e c i f i c r a t e c o n s ta n t f o r th e h e te ro g e n e o u s , c a ta ly z e d
r e a c t i o n , % i s th e s p e c i f i c r a t e cone ta u t f o r th e UcMaoyamoua, u n c a ta lyzied r e a c t i o n , and
k i s th e d if f e r e n c e between t i e a c t i v a t i o n e n e r­
g ie s f o r tlie u n c a t a ly a e d and c a ta ly z e d i-e a c t io n s ,
i t is in ^ d ia to ly ap-
M re n t t h a t in. o rd e r t o be e f f e c t i v e , a c a t a l y s t must p o s s e s s a Iu rg s
o u r f a c e , end m a t low er th e en erg y o f a c t i v a t i o n a p p r e c ia b ly .
The lo w e rin g o f th e a c t i v a t i o n en erg y due to an a d s o r p tio n c a t a l y s t
can be r e l a t e d t o th e n e a ts o f a d s o r p tio n ( I ? ) ,
Wiien th e r e a c ta n t mole­
c u le i s adsorbed on a s u r f a c e , b e a t i s e v o lv e d , and th e m o leco ls assum es
a low er en erg y s t a t e .
But f a r lo s s e n e rg y i s re q u ir e d t o a c tiv a te t i e
adsorbed m olecule ( I ? ) , s in c e i t may be shown (5 ) t h a t th e c a t a l y t i c a e -
13
t i v a t i o n e n e rg y e q u a lo th e n o n - c a ta ly t ic a c t i v a t i o n e n erg y p lu s th e
en erg y o f a d s o r p tio n o f th e r e a c ta n t minus th e energy o f a d s o rp tio n
o f th e a c ti v a te d m o le c u le .
Because th e e n erg y o f a d s o r p tio n o f th e
a c ti v a te d m olecule i s g r e a te r th a n th e energy o f a d s o r p tio n o f th e r e ­
a c t a n t , th e r e a c tio n p ro ceed s more e a s i l y .
I t i s p o s s ib le t o combine s e v e r a l ty p e s o f c a t a l y s t s in to one by
a d so rb in g a la y e r o f hydrogen f lu o r id e on a c tiv a te d alu m in a.
Kindschy
( 9 ) , Lulm (1 0 ), and H e rz e l (7) have d em o n strated th e u s e f u ln e s s o f
t h i s com bination o f c a t a l y s t s in a ro m a tic d e a lk y la tio n , o l e f i n iso m e ri­
z a tio n and c a t a l y t i c c ra c k in g r e s p e c tiv e ly and i t was th o u g h t t h a t s e ­
l e c t i v e d e a lk y la tio n o f p a r a f f i n s and n ap h th en es could be b ro u g h t about
by means o f t h i s c a t a l y s t .
The purpose o f t h i s t h e s i s , t h e r e f o r e , la t o e v a lu a te hydrogen
f lu o r id e a c ti v a te d alum ina a s a d e a lk y la tio n c a ta ly s t f o r n ap h th en es
and p a r a f f i n s .
— 14 —
r a J ia m a ,
methods, akd matmials
Equiiam at
The eq u ip iien t u sed in t h i s in v e s t ig a ti o n c o n s is te d o f th e r e a c to r
assem bly d e p ic te d in F ig u re I , a p r e c is io n r e c t i f i c a t i o n column, a low
te m p e ra tu re f r a c t i o n a t i o n gas a n a ly s is sy stem , an O rsat g a s a n a ly s is
u n i t , and a r e f r a c t o a e t o r .
The r e a c t o r was c o n s tr u c te d from a 30 in c h s e c tio n o f 2 in ch sched­
u le 80 s t e e l p ip e , b o th ends o f which were c lo se d w ith w elded c a p s.
In
each c a p , a h o le was d r i l l e d a x i a l l y and th re a d e d to r e c e iv e 3 /4 in c h
pipe*
On th e upper end a 3 /4 X 3 /4 x 1 /8 te e was screwed in to th e cap
th ro u g h a s h o r t n ip p le and con n ected th e fe e d system t o th e re a c to r*
The to p o f th e te e was c lo s e d w ith a 3 /4 in c h p lu g .
T h is arrangem ent
p e rm itte d th e c a t a l y s t t o be in s e r te d o r changed th ro u g h th e to p o f th e
re a c to r.
Three th e rm o w e lls, made from 1 /8 in c h s t e e l p ip e , were w elded in to
th e r e a c t o r e ig h t in c h e s a p a r t , th e lo w e st one s i x in c h e s above th e
bottom o f th e r e a c t o r .
a x is o f th e r e a c t o r .
The ends o f th e th erm o w ells were p la c e d in th e
When so p la c e d , e a c h th erm o w ell was ap p ro x im ately
halfw ay up each t h i r d o f th e c a t a l y s t b ed .
T em perature m easurem ents were made w ith iro n - c o n s ta n ta n therm o­
c o u p le s on a Leeds and H orthrup p o te n tio ire te r c a li b r a t e d to re a d d i ­
r e c t l y in d e g re e s C e n tig ra d e .
The r e a c t o r was h e a te d by two r e s i s t a n c e w in d in g s, s e p a ra te d from
th e r e a c t o r and e ac h o th e r by la y e r s o f a s b e s to s ta p e .
The in n e r h e a te r
c o n s is te d o f about 50 f e e t o f B&3 20 gauge Hichroma w ire (R = 35 ohms)
-1 5 wound s p i r a l l y from one end o f th e r e a c t o r to th e o th e r* th e n back a g a in .
The o u te r h e a te r was ooim.osed o f ab o u t HO f e a t o f th e same w ire (R =
75 ohm s), wound in th e same m anner.
The in n e r w inding was connected t o
a HO v o l t a u to tra n s f o rm e r, th e o u te r t o a 220 v o l t a u to tr a n s f o r im r .
Tho
r e a c t o r and h e a te r s were in s u l t a t e d w ith a la y e r o f a s b e s to s ta p e , b lo c k s
o f m agnosite one in c h t h i c k , and an in c h th ic k c o a tin g o f a s b e s to s mud.
The r e a c t o r was f i l l e d w ith a two in c h la y e r o f B e rl s a d d le s which
a c te d a s a c a t a l y s t s u p p o rt, follo w ed by 900 m l. o f 1 /8 in c h Harshaw
Alumina p e l l e t s .
The rem ain in g space above th e c a t a l y s t was f i l l e d w ith
1 /2 in c h s t e e l b a l l b e a r in g s whose h ig h e r h e a t c o n d u c tiv ity in su re d t h a t
th e fe e d would approach th e c a t a l y s t te m p e ra tu re b e fo re p a s s in g in to th e
c a ta ly s t bed.
Feed was su p p lie d t o th e r e a c to r from a 1000 m l. g ra d u a te d e y e U n d e r
by a M srk le -K b rff ty p e b e llo w s pump.
S a ra n tu b in g was u sed f o r th e fe e d
l in e t o w ith in s ix in c h es o f th e r e a c t o r .
Copper tu b in g was used f o r
th e l a s t s i x in c h e s o f l i n e le a d in g t o th e r o a c to r because th e tem pera­
tu r e o f p a r t o f t h i s s e c tio n o f lin e som etim es exceeded th e s o fte n in g
p o in t o f th e S aran tu b in g .
Copper tu b in g was n o t used th ro u g h o u t be­
cause th e l i q u i d rem ain in g in th e b e llo w s o f th e pump a f t e r a run could
o n ly be removed by in v e r tin g th e pump, and th e f l e x i b i l i t y o f Saran tu b ­
ing allow ed th e pump to be in v e rte d e a s i l y .
Two w a ter co n d en sers cooled th e r e a c t o r e f f l u e n t .
The f i r s t was
made from th r e e f e e t o f l / 8 in ch copper tu b in g en cased in a le a d pipe
w a ter ja c k e t.
The second condenser was a s ta n d a rd 20 in c h bulb type
- IG
g la s s c o n d en se r.
G ases p a s s in g through th e s e co n d en sers were conducted
e i t h e r t o a gas a m p le b o t t l e o r to a th r e e l i t e r wet g a s m o to r.
Tlio p r e c is io n r e c t i f i c a t i o n column was packed w ith 1 /8 in c h Sbnske
he; I ic e a , and was c a li b r a t e d a t 30 p e r f e c t p l a t e s a t t o t a l r e f l u x .
column was 48 in c h e s h ig h .
Cored d i s t i l l i n g head.
T h is
R eflu x r a t i o s were c o n tr o lle d th ro u g h a
Condenser te m p e ra tu re s were m easured b y a O-SOO0 C.
g la s s therm om eter g ra d u a te d a t i n t e r v a l s o f 0 .1 ° C.
T h is therm om eter was
c a li b r a t e d in co ndensing steam and m e ltin g ic e .
A system was used f o r vacuum d i s t i l l a t i o n s Comi Osed o f a Cenco
Megavac pump jo in e d th ro u g h two su rg e ta n k s t o th e r e c t i f i c a t i o n column.
Between th e two ta n k s , a so le n o id v a lv e , a c ti v a te d th ro u g h a m ercury
sw itc h and an e l e c t r o n i c r e l a y , m a in ta in e d th e d e s ir e d p re s s u re in the
second ta n k to w ith in jKL mm Hg.
R e f r a c tiv e in d ic e s were re a d to f iv e s i g n i f i c a n t f i g u r e s on a V al­
e n tin e refT & ctom etor a t 3 0 .0 - 0 .1 ° 0.
17 Ifethoda
A c tiv a tio n o f C a ta ly s t
The c a t a l y s t was a c ti v a te d by a method s im ila r to t h a t o u tlin e d
by B erg e t a l (B),
D rying th o c a t a l y s t was a c c o a p lislB d by h e a tin g
th e r e a c t o r t o 250-3000 C, f o r a t l e a s t two h o u rs,
/my w a te r vapor
rem ain in g in th e r e a c to r was swept ou t by p a ss in g n itr o g e n th ro u g h
th e r e a c t o r f o r one o r two m in u te s .
A calciu m c h lo rid e d ry in g tube
was placed, in th e o u t l e t l i n e t o p re v e n t w ater v ap o r from e n te r in g
th e r e a c t o r w h ile i t c o o led to room te m p e ra tu re .
The fe e d and condenser system s were d is c o n n e c te d from th e r e a c t o r
and a c y lin d e r o f anhydrous hydrogen f lu o r id e connected to th e to p o f
th e r e a c t o r by means o f copper tu b in g ,
A k ero sen e b u b b le r and blowout
lin e were s u b s t i t u t e d f o r th e co n d en ser system .
Anhydrous hydrogen
f lu o r i d e was pad sod th ro u g h th e r e a c t o r a t room te m p e ra tu re f o r an h o u r,
a f t e r which th e r e a c t o r was h e a te d to 400° C. and h e ld a t t h a t tem pera­
t u r e f o r two h o u rs , w hile hydrogen f lu o r id e was s t i l l p a s s in g th ro u g h .
A fte r t h i s , n itr o g e n was u sed t o purge th e c a t a l y s t o f e x c e s s hydrogen
flu o rid e .
D uring a c t i v a t i o n , a lumium f l u o s i l i c a t e was formed from th e s i l i c a
im p u rity i n th> c a t a l y s t .
A lthough most o f t h i s compound was c a r r ie d
down t o th e k ero sen e b u b b le r, enough u s u a ll y rem ained in th e f i t t i n g s
a tta c h e d to th e bottom o f th e r e a c to r (which were n o t h e a te d t o th e sub­
lim a tio n te m p e ra tu re o f th e f l u o s i l i c a t e ) to n e c e s s i t a t e th e I r removal
and u n p lu g g in g .
-
18
-
R e a c tio n Runs
Tho r e a c t o r waa h e a te d u n t i l th e c e n te r therm ocouple gave a re a d ­
ing a p p ro x im a te ly 5°C, above th e d e s ir e d te m p e ra tu re .
M eanwhile, th e
d e n s ity o f th e fe e d had been d eterm in ed on a W estphal b a la n c e , and ab o u t
500 m l, o f charge p la c e d in th e fe e d c y lin d e r .
r e a c t o r by n 15 m inute n itr o g e n p u rg e .
A ir was swept from th e
F ollow ing t h i s , th e fe e d pump
was s t a r t e d and th e g a s re t a r s e t a t a re a d in g o f a e r o .
As th e l i q u i d
fe e d re a ch e d th e r e a c t o r , {the l i q u i d l e v e l was v i s i b l e th ro u g h th e
Saran food lin e ) th e l i q u i d l e v e l in th e fe e d c y lin d e r , th e re a d in g o f
th e gas m e te r, and th e th r e e therm ocouple re a d in g s wore re c o rd e d .
The fe e d l e v e l , gas volum e, and te m p e ra tu re s were re c o rd e d a t 15
m inute i n t e r v a l s , so t h a t th e te m p e ra tu re co u ld be averaged o v er n in e
p o in ts d u rin g th e two hour r u n s .
I f la r g e volumes o f gas w ere form ed, some l i q u i d was e n tr a in e d
in th e g a s stre a m .
On th e ru n s in which t h i s o c c u rre d , th e d e n s ity
o f th e o f f lu o n t gas stre a m waa d eterm in ed by f i l l i n g a 0 .3 0 8 2 l i t e r
e v a c u a te d f l a s k w ith th e e f f l u e n t v a p o rs .
The f la s k was w eighed t o
0 .1 mg. on an a n a l y t i c a l b a lan c e t o d eterm in e d e n s ity .
The w eight o f
g as a s d eterm in ed by gas a n a ly s is was su b tu c ta d from th e w eig h t o f gas
and e n tr a in e d l i q u i d t o y ie ld th e amount o f e n tr a in e d l i q u i d .
In mak­
in g a m a te r ia l b a la n c e , th e W ig h t o f e n tr a in e d l i q u i d was added t o
th e w eight o f l i q u i d r e a c t o r e f f l u e n t .
A fto r an h o u r on stre am , th e n o n -o o n d en sib le v ap o r was allow ed to
d is p la c e 6 -8 l i t e r s o f w a te r from a g as sam ple b o t t l e .
The volume o f
th e v a p o r in th e b o t t l e was determ in ed by w eighing th e w a te r d is p la c e d .
T h is volume was added on t o th e t o t a l volume re c o rd e d by th e g as m a te r.
- 19 *
Runs w ere u s u a ll y te rm in a te d a f t e r two h o u rs on stre a m ,
R y drooar-
bon var<«*s were removed from th e r e a c t o r by a 15 m inute n itr o g e n purge
f o r IigM i fe e d s , o r 15 m inute e v a c u a tio n f o r heavy l i q u i d s .
The liq u id
p ro d u c t wua vjeisb<i4 t o 0 .1 gram and allo w ed to s ta n d a t -40°U . u n t i l
re c tifie d .
B urnoffg
As th e h ydrocarbons w ere d o alk y l a t o d , sm a ll amounto o f carbon
were d e p o s ite d on th e c a t a l y s t , s e c o s s l t n t i n g p a i'io d ic b m m o ffs.
These
b u rn o f fs w ere made in e a sd ia te ly a f t e r aach ru n w hile th e r e a c t o r m s
o t i l l h o t.
A ir was blown th ro u g h th e r e a c t o r u n t i l an O rsat analy s iu
o f th e e f f l u e n t g a se s ehcm d an a p p re c ia b le amount o f oxygen.
The -tem­
p e ra tu re o f th e r e a c to r bod was n e v e r allo w ed to re a c h 600o0 . d u rin g
th e s e b u r n o f f s , s in c e th e c a t a l y s t began t o s i n t e r above t h i s tem pera­
tu re .
R e c tific a tio n
Rroduot r e c t i f i c a t i o n v/us s t a r t e d by flo o d in g th e column to wet
th e p a c k in g , th e n p la c in g th e column on t o t a l r e f l u x f o r a t l e a s t one
h o u r.
A d ry ic e t r a p co n n ected t o th e column v e n t cau g h t any h y d ro c a r­
bons w hich b o i l below th e minimum co n d en ser te m p e ra tu re .
A fte r th e
column had re a d ie d e q u ilib r iu m , th e Cored head was s e t a t a r e f lu x r a t i o
o f 3 0 :1 , and th e p ro d u c t w ithdraw n.
The a Izo o f th e sam ples drawn way
d etorrained b y th e r a t e o f change o f c n d en ao r te m p e ra tu re , so th a t
saKplog ranged from 2 t o 50 gram s.
I f th e condenser te m p e ratu re re a ch e d
SOO0C. th e column was c o o led and d i s t i l l a t i o n c o n tin u e d a t red u ced p r e s ­
sure,
- 20 Gaa A a aly a ia
Gaa sam ples wore a n a ly z e d In a low-tem por a t u r e - f r a c t l o n a t lo n -g a s a n a ly s ia u n i t u s in g l i q u i d n itr o g e n a s a c o o la n t.
The u n i t a u to m a ti­
c a l l y re c o rd e d column head te m p e ra tu re a s a fu n c tio n o f volume o f gas
d i s t i l l e d , so t h a t mol p e rc e n ta g e s o f each component could be read a l ­
most d i r e c t l y .
The b re a k s betw een a l l hydrocarbon g ases b o ilin g b e­
low is o b u ty le n e (methane th ro u g h is o b u ta n e ) were v e ry s h a rp , bu t is o b u t­
y le n e , b u te n e s and n -b u ta n e could n o t be d is tin g u is h e d a c c u r a te ly , and
were r e p o r te d a s
A d d iti n a l n o te s
At f i r s t , s e v e r a l d ry ic e tr a p s ware p la ce d betw een th e r e a c to r
w a te r condenser and th e gas m eter t o r e t a i n Cg, C4, and C5 h y d ro c a r­
b ons.
When th e a n a ly s is o f th e s e l i g h t h y d ro carb o n s was a tte m p te d in
a vacuum ja c k e te d packed colum n, no u s e f u l in fo rm a tio n c o u ld be o b ta in e d
s in c e th e d i s t i l l a t i o n c u rv e s had an alm ost c o n s ta n t s l6 p e , and lo s s e s
alw ays exceeded 10,».
M a te ria ls
A ll compounds used a s charge s to c k s w ere p u r if ie d t o th e s p e c i f i ­
c a tio n l i s t e d below .
N orm ally, t h i s p u r i f i c a t i o n was accom plished b y
r e c t i f i c a t i o n a lo n e , b u t in some c a s e s where th e p re se n c e o f a ro m a tic s
was s u s p e c te d , r e c t i f i c a t i o n was p re c ed e d b y an e x t r a c t i o n w ith oleum*
Ccsnpound
Source
B o ilin g
P o in t °C.
4 4 .0
P re s s u re
m i Hr .
640
Neohezane
R i l l l i p s , Tech Grade
f
1 .3 6 %
2,3-D im ethylb u ta n e
R i i l l i p s , % c h Grade
1.3746
5 2 ,6 -5 2 .8
640
3-M ethylpentane
Huinphrey-N i l k lneon
1.3769
59.0-58*4
640
n-Hexane
R i i l l i p a , Uech Grade
1.3749
62.7
640
2,4-D im et h y l pentane
P h i l l i p s , Uech Grade
1.3810
7 4 .4 -7 4 .5
630
n-H ap tan e
P h i l l i p s , A ire Grade
1.3879
9 2 .1 -9 2 .3
640
2 , 2 , 4 -T r^ B th ylp en tan e R i i l l i p s , A ire Grade
1.3907
92 .9
640
S-M athylhe p tan e
P h i l l i p s , Uech Grade
1.3990
H I . 2 -1 1 2 ,0
640
2 ,2 , S-fPr lm ethy Ihexnne
R x iH ip a , Teeh Grade
1.3992
1 1 5 .5 -1 1 5 .7
630
n -O ctase
Hmnphrey-W ilkinson
1.3983
H 9*1-119.5
640
n-Oodeeane
Hwaphrey-Vs i l k ln so n
1.4217
145
-147
100
n-H exadecane
IB iaphrey-W ilkinson
1.4340
162
-164
20
P tethylcyclopentane
P h i l l i p s , Teeh Grade
1.4102
6 6 .1 -6 6 .5
640
Cyclohexane
E ia e r & AnBnd, G .P, Grade
1.4260
75 .3
640
M ethyloyclohexane
S astmau-Kodak
1.4330
9 3 .0 -9 4 .0
640
E th y lcy clo h sx aito
Sastm
Eastm an-Eodak
1.4340
123-134
640
3 AMttiS OAi-OOLATIONS
The sample c a lc u la tio n o f m a te r ia l b alan ce and a c t i v a t i o n energya re based on ru n #4»
The fo llo w in g d a ta were o b ta in e d :
Volume o f n eth y lcy clo h ex tm e
c h arg ed ..................365
m l.
W eight o f im th y I c y c I one z one c h a rg e d ...................3 7 0
gmo.
Weight o f l i q u i d p r o d u c t.. . . . . . . . . . . . . . . . . . . . 149.5
gras.
Weight o f gaseous p ro d u c t and e n ­
tr a in e d l i q u i d .................................................. 116.5
gms.
Mols o f gaseous p ro d u c t........... ..................................
3 .5 8 iaola.
Time of run............................ ........... ..
3
Average R e a c to r T em p eratu re...................... ..
hrs.
654° C.
An a n a ly s is o f th e l i q u i d p ro d u c t shows t h a t th e l i q u i d c o n ta in e d :
L iq u id b o i l i n g below charge s to c k .................... .. 1 1 .5 w eight
p e r cen t
M ethylcyclohoxane........................ ...................
6 7 .0
H e a v ie r b o ilin g compounds
.................. 3 1 .5
The gaseous p ro d u c t a n a ly z e d :
1 7 .6 mol p e r cent
1 .1 w eight per cent
33 Average m o le c u la r w eight o f gaseous p ro d u c t from gas
a n a ly s is = 30.45
The w eig h t o f gas was th e r e f o r e 3 0 .4 5 x 3 .5 8 = 109.0 gms.
The e n tr a in e d l i q u i d , 116.5 - 109.0 » 7 .5 gm s.,
must be added on t o th e w eight o f l i q u id p ro d u ct
Carbon and lo s s e s t o t a l , by d if f e r e n c e » 278 - 116.5 ~
149.5 • 1 2 .0 gms*
Tliese d a ta y ie ld th e f i n a l m a te r ia l b a la n c e i
w oiglit p e r cent
Hg ...............................
CH....................... ....
CyHi-. . . . . . . . . . . . . .
GdKlO..........................
L iq u id b o ilin g below
chiarga s t o c k . . . . . . . . . . . . . . . . . .
6.5 0
Ib th y lc y c lo h e x a n e ...................... .. .3 7 .8 3
H eav ier b o ilin g r e s i d u e . . . . . . . 1 2 . 1 4
Carbon and L o s s e s ,
......... ..
4,5 2
The u ltim a te c o n v e rsio n i s o b ta in e d by d iv id in g th e p e r paor composi­
t i o n by th e p e r c e n t o f meth y lc y c lohexane c o n v e rte d , to y i e l d ;
Hy......... ................................ ............ ..
0 .7 w eig h t .per c e n t
CH4 ..............................
6 .7
C3Li6 ....................................................... 9 .6
C3H6 .......................................
3 2 .1
C4Ii8 ................................................, . . . 1 1 . 5
% 0
12.4
<** «<& *•
L iq u id b o i l i n g b o le * Chsaqp tssook
lio a v io r b o ilin g rssid lu e
10*S w slg u t p e r oont
19«b
Carbon, sa d lo e s s s
7*S
D b fin ia g l i e l i q u i d apaee w l o o i t y «* tW v e lu m o f l i q u i d o&argpd p e r
v o im o o f tt& tulyat p e r h o u r s ,
LJ? = oG5 f it . C eaqpu
^ 'T S o a S s
X
I
,
» 0*^X5
O T SSL# o f H t a l y s t
I f th e Q p eolfic r a te o m a ta a t i s d o flm d fo r a f i r s t order r e a c t Iobi
k - 3.303
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L3F
K irc e a t U aeoavcrtoC
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100
37.G3
i- is F
=» 5 .4 3 X IO*6 oao-1 a t 334° C.
Hun $8 sluytia t h a t I
k - 2 .8 6 x IO -6 s o o - l a t 493° 0 .
The t a t e r g r a t e d /o v lw n iu s a q u a tio n
■:•• y#.
"
be ear. at
' "
-
M
l n M
-.I-:),!;.
1
Ba * «1,675
w 13400 c o l o r ion * 1 3 ,4 k - C a l/a o l,
The
Croqueaoy fa cto r, a , in the Arrhealue equation
& * @ **S/HT
i a o a lo u la to d a s
6 .4 8 x 10"u a S e - 1 3 ^
1+93? (S M
S = 1 ,6 8 $ IO*6
373)
- 25
RESULTS JVHB DI3GU331GE
F o llo w in g th e e x p e rim e n ta l work co n n ected w ith t h i s in v e s t ig a ti o n ,
i t was found t h a t hydrogen f lu o r id e a c ti v a te d alum ina d id n o t s e le c ­
t i v e j.y dea lk y la te n ap h th en es and p a r a f f i n s b u t r a t h e r caused f a i r l y
random bond r u p tu r e , g iv in g p r e f e r e n c e , how ever, t o th e fo rm a tio n o f
p ro p y le n e .
In e v e ry r u n , th e main r e a c t i o n p ro d u c t was a m ix tu re o f
gaseous o l e f i n s and p a r a f f in s c o n ta in in g p ro p y len e e i t h e r a s one o f
th e main c o n s ti tu e n ts o r a s th e o n ly gas p r e s e n t in s i g n i f i c a n t am ounts.
A nother p ro d u c t common to a l l r u n s , r e g a r d le s s o f th e n a tu re o f th e
charge s to c k , was a l i q u i d w ith a low er b o ilin g p o in t th a n th e o r ig i n a l
charge s to c k .
Because o f th e a n a l y t i c a l d i f f i c u l t i e s a tta c h e d to th e
I d e n t i f i c a t i o n o f th e s e hydrocarb o n s b o i l i n g below th e charge stocky
no in q u ir y in to t h e i r n a tu r e was made.
These confounds m y have been
formed e i t h e r a s prim ary deco m p o sitio n p ro d u c ts , o r a s th e r e s u l t o f
seco n d ary a lk y la tio n r e a c t i o n s .
The l a t t e r mechanism i s fa v o re d n o t
o n ly because hydrogen f lu o r id e i s known t o be an e f f i c i e n t a lk y la tio n
c a t a l y s t , b u t a ls o because a r e s id u e w ith a h ig h e r b o i l i n g p o in t th a n
th e o r i g i n a l charge was p ro d u ced , and th e amount o f methane and o th e r
l i g h t g a se s would r a r e l y be e q u iv a le n t t o th e amount o f l i g h t l iq u id hy­
d ro carb o n form ed.
Goioe form at io n was s l i g h t , a v e ra g in g l e s s th a n two p e r c e n t o f th e
m a te r ia l c h arg ed .
In o n ly a few c a s e s d id a com bination o f coke and
lo s s e s exceed f iv e p e r c e n t, and in no case d id t h i s co m b in atio n re a ch
te n p e r c e n t.
— 26 —
A d i r e c t c o r r e l a t i o n was found betw een th e s t r u c t u r e o f a s a tu r a te d hy­
d ro carb o n and th e deco m p o sitio n a c t i v a t i o n e n e rg y .
As F ig u re 2 shows,
norm al p a r a f f i n s r e q u ir e an a c t i v a t i o n en erg y o f 40-45 k - c a l / t u o l ., w h ile
p a r a f f in s c o n ta in in g a t l e a s t one t e r t i a r y carbon atom need o n ly 18 k - e a l .
Cyclohexane d e r i v i t i v e s a re s t i l l e a s i e r to decompose, h a v in g an a c ti v a ­
t i o n energy o f 12 k - c a l / m o l ,, w h ile n e th y lc y c lo p e n ta n o i s somewhat more
s t a b l e , s in c e i t r e q u ir e s an a c t i v a t i o n e n erg y o f 25 k - c a l .
Iteohexane is
o n ly s l i g h t l y l e s s s ta b l e th a n norm al p a r a f f i n s , as d e m o n strated by an
a c t i v a t i o n e n erg y o f 35 k -c a l/m o l.
The s t a b i l i t y o f a g iv e n p a r a f f in de­
pends somewhat on i t s m ass, s in c e th e d eco m p o sitio n a c t i v a t i o n en erg y de­
c r e a s e s s l i g h t l y w ith in c re a s in g c h a in le n g th .
K ap h th en as:
Four n a p h th e n ic compounds were u sed a s charge s to c k s in t h i s in v e s­
tig a tio n :
c y clo h e x a n e , m th y lo y c lo h e x a n e , e th y !c y c lo h e x a n e , and E B thyl-
c y c lo p e n ta n e ,
The th r e e cyclo h ex an es were chosen to d eterm in e th e e f f e c t
o f m ethyl and e th y l s id e c h a in s on a n a p h th e n ic r i n g .
M athyl cy clo p en tan e
was in v e s tig a te d to d e term in e th e d if f e r e n c e In r e a c t i v i t y betw een f iv e
and s i x
B bo ro d r i n g s .
Cynlohexane d i f f e r e d from a l l o th e r charge s to c k s in t h a t i t y ie ld e d
la r g e amounts o f hydrogen.
s o u rc e s :
T h is hydrogen co u ld have o r ig in a te d from two
fo rm a tio n o f benzene and form at io n o f b u ta d ie n e .
The h ig h e r r e ­
f r a c t i v e in d ic e s o f th e 70-75° 0 . l i q u i d p ro d u c t c u ts (T able XXII) in d i­
c a te s th e p re se n c e o f some a ro m a tic s , b u t s in c e no s e p a r a tio n o f th e s e c u ts
was a tte m p te d , th e e x a c t amount o f benzene formed i s unknown. Cyclohexane
27
i s known, u n d er c e r t a i n c o n d itio n s , t o produce h ig h y ie ld s o f b u ta ­
d ie n e (1 6 ), b u t in t h i s i n v e s t i g a t i o n , th e r e was no ev id en ce f o r o r
a g a in s t th e fo rm a tio n o f b u ta d ie n e .
I f any had been form ed, th e
method o f a n a ly s is used co u ld n o t have d is tin g u is h e d i t from C4I%.
ho n B th y lc y c lo p e n tone was found in tlie r e a c t i o n p ro d u c t, presum ably
because c o n d itio n s were to o aovero f o r i o o a o r l s a t ion*
The d i s t i l l a t i o n c u rv e s f o r th e l i q u i d p ro d u c ts r e s u l t i n g from
th e de lk y l a t i o n o f n ap h th en es a l l showed t h a t no m a t e r i a l s b o ilin g
above th e minimum condenser e x c e p t th e u n co n v erted charge s to c k were
p r e s e n t.
A p l o t o f condenser te m p e ra tu re v e rs u s p e r c o at d i s t i l l e d
ro s e alm ost v e r t i c a l l y to th e b o ilin g p o in t o f th e charge s to c k .
The
curve rem ained h o r iz o n ta l a t th e b o ilin g te m p e ra tu re o f th e charge
s to c k , th e n ro s e alm ost v e r t i c a l l y a g a in .
Ividt h y l eyeIohexane y ie ld e d v e ry l i t t l e to lu e n e and h y d ro g en , p re ­
sumably because th e p re se n c e o f a t e r t i a r y carbon atom, caused r in g
r u p tu r e b e fo re arouiat iz a t i o n could o c c u r .
M ethylcyclohoxane deconpo-
a i t i o n produced no cy clo h ex an e, and v e ry l i t t l e iso th a n e , in d ic a tin g
th a t th e r i n g c le a v e s f i r s t t o form an a c tiv a te d n o rm al- o r is o - o l e f i n , which th e n u n dergoes f u r th e r d e co m p o sitio n .
IS thyloyclohexane ia o ra eriaa a a sw e ll a s docomposea.
Thermodynam­
i c a l l y , an e q u ilib riu m m ix tu re o f e t h y l and diioauhyl cy clo h ex an es i n ^Dudes o n ly ab o u t f i f t e e n i<er c e n t e th y Icy c Iohe xane a t 527° 0 . (Table
X X III), so t h a t th e form at Ion o f d im e th y lc y c Io h exane s should be e x p e c te d .
The p resen ce o f 1 ,2 - and 1 , 3 -d im eth y lc y c lo h ex a n e s in th e r e a c tio n p ro ­
d u c ts could be d e m o n stra te d .
The 118-127° C. d i s t i l l a t i o n c u ts from ru n
—
28
—
/5 (eth y ^o y cIo M x a a e ) wore found to p o s se ss h ig h r e f r a c t i v e in d ic e s ,
in d ic a tin g th e p re se n c e o f a r o m t i c s .
When th e v a rio u s c u ts were
t r e a t e d w ith 20;» oleum , 0 ,1 N MaOll, and w a te r, th e r e f r a c t i v e in d ic e s
dropped t o c o n s ta n t v a lu e s , and th e s e r e f r a c t i v e in d ic e s in d ic a te d
t h a t iso m e ric form s o f e t h y l and d im e th y l cyclohexane were p re s e n t
(T ables XXII and X X III).
In c a l c u la tin g th e k i n e t i c d a ta f o r th e e th y l cyclohexane r u n s ,
how ever, a l l isom ers were c o n sid e re d a s b e in g pure e th y lc y c lo h e x a n e .
Ho c y clo h e x a n e , c y clo h ex an e, m othylcycIo h ex a n c , o r mothyIcyclohexone
wore form ed, in d ic a tin g t h a t r in g ru p tu r e predom inated a s th e decom­
p o s itio n r e a c t i o n .
Is o m e riz a tio n i s more p ro b ab ly a com peting re a c ­
t i o n th a n an i n i t i a l s te p in d eco m p o sitio n .
Ite th y lc y c lo p e n ta n e undei'gocs random r i n g r u p tu r e , a s ev id en ced
by th e v a r i e t y o f g a se s form ed.
N e ith e r cyclohexane n o r cy clo p en ten e
were found in th e r e a c tio n p ro d u c ts , in d ic a tin g t h a t c o n d itio n s were
to o s e v e re f o r is o ia a riz a tio n o r dome th y I a t io n .
As w ith th e cy clo h ex ­
a n e s , m eth y lc y c I o pentane u n derg o es r i n g ru p tu r e f i r s t , fa llo w e d by de­
com position*
The h ig h e r e n erg y o f a c t i v a t i o n f o r m eth y lcy clo p en tan e
d e m o n stra te s t h a t a f iv e aomberod r i n g i s more s ta b le th a n a s ix esela­
bored r i n g , a r e s u l t t h a t co u ld have b een p re d ic te d on th e b a s is o f
bond s t r a i n .
P a ra ffin s :
Twelve d i f f e r e n t p a r a f f i n s were used a s charge s to c k s .
p a ra ffin s :
Five norm al
hexane, h e p ta n e , o c ta n e , d o deeane, and h ex ad ecan e, served
to d e te rm in e th e e f f e c t s o f In c re a s e d c h a in le n g th .
2 , 3-Dimeth y lb u ta n o
- 29
and 2 ,4 -d im eth y lp e n ta n e wore used In o rd e r t o a s c e r t a i n th e e f f e c t o f
c h a in b ra n c h in g s in c e tlie se compounds c o n ta in two
atom s,
t e r t i a r y carbon
Meohexane m s ru n so t h a t th e e f f e c t o f a q u a te rn a ry carbon
atom could be o b serv ed ,
2 , 2 , d - f r im eth y lp en tan e and 2 , 2 , 5 - trirn e t Iiy l-
hextme serv ed t o show t t o e f f e c t o f com bining a q u a te n o ry and a t e r ­
t i a r y carbon atom in th e siarae m o lecu le,
3-1,le tIiy lpentane and 3-met h y l -
h ep tan e were ru n in o rd e r to d eterm in e w hether th e k i n e t i c e f f e c t s
w ere unique t o c e r t a i n
t e r t i a r y carbon atom s, o r w hether th e y ap p ly
to a l l t e r t i a r y carbon atom s,
Hoimal hexane r e p r e s e n ts th e s o le e ase in t h i s in v e s t ig a ti o n where
th e deco m p o sitio n a c t i v a t i o n en erg y i s abnorm al.
pounds e x c e p t n-hexane p l o t on smooth, c u rv e s .
In f ig u r e 2 , a l l com­
In an e f f o r t to d is c o v e r
wliere th e anomaly l a y , a d d itio n a l ru n s were made on n-hexane and n -h e p ta n e , b u t , as shown in f ig u r e 3 , th e d a ta f o r each, compound a re c o n s is ­
t e n t , so t h a t s i g n i f i c a n t e r r o r s in m easurem ents o r a n a ly s is a re un­
lik e ly ,
S ince a l l compounds were c a r t f u l l y p u r if ie d b e fo re u s e , t lie re
would n o t be c o n sid e ra b le q u a n t i t i e s o f iso h ex an es in th e f®*d s to c k .
The o th e r norm al a lk a n e s sliow tl i a t th e d eco m p o sitio n a c ti v a tio n
en erg y f a l l s o f f slo w ly w ith in c re a s e d c h a in le n g th .
In th e case o f
norm al a lk a n e s , d a ta on th e a c t i v a t i o n e n erg y o f th e n o n -o a ta ly a e d , t h e r ­
mal deco m p o sitio n r e a c tio n a re a v a ila b le in th e l i t e r a t u r e (IQ ), so t h a t
th e a c c e le r a ti n g in flu e n c e o f th e c a t a l y s t can be d eterm in ed d i r e c t l y .
I f th e a c t i v a t i o n energy f o r the C ataly zed r e a c tio n s i s 40 k - c a l / n o l .
and i s 64 k - c a l/m o l. f o r th e n o n -c a ta ly z e d r e a c t i o n , th e n th e v e l o c i t i e s
30 o f th e tvfo r e a c t i o n s a r e in tho r a t i o s
J i
%
* “ - 12 ( « i ) s
I f th e e f f e c t i v e c a t a l y t i c a re a I s 3 ,3 0 z 10® C u .“ ( f a b le XOTI) th e n :
he
%
* (3 .3 3 x 10e ) (!O’*1 2 )
he
- 730 at 538* C,
64000-40000
Rf
or
"C
T h e re fo re , th e c a ta ly z e d r e a c t i o n I s e s tim a te d t o bo a b o u t 750 tin e a
f a s t e r th a n th e n on-oat a I y &ed r e a c tio n undo ;* th e o m d i t i m a o f th e In*
ve ; t l ( ’;;tio n .
3 ,5 - Jicsothylbutaitte, J , J - ^ i s o t h y l 1O n ta n s , 8 , 8 , 4 » tr im th y lp o n ta a a ,
3 ,8 ,5 - t r i m t h y l b e x a a e , S fM h y liiea fc an e and S n M h y lh e vtano a l l have
a c t i v a t i o n C B ergioe m & t IS k - c a l ^ o l . show ing t h a t mawneror a. W t i a r y c a r to n a t m i s p r e s e n t in a p a r a f f i n , th e anme a c t I v a tic n en ­
e rg y i s re q u ire d #
^feohexane, on th e o th e r h an d , h a s on n e t Iv e tld R e n a rg y n e a re r
t o t h a t o f norm al p a r s i iris , la d lo ^ tln g t h a t a q u a te r n a r y carb o n atom
h a s v e ry l i t t l e e f f e c t on th e s t a b i l i t y o f n s a ra ffia #
B ecause 2 ,2 ,4 -
t r t o i thylv*nt«ine and 3 , J , M rln a tb y lh e x a n o a r e ju s t a s u n s ta b le m
o th e r ia o lc cu le s c o n ta in in g a t e r t i a r y carb o n atom , th e neo s tr u c tu r e
a p p a r e n tly w i t h e r a i d s nor in h ib it a th e d o c o j^ o s itio n o f th e s c le e u le #
31 CATALYST
B ro p a rtia s o f th e e a ta ly & t d e te r a ia e d d u rin g th e c o u rse o f t h i s
in v e s t ig a ti o n aro re p o rte d in T able JOJV•
In o rd e r t o d eterm ine th e
amount o f a v a ila b le hydrogen f I u o r Ida on th e c a t a l y s t , sam ples o f c a t ­
a l y s t were t r e a t e d w ith d i s t i l l o d
vater*
S v sry fiv e m in u te s , th e s o lu ­
t i o n s w ere shaken v ig o ro u s ly .
A fter an h o u rs* a le a c h in g , th e s o lu tio n s
were t i t r a t e d w ith 0 .1 K BeQH,
T h is p ro c e d u re m a chosen because o f
tfce d i f f i c u l t y in a n a ly z in g f o r f lu o r id e in th e p re sen c e o f alum ina and
b ecause s a r io u a a n a l y t i c a l e r r o r s would have dcv o lo .o d i f tfco p e l l e t s
were allow ed t o l o c h lo n g enough f o r a l l th o Hf t o d i f f u s e ou t o f She
p o re s o f th e c a t a l y s t b e a d s .
Since th e h y d ro carb o n s b e in g d e a lk y la te d
over th e c a t a l y s t a re n o t in c o n ta c t w ith th e c a t a l y s t f o r more th an
a m inute o r s c , most o f tho hydrogen f lu o r id e r e a d i l y a v a ila b ly t o th e
hydrocarbon v a p o rs should have been loachod o u t a f t e r one h o u r.
A ccording to t h i s a n a l y s i s , th e c a t a l y s t bed c o n ta in s ro u g h ly one
f o u r th o f a mol o f r e a d i l y a v a il a b le hydrogen f l u o r id e .
E v e ry hydro­
carbon m o le c u le, th e n , h a s ample o p p o rtu n ity t o c o o rd in a te w ith a hy­
drogen f lu o r id e m olecule and undergo d e a lk y la tio n .
From th e sm a ll con­
v e rs io n s o b ta in e d and from th e m agnitude o f th e A rrh en iu s freq u en cy
f a c t o r (T able XXI), i t Io a p p a re n t t h a t p a r a f f i n s and n a p h th en e s cannot
c o o rd in a te w ith hydrogen f lu o r id e u n le s s o r ie n te d c o r r e c t l y , t h a t i s ,
th e c a t a l y s t i s s p e c i f i c in i t s a c ti o n .
The v a r i e t y o f p ro d u c ts o b ta in e d ,
how ever, can be e x p la in e d by hy p o th as iz i n g t h a t th o d e a lk y la tio n p ro d u c ts
a re more d i f f i c u l t l y d eso rb ed th a n th e o r i g i n a l m o le c u le s , and because
— 32 —
o f t h e I r lo n g e r re s id e n c e tim e on th e c a t a l y s t s u r f a c e s , c o n tin u e to de­
g e n e ra te u n t i l th e y become th e e a s i l y d eso rb ed l i g h t g a se s .
The te m p e ra tu re range chosen f o r t h i s in v e s t ig a ti o n was lim ite d to
500-550° C, s in c e no m easurable r e a c tio n to o k p la c e below 5 0 0 °, and th e
C a ta ly s t began t o s i n t e r above 500° 0 .
h r. m
A l i q u i d apace v e l o c i t y o f 0 . 2 /
chosen to g iv e c o n v e rsio n o f betw een 10 and 50,%
None o f th e s ta n d a rd methods o f c a lc u la tin g th e s u r f : ce a re a o f th e
c a t a l y s t (B n m a u e r, S r m e tt, T e l l e r , o r H s rk ln 3 -J u ra ) (23) i s p r a c tic a b le
w ith hydrogen f lu o r id e a c t i v a t e 3 alu m in a.
D uring th e a c t i v a t i o n , la rg e
amounts o f s i l i c a a re rem oved, so t h a t t i e a re a o f th e a c ti v a te d c a t a l y s t
m ight n o t be th e same.
The f l n o r i i a i s h o ld so te n a c io u s ly t h a t s i n t e r ­
ing, a p p e a rs t o be n e c e s s a ry t o remove th e hydrogen f l u o r i d o .
The e f f e c t i v e
c a t a l y s t a re a was th e r e f o r e c a lc u la te d from th e amount o f f lu o r id e on th e
c a t a l y s t , and th e a re a o f th e HF m o le c u le, assum ing a m onolayer o f adsorbed
f l u o r i d e , and c lo s e s t p a ck in g o f MF in th e l i q u i d s t a t e .
The a re a so ob­
ta in e d i s 2 .5 4 x IO5 cm2 p e r m i l l i l i t e r (b u lk volume) o f c a t a l y s t .
P e r i o d i c a l l y , check ru n s were made on th e c a t a l y s t to determ ine i f i t s
a c t i v i t y had f a l l e n o f f .
These check ru n s were made under th e same co n d i­
t i o n s u sed by K indschy ( 9) , u s in g th e same charge s to c k , cumene.
In e v e ry
c a s e , th e y i e l d o f benzene formed from cumene was i d e n t i c a l w ith th e y ie ld
r e p o rte d by E indschy f o r a f u l l y a c ti v a te d c a t a l y s t .
No n o tic e a b le le s s e n ­
in g o f c a t a l y t i c a c t i v i t y o c c u rre d even a f t e r more th a n s i x t y ru n s in d i c a t ­
in g t h a t as lo n g a s th e c a t a l y s t i s h e ld below i t s s i n t e r i n g p o in t and c a r ­
bon i s burned o f f r e g u l a r l y , th e c a ta ly s t r e t a i n s f u l l a c t i v i t y .
33 From th e spread in th e a c tiv a tio n e n e rg y d a ta , i t may be concluded
t h a t th e av erag e d e v ia tio n amounts t o a p p ro x im a te ly I k -c a l/m o l.
The
c o rre sp o n d in g fre q u e n c y f a c t o r s a re presum ably a c c u ra te to th e a p p ro p ri­
a te power o f 10.
The v a lu e s o f th e d ecom positio n T O action r a t e c o n s ta n t re p o rte d in
th e summary o f t h i s in v e s t ig a ti o n were o b ta in e d by a v e ra g in g th e appro­
p r i a t e a c t i v a t i o n e n e r g ie s and th e lo g a rith m s o f th e a p p r o p r ia te f r e ­
quency f a c t o r s .
- 34 SUlfflIAST
The r e s u l t s and ccm oluslons d e riv e d from th e e x p e rlro e n ta l p a r t
o f t h i s in v e s t ig a ti o n may be summarized a s fo llo w s :
(1)
Hydrogen f lu o r id e a c ti v a te d alu m in a c au se s random c arb o n -ca rb o n
r u p tu r e in p a r a f f i n s and n ap h th en es a t low p r e s s u r e s and e le v a ­
te d te m p e ra tu re s , b u t does te n d t o f o r a la r g e amounts o f p ro p y l­
e n e.
(2)
Large amounts o f hydrocarbons b o i l i n g below th e charge s to c k a re
form ed, p ro b a b ly a s a r e s u l t o f secondary r e a l k y l a t io n r e a c tio n s .
(3)
The k i n e t i c d a ta o b ta in e d w ith hydrogen f lu o r id e a c ti v a te d alum­
in a can be r e l a t e d t o th e s t r u c t u r e o f th e p a r a f f i n o r naphthene
d e a lk y l a t e d .
(4)
Average v a lu e s f o r th e deco m p o sitio n r a t e c o n s ta n t d e fin e d in
term s o f l i q u i d space v e lo c i ty a r e :
Cyclohexane d e r iv a tiv e s
k - 2 .6 x 10~ 8e-12500/R T
n - P a r a f f in s
k = 3 .5 x ICT16 e~41300/HT
P a r a f f in s c o n ta in in g a
t e r t i a r y CaPbon atom
k * 3 ,0 x 10**1 0 e-1 6 3 0 0 /R T
Neohexane
k = 4 .1 x 10-15 e~3S500/RT
lie t hy I c yc lope n t ane
k = 1 .7
X
10-12 e~25000/RT
- 35
ACKKOV1tLS DGmDrIT
The a u th o r g r a t e f u l l y th a n k s th e P h i l l i p s I h tr o le u n Company
f o r sp o n so rin g th e fe llo w s h ip u n d er which t h i s in v e s t ig a ti o n was
C a rrie d out*
36
Lrm iA Ttias Citz d
1.
S e le c te d V alues o f th e P r o p e r tie s o f H ydrocarbons, Ci r e . C-461,
N a t. Bu1 o f S td s , (1947)
2.
B erg, Sumner, and Montgomery, U. S. P at 2 ,3 9 7 ,6 9 3 (1946)
3.
P re y , ? . S , , In d . Sng. Chem. 26,
4.
Froy and Hepp, ib id
5.
G la n sto n e , S, Textbook o f P h y s ic a l C h em istry , 2nd. S d .,
Van N o stra n d , New York (1946)
6.
Good, Voge, G re a n fe ld e r, In d . Eng. Chetn, 3 9 , 1032 (1947)
7.
H e r z e l, H. A ., BUS* T h e s is , Montana S ta te C ollege
8.
Hobbs & H inahe!wood, P ro c. Roy. Soo. (London) .1167, 447 (1938)
9.
K indschy, E . O ., M*S. TIios i s , Montana S ta te C ollege (1948)
198 (1934j)
2 5 , 441 (1933)
(1948)
10. Luke, W* J . , M.3. T h e s is , Montana S ta te C ollege (1949)
11. Reirdck, A ., E le c tr o n ic I n t e r p r e t a t i o n s o f O rganic C Iiem iatry,
2nd. E d ., W iley, New York (1949)
12. R ice & D ooley, I . An. Cham. Soc. SSe, 4245 (1933)
13. R ice Sc H e r z f e ld , ib id
56 , 204 (1934)
14. R ice & R ic e , The A lip h a tic F ree R a d ic a ls , B altiiriore (1935)
15. R osen, R ., O il-G as J , p 45, F e b r. 2 0 , 1941
16. Sachanen , A ., C onversion o f P e tro leu m , 2nd E d ., Rein h o ld , New York
(1948)
17. Schwab, T ay lo r & S p en se, C a t a ly s is , 2nd E d ., Van H o stra n d , New York
(1937)
18. S t e a c l e , S« W., F ree R a d ic a l M echanisms, Roln h o ld , New Y ork, (1946)
19. Thomas, C. A ., Anhydrous Aluminum C h lo rid e in O rganic C hem istry,
ACS Monograph 8 7 , Re in h o ld , Mew York (1941)
20. T ilic h e y e v (1 959), quoted in d o aen , op c i t
21. T ilic h e y e v & F e ig in , (1 931), ib id
22.
j e i a e r , H. B ., C o llo id O hecd stry , 2nd 2 d . , W iley, Bew York
(1949)
- 38
TO NITROGEN OR
COMPRESSED AIR
INSULATION
BALL BEARINGS
FEED
CYLINDER
TO
BLOW­
DOWN
CATALYST —
THERMOWELLS
FEED
PUMP
BALL BEARINGS
GAS METER
WATER OUT
CONDENSERS
WATER IN
GAS
SAMPLE
LIQUID
PRODUCT
RECEI VER
F ig u re I
Diagram o f Equipment
<
70
thermal
decom position
of normal
PARAFFINS
S 2 5 i!* i^ A L M N E S
NEOALKANFS
CYCLOPENTANES
— I--------- :---------- — PARAFFINS CONTAINING
CYCLOHEXANES
TERTIARY CARBON
NUMBER OF CARBON ATOMS IN MOLECULE
F ig u re 2 - A c tiv a tio n Energy P lo ts
5.7
< To.
-P‘0.
I Xv
l^£.
*<
IO
„
2
*
X
—
—
____ l \
o
CD 4.9
A,
O
% >
%
0
1
\
\
l \
s.
_ i ____
4.3
1.20
1.24
126
J.28
10 0 0 / TEMP.;K
Figure 3 - Arrhenius Equation Plots
O
1.30
1.32
- 41
TABLE V
DEALKH.ATI ON OF GYCLOIiEXANS
Run Number
Gras, charge
Mols charged
I
305.5
3. 64
2
294
3.50
Reactor Temp., °C.
Time o f run , hr s.
Liq. Sp. V e l., hr."*1
518
2o0
0 .g l9
545
2.0
0.211
gg.4
0.76
9.7
44.4
1.512
21.7
Gas Produced, L it.
Mols
Gms.
Gms. Liquid Produced
Grns. Coke & Losses
Gas
Analysis
Weight
Per Cent
Liq. Anal.
WeIght
Par Cent
Hg
CH4
OgH4
CgHg
OsH6
C3 H8
O4Hg
C4Hio
Cs
Low B oil Frac. *
Unconvent.
Residue
288.4
7.4
10.84
16.57
13.50
——
——
41.70
——
17.39
———
———
8.0
91.0
10.47
2.60
6.80
31.53
—i —
48.60
—
——
6.9
85.1
8 .0
1 .0
Per
Pass
Product
Analysis,
Weight
Per Cent
268.1
4.2
0.344
Hg
CH4
0.526
CgH4
0.429
CgH6
1.324
CSH6
——
——
*
C3 H8
C4 Hq
0.552
C4 Hiq
Low Boil Frac. * 7.55
Unconvert.
85.90
Residue
0.94
Coke & Losses
2.42
U ltiv
mate
tor
toss
U ltimate
2.44
3.73
3.04
0.77
0.19
0.50
3.44
0.85
2.23
9.39
———
3.91
2.33
10.40
3.59
16.06
********
28.06
********
38.59
6.38
53.55
»■<»*»
6.67
17.16
*Condensible liq u id b o ilin g below charge sto ck
*******
6.29
77.60
7.30
1.43
t
- 42 -
TABLE VI
DEALKYLATION OF MSmiLCTCLCHEXANE
Run Number
Cms. charged
Mols charged
g
279.4
2.65
4
278
2.58
Reactor Temp.,°C.
Time of run , hrs.
Liq. Sp. V e l., hr."1
495
2.0
0.189
554
2.0
0.203
I
Gas Produced, L it.
Mols.
Gras.
Gras. Liquid Produced
Gras. Coke & Losses
Gas
Analysis
Weight
Per Cent
Liq. Anal.
ight
Per Cent
'He
Product
Analysis,
Weight
Ibr Cent
29.7
1.00
40.5
105.5
3.58
109.0
230.5
8.8
157.0
12.0
Hg
CH4
CgH4
CgHe
CgHe
CgH8
C4H6
C4H10
C5
0.4
0.8
—
13.0
45.4
14.7
25.7
1.1
10.7
— 15.3
35.0
———
18.3
19.6
Low B o il. Frac. ♦
Unconvert.
Residue
14.5
70.5
15.0
11.5
67.0
21.5
Ibr
Pass
U lt igate
Ibr
Pass
U ltimate
0.06
0.12
---- 1.87
6.53
0.1
0.3
—
4.5
15.6
0.43
4.20
6.00
13.72
0.7
6.7
—
9.6
22.1
2.12
C4H8
3.70
C4H10
Low B o il. Frac. *11.95
58.13
Unconvert.
Residue
12.37
Coke &. Losses
3.15
5.1
8.9
28.5
7.18
7.69
6.50
37.82
12.14
4.32
11.5
12.4
10.5
—
19.5
7.0
Hg
CH4
CgH4
CgHe
CgHe
—
Ir i r-T T J
CgH8
29.5
7.5
♦Condensible liq u id b o ilin g below charge stock
- 43
TABLE V II
DEALKYLATION OF ETHY^CYCLOHEXANE
Run Number
Cns. charged
M ols. charged
5
276.8
2.8]I
6
272.6
2 .78
R e a c to r Temp., 0C.
Time o f run , h r a .
L iq . Sp. VeI . , h r .
502
2 .0
0 .2 0 9
546
2 .0
0 .1 9 2
Gas Produced, L i t .
Mols .
Oms.
5 5 .4
1.86
59.7
107.6
3 .6 4
125.2
Gms. L iquid Produced
Gms. Coke & L osses
215.2
1 .9
139.8
7 .6
Gas
A n aly sis
'.Veig h t
Per Cent
H2
CH4
C2IU
C211G
0SiiG
CgHg
CqHe
C4Hio
°5
1 .9
0 .7
12.0
—
3 9 .3
2 .3
6 .3
19.7
1 7 .8
8 .8
0 .9
17 .1
28 .8
26 .3
1 .5
4 .6
1 8 .6
—
L iq . A nal.
We ig h t
Per Cent
Low B o il Frao .*
U n convert.
R esidue
17.5
70.5
12.0
15 .0
72.5
12.5
Ib r
Pass
P roduct
A n a ly sis ,
Weight
P e r Cent
0 .4 1
H2
0 .1 5
CH4
2.60
C2H4
—
——
C2Hg
8.50
C3H6
0 .5 0
C3He
C4Hq
1 .3 6
4 .2 6
C4Hio
Low B o il Frac .* 17.45
58.78
U nconvert.
9.32
R esidue
Coke &
L osses
0 .6 9
U ltimate
Ib r
Pass
0 .9 1
0 .3 3
5 .7 4
———
18.80
1 .1 0
3.0 0
9.43
38.58
20.59
1 .0 1
0 .4 1
7 .8 6
13.24
12.10
0 .6 9
2 .1 2
8 .5 5
7 .6 9
37 «20
6 .4 1
1.6 1
0 .6 5
1 2.52
21.11
19.31
1 .1 0
3 .3 8
13.61
12.24
— —
10.02
1.5 2
2 .7 9
4.4 5
*CondenaibIe liq u id b o ilin g below charge sto ck
U ltimate
44
TABIS V III
DEAUO&ATIGN OF METHYLCYCLOISNTAMS
Run Number
GrEiS. charged
Mols. charged
7
306.0
3.65
269.0
3.14
Reactor Temp., 0 C.
Time o f run , hr s.
Llq. 3p. V e l., hr . -1
512
549
Gas Produced, L it.
Mols .
Gms .
Gms. Liquid Produced
Gms. Coke & Losses
Gas
Analysis
Weight
Per Cent
LiQit Anal.
Weight
Per Cent
Product
Analysis
Weight
Per Cent
2 .0
2 .0
0.187
0.203
25.9
0.887
31.7
62.6
2.13
71.5
265.3
9.0
HS
CH4
cBH4
CgHG
cBhG
c5%
C4HO
C4HlO
c5
0.75
2.61
10.16
9.95
47.71
——
—
Low B oil FTac.*
Unconvert.
Residue
Hg
CII4
CgH4
CgHg
C3 H6
CsEIg
C4Hg
C4Hio
Low Boil Frac.*
Unoonvert.
Residue
Coke & Losses
8
182.5
15.0
1 .1
3.3
16.7
1 0 .1 2
53.2
—
— 5.7
18.71
2 0 .0
8 .0
8 6 .0
6 .0
6.5
84.5
9.0
Per
Paas
U lt imate
Per
Pass
U lt i­
mate^
0.08
0.27
1.05
1.03
4.94
— -
0.3
1.1
4.1
4.0
19.4
—
0.29
0.85
4.45
0.7
10.3
14.16
33.2
1.05
8.87
74.56
5.20
2.95
4.1
34.9
——
20.5
11.6
1.52
9.73
57.32
2 2 .8
6 .1 0
14.3
13.1
♦Condensible liq u id b o ilin g below charge sto ck
5.58
2 .0
3.6
- 45
TABLE IX
DEALKYLATION PRODUCTS OF n-HEXANE
Run Number
Oraa. charged
Iiols charged
9
2.57
Reactor Temp., 0 C1
Time of run, hra.
Liq. Sp. VeI . , hr . * 1
507
Gas Produced, L it.
Mols.
Oms.
Gkaa. Liquid Produced
Gras. Coke & Losses
Hg
CH4
C3I4
CgHg
CsH6
C3H8
C4 H6
C4h10
Cs
Liq. Anal. Low Boil Frac.*
Weight
Unconvert.
Per Cent Residue
2 0 1 .2
537
561
2.34
2 .0
2 .0
0.186
0.286
2.235
9.9
0.338
9.9
23.5
0.830
26.0
36.7
1.26
42.2
295.2
155.0
4.0
0 .8
1 .0
2.3
36.8
5.9
54.0
——
2.5
97,5
——
Bsr
Pass
0 .6
no
1.9
29.7
analy-
8 .2
32.2
s is
27.4
———
3.3
96.7
—
8.4
81.3
10.3
U lt lmate
Hg
0.05
0.6
CH4
0 .1 0
1 .1
1.65
18.9
CgH4
CgHg
0.26
3.0
2.42
27.8
C3Hg
————
CsH8
— — ——
C4 H6
-------------- —
C4Hio
Low Boil Free,.*2.34 26.8
91.28 ----Unconvert.
Residue
Coka & Losses 1.90 21.8
no
analys is
*Condenaible liq u id b o ilin g below charge sto ck
9
U
322.0
3.86
2 .0
206.9
4.2
Gas
Analysis
Weight
fbr Cent
Product
Analysis,
Weight
Ibr Cent
10
2 2 1 .0
Per
Pass
UltL
mate
0 .1 2
0.5
0.40
6.24
1.72
6.76
—
——
—
***»
5.76
2.54
74.47
1.99
1 .6
24.5
6.7
26.4
22.5
1 0 .0
——
——
7.8
- 46
TABLE X
DSALKYLATICffJ OF n-HSITAHE
Run Number
Cma1 charged
Mols charged
284.5
2.85
R e a c to r Temp., ° C.
Time o f ru n , h r s . n
L lq . Sp. VeI . , hr*"1
494
1.75
0.274
Gas Produced, L i t .
Mol s .
Gms,
4.8
0.167
3.4
Ig
Ckns. L iq u id Produced
Gms. Coke & L osses
Gas
A n a ly sis
ITe ig h t
Bar Cent
no
C4%
s is
2 0 2 .1
2 .0 2
525
548
14
2 .0
2 .0
0.203
0.164
30.9
1.045
36.5
280.6
0.5
Hg
CH4
CgR4
GgRg
0S11B
Cs Hq
13
244.5
2.45
52.0
1.81
64.0
201.7
6.3
130.3
6.9
0.625
6.63
a n a ly -
0.395
8 .0 0
1 2 .0 0
1 0 .1 0
18.11
37.40
34.54
5.9 4
——-
——
14.90
16.83
C4Hio
— —
——
C5
18.34
16.18
2 .0
1 0 .6
97.0
87.6
12.5
77.5-
L iq . A nal.
',Te ig h t
Bar Cent
'
Low B o il P ra c .*
U nconvert.
Residue
P roduct
A n a ly s is ,
V/eight
P er Cent
Hg
CH4
CgH4
CgHg
IoO
Per
Pass
°3H6
C3H8
C4H6
C4HiQ
Low B o il F ra c .*
U n co n v ert.
R esidue
Coke Sc. L osses
no
0.056
0.59
1.07
0.90
3.34
a n a ly -
0.26
2.75
4.96
4.18
15.50
1 0 .0
Per
Pass
U ltlmate
0 .1 2
10.84
0.24
5.12
11.56
" 3.79
21.94
5.34
——
10.75
2.54
5,74
1 .8 8
——
1.33
s is
1 .8
U ltlmate
6.17
——
——
——
11.13
78.44
1.61
1.54
51.70
13.85
50.27
6.48
3.42
^Condensible liq u id b o ilin g below charge stock
7.48
7.15
26.64
13.08
6.89
TABLE XI
DEALKYLATION OF n-OCTANS
Run Number
Gma. charged
Mole charged
15
234.0
2.05
16
231.0
Reactor Temp,, 0 C.
Time of run , hrs.
Liq. Sp, V ell hr . -1
501
538
Oes Produced, L it.
Mbls.
Gms.
2 .0 2
2 .0
2 .0
0.186
0.198
29.3
0.998
40.5
Gms. Liquid Produced
Gms. Coke & Losses
188.4
5.0
Gas
Analysis
Weight
Per Cent
0.28
2.47
11.51
1.04
43.12
— —
Hg
CH4
C2H4
CgHG
CjjHg
C3H8
Liq. Anal.
Weight
Bar Cent
C4Ha
C4Hio
=5
Low B oil Frac.*
Unconvert.
Residue
Hg
CH4
CgH4
CgH6
CjjHg
CjjHe
C4Ho
C4HlO
Low Boll Frac.*
Unconvert.
Residue
Coke & Losses
127.7
9.6
0 . 1*
2 .0 0
22.23
5.88
22.79
13.69
12.82
8.60
11.82
33.92
7.66
12.5
87.0
0.5
8 .2
91.3
0.5
Per
Ppiss
Product
Analysis,
Weight
Per Cent
71.4
2.43
93.7
0.05
0.43
2.00
0.18
7.48
——
— —
5.89
*.95
73.49
0.40
2.14
U lt imate
Per
Pass
U lt imate
0.19
1.62
7.55
0.07
0.81
9.02
2.38
9.24
5.55
5.20
3.49
11.70
48.09
0.27
4.16
0.13
1.56
17.38
4.58
17.80
10.69
10.02
6.72
22.54
- —0.52
8.01
0 .6 8
28.21
----— —
22.21
30.04
-----1.51
8.09
s Condensible liq u id b o ilin g below charge sto ck
- 43 -
TABLE XII
DEALKYLATION OF n-DODECAHB
Run Number
Oma. charge
Mols. charged
17
130.0
0.764
18
252.0
1.48
Reactor Temp., 0C.
Time of run , Ilrs.
Liq. Sp. Ve:I , h r ."I
508
2.0
0.097
547
2.0
0.189
Oas Produced, L it.
Mols.
Oms.
40.1
1.37
35.9
118.5
4.07
116.8
Oms. Liquid Produced
Oms. Coke & Losses
90.4
3.5
127.1
8.1
Oas
Analysis
WeIght
Iter Cent
Liq. Anal.
Weight
Per Cent
Product
Analysis,
WeIght
Iter Cent
Hg
CH4
C2H*
CgHe
C3 H6
C3Ha
C4He
C4H10
C5
27.93
26.71
3.26
4.58
11.97
2.11
38.88
3.09
9.52
10.53
17.06
Low Boil Frac.*
Unconvert.
Residue
12.5
81.5
6.0
20.9.
73.1
6.0
Hp
CgH4
CgHg
C3Hfi
C3H^
C4H6
C4hIO
Low Boil Frac.*
Unconvert.
Re aIdue
Coke & Losses
3.24
8.52
6.04
27.56
Iter
Pass
. U lt lmate
Pter
Pass
U lt lmate
0.90
2.35
2.08
5.44
1.67
3.86
7.62
17.63
——
17.87
37.12
1.05
2.12
5.55
0.98
18.02
1.43
4.41
4.88
18.45
56.87
3.03
3.21
1.66
3.36
8.79
1.55
28.54
2.27
6. 99
7.73
29.23
7.72
16.09
56.78
4.18
2.69
mmmm
9.67
6.23
*Condensible liq u id b o ilin g below charge sto ck
4.80
5.08
49 -
TABLE X III
DEALKYLATION OF n-HKXAD2CANE
Run Nuriber
Gras, charged
Mols charged
19
369.0
1 .6 3
20
391.0
1 .7 3
R e a c to r Tem p., 0C.
Time o f ru n , h r s .
L iq . Sp. V e l, hr.*"
484
2.25
0.237
546
2 .0
0.275
Gas P roduced, L i t .
Mols .
Gras.
107.6
3 ,6 1
168.0
193.5
6 .5 0
281.0
Gms. L iq u id Produced
Gms. Coke & Losses
173.2
1 7.8
8 9 ,0
2 1 .0
V
Hg
CH4
O2Hlr
OoHfi
C3%
6 3 %
rnmmtmmrnm
1 .50
5 .99
—---32.28
1 .4 5
8 .8 2
—— 4 6 .8 9
26.82
2 1 .5 9
C411IO
—
C5
L iq . A nal,
W eight
P er Cent
Low B o il F ra c .*
U nco n v ert.
R esidue
21.25
2 1 .9
72.0
6 .1
2 6 .2
77.0
6 .8
Bar
U ltiPass______ mate
P roduct
A n a ly sis ,
W eight
P ar Cent
H2
C%
C2H4
C2Hg
c5%
CsHg
C4HQ
C4H10
Low B o il F ra c .*
U nconvert.
R esidue
Coke & L osses
—
33.41
———0 .6 8
2.73
——14.70
--—
12.21
— —
1.0 3
4 .1 2
——
22.20
— 18.44
25.49
33.80
2.86
4 .8 2
38.50
4 .3 2
7.2 8
*Condensible Liquid b o ilin g below charge sto ck
Per
P ass
U ;t i'
mate
1 .0 4
6 .3 4
1.26
7.69
3 3.70
40.86
1 5 .5 8
18.82
21.43
17.53
1 .55
5 .3 7
26.
—
I.
6.51
CT I S I
Gas
A n a ly sis
W eight
P s r Cent
- 50
TABLS XIV
DSALKYLATION OF NEOHSX-XNB
Run Number
Gms. charged
Mols charged
21
255.5
2.9 7
22
178.5
2 .0 8
R e a c to r Tem p., 0C.
Time o f run , h r s .
L iq . Sp. VeiL, h r . * 1
500
2 .0
0 .2 1 7
552
2 .0
0 .153
Gas Produced, L i t .
Ifo ls.
Gms.
8 .3
0.245
7 .5
Gms. L iquid Produced
Gms. Coks Sc L osses
Gas
A n a ly sis
We Ig h t
IB r Cent
L iq . A nal,
WeIght
Per Cent
242.7
5 .3
1 31.1
5 .2
0=7
2 1 .2
1 0 .3
4 .4
1 5 .9
0 .4
9.5
14 .9
4 .7
17 .1
1 .9
3 .3
2 .6
4 5 .6
H2
CII4
C2H4
C2Hg
CsH6
c 3%
%
C4HlQ
C5
——
————
4 7 .5
Low B o il F ra c .*
U nconvert.
R esidue
1 ,9
98.1
Par
IBs.‘3
P roduct
A n a ly sis
Weight
Per Cent
Hg
CH4
C2H4
C2H6
C3H6
C3He
C4H8
C411IO
Low Boil. F ra c .*
Unco h v e rto
R esidue
Coke Sc L osses
3 8 .5
1 .3 1
5 0 .2
0 .0 2
0 .6 2
0 .3 0
0 .1 3
0 .4 7
— ——
——
3.2 1
93.17
2 .0 8
6 .6
93.4
——U ltimate
0 .3
'9.1
4 .4
1 .9
6 .9
——
-----— 4 7 .1
-----— —
3 0 .3
•C ondensible liq u id b o ilin g below charge stock
Per
Pass
U ltimate
0 .1 1
2.6 7
4.2 0
1.3 3
4 .8 2
0 .5 4
0 .9 3
0 .7 3
17.37
64.38
— ——
2 .9 2
0 .3
7.5
11.8
3 .7
13.5
1 .5
2 .6
2 .1
4 8 .8
8 .2
4
- 51
TABLE XV
DEALKYLATION OF 2 ,2 ,4-TRIMETHYLPSNTANK
Run Number
Gns, Charged
Mols charged
25
276.0
2 .4 2
24
276.0
2.4 2
R ea c to r Tem p., °C.
Tina o f ru n , h r s .
L iq . Sp. Ve'.L, h r . " 1
507
2 .0
0 .2 2 3
553
2.0
0.223
Gas Produced, L i t ,
M ols.
Gms.
23 .1
0.7 8
3 1 .8
6 4.0
2.18
75.7
Gms. L iquid Produced
Gms. Coke & L osses
Gas
A n a ly sis
We ig h t
Tfer Cent
L iq . A nal.
We I glit
P e r Cent
P roduct
A n a ly sis
Weight
Per Cent
237.1
7 .1
L91.2
9 .1
H2
CH4
CgH4
c 2n 6
%
C3H6
C4H6
C4H l0
C5
0 .2
5 .1
7 .8
———
4 2 .0
Low B o il F ra c .*
U n convert.
R esidue
14 .0
8 6 .0
—
H2
CH4
C2H4
^2%
C3H6
C4H0
C4nIO
Low B o il F r a c t.*
U n co n v ert.
R esidue
Coke & L osses
0 .4
13.7
3 .6
3 .2
29.0
——
5 .5
25.5
14 .1
5 .0
2 8 .4
11.5
17 .0
8 3 .0
Par
Pass
U ltimate
Par
Pas s
U lti
mate
0 .0 2
0 .5 9
0 .9 0
*»—-4 .8 3
0 .1
2 .3
3 .5
0 .1 1
3 .7 6
0 .9 9
2.25
7.9 6
0 .3
8 .8
2 .3
5 .3
18.7
1 .5 1
7.00
1 5.64
5 7 .4 8
— —*
3 .3 0
3 .6
16.6
3 6 .8
—
—
8 .2
0 .5 8
3.27
13.35
73.89
——
2.57
18.5
2 .2
12.5
51 .7
9 .8
"1Condensible liq u id b o ilin g below charge sto ck
- 52
TABLS XVI
DS<'iLKZLATI CL OF 2,2,5-T R II 3THY1KBXAH3
Run Number
Gcis. charged
Mols charged
25
299.0
2.33
R eactor Temp., 0C.
Time o f run,, h rs.
14q. Bp. VeI . , h r.
501
1.75
0.263
Gas Produced, L it.
LtoIs .
Gms .
15.3
0.551
21.4
Gms. Liquid Produced
Gms. Coke & Losses
Gas
Analysis
Vieight
lo r Cent
Liq. Anal.
r?e Ig h t
Per Cent
Product
Analysis,
VeIght
Per Cent
26
275.0
2.16
535
2.08
0.226
67.8
2.23
83.7
175.5
15.3
264.6
13.0
0.655
7.86
16.36
27
308.0
2.41
555
2.0
0.343
86.4
2.90
102.9
196.8
19.4
0.378
2.74
11.03
15.00
53. 66
analy-
28.50
—-- —
25.03
37.141k
s is
10.9
87.4
1.7
15.7
81.6
2.7
H2
GH4
C2H4
CgHg
03%
%
OqHs
G4 H1 0
%
27.10
Low Boil Frac. *
Unconvert.
Residue
Per
U lti-
Pass
mate
Per
Pas 3
0.047
0.21
0.115
0.835
0.56
2.48
CR.
0.21
5.32
3.37
C2II4
—
—
—
—
—
—
”w
4.56
02%
1.94
8.55
10.24
(%%
—
———
C3H8
2.04
9.00 11.30
Ci H6
—
—
—
——
C4Hi0
9.86
Low B o il F ra c . M l.44 49.68
77.33
----- 53.50
U nconvert.
1.70
Residue
1.51
6.66
5.75
4.35
13.20
Cokn & L osses
H2
^Condensible liq u id boiling- below charge stock
no
18.1
78.0
3 .9
U ltimate
0.24
1.75
7.05
9.55
21.45
analy-
23.52
s is
20.68
----3.56
12.03
no
#
53 -
T,\BLB XVII
MALKYLATIOtJ OF 2,3-DIMBTHYLBUTANE
Run Number
Cm. charged
Uols charged
28
317.0
3.68
29
204.6
1.70
Reactor Temp., °C.
Tins of run , hrs.
Liq. Sp. V e l., hr . - 1
513
568
Gas Produced, l i t .
Uols .
Gma.
Gms. Liquid Produced
Gms. Coke & Losses
Gas
Analysis
We ight
Bar Cent
Liq. Anal.
Weight
Par Cent
2 .0
0.226
0.180
20.3
0.503
23.9
68.5
2.33
78.3
285.8
7.3
H2
CH4
C2Hd
C2Hg
cShG
03 %
C4H6
C4 H10
C5
0.04
4.54
0.89
0.75
22.43
----—
Low Boil Frac.*
Unconvert.
Residue
15.7
84.3
109.5
16.7
0.08
17.20
6.87
3.37
33.98
----———
38.50
71.35
Par
Pass
Product
Analysis
Weight
Bar Cent
2 .0
0.003
H2
0.343
CH4
0.067
C2 H4
0.057
C2H6
1.69
C3 H5
uStiB
C4H8
C4H]n
Low B o il. Frac. *19.54
75.99
Unconvert.
Residue
Coke & Losses
2.30
19.0
81.0
—
U ltimate
0 .0 1 2
1.43
0.28
0.24
4.05
Par
Pass
U ltimate
0.03
6.59
2.63
1.28
13.00
0.05
11.65
4.64
2.26
22.95
24.92
43.35
———
43.95
—
81.48
— 9.60
♦Condensible liq u id b o ilin g below charge sto ck
8 .2 0
——
14.50
- 54 -
TABLE XVIII
DEALKYJ1ATI ON OF 2,4-DDJ3THYLFEHT^NE
Run Number
Ctas. charged
Mols charged
30
178.7
1.79
31
234.5
2.35
32
204.3
2.04
Reactor Temp., 0 C.
Time of run, hrs.
Liq. Sp. V el., hr."1-
493
516
557
Gas Produced, L it.
!.Sols.
Oms.
Oms. Liquid Produced
Gras. Coke & Losses
Oas
Analysis
Weight
Itir Cent
H2
CH4
C3 II4
CgHg
C3 H6
C3 H8
C4Ha
C4 II1 0
Cs
2 .0
2 .0
2 .0
0.251
0.195
0.226
14.4
0.495
18.9
2 0 .2
0.73
22.4
154.2
308.0
7.6
2 .1
Hg
CH4
CBH4
CBHg
C3 H6
C3 H8
C4 H8
C4HlO
Low B o il. Frac.*
Unconvert.
Residue
Coke a Losses
1.25
15.75
5.30
5.00
31.90
6 .1 0
analy-
3.06
47.51
———21.35
------17.10
s is
Liq. Anal. Low Boil Frac. * 2 . 8
.''eight
Unconvort.
93.2
Itir Cent Residue
4.0
Product
Analysis
Weight
Per Cent
119.8
19.0
0.82
2.06
no
no
analy-
62.4
2.14
65.5
15.10
——
———
25.40
4.9
90.1
5.0
2.5
92.5
5.0
Per
Pass
U ltimate
Ftir
Pass
0.066
0.166
0.654
0.347
3.835
0.33
0.82
3.24
0.40
5.05
1.70
1.60
10.22
—
—**
4.84
s is
1.72
5.73
79.81
4.43
3.24
^Condensible liq u id b o ilin g below charge stock
1 .2 2
19.00
8.52
———
28.40
9.61
54.25
21.95
2.94
16.03
9.30
U lt imate
0.88
11.05
3.72
3.50
22.40
———
—
10.58
——
—■
21.00
— —
6.40
20.35
- 55
TABLE XIX
D2ALI2L'vTICi; OF 3-1.XTKYLPXIWZiHE
Run Number
Gns charged
Ilols cIiarged
33
119.0
1.75
34
276. 2
4.03
Reactor Temp., °G.
Time of run , hr s.
Lin. Sp. V e l., hr . ” 1
5IB
553
.
1 .0
2 .0
0 .2 0 0
0.232
Gas Produced, L it.
Hols
Gras
15.6
0.530
15.3
Gns. Liquid Produced
Gms. Coke & Losses
93.8
9.9
.
Gas
Analysis
,'eight
iter Cent
Liq. Anal.
He ight
Per Gent
Hy
CH4
Goii4
CoHG
C3 H6
cS11S
C4 H8
G4HlO
C5
Low B oil Frac. *
Unconvert.
Residue
190.1
23.9
0.14
3.38
17.20
0 .2 1
3.31
18. 25
10.40
26.72
8 .0 0
26.80
41.11
44.48
17.3
82.7
16.8
73.2
--- ---- ----------
1 0 .0
I^or
Pass
Product
Analysis,
Ie ight
Por Cent
59.0
2.035
62.2
Ult i mate
0.027
0.426
2.35
1.34
3.44
0.063
——C4%
• -C4Hio
Low Boil Frac. ‘ 10.92
65.17
Unconvert0
——
—
Residue
8.32
Goto & Losses
———
H2
CII4
CoII4
GgHs
C3 IIG
1 .2 2
6.75
3.85
9.08
Par
Pass
U ltimate
0.03
0.73
3.70
1.72
5.77
0.06
1.49
7.56
3.52
11.30
——
-21. 29
51.10
5.90
0.67
43.50
——
-14.30
17.75
P r .T T -,
54.35
—————
23.09
*Condensible l i i u i d b o ilin g below charge sto ck
- 56
T.XBLE XX
D . UJ-YLtTION
CF
S-^TIIYUKiTANK
Run Kunber
Gns. charged
Kols charged
35
386.3
3.38
36
207.0
1.31
Reactor Temp., °C.
Time of run , lire. _
Lif1, O1'* Voi* I -ir*
508
538
I-Jus ih’oduced, L it.
Ib is .
Gus.
Lroduct
Analysis,
Veigiit
Ibr Cent
0.164
59.4
1.90
Cl. 8
336.6
9.4
129.5
15.9
0.63
1.37
13.65
2.84
37.41
0.83
12.28
7.28
6.30
30.95
cd:@
0 L11IO
C5
10.83
22.55
10.67
13.16
16.20
13.00
Low B oil Lrao.*
rJnconvert.
Residue
12. 9
05.3
H3
C2 H4
Gi1O
0
c4
Liq. .Uial.
Vfe ight
L ;r Cent
2 .0
0.305
36.3
1.21840.3
G o . Liquid Lroduced
Gns. Coke & Losses
CrUS
nialysis
,eight
Ibr Cent
2 .0
Ho
CH4
0
GH^
co%
C4 H0
C-HlO
Low Boil Krac.*
Unconvert0
Residue
Coke & Losses
1 0 .1
84.9
5.0
1 .8
Ibr
la ss
U ltirate
Fbr
Lass
U ltimate
0.07
0.14
1 .42
0.30
3.00
0.23
0.55
5.53
1.17
15.19
0.25
3.67
2.17
1.33
9.24
0.53
7.82
4.62
4.00
19.60
1.13
2.45
12.35
74.33
1.56
2.43
4.40
9.15
40.11
3.93
4.34
10.19
53.04
3.12
7.68
8.37
10.31
21.70
6 .0 0
9.47
* Gondonsiblo liq u id b o ilin g bo low charge sto ck
——
—
6.61
16.35
TABLB :ca
EIMETIC DATA TOR TliE DKUCfL-J IOM OF NAHfTTEHES aHD LALJFIHS
Conpound
Run
No.
Tempera­
ture 0 C.
Liquid Space
Velocity hr - -1
O093 x :LO- 5
1.49
22.7
1 .0 1
0 .2 1 1
14.10
22.40
493
554
0.139
0.203
41.87
62.18
2.96
5.48
13.4
1.65 x IO" 8
502
545
0.209
0.132
45.22
62.30
3.51
5.28
11.7
4.28 x IO" 8
512
549
0.187
0.203
25.44
42.68
1.54
3.15
25.0
1.72 x IO" 1 2
507
537
561
0.196
0.236
0.235
8.72
24.40
25.53
0.43
Tt
31.2
8.45 x IO" 1 3
1 .1 1
n
1 .8 4
ft
494
525
548
0.274
0.203
0.154
5.00
21.55
49.73
0.40
1.38
3.33
47.3
9.17
0.136
0.190
26.51
51.91
1 .1 2
it
43.2
7.05 x IO" 1 7
16
501
538
4.03
it
17
18
508
547
0 .0 9 7
1.53
5.24
it
40.2
8.30 x IO" 1 6
0.189
43.22
63.13
19
434
546
0.237
0.275
66.30
32.47
7.14
13.31
Tf
39.9
2.20 x IO* 1 6
510
545
0.219
2
Methylcyclohexane
5
4
Ethylcyclohexane
5
Lethylcyclopentane
7
8
n-Hexane
9
CycloTioxane
I
6
10
11
n-IIeptane
12
13
14
n-Octane
n-Dodecane
n-IIexadecane
Activation
Conversion Velocity Con- E n e r g y , Ea Frequency
Ler Cent
sla n t, k see. ~ L k-cal/m cl. %Factors
15
20
x IO" 1 1
Tt
ft
ft
ft
It
Tl
Tt
it
x
10
- T
7
ft
it
IT
ft
TABLE XvI (co n t.)
KINETIC DATA FOR
Coi- ound
Keohexane
Bun
No.
Tempera­
ture °C.
THS
DE-LLKYLVrI ON OF EUirriLSKIiS AKD ±ATAFFINS
Liquid Space
V elocity hr"I
Conversion Velocity ConPer Cent
s Ltyat, k eoc.
500
552*
0.217
0.153
6.83
35.52
24
507
553
0.233
0. 223
25.11
42.52
3.42
2 ,2 ,5 -TrimsthyI-25
hexane
26
27
501
535
555
0.250
0.226
0.243
22.67
47.30
47.32
1.92
4.09
4.31
"
"
2 ,B-Dirathylbutane
28
29
513
568
0.265
0.130
24.01
56.65
£.05
4.21
2,4-D irathylpentane
30
31
32
493
516
557
0.251
0.195
0.226
19.52
20.19
45.75
1.53
1.23
3.86
3-I.jethylpentane 33
34
512
553
0 .2 0 0
0.232
34.83
48.90
2.41
4.61
B-IVethy Ihe ptane 35
36
508
533
0.306
0.164
25.67
46. 96
2.52
3.09
21
22
2 ,2 ,4-Trimothyl-23
pentane
0.44 x SO- 5
Vctivation
Ene rgy, £ a Fre que ncy
k-cal/m ol.
Factors
35.5
4.07 x IO- 1 0
15.7
1.30 x 10“ 1 0
19.1
6.65 x 10“ 1 0
"
"
17.1
5.35 x IO" 1 0
"
18.3
3.52 x IO- 1 0
20.4
1.84 x 10~ 1 0
18.2
2.02 x IO- 1 0
1 .3 3
1 .3 3
"
"
«
- 59
TABLE XHI
REFRACTIVE INDICES CF SEVERAL CYCLOIEXEffi
AND ETEiYL CYCLOHEXiIffi CUTS
Cyclohexaiio Cuts, Run
j/l
Refractive index of pure cyclohexane, n^ 0
-
1.4262
Refractive index of pure benzene,
= 1.50110
Refractive indices of cuts b oiling at 640 ran. Hg.
between:
70-71° C., Uq0
1.4310
71- 72° C., n^ 0 = 1.4315
72- 73° C., nj# - 1.4506
73-74° C., ngO = 1.4411
74-75° C., n^ 0
= 1.4205
Ethylcyclohexane Cuts, Run i-5
Boiling
Range
640 ran. Hg.
118.0-119.0
119.0-120.0
1 2 0 . 0 - 1 2 1 .0
1 2 1 . 0 -1 2 2 .0
122.0-123.0
123.0-124.0
124.0-125.0
125.0-127.0
Refractive
Index
before wash
1.4359
1.4363
1.4376
1.4404
1.4434
1.4564
1.4623
1.4673
RI after
I oleum
wash
RI after
2 oleum
washe s
RI after
3 oleum
washes
1.4298
1.4315
1.4312
1.4313
1.4366
1.4434
1.4335
1.4335
1.4297
1.4307
1.4306
1.4313
1.4362
1.4361
1.4335
1.4304
1.4306
1.4312
1.4362
1.4361
—
— 60 “
TABUS X H II
E iUILIBRICJI.: OF DIMSTHYL- AND ETHYL- CYCLOHEXANES
(Calculated at GOO0K from Bureau of Standards Data)
Isomer
B oiling
ItUnt at
760 mm, Hg,
Refractive
Index n“U
Equilibrium
concentra­
tion at GOO0K
per cent
Ethyl Cyclohexane
131.78
1.43.504
15.12
I , I-Dimathylcyclohe xane
119.54
1.42895
5.56
c is
"
129.73
1.43596
5.78
”
123.42
1.42695
13. 98
n
120.09
1.42494
24.51
trans 1 ,3 - "
124.45
1.43085
13.98
c is 1 ,4 -
124.32
1.42966
6.97
119.35
1.42090
13.10
1
trans
,2 1
,2 -
c is 1 ,3 -
"
trans 1 ,4 - "
- S l -
IVlBLS XSIV
IROijSRTIES CF TTE CATALYST
Grams catalyst titra ted :
M illilit e r s 0«IM HaOH needed:
4.287
11.8
4.312
12.0
Bulk density of catalyst
0.371 gms/ml.
IjDls TiF/liter of catalyst
0.242
G j'a m s
H F/liter of catalyst
Average Area of HF molecule *
4.35
17.4 x 10"15 cra^
Area of ca ta ly st/ I ite r
2.53 x IO3 cm2
Catalyst in bed
0.900 lit e r
,Irea of catalyst bed
2.28 x IO3 cm2
*Assuming clo sest packing of HF in liq uid state (22)
2.153
5.9
MONTANA STATE UNIVERSITY LIBRARIES
N378
R73c__
93225
cop. 2 .
__Ro s s , James F ,
C a ta ly tic d e a lk y la tio n o f
naphthenes and p a r a f f i n s .
8378
R73c
c o p .2 .
mmmmmmmm
93225