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A STUDY OF
THE" CRACK I NG " OF PETR OL EUM
.
A T HES IS
P re s e nt e d by
CLARK CABLE gER ITAGE,
FRANK WILL IAM HOOK .
T O T he
PRES IDENT AND FACU LTY
O f
ARMOUR INST ITUTE OF TECHNOL OGY
FOR T HE DEGREE OF
BACHEL OR OF SC IE NCE I N CHEM ICAL ENG I NEER ING
HAVI NG COMP L ETED T HE PRESCR IBED C OURSE OF ST U DY I N
CH E MICAL ENG INEER ING lLLNOISNSTITUTEOFTECWOEOGYPAUL VGALWN LBRARY
1914 35WEST33RD STREETCH1CAGO IL 60616
APPROVED
P r ofe s s or of Chemica l Eng ine er ing .
APPR OVED
f the Eng ine e r ing St ud i e s .
TABLE OF C ONTENT S .
P re fa c e
L i s t of Tab le s
L i s t o f P la t e s
L i s t o f Draw ing s
L i s t of Curve s
Int r oduc t i on
Part I . L ibra ry Work .
Gene ra l
H i s t or i c a l
Pa rt I I . La b orat or y Work
Genera l
Appa ratus
Ana lyt i ca l
D i s t i l la t i ons
C omme r c ia l Mot or Sp ir i t s a nd Ga s o le ne
PREFACE .
T he t ime ha s c ome whe n the dema nd f or
greater e ff i c i e nc y,b oth in ma nufac ture a nd
lab or,i s f or emos t . I t i s o f v ita l imp ortanc e
t o the ma nufa c ture r t o obta in the grea te st p os-
i b le r e turns fr om h i s indust ry ,and he i s c on -
s tant l y e nde av or ing t o cut d own the w ork ing
l os s by ut i l iz ing wha t ha s,in the pa s t
,be e n
c ons ide r ed wa s t e "
,or i f n ot wa s t e
,a pr oduc t
of m in or va lue . I t be c ome s then the pr ime
func t i on o f t he Che mi c a l Eng inee r t o f ind s ome
more va lua b le pr oduc t and then t o de s ign s ome
mea ns b y wh i ch i t ma y be e c onomi c a l ly manufa c t -
ured a nd c ons ume d .
T he t e c hno l ogy of p et r ole um d i s t i l la t i on
offe r s many pr ob le ms,in wh i ch a re l inke d s ome
o f t he mo s t inte re s t ing phe nome na o f Chem i s t r y
t oge the r w ith the fundame nta l pr inc ip le s of
e ng ine e r ing,wh i c h fa c t s rende r the s ub j e c t in -
terest ing a nd va luab le t o one wh os e pr ofe s s i on
i s Che mi c a l Eng ine er ing . The s e c ons i de ra t i ons
pr imar i ly le d t o t he c ho i c e o f th i s t he s i s .
I t i s o f c our s e unde r s t o od tha t the wh ole
f ie ld o f pe tr o le um d i s t i l la t i on c ould not be
t reat ed in the br i e fe s t manne r in the sh ort
S pa c e o f t wo months and there f ore s ome part -
i cu l ar pha s e ha d t o be ch os en . The int ens e
int e re s t wh i c h ha s be en c e nt e r ing ab out the
e c on omi c s o f ga s o le ne s i nc e the a dve nt o f the
int e rna l exp l os i on e ng ine,
not the pr ob le m
o f the int erna l c ombus t i on e ng ine wh i ch inc lude s
the D i e s e l t ype,
re c omme nd ed t o our a t te nt i on
a nd f or our w ork th i s part i cular pha s e o f ih -
c re a s ed ga s o lene pr oduc t i on .
The l ibra ry w ork wa s a c c omp l i shed a t t he
l ibra ry of the Armour Ins t i tut e of T e chn o l ogy
and a t t he C re rar L ibrary,in ne i the r of wh i ch
we re f ound any b o oks d ev ot e d e nt ire l y t o the
c ra c k ing phe nome n on,its h i s t or y a nd deve l opme nt .
Ne i the r have the re b e e n pub l i she d any up - t o-da t e
b o oks up on the wh o le s ub j e c t o f pe tr ole um w it h
t he exc e pt i on o f S ir B ove rt on Redw o od ' s w ork of
1913 . That t he s e v o lume s of Re dw ood are ex -
ce l l ent e ve r y one kn ow s . The only ava i la b le
“pe t r o le um pe r i od i c a l wa s " P e t r o le um "
,a Ge rman
magaz ine . Many a rt i c le s a b s t ra c t e d fr om t he
"Na t i ona l Pe t r o le um Ne w s " ,
pub l i she d in C leve -
land,and the "
Petrol eumiiev iew "
,pub l i s he d
i n L ond on,we re n ot ava i lab le
,th ough the f ormer
gra c i ous ly f orwa rde d t o the auth ors one C opy
e spe c ia l ly de s ire d . The re i s ve ry l i tt le
ma t er ia l i n the c urre nt l it e ra ture on c ra c k ing
in c ompar is onnggéthe great wea lth of pa t e nt s
in a l l c ount r ie s wh i ch have be e n grante d in the
la s t de cade,due t o t he r i s e of the aut omob i le
i ndus t r y .
The d i ff i c ult i e s e nc ounte re d in ma inta in -
i ng d i s t i l la t i on ar ound 3 0 0 ? C . and h igher,due
t o leak ing s t i l ls a nd j o int s ,we re many . I t
i s h ope d that the reade r w i ll be len ie nt in
j udg ing the f o l l ow ing page s be caus e o f t he s e
d i f f i c ult ie s,the short t ime ava i lab le f or w ork
a nd the inexpe r ie nc e o f t he inve s t igat or s .
I t is a s s ume d tha t the re ade r i s fami l ia r
w i th the pr inc i p le s of Chemi ca l Eng ine e r ing
a nd organ i c chemi s t r y . The auth or s w i sh t o
me nt i on the name s of Pr ofe s s or H . Mcc orma c k,
Dr . C . A . T ibba l s,and A s s o . Pr ofe s s or B . B .
Freud a s lend ing a id in var i ous p o int s thr ough -
the the s i s .
L IST OF TABLE S.
I . P re s e nt Ea s t e rn Cra ck ing Pra c t ic e .
I I . C ra c k ing D i s t i l la t i on Pr oduct s .
I I I . C la s s i f i c at i on of Pat e nt s .
IV Time T e s t on S ludge .
S ludge Numbe r a nd Br omine Number Ra t i os .
Ana lys e s of C rude Pe t r ole ums .
Run #1 ,Da ta on .
Run #3 ,Da ta on .
Run #4 ,Da ta on .
Run #6 ,Data on . A ls o ana lyt ica l D i s t i l l -
a t ions on Runs #8 and #9 .
D i s t i l la t i ons .
Re d is t i l la t i ons .
Re f lux Data .
Run #8 ,Da ta on .
Run #9 ,Da ta on .
Mot or Sp ir it and Ga s o le ne Data .
L I ST OF C URVE S .
Quant ity -L os s w ith s ludge t e s t .
A l l Data of Run #8 .
A ll Da ta of Run #9
Area unsatura t e d Run #8 .
Area unsa tura te d Run #9 .
Grav ity- Index Run #8 .
Grav ity- Index Run #9 .
L IST OF DR AWI NGS .
l . C opp e r St i l l .
2 . Wr ought I r on St i l l .
3 . Enlarge d St i l l Head .
L I ST OF PLATES.
D oub le Re f lux and D i s t i l la t i on St i ll .
S ing le Re f lux St i l l
Ana lyt i c a l St i l l in Operat i on .
Var i ous T ype s of St i l ls U s e d .
Wr ought I r on St i l l w it h Enlarged Head .
Ana lyt i ca l De p artme nt .
I t s e e ms f it t ing t o int r oduc e a ge ne ra l
d i s cus s i on o f c ra ck ing by f ir st de f in ing the
va r i ous t e rms wh i ch w i l l be us e d thr ough out the
w ork . B y p e t r o le um w i l l be meant the c rude o i l
a s it le ave s the we ll ; and the var i ous fra c t i ons
of p e t role um on d i s t i l lat i on we w i ll t e rm c rude
naptha be l ow 1 5 00or be l ow grav i t y ; burn -
ing o i l 15 00-3 0 0
o or be l ow grav it y ; and
lubr i c a t i ng o i l ove r 3 0 00
. A l l t e mp e rature s
g ive n a re C e nt igrade thr oughout unle s s de s ig-
nated Fahre nhe it .
The c rude naptha on s t eam d i s t i lla t i on
y ie ld s thre e grade s of naptha s and ga s o le ne .
T he re a re ma ny grade s o f ga s o le ne on the marke t
w i th grav i t ies va ry ing fr om d own t o
a nd we w i l l d e s igna t e ga s o le ne t hat nat ura l d is -
t i l l ate not due t o c ra ck ing wh i ch is out w it h in
the s e l imi t s . Ga s o lene rea lly sh ould not be
va lue d up on i t s grav i t y a c c ord ing t o Mr . T ipp e r
o f the Texa s O i l C o . but ra the r it s b o i l ing
po int a nd e ndp o int . He ma ke s the a s t ound ing
s ta t e me nt that a Pe nns ylvan ia fra c t i on o f
grav it y w i ll p os s e s s no mor e v o la t i l i t y fr om
the s tandp o int of l ow b o i l ing p o int a nd l ow e nd
p o int tha n a Ca l i f orn ia fra c t i on of grav i t y .
He c onc lude s t hat the grav it y is the n of n o va lue
a s a t e s t f or t hre e rea s ons : f i r s t,t he grav it y
var i e s a c c ord ing t o t he s tat e in wh i ch t he fra c t i on
i s pr oduc e d a nd a l s o in wh i ch i t is s o ld ; s e c ond,
t he grav it y and v o la t i l it y have n o c onne c t i on ;
th i rd,one grav i t y cannot be s ta te d for a l l
fra c t i ons of the same fue l va lue . The t e rm pe t r o l
i s the fore ign nome n for the .Amer i can w ord ga s o -
le ne a nd w i ll only be us e d in thi s w ork whe n
quot ing fr om f ore ign art i c le s .
One more i mp ortant d i s t i nct i on nee d s t o b e
e mpha s i z e d and that i s the d i f fe re nce be twee n
ga s ole ne and mot or Sp ir it . B y mot or Sp ir it we
s ha l l mean that v olat i le fra c t i on of pe t r ole um
f or us e in e ng ine s wh i ch ha s b e e n pr oduce d by
( 1 ) Na t i ona l P e t r o le um Ne ws ,V
. 5 , N o . 5 , p .44 .
c ra ck ing,by b le nd ing
,by c ompre s s i on of na tura l
ga s ,or in any othe r wa y be s id e s s tr i c t fra c t i on—
a l d i s t i l lat i on . I t i s a lmos t ne ed le s s t o sa y
that mot or Sp ir it i s infe r i or t o ga s o le ne,f or
the f ormer ha s a d i s t i lla t i on c urve ful l of
breaks,wh i le t he la tt e r ma inta ins a regu la r ly
a s c e nd ing d i s t i l la t i on curve . The la t te r w i l l
then be much more e f fe c t ive and ea s ie r t o vap or -
i z e th ough its b o i l ing p o int be h ighe r a s a
wh o le t han that of the mot or S p ir it a s a whole .
A l l grav it ie s w i l l be g ive n in t e rms o f a n
e qua l v olume of wat e r a t great e s t dens it y a nd
f or t he be ne f i t o f reade r s us ing the Baumé s c a le,
wh i c h i s b oth ina c c urat e and inc onve n i ent,the
f o l l ow ing c onve r s i on f ormula e a re ins e rt e d he re
Fr om Baumé t o grav i t y
Fr om grav i t y t o Baumé 13 0 =Be
P e t r o le um is c hemi ca l ly an ext reme ly var ie d
mixture of hydr ocarb ons b oth a l iphat i c and a r om-
a t i c o f grea t ly vary ing degre e s of s taurat ion .
w i l l the n d r op ba c k int o the much hot t e r b ody
o f p et r o le um ye t rema in ing in the s t i l l and w i l l
t hus be de c omp os e d ; s e c ond,by a pp ly ing pre s s -
ure t o the s t i l l s o t hat the f or c e d b o i l ing
p o int w i l l be much i n exc e s s o f the norma l
b o i l ing p o int and s omewhat in exc e s s of the
de c omp os it i on p o int ; and th ird,by Sub j e c t ing
the vap or s pr oduc e d in an ord inary s t i l l t o
hea t fr om s ome ot her ext e rna l s ourc e in a s e c ond
s t i l l or re ce pta c le . I t i s thus e a s i ly s ee n
that ma ny me chan i ca l fac t or s bear on the pr o-
duc t s ob ta ine d,c h i e f among wh i ch a re the de s ign
o f s t i l l,the t e mpe rature ma inta ine d and the
le ngth o f the c ampa ign . I t i s ge nera l ly unde r -
s t o od,a c c ord ing t o Redwood
( l )that eve n the
p r oduc t s o f a c are ful fra c t i ona l d i s t i lla t i on
a re not th os e in the or ig ina l o i l .
The se ne w pr oduc t s obta ine d va ry the re f ore
gre at ly a nd ma y be made anyth ing fr om the ve ry
s ma l l change s induc e d in a fra c t i ona l d i st i l l -
a t i on t o a c omp le te d i s s oc ia t i on t o Carb on a nd
T rea t i s e on Pe t r o l e um , 1913 ,
Hydr oge n . Of c ours e t he i dea l c ond i t i ons a re
t hos e wh ic h make the re s ult ing pr oduc t a max -
imum o f l ight d i s t i l la te w ith a min imum of p er -
manent ga s e s and c oke . Thorpe and Y oung( l ) in
exoer imenting in 18 7 1 by hea t ing s o l id pa ra -
ffins under pre s s ure obta ined ve ry l i tt le gas
and a n a lmos t p er fe c t change t o l iqu id pr oduct s
o f an ole f in i c natur e " . The y the re f ore wr ot e
t he f o l low ing t ype r ea c t i on wh i ch the y be l i eve d
expre s s e d the who le reac t i on : -
hea te dC H
n 2n+ 2 n-x 2 ( n-x ) 2 x 2x
A s a ma tt e r of fa c t,
a s sh own ab ove,the pr o -
duc t s ma y be of a ny pha s e a nd a ny degree of un-
s a turat i on . I t i s the n the pr ob lem t o s o reg -
u l ate t he degr e e o f hea t ing a c c e le rat i on of
he at ing,and de s ign o f st i l l and flue s s o that
the l ight e s t ye t le a s t unsa turat e d pr oduc t s w i l l
( 2 )re sult . Brann t s ta te s that be s ide the l ight
Pr oc e e d ings,R oya l S oc ie t y , XIX ,
3 7 0
P e t r ole um,it s H i s t ory and Or ig in .
hydr oca rb ons formed by the de c omp os i t i on,the re
i s a ls o pr oduc e d a c orre sp ond ing quant it y o f
heavy hydr oc arb ons n ot or ig ina l ly p re s e nt,the
pr op ort i on be twee n t he t w o be ing quit e c ons tant ,
( i . e . the more o f the l ighte r the m ore o f the
v e r y much heav ie r . )
Another pra c t i c a l p o int ar i s e s i n the pr ob -
( I )a b le burning of the vap or s wh i ch augme nt s the
d i ff i c ult i e s of d e od or i z ing and b le a ch ing the
p r oduct . The t e mpe rature of the s t i l l t O p mus t
b e h igh e nough t o a l l ow a c e rta in f l ow of d i s t i l l -
a t e but not h igh e nough t o burn the vap or s a s
the y c ome in c onta c t w i th the s id e s of the st i l l .
T he pra c t i ca b i l it y of the pr oc e s s de pe nd s
on the demand and s upp ly of gas o i l a nd lub -
r icat ing o i l on the one hand and mot or S p ir it
on the ot he r , t oge t he r w ith var i ous que s t i ons
o f grea t er fue l c ons umpt i on and inve stme nt in
t h i s pr oc e s s . The fue l c onsumpt i on i s sa i d t o
be f ive t ime s a s great for a c ra c k ing d i s t i l l -
P e t r o le um D i s t i l la t i on, A . N .L eet , 188 5 .
The s t or y of -th is a c c ide nta l d i s cove ry in
a Ne w Je r s e y re f ine ry,
one c o ld a ft erno on in
N ov . of when the s t i l l man we nt h ome t o
d inner and on be ing take n w it h a f it d id not
re turn unt i l la te in the a ft e rn o on,whe n he
f ound a fra c t i on of a s t on i sh ing ly l ight grav i t y
i s su ing fr om t he is fam i l iar t o
any one wh o ha s read any o f the o i l l it e rature ( 1 )
a t a ll .The pr opr ie t or la t e r had a g la s s s t i l l
bui lt in which he s t ud ie d the phenome non and
d i s c ove re d the pr oc e s s of c onde nsa t i on on the
uppe r part o f the s t i l l and c ons e que nt dr ipp ing
ba c k . The re neve r we re any'
patents grant e d on
th i s and a s the informa t i on S pre ad,a l l d i s t i l l -
e r s we re s o on re mode l i ng the ir s t i l ls t o ut i l ise
th e new idea,by s imp ly unc ove r ing the uppe r
ha l f wh i c h had prev i ous ly be e n br i c ke d ove r,the
or ig ina l ide a in d i s t i l la t i on be ing t o carry out
t he O pe rat i on in the lea s t t ime,thus e c onomi z ing
fue l .
Th i s Amer i can pr oce s s ha s be e n us e d unive r -
sa l ly s inc e it s a c c identa l d i s c ove ry w i th more
( 1) F or ful l de t a i ls s e e P e t r ole um D i s t i l l -
or le s s c hange in s t i l l de s ign,the t e nde nc y
b e ing t o e l ongate the s t i l l ve rt i ca l ly and
e ve n use dephegmators on t O p ,t o fa c i l l ate c on-
de nsa t i on . I n 1895 ,Brannt
( 1 ) de s c r ibe s the
pr oce s s t he n in v ogue a s be ing carr ie d out in
s t i l ls c ons truc t e d e s pe c ia l ly f or th i s purp os e .
The upr ight f orm wa s the mos t s u ita b le be c aus e
the va p or s,hav ing t o t rave r se a l ong d i s tanc e
in the s t i l l it s e l f,have a c hange t o c onde ns e
part ia l ly a nd in f low ing ba c k on the overhe at e d
s ide s t o s uf fer de c omp os it i on and vap or i za t i on .
The s t i l l wa s the re f ore pr ov i de d w it h a large
c onde ns ing d ome and su i ta b le de phlegma t or ,t he
us e o f t he la t t e r be ing a bs olute ly ne c e s sary
t o inc rea s e t he y i e ld . The y we re s o arranged
that t he o i l vap ors me t large c onde ns ing sur -
fa c e s,that the heavy l i quid a l l f l owed back
i nt o the s t i ll,a nd only the mo st v o la t i le p or -
t i on we nt ove r . The mat er i a l o f the s t i l l wa s
mangane s e ir on and the he ight was tw o t o tw o and
Pe tr oleum , It s H i s t or y and Or ig in .
one -ha l f t ime s the d iame t e r . The f lue s a re s o
a rrange d that the heat c an be a dmit t e d t o a ll
t he s t i l l wa l ls dur ing the e ar ly part of t he
d i s t i l la t i on and lat e r cut off fr om the uppe r
part t o fa c i l ixtate the c ra c k ing .
An addre s s by F . C e R ob ins on of the
At lant i c Re f in ing C o . g ive s t he pr oc e dure wh i ch
h i s c ompany is us ing. Pe t r oleum i s pumpe d int o
s t i l ls c onta in in g 5 0 0 t o 10 0 0 barre l s,wh i ch c on-
s i s t s imp ly o f h or i z onta l s te e l c yl inde r s made
o f she e t s o f b o i l e r s t ee l r ive t e d t oge ther and
pr ov ide d w i t h manh ole s in t op and e nd s,w ith
p e t r ole um l ine,vap or l ine
,sa fe t y va lve
,c om-
bust i on c hambe r,a nd f lue s
,fra c t i ona l a i r con-
d e ns e r,wa t er c onde ns e r s
,and ga s e x i t p ipe .
The f o ll ow ing ta b le g ive s the da ta on a run : -
T a b le I .
8fFahr . fra c t i on . F fra c t i on
Crude naptha . 20 0
C rude hv ynaptha
Nat . lamoo i l d i s t .
C ra c ke d d i s t .
I t is n o more than fa ir a ft er quot ing the ab ov e
fr om ea s t e rn pra c t i c e wh i ch c ons i s t s large ly of
w ork w i th para ff in ba s e p e t r o le um t o ment i on
b r i e fl y wha t i s sa id b y the Ca l i f orn ia Sta t e
M in ing Bureau on the we s t ern s it uat i on . ”Ma nya t t emp t s have bee n made t o c onvert the s e heavy
a spha lt i c d i s t i l la t e s int o l ight e r pr oduc t s,
e i ther b y man i pulat i on of the or ig ina l d i s t i l l -
a t i on or b y sub s e quent tre a tment,but thus far
( 190 4 ) none o f the pr oc e s ses have me t w i th c om-
merc ia l s uc c e s s . The s e pe t r o leums are sub j e c t
t o c ra c k ing j us t a s a ny other but ow ing t o
t he ir chemi c a l c ons t i tut i on,the l ight p r oduc t s
of the de c omp os i t i on have l it t le c ommer c ia l va lue
b e ing ver y f oul,d i f f i c ult t o pur i fy and b lea ch a nd
not re t a in ing the ir c o l or whe n pur i f ie d . The as -
pha l t i s s e r i ous l y in j ured a ft er c rac k ing a nd the
ga s e ous de c omp os it i on is Ca l i f orn ia p e t -
r ol eum c onta ins r oug hly ole f ins,
be n-
z eme s and napthene s ,and pa ra ff ins . Of the s e
,
(”Bul le t in #3 2 ,March 1 90 4 , p . soe .
i t i s s e e n pr obab ly"
7 0% cann ot be c ra c ke d,a nd
t h i s ma y be the ke y t o the d i ff i c ult y .
In t ra c ing the var i ous othe r me t hod s o f
f or c ib ly pr oduc ing l ight er fra c t i ons we f ind in
the mult i t ude o f pa t e nt s,rea l ly but f ive fund -
amenta l l y d i ffe re nt idea s,th ough many c omb ih -
e t i ons of mor e than one . The s e give i n the or -
de r o f t he ir app ea ranc e a re : f ir st,e mp l oyment
o f p re s s ure on the s t i l l and lat e r on the c on-
d ens e r or b oth ; s e c ond,the pa s s ing of the vapor s
thr ough an ext e rna l ly hea t e d uni t be twee n the
s t i l l and t he c onde ns e r ; th ird,t he use of c on -
ta c t or ca t a lyt i c ma t e r ia l s omewhe re in the s ys-
t em ; f ourth,the pa s sage o f a ga s thr ough the
o i l in the s t i l l w i th p os s i b le use o f a c om-
pre s s or in the s ys t e m ; and f i fth,the us e of a n
e le c t r i c c urre nt t o sup erhe at or de c omp o se the
p e t r o le um . The auth or s d o not c la im c omp le t e -
ne s s f or Ta b le I I I,but i t wa s ra th er a s s e mb le d
w i th t he v ie w of a s c e rta in ing the t re nd of mot or
S p ir i t pr oduc t i on . The us e of ca ta lyt i c age nt s
i s e spe c ia l ly n ot i c eab le and among t he se a re
f ound Sc rap Ir on,C la y
,Bauxit e , C cfi e
,Br i c k
,
A1203
,ox id e s of T h
,V, N i , Mn
,Cu
,e t c . Wat e r
is us e d oft e n and a ls o und oubt ed ly p la ys the
r o l l o f a c a ta lys e r . I n C .W.Turner's Br it i sh
pat e nt #2 583 2 of 1912 ,s t e am and o i l are s up er -
heat ed in Sp ira l ly wound tube s whe re by the Ox y -
ge n of the wa te r g oe s w ith the Ca rb on f orme d in
the c ra ck ing,t o pr oduc e Ca rb on D i ox id e ; a nd
the Hydr ogen i s l ibe ra t e d and g oe s t o sa turat e
t he unsaturat ed b od i e s,pr oduc ing naptha
,gas o -
lene,e t c . The wa t e r he re s erve s n ot only t o
c ata lys e the rea c t i on but ta ke s part in i t .
L . U bbe l ahde‘ l ) ha s s tud i ed the influe nc e
o f f our ca ta lys e r s,Pul le r s e arth
,Ka o l in
, A l-
umina ,a nd N i c ke l
,and c onc lud e s that the y i e ld
o f unsa t urat ed hydr ocarb ons d e c rea s e s w i th r i s e
in t e mp e rat ure wh i le t he I od ine number in gene ra l
inc r ea s e s . The s e tw o s t at e ment s are hard ly c om-
patab l e . The n i c e s t b it o f the or y h oweve r ap-
pea rs an onymous ly und er the c apt i on o f "T he
Ca ta lyt i c P r oduc t i on o f Pe tr ol" ( l ) in whi ch
( 1 ) P e t r oleum 7 ,
( 2 ) Petr ol eum. Rev iew 28 ,7 23 .
a c ont inuous fl ow of pe tr ole um and hydr oge n a re
le d int o the b ott om o f a h igh s t i l l . In t he
s t i ll i s p la c e d f ine n i c ke l a nd the c ont e nt s
a re ag ita t e d . The l ight e r va p or s a re carr ie d
ove r by the s t re am o f t he hydr oge n and the heav ie r
c onde ns e and fa l l ba c k in the s t i l l . The pe t -
r ol eum i s thus s upp os e d t o be c ra cke d t o a sa t -
urated b od y a nd a heav i e r unsa turat e d b ody whic h
i s hydr oge nat e d in the pre s e nc e o f t he cata lyt i c
age nt and is thus aga in c ra c ke d,aga in hydr oge n -
a t ed,and s o on . The ore t i ca l ly t hi s s hould pr o -
d uc e 1 0 0% ga s o le ne .
Lo ok ing onc e more a t Tab le I I I we s e e the
tw o pa t e nte e s Mr . Burke o f t he I nde pe nde nt s and
Mr . Burt on 6? the Standard . The la t t e r ' s pr o -
c e s s a pp ea r s t o be l it t le in a dvanc e o f Dewa r
a nd Re dw o od ' s o f 1889 ,wh i le the f orme r ha s h it
on the ne w id ea o f c ompre s s ing the va p or s wh i le
a t a c ons i derab le heat a nd p erhap s a id ing a
p olymer i za t i on wh i ch othe rw i s e take s p la c e but
s l ow ly . I n a re c e nt t e s t Mr . Burke sh ows a pr o -
duc t 6 8% of wh i ch i s of grav i t y .
In s umming up the ent ire ga s o lene and mot or
( 2 ) 1!AS p ir i t s it uat i on
,Mr . B . Re dw o od sa ys
fa ir ave rage o f th e w or ld s oroduct i on o f pe t r ol
i s S inc e t he gr owth o f de mand is much
great e r than tha t of p roduc t i on,it i s ext re me ly
unl ike l y tha t the pr i c e w i l l fa i l t o inc rea s e
I n v i ew o f th is , p os s ib l e s ourc e s of mot or
S p ir i t s be c ome imp ortant . The s e are : ( 1 ) thos e
p e t r o leum frac t i ons ot her than the na ptha
fra c t i on ; ( 2 ) the pr oduc t s of de s truc t ive d i s -
t i l l at i on -
pf c oa l and sha le ; and ( 3 ) p r oduct s of
fe rmenta t i on . La rge quant it i e s of p e t r o l are
n ow obta ine d fr om na t ura l ga s . Even pe t r o le um
wel ls tha t pr oduc e c rude s c onta in ing no l ight
fra c t i ons y ie ld ma ny th ousand s of ga l l ons fr om
c onde nsa b le vap or s . By impr oveme nt o f c arbure t
t or s i t ma y be p os s i b le t o use the l ight e r
fra c t i ons of ke r os ene in a m ixture w ith pe t r ol,
( 1 )Nat i ona l P etr o leum NeWS ,
Vol . 5 ,No . 5 .
( 2 ) P e tr ole um Rev iew,29 ,
LAB ORAT ORY WORK .
Ge ne ra l .
I t wa s man i fe s t ly imp os s ib le t o trea t t he
who le s ub j e c t o f p yr oge net i c de c omp os it i on of
p e tr o le um a s rev iewe d in the pre c e e d ing page s
i n ma ny t ime s the t ime ava i lab le f or lab orat ory
w ork . T he a uth ors there f ore d e c id e d ina smuch a s
n o the s i s w ork o f th i s nature ha d b e e n ca rr i ed
t hr ough a t the Armour Ins t i tut e of T e c hno l ogy
previ ous ly ,t o c onf ine t he mse lve s t o a s t udy
o f the s imp le c rac k ing phen ome non oc cur ing in
the s t i l l it s e l f,t o t he c ond i t i ons ne c e s sary
f or t he be s t re s ult s und er a tmos phe r i c pre s sure,
and to t e s t ing a l l the t ype s o f s t i l l s ava i lab le .
That th i s pre s e nt w ork ma y the n be the ba s i s of
future s tud i e s,i s t he de s ire of t he a uth or s .
Tw o pe t r o le ums we re ava i lab le and thre e
t ype s o f st i l l s,t 0 ge ther w ith a re flux s t i l l ;
a nd t he mode o f a t ta c k wa s s imp ly t o pe r f orm
d i s t i l la t i ons w i th t he va r i ous p et r o leums in the
var i ous s t i l l s,vary ing t he S p ee d of heat ing a nd
degre e o f heat a s muc h a s p os s ib le and re d i s t i l l -
i ng the pr oduc t s thus obta ine d,ana lyt i ca l ly int o
fra c t i ons wh i c h c ould in turn be t e s t ed f or re —
fra ct ive index,S pe c i f i c grav it y
,c o l or and od or
,
s tab i l i t y,unsatura t i on
,e t c .
T he lab ora t or y w ork wa s carr i ed out w ith a
rea s onab le amount of ca re but no f ine a c c ura c y i s
c la ime d f or t he re sult s . T he the rmome t e r s use d
we re t ake n a s re ad ing c orre c t,f or t he e rr or s in
tak ing the t empe ra ture s on t he var i ous fra ct i ons
we re no d oub t in exc e s s of any c a l ibra t i on e rr or s .
APPARAT U S .
The We s tpha l ba lanc e wa s use d t o de t e rmine a ll
grav it i e s .The s e we re take n a t and we re
re ad usua l ly t o f ive un i t s in the f ourth p la c e .
C orre c t i ons for t e mpe ra ture we re made a s f o l l ow s
T emp . Grav it ie s .
. 0 0 0 9. 0 0 0 8 . 0 0 0 8
. 0 0 19. 0 0 17 . 0 0 1 6
( 1 ) T e c hno l ogy o f pe t r o le um , Neubarger
and Noa lhat, 19 0 1 .
The re fra c t ive index was re ad of f d ir e c t ly on
a C . Z e i s s ins t rument . The ind i c e s we re a l l
taken f or t he same run a t ab out the same t ime
s o t hat t e mpe ratur e c or re c t i ons were e l imina t ed
a s much a s p os s ib le . Th i s w or k wa s a ls o d one
ma inly dur ing t he f ore no ons when the t empe ra ture
wa s a lmos t c ons tant a t 220
. The ins t rument wa s
t e s t ed aga ins t pure d i s t i l le d wa t er a nd f ound
t o be pra c t i c a l ly c orre c t .
The f ir s t r e f lux c ondens e r whi ch was us e d,
i s sh own in P la t e I and c ons i s t ed of a s t i l l of
bra s s o f inch th i c kne s s,a b out 10 inche s in
d iame t e r b y 10 in c he s h igh .The cap on too ,
bra z e d t o the b od y,c ont a ined the out le t t w o ih -
che s in d iame t e r,whi ch f ormed the fe ma le s id e
o f a uni on . The ma le s ide of the un i on s e rve d a s
the b ot t om of the c o lumn shown in t he p la t e . Th i s
c o lumn wa s 1 5 inche s h igh and three inche s in d ia -
me t e r and wa s s up pos e d t o s e rve a s the ma i n
c ondens ing sur fac e . I t t e rminat ed a t the t 0 p
i n tw o tap er ing tube s,one lead ing at a s l ight
a ng le t o the h or i zonta l upwa rd t o a bra s s c on-
de ns er,and the othe r a t the same ang le d own —
ward t o a s imi l ar ~ c ondens er . A sma ll o i l c up
s erve d t o h old the t he rmome t e r at t he t op o f
the c o lumn . The de s ign of the s t i l l wa s such
that a ny am ount o f the more v o la t i le pr oduct s
of the pe t r o leum c ould be d i s t i l led o ff v ia the
l owe r c onde ns e r,and t hen th i s c ould be p lugge d
a nd w i th out any trans fe r of t he l igu id ,t he
ma t e r ia l c ould be s ub j e c t ed t o a re flux d i s t i l l -
a t i on . When t hi s ha d be en carr i ed a s far a s
d e s i re d t he l owe r c ondens e r c ould aga in be O pe ne d
a nd the pr oduc t s d i st i l le d o ff . Thus in one
s t i l l we re c omb ine d a l l the ne c e s sary means. for
the s tud y o f the c ond it i on and pr oduct s o f the
d e s truc t ive d i s t i l la t i on .
Ow ing t o t he fac t that the ab ove a pparatus
-
w a s put t oge ther ab ove the un i on wh i ch j o ined
the c o lumn t o t he s t i l l,w ith ord ina ry s o lde r
,
i t s o on gave wa y unde r the heat t o wh i c h it wa s
ne c e s sa ry t o s ub j e c t the a pparatus . Th i s wa s
much t o be lame nted a s the re i s no d oubt but ithat
s ome ve ry i nte re s t ing result s c ould have bee n
obta ine d . I n t he sh or t t ime re ma in ing a make
shi ft c o lumn sh own in P la te I I wa s made of
p ra c t i ca l ly t he same d ime ns i ons a s th e f ormer
and f i t t ing t he same s t i l l a nd upp er c onde ns e r .
The l owe r d e l ive r y p ipe wa s h owever e l iminat e d
wh i ch t o ok fr om the a pparatus i t s mo s t imp ort -
ant p o int and the w ork w i th th i s c o lumn wa s far
fr om sa t i s fa c t or y .
P lat e I I I sh ows the st i ll whi c h wa s us e d
f or ana lyt i c a l purp os e s and wa s made w i th the
v i ew o f e l imina t ing a l l de c omp os it i on dur ing t he
c our s e o f the d i s t i l la t i on and s e cur ing s imp le
fra c t i ona t i on o f pr oduc t s a s the y we re whe n put
int o the s t i ll .
Th i s wa s a c c omp l i she d ni c e ly
e s pe c ia l ly when the d i st i l la t i on wa s made in a
sh or t S pa c e o f t ime . A ll a na lyt i ca l fra c t i ons
we re obta ine d by c oming up t o t he not ed te mp -
e rature tw i c e . The é- inch p ipe lead i ng fr om
the s t i l l served a s an a i r c onde nse r for a b out
tw o fe e t be f ore ent e r ing t he wat er c onde ns er .
The a b ov e st i ll wa s mad e fr om a 6 - i nch wrot
i r on p ip e , tw o f ee t l ong,b y c l os in g t he e nd s
w ith cap s and tapp ing one cap f or a l é- inch
p lug t o s e rve a s a fi l l ing or i f i c e a nd a é- inch
h o le t o take the vap or p ipe .
P la t e IV s hows the t wo t yp e s of s t i l ls us e d,
t he s ma l le r one be ing shown in Draw ing I and the
la rge r in Draw ing I I . A~ further de s c r ipt i on
o f t he s e i s unne c e ss ary exc e pt t o s tat e tha t the
head o f the Sma l l oéppe r s t i l l wa s fa s t e ne d t o
t he s t i l l pr op er b y 18 5!8 - inc h s tud b o lt s,the
j o i nt be i ngmade t ight by a sbe s t os she e t pa c k ing .
I n the ca s e o f t he large s t i ll,the head sh own
in the t 0 p V i ew a t t he ext reme r ight o f P la te
IV wa s s c rewe d on,t he thread s be ing a s c are -
fu l l j turned a s p os s ib le t o pr eve nt any p lay in
the j o int .
The e nlarge d s t i l l he ad,t o te s t whi ch th i s
the s i s wa s or ig ina l ly pr op os ed,a pp ea r s in P la te
V,s c re we d in p la c e on t 0 p of one of the large
s t i l ls . A w ork ing draw ing o f i t a ls o appe a r s
a s Draw ing I I I . At th e t ime th i s draw ing wa s
made,i t was us e d in c onne c t i on w ith t he sma ll
s t i l ls and he nc e i s s hown c oup le d t o a s ma ll
s t i l l head . The P la te,made lat e r a ft e r a l l t he
sma ll s t i l ls had burned out,s hows the c oup l ing
t urne d out and t app e d t o f i t the newe r large
s t i l ls .
In d i s c us s ing t he s t i l ls us ed it sh ould be
s a id,that t he c onne c t i ons we re a lwa ys s ourc e s
o f c ons ide rab le t r oub le i n pre vent ing le akage .
Wi th th i s me chan i c a l l eakage g o ing on i t wa s of
c ours e imp o s s i b le t o arr ive at any figure s a s t o
t he l o s s inhe re nt in the c ra c k ing pr oc e s s i t s e l f ,
a s gas a nd c oke .
The large s t i l ls,ob ta ine d a ft e r t he s ma l l
c opp er one s le ake d s o bad ly a b out the b olt e d
j o int a s t o be us e le s s,we re cons truc t ed wr ong .
I ns t ead of be ing one p ie c e of ca s t s t ee l a s l n -
t e nded,t he b ot t oms we re ma ch ine d out of c a st
s t ee l and then threade d s o that the y s c re we d
int o the wrot ir on p i pe s e rv ing a s the st i l l
ca s t in one p ie c e,i t wa s o f c our se ne c e s sary
t o inc re a s e the th ic kne s s t o ge t anyth ing l ike
a n e ff i c i ent j o int . Th i s bulk of me ta l a l s o
made any t e mpe rature c ontr o l a lmos t out of the
que s t i on . The ga lvan iz e d meta l c yl inde r s ment i on-
e d a b ove we re remove d e nt ire ly be f ore us ing the
s t i l ls .
The s e p o int s in s t i l l de s ign and the tr oub le s
e nc ount e re d are he re e numerat e d be caus e t he y
a re c ons id e red a s ra the r imp ortant re sul t s of
t he w ork a nd sh ould b e care ful ly c ons id e red in
a ny s ub s e quent w ork a l ong th os e l ine s .
ANALYT ICAL .
Ear ly in the O pe ra t i on o f the s t i ll s,i t
be came ne c e s sar y t o kn ow t he a mount o f c ra c k ing
wh i ch wa s t ak ing p la c e ; and the chemi ca l pr op -
e rty wh i ch w ould t e l l the mos t i n rega rd t o th i s
wa s the unsaturat i on o f the frac t i ons . The
f ir s t w ork on unsaturat i on wa s ca rr ie d out w ith
sulphur i c a c id,up on the add i t i on of wh i c h
,a
da rk re dd i sh br own v i s c ous pre c ip ita te wa s
t hr own d own,th i s pre c ip ita te be ing pra c t ic a lly
the s ame a s the s ludge of the re f ine r i e s .
T umsk i( l ) sa ys that the tar s d is s ol we in t he
a c id wh i le the armmat ic a nd unsaturat ed c omp ounds
f orm su l pho-a c ids w ith ev o lut i on of SO In the
o le f ine s ( CnHZn ) ’ 80
2i s sa id by S . F . Pe c kham
( 2 )
t o re p la c e tw o a t oms of H ydr oge n a nd the se be ing
fre e un it e w ith the fre e oxyge n a t om fr om the
a c id t o form. water . F . C . R ob ins on ( 5 ) d i f fe r -
e nt iate s be twe en the a c t i on of fuming s ulphur i c
a nd the c onc e nt rat ed s ulphur i c c la iming that the
la t te r take s out only the unsa turat ed c omp ounds
and the od i fe r ous s ulphur de r i va t ive s,wh i le t he
f orme r a ls o a t ta c ks the a r omat i c s er ie s . inc l ud ing
naptha l ene a nd anthra c e ne . The a uth or s there f ore
c onf ine d the ms e lve s t o t he use of the c onc e ntrat e d
a c id .
( l ) .
T e chno l ogy of Naptha, p .2 0 4 .
( 2 ) Pe tr oleum Rep ort,C e nsus of U . S . k880
( 3 ) Met , and Che m , Eng . XI , 389 .
ed and was carr ied'
out by ad d ing a c id to
10 0 0 0 . o f o i l and a ft e r shak ing,read ing of f
the v olume of o i l l os t . Ina s muc h a s one
hundre d c ub i c c e nt ime t e r s w ould me an a l l o f
many of the fra c t i ons ava i lab le and ofte n more
than wa s ava i la b le,f ort y cub i c c e nt ime t e r s we re
f ir s t us e d w i th thre e c ub i c c e nt ime t e rs of a c id,
the mixture shake n we ll a nd a l l owe d t o s tand .
The quant it i e s us e d we re s o on furthe r reduce d t o
2 0 c c . o i l and 4 c c . a c id . I t wa s at onc e not ed
h oweve r that c he c k re s ult s c ould not be obta ine d,
one ana lys i s g iv ing a l os s on thre e p ort i ons o f
t he same fra c t i on a s and l . l c c . re s -
p e c t ive l y ,on ZO c c . us e d . I t rema ine d t o a s c er —
t a in whe ther the tr oub le wa s due t o d i ffe re nt
rat e s o f s e tt l ing,t o ins uff i c ie nt mix ing
,or
t o ins uff i c ie nt a c id . A t ime t e st wa s the re -
f ore made up on t w o fra c t i ons,Fra c t i on #11 wh i ch
had a grav i t y of a nd Fra c t i on #2 6 w ith a
grav it y of b oth red i s t i llat i on p r oduc t s .
T he tab le sh ows tha t a ft er tw o h our s the read ings
be c ome c ons ta nt .
At t he same t ime the s e re ad ings we re
made,f ive s amp le s fr om Fra c t i on #3 5 we re
fuged a nd t he re s ult s aga in pr ove d n ot t o che c k
#1 l os s in 2 0 c c .
#2 .4U
o
#3 5l l H I1
.
#4 OH N H
0
#5 0 8N H I! l l
The mix i ng wa s a ls o found t o have no bea r ing
on t he re s ult s pr ov id ed t he ag i tat i on wa s th or ough
f or ove r a m inute .
The a mount o f s ulphur i c a c id wa s n ow in -
c r ea s e d and t he re s ult s a re a s sh own in Curve #1 .
We s e e that the re s ult s che c k a ft er the pe rc e nt
a c id ha s rea c he d 7 5 ( 15 c c . a c id added t o 20 6 6 .
o i l ) and the re f or e t o b e on the sa fe s ide the
quant it ie s f or the s ludge t e s t we re made 10 c c .
o f a c id t o loc c . of d i s t i llat e .Th i s wa s f ound
t o g ive c he c ks w ith in a nd of c our s e c ould
be made much more re f ine d b y us ing large r qua n -
t it ie s o f the mat e r ia ls . I n orde r t o ge t re sult s
S p e e d i ly,the c entr i fug e wa s us ed a nd thus the
s ludge number method ,o the r meth od s we re s ought
f or in the l it e rature,whmch w ould be fa s t a nd
rea s onab ly a c c ura t e . 0 ne( l ) was ba se d on mat ch ing
the c o l or of the s ludge f ormed,
- -byadd ing
s ulphur i c a c i d,
w ith s tandard s o lut i ons of
B i smarc k Br own ; a s e c ond on the hea t of br omin -
a t i on ( 2 ) ; a th ird on the f ormol it ic index (3 )
;
a nd a fourth on Br om inat i on w it h var i ous c omp -
l ementary s olut i ons : v i z : t urpe nt ine‘ 4 )
,Be ta -
napth ol( 5 )
,and s od ium th i os ulphate ( 6 ) .
Of t he f ir s t i t ma y be sa id that matth ing
o f s ludge c o lor s w ould c e rta inly be de l i c ate
w ork . The heat o f br om inat i on wa s not a tt e mpt e d ;
and t he me th od o f obta ining the formol it ic index
a ppea re d t o o l ong and c omp l ic a t e d w it h no
a s s ura nc e o f a c c urac y . S c hmit z in P e tr ol eum, 7 ,
23 9
d our . S oc . Chem . I nd . Vol . 15 , p . 6 7 8
Jour . Ame r . Chem . S oc . XVI I ISeve nth Int . C ong .
App. Chem
, 19 0 9 Se c t .
IV,A . I .
d our . S oc . Chem . Ind .
Pe t r o le umJour . S oc . Che m . Ind .
Vo l . l I p .43 5 .
O i ls,Fat
,and Taxe s
,L ewkow its ch , I , 3 93 .
Jour . _S oc . Chem . Ind . Mi l l s a nd Sn odgra s s
Organ i c Ana l ys is - -A l l en Vol . I I I , p .4 , 5 .
b i s ulph ide s ol ut ion ,
”a nd d i lut e d t o a b out 25 c c .
w ith ca rb on b i sulph ide . 25 c c o f Br omine s o l-
ut i on i s a dde d whe re up on the s o lut i on sh ould be
d i s t inc t ly re d and rema in s o . The f la s k is
s t oppe red,ag ita t ed and p la c e d in the da rk f or
f i ft e e n minut e s . At the e nd o f th i s pe r i od an
e x c e s s o f an aque ous s o lut i on of p ota s s ium i od i de
is p oure d in a nd a ft er ag i ta t i on,the ex ce s s o f
i od ine i s t i t ra te d w i th a de c inorma l s o lut i on
o f th i os ulpha te . The va lue of t he br om ine s o l -
ut i on i s f ound b y runn ing a b lank . A lle n not e s
t he f o l l ow ing pre caut i ons : f i r st,the bromina -
t i on mus t b e c arr ie d out in t he dark ; s e c ond,
f i ft e e n minut e s mus t not be e xc ee de d a s add i t i on
s o on i s s up er c ede d by subs t i tut i on a nd br omine
i s th en us e d up a s hydr obr omi c a c id ; th ird,
mo i s ture mus t be abs ent a s th i s ca ta lys e s the
f ormat i on o f hydr oge n br om ide ; f ourth,the v o l -
ume of br omine s o lut i on sh ould be t w i ce t hat
a bs orbe d ; a nd f i fth , the o i l s o lut i on sh ould be
thes e t ime s the br omine s o lut i on adde d . I f
w ould thus be int r oduc ed . The t urp ent ine s ol—
ut i on wa s made up,a s p er ins t ruc t i ons
,4 0 0 .
i n 2 5 0 0 0 . As suming turpent i ne t o be ma inly
p ine ne ( C l OH l 6 ) w ith a grav it y of and
that the p inene mo le c ule add s four at oms of
br omine,t he t urp e nt ine s o lut i on is a l it t le
ove r n orma l or grams per c c . T he
br omine s o lut i on la t er s tandard i z e d aga ins t
th i osulphat e wa s grams pe r c c . The rat i o
b e twe e n turp ent ine and br omine was 1 0 0 . br omine
- 0 . 6 6 c c t urpe nt ine . The re f ore sh ould be
e qua l t o wh i ch i s v er y nea r ly t rue .
T he s e t urpe nt ine t it ra t i ons we re mad e w it h a
p ota s s ium i od ide - s tarch s o lut i on a s an ext erna l
ind i cat or . Thre e da ys a ft er runn ing the a b ove
ra t i o,t he t urpe nt ine s olut i on had de t er i ora te d
t o s uch a n ext e nt that n o e nd p o int c ould be
s e cur ed a ft er the add it i on of t e n t ime s a s muc h
t urpe nt ine as br omine . The r e f or e th i s meth od
wa s a band one d th ough f or one da y ' s w ork i t
w ould pr oba b ly s e rve very we l l . Seve ra l wr i t e rs
i nt o a sma l l b ot t le a nd a dd ing 25 c c o f t e t ra —
c h l or id e . Te n c ub i c c ent ime ter s of th i s s o l -
ut ion wa s t hen b r ominat e d by add ing fr om 15 t o
25 c c . br omine a s the unsa turat i on o f the samp le
de mande d . Th i s l e ft 15 c c o f the o i l s o lut i on
f or a dupl i c a t e de t e rmina t i on,s hould anyth ing
g o wr ong w i th the f i r st one .
The pr oduc t formed whe n beta -napthol and
br omine rea c t i s s upp o s ed to be a mon o-brom-
napthol . The amount of be ta -napthol p er c c wa s
de t e rmine d by s l owly evap ora t ing the t e t ra -
c hl or ide fr om 5 c c o f the s o lut i on and we igh ing
the r e s idue . An ave rage of thre e de t e rmina t i ons
wa s grams p e r c c .
C H OH 3 Br . 1 c c beta — napthol10 7c c br om i ne .
The re f ore : 1 c c Br .
O ' OO 7 X80 grams pe r144x l .34
Sub s e que nt s ta ndard iza t i on a s not e d ab ove w it h
th i os u lphat e gave grams br omine p e r c c .
Th i s me thod wa s f ound t o g ive g o od re s ult s
in min imum t ime w ith dup l i cat e s oft e n che c k ing
exa c t ly .
numbe r,wh ic h is a ls o s imp ly a re la t ive numbe r
and not abs olut e,ma y b e s ta t e d thus : 10 0
n b-
125
-
br ominat i on numbe r,whe re n i s t he number of
c ub i c c e nt ime t e rs o f br omine us ed,b i s the
br omine s tanda rd,and g the grav it y o f t he
fra c t i on . Whe re the br om ine s o lut i on i s us e d
ove r and ove r f or da ys it ma y be further s imp -
l i f ied t ok n
numbe r .
A c ompir is on of the t w o a c c e ptab le me th od s,
v iz : s ludge number a nd br omine numb er,was made
w ith the h O pe of f ind ing a c ons tant rat i o be -
t ween the m . Tab le V g ive s t he s e re s ult s,and
it w i l l be n ot ed tha t t h ough th e ma j or it y o f
the rat i os fa ll a r ound thre e,t h i s f igure i s
not suff i c ie nt ly c onst ant t o be of anyth ing l ike
a quant it at ive natur e . The rat i o fa l ls c ons id
erab l y in the t w o c a s e s marke d Run #5 and .Run ;#7
due no d oubt t o t he fa c t that the s e p r oduc t s
had not b ee n d i s t i l le d and the ta rry pr oduc t s
r ema in ing in the o i l made an abnorma l s ludge num-
be r .
in the ne ighb orh o od o f 3 0 00C . vary ing e it he r
wa y 2 0 degre e s a c c ord ing t o the s i z e and na tur e
o f t he cha rge be ing c ra cke d . As the c ra c k ing
pr ogre s se d the t e mpe rature w ould r i s e for a
c e rta in t ime and a s t he de c omp os i t i on p o int
wa s re a che d w ould d r op qu i c k ly,s ome t ime s twe nt y
degre e s or more,a nd then bui ld up aga in . It
wa s pr ove d b y w ork w ith the re flux s t i l l that
an o i l c annot be c rac ke d in th i s manne r a s l ong
a s the b o i l ing p o int o f the who le ma s s of l iquid
i s be l ow 2 7 50C . Th i s i s s hown b y the a na lyt i ca l
d i s t i lla t i on o f a l l of fra c t i on #4 5 a ft e r re flux
boi l ingj
a ppear ing in Tab le X ; _al s o_the data tab -
u l ated in Tab le XI I I a lth ough t he Oh i o o i l d id
s uffe r s ome re duc t i on in grav i ty ina smuch a s it
wa s s uch a heavy p e t r o le um . Th i s br ings up the
p o i nt,
- -wh i ch i s s imp ly an ot he r wa y of s ta t ing
the that th e heav ie r the p e t r o leum the
e a s ie r i t i s t o c ra c k .The s ummary of the wh o le
bus ine s s is t hen,that t he l ight e r p ort i ons
mus t be d i s t i l le d of f be f ore cra ck ing can be
p r oduc e d the - l ighte st fract i ons a lt hough not
ne c e s sa r i ly t he great e st p er c e nt of v o lume
c harged . The t ot a l t ime in whi ch the d i s t i l l -
a t i on wa s made p e rhap s ha s not s o much bear ing
on the pr oduc t s a s the fra c t i on o f the t ota l
t ime c onsumed be t wee n e a ch t e mpe rature . A l l
t he s e va r ia b le s a re inc lude d in the tab le s and
a n a lmos t e nd le s s d i s c us s i on of the re s ult s
c ou ld be e nt e re d int o,and a great numb e r o f
c urve s p lo tt ed o f ea ch var ia b le agains t s ome
othe r . The va lue of ma ny o f t he se w ould no
d oubt be que s t i onab l e a nd he nc e the auth or s
leave t he c los e pe rusa l of the data tab le s
t o t he reade rs ' inc l ina t i ons .
An a dd it i ona l w ord sh ould be sa i d in
rega rd t o the c o l or and od or of the d i s t i l la te s .
D is c ol ora t ionwe S pec ia l l y w ith t ime
,and bad od or
be came w ors e w i th the fra c t i ons o f h igher b o i l -
ing p o int,a nd not ne c e s sar i ly w ith thos e o f
h igh unsa tura t i on a s would be e xpe c t e d . N one
o f the d i s t i lla te s we re pur i f ie d a c c ord ing t o
t he r egular pr ogram of t he r e f iner ie s,wh i ch
but w ith out s uc c e s s,a lth ough it ma y be s e e n
fr om the c urve s that the rat i o i s p ra c t i ca l l y
c ons tant .
I t is ne ed le s s t o furthe r d i s c us s the
re sult s a s the c urve s are s e lf exp lanat or y .
C urve #2 ma y be not ed a s e s pe c ia lly go od in
b r ing ing out sha rp ly the c ra c k ing p e r i od w i th
the var i ous c hange s induc ed b y the phe nome non
in the d iver s var iab le s .
C OMMERGIAL MOT OR SP IR ITS AND GASOLENE .
RU N'
310 .
Th i s run c ons i s te d of a d i s t i l la t i on of
c omme r c ia l ga s o le ne in the tube s t i l l . A s W i l l
b e s e e n fr om the f oll ow ing da ta,the fra c t i on
wa s t o o l ight t o d raw muc h o f a c ompar i s on be -
twe en th i s a nd the c rude o i l d i s t i l la te s wh i ch
have be en de s c r ibe d in the f orego ing w ork .
One l it e r o f the ga s o le ne ( S p .gr . a t
2 00) was charge d int o the s t i l l and the fra c t i ons
obta ine d a re sh own in Tab le XV I .
pur i fy it . The rema i ning o i l i s furthe r he a te d
i n the s t i l ls unt i l a l l the lubr i c at ing fra c t i on
ha s b e e n re move d . Th i s lubr i ca t ing o i l i s the
on ly o i l on the marke t wh i c h i s hea v ie r than
wa t er . The r e s i due le ft in the s t i l l s is ch ie f -
l y c oke a nd ow ing t o the na ture o f th e or ig ina l
c harge,th i s c oke i s the pure s t ob ta ina b le and
f ind s a rea dy ma rke t .
T o summar ize the e c onomi c va lue of t h i s
pr oduc t we have only t o g lanc e a t the c urre nt
f igure s fr om the ma rke t . A fra c t i on,fue l o i l
,
wh i ch ha s b e e n p ra c t i c a l ly w orth le s s,be i ng
d i sp os e d o f at 3 ¢ p e r ga l l on,ha s be e n " c ra c ked "
w ithout any e lab orat e pr oc e s s,and t he re s ult ing
fra c t i on is now put on the marke t at 2¢ le s s
p e r ga l l on than the marke t pr i c e o f ga s o lene .
TABLE V .
F ra ct i on : Grav ity : S l udge N 0 . : Br omine No .
31 0 3 8 p er zAdd it ion p er10 0 c c . . 310 0 cc .
fOh i o 0 11
34 7 3 6 E
3 7 84 2
3 8 83 9
3 9 g.87 l
4 0 2 . 7 4 9
4 1 825
4 2 8 64 3
C rude . 8 94 3
Run. #5 f
.8 94
Run #7 E. 888 x
E. 7 19
E. 7 84
8 5 2
Kansa s O i l
TABLE V I I .
RU N #1 .
D IST ILLAT I ON .
C opp e r s t i l l Empt y Enlarge d head . 14 2 0 c c .
Fra c t — T ime % T ota l T e mp . Sp .Gr . Vo l . Vol .
i on No . t ime . Ch'
ged .
l 4 30 0 2 7 3 0 0 . 84 6 15 0
2,3 5 0 3 28 . 83 9
‘
6 3 0
4 23 33 5 .834 3 6 0
l et REDIST ILLAT I ON . Same §t i i i .
27 15 0 . 7 34 7 5
5 0 3 0 0 .82 0 4 3 0
2 5 3 3 0 .8 6 1 23 0
2nd RED IST ILLAT I ON .
5 3 15 0 . 7 4 6
3 8 3 0 0 .838
9 3 2 5 .8 5 9
D i s t i l lat i on s tart ed T ota l t ime 13 0 mins .
Re s idue - -none . Los s =28 0 0 0 =2 0%
1st Red i s t i l la t i on s tart ed T ota l t ime 4 0
m ins ; T ota l charge 1 14 0 ;
2nd Red i s t i l la t i on s tart ed T ot a l t ime 12 0
mins . T ota l c harge 7 3 0 ; Re s idueinc lude d )
Same St i l l
5 5
2 6 0
8 0'
TABLE IX .
D I ST ILLAT ION .
C oppe r St i l l . Empt y e nlarged head .
Fra c : :% T ot :No :T ime :T ime :T e m
E?
S 81 .
288 7 8 . 3 0 0 . 83 7 17 0
2 9'
l 2 : 16 5 . 3 3 0 . 8 54 425
3 0 17 . 3 5 0 .843 7 15
Sta rt ed T ot a l t ime 16 0 m ins a ; T ota l c harge - -
15 0 0 ; Re s idue- - l Oc c or L os s - - l 8 0 0 0 or
l st RED IST ILLAT I ON .
3 1 15 0 . 7 24 10 6
3 2 3 0 0 .822 3 85
3 3 3 0 . 3 90 .8 6 5 6 2 0
Sta rt e d T ota l t ime 17 0 m ins . ; T ota l charge - -
13 0 0 0 0 ; Re s idue 120 0 0 or 9 . 25z; Los s - -6 0 0 0 or
Br .
34 15 0 . 7 3 6 12 0
3 5 3 7 . 3 0 0 .82 6 44 5
3 6 3 7 5 . 8 7 0 43 0
!S ludge me th od changed he re fr om 2 0 0 0 o i l and 4 0 0
a c id t o l Oc c o i l and 10 0 0 a c id .
Start e d T ota l t ime 13 0 mins . ; T ota l cha rge — —
10 4 5 0 0 ; Re s idue - - 25 0 0 or L os s - — 2 5 o c or
TABLE XI I I .
REFLUX WORK .
RU N #2 .
oCharge 7 4 0 0 0 ; T ime 13 0 mins . Max .T emp . 15 5 L os s — -
90 0 0 or
ANALYT I CAL D IST ILLAT I ON .
D i s t .
No . T emp . S .Gr . Vo l . Vol . 8 1 . Br .
13 17 5 . 7 7 4 4 0
14 2 5 0 0 824 80 10 0 0
15 3 25 .86 1 190
Vo l . c ha rged 6 4 5 c c ; Re s idue - -285 or L os s - -
5 0 0 0 or 7 . N o t empe ra ture unde r
Charge - - 10 0 0 0 0 . Max .T emp . 220 .Leaky s t i l l .
. l oo.
--10 0 0 c c . . 2 7 5 .
T e mp . Sp .Gr . S l . Br . N
. 894 915 3 1 .
Cha rge 10 0 0 0 0 ; T ime 10 5 mins . ; Max . T emp . 280 .
ANALY S IS OF ENT I RE RUN .
Sp .Gr . Br . S ludge N2 5
. 888 17
ANAL XT ICAL D IST ILLAT I ON .
( a b out 20 0 0 over be twe e n 15 0 and 2 5 0
No . T emp . Sp .Gr . Vo l . Vo l . Br . N
4 7 3 0 0 . 8 54 3 6 0 3 6 .
48 Re s idue 48 0 4 8 . L os s o f 12%
RUN #5
T ime 85 mins .
it 25H
:IH4 2
H
Bol . V ol .
TABLE xv .
RUN #9
3 0 0 0 0 0 . Kansa s,Wr ought ir on s t i l l .
1 10 0. 7 0 4 23
212 0
3 13 5. 7 34 12 0
4 15 0 . 7 5 3 825 164
. 7 64 7 86 17 7
. 7 7 6 7 87 18 5
. 7 7 7 7 48 196
. 7 91 4 09 2 0 5
. 7 98 4 910 22 1
.s99 7 411 23 5
. 813 8 712
5 213
2914 2 5 2
.823 2415 2 5 9
. 82 6 4816 2 6 2
.82 9 3 217 27 0
. 83 1 4 018 2 7 2
.83 2 2 619 4 : 5 5 282
.83 5 6 120 28 9
. 83 9 5 02 1 292
. 83 9 4 022 3 0 5
. 83 5 5 023 3 19
. 848 10 624 3 2 1
.84 6 9225 3 20
. 83 3 13 02 6 3 20
. 83 6 9 02 7 3 12
. 83 1 11028 3 0 5
. 818 8 029 3 0 6
. 80 6 6 53 0 3 10
. 80 8 5 83 1 3 0 2
.80 3 4 05 2 3 0 3
.80 0 2933 3 13
. 80 7 5 5
Re s idue 5 10 0 0 .
Los s 3 5 0 c c .
