Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923
Transcript of Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923
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December,
1923 I N D U S T R I A L
A N D
E N G I N E E R I N G C H E M I S T R Y 1233
T h e Lubricant and Asphaltic Hydrocarbons in Petroleum'
By Charles F.Mabery
CASE SCHOOL OF
APPLIED
CIENCE, CLEVWLAND, OHIO
ALTHOUGH
ime hasbeendevotedu c h
in this laboratory to
the composition of the dis-
tillable hydrocarbons in
petroleum, no attention has
hitherto been given here and
little elsewhere to t he iden-
tification of the hydrocar-
bons th at cannot be distilled
without decomposition. Of
the fe w .attempts to sepa-
rate these constituents of
petroleum by cold solution
and precipitation, cold
fractionation, the most
noteworthy is th e work of
Charitschoff, who described
the following hydrocarbons
with the ir specific grav-
ity: C19H38 0.8930;
C~ O,
0.9050;
CzzHa,
0.9080;
C24H.16, 0.9130; C35Hm1
0.9150;
and
it
has doubt-
less suggested the frequent
allusions to the presence of
naDhthene lubricants in
This work. is a s tudy of the hydrocarbons in petroleum which
cannot be dis t i l led without decomposi tion. The method used fo r
their separat ion w as fract ion al solut ion in a hot mixture of ether
an d alcohol , af ter f irs t d is t i l l ing the crude oi l to
300 C
f i r s t s ep -
arating the homologs of each series and then dividing the series into
fract io ns. Identif icat ion of the hydrocarbons wa s then accomplished
by determina tion of specif ic gravi ty , molecular weight , and percentage
compos i t ion .
Th is me thod o f separa t ion and ana lys i s was app l i ed to f i ve
c ru de o i l s, f r o m W e s t V i r g i n i a , P e n n s y lv a n i a , Oh i o , T e x a s , a n d
Ru ssi a . The Ohio oi l being one of peculiar composi t ion, a s tudy
of
its distillable constituents as well
as
of i ts fract ion s separated
by solution is given. Th e homologs of the heavier series above300 C
vacuum appear to increase regularly and are divided into 1 ) the D
hydrocarbons, lubricants to the f inal heavy ends, and
( 2 )
the H
group, asphalt ic in tbe heauy ends.
A
comparison of the various
oi l s
shows a well-defined distinction between the lubricant and the
asphaltic hydrocarbons, and the higher specific gravity of the Texas
and Russian lubricant hydrocarbons is due to their inherent s truc-
ture. The wide variat ion in specif ic gravi ty of individual fract ions
of the heavy crudes indicates the presence of carboxyl acid s or ester s.
Iodine number determina tions show that only the r ing fo rm of un -
saturat ion applies to the lubricant hydrocarbons, and they do not
appea r to enter into the form ali te react ion as app lied by the M ar -
cusson method.
from the Appalachian oils,
the solid residue was dis-
solved in ether to a dilute
solution, alcohol added until
the paraffin began to partic-
ipate flocculent, the solution
cooled to
0
C., filtered cold,
again cooled to
-20'
C.,
and again filtered, with very
little paraffin remaining in
the oil after the first filtra-
tion. There is some diffi-
culty in reaching the point
where flocculent precipita-
tion begins without carry-
ing down a large amount
of the semisolidified oil,
HOMOLOGEPARATION
In lots of
1000 t o
1500
grams the vacuum residue,
free from paraffin, was
heated to the boiling point
of the solvent in flat, cork-
stoppered bottles in a hot
water bath with frequent
shaking, the stopper being
held in with the finger and
G e r i c a n petroleum. However, none of the hydrocarbons
from Baku oil, described i n this paper, contain the series
CnH2n,
or the CnHzn--2 although some of these specific gravi-
ties are about the same as those of the series
C,Hz,-8
in
Baku oil, to be described later, and none of the varieties
ofkAmericanpetroleum have shown such composition.
Since petroleum hydrocarbons begin to decompose in dis-
tillation a t about
200
c., nd above 300'
c.
most crude oils,
even under pressures reduced to 20 mm., show evidence of
decomposition, i t is impossible t o separate the constituents of
petroloum by any form of distillation tha t will not distil a t
300
C. vacuum.
SEPARATION
Y FRACTIONAL
OLUTION
With the exclusion of distillation th e only remaining possi-
bility appeared to be frac tional solution, and, in view of the
variations in othe r physical constants, there seemed to be no
reason why the different series and homologs should not
possess sufficient differences in solubility to permit their
approximate separat ion in this manner. Tria l of the various
solvents excluded all but a mixture of e ther and ethy l alcohol,
and since all the constituents of petroleum dissolve freely
in ether, but are qu ite insoluble in alcohol, it seemed possible
to prepare from them a convenient solvent. For general
use a mixture of equal pa rts by volume, with suitable varia-
tions for the more soluble lighter ends, and the less soluble
constih ents of th e heavier ends proved efficient for all the
varietEes of crude oil.
For convenience of reference, the
lighter. fractions will be referred to as the higher or upper
ends, and tthe heavier as the lower ends of the series or
group.
Under a pressure of 30 mm. the crude oil was first distilled
to
300
C. For the removal of the paraffin hydrocarbons
Received
December
4,
1922.
frequent ly removed to relieve excessive pressure. For col-
lection of t he homologs of all the series into tenor fifteengroups,
the hot solution was poured off from each extraction and the
solvent distilled, the first fractions containing the more soluble
upper end, and the diminishing solubility giving the consecu-
tive fractions down to thel ast residue.
For fu rthe r separation
of the series homologs, th e lowest group was first heated with
the solvent of proper concentration, sufficient to dissolve a
considerable part, and the hot solution poured off cooled,
and again poured off from the separated oil. T o this was
added the next fraction, which was again heated, and the
solution poured off for the treatment of the next fraction.
This procedure was continued to the upper end. The sol-
vent distilled off from the last treatment gave the first
member of the group, and this procedure was repeated six
times. Since the specific gravities of the fifth an ds ix th
fractions were approximately the same, it was assumed that
the homologs of all the series were fair ly well collected within
the respective groups. The efficiency of this method appeared
in the differences in consistency between the lowest frac-
tions, extremely thick, viscous, or nearly solid lubricants,
as in the Appalachian oils, or thick, black, tarry o r solid as-
phalts, as in the Texas and Russian oils, and the upper
fractions, thin, amber-colored lubricants.
SERIES
BPARATION-Beginning a t the lower end of the
group each fraction was about half dissolved in rich, hot
solvent, decanted, leaving a residual oil,
H ,
the solvent dis-
tilled, giving another residual oil
D ,
and this was continued
with all the fractions to the upper end.
To be sure that a
single extraction gave an approximate separation, it was
followed by another similar treatment, giving two series, Da
and Dh. The specific gravities of a and h proved to be suffi-
ciently concordant to indicate a fairly satisfactory separation
by the first treatment.
~
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In a second mode of series separation each of the first group
fractions was heated to boiling with the solvent, the hot
solution decanted, cooled, again poured off from the separated
oil and distilled, giving three oils-H, the first residue; C,
th e residue from cooling; and
D ,
the residue from the distilled
solvent. Each of these oils was again treated in a similar
manner, and this treatment continued three or four times,
thus dividing the original oils into eight or twelve fractions,
did not materially change the specific gravity from the results
of a single cross separation, from which it was inferred that
the marked difference in solubility gave
a
fairly good sep-
aration in the first extraction. The following examples of
it s applica tion on some of t he oils as a means of control show
the rapid separation by this method. A top fraction of a
Russian vacuum residue containing more soluble, heavier
carboxyl constituents brought up from below, and another
from the Rosenbury oil, were separated by a single extraction
into light and heavier constituents, as follows:
0.9594
H residue hot
0.9198 C esidue'solvcnt cooled
0.8925
D residue: solvent distilled
0.9230 H
0.8908
C
0.8875:
Russian fraction, specific
Rosenbury (Pa specific
gravity 0.9236
gravity
0.90i-i
1
No
doubt the petroleum hydrocarbons under the condition
of cold solution used by Charitschoff do exert
a
mutual sol-
ubility and interfere with the use of specific gravity
as
means of identification, but under the influence of a hot solvent
it
seems to be quite otherwise.
The constants relied upon for grouping and identification
were specific gravity, molecular weight, and composition by
analysis. Determinations of specific gravity, except of the
most viscous tars, which were weighed under water by the
method of Kirschbraun, were made in a Sprengel pycnometer
a t
20
C.
In the beginning, molecular weights, especially of t he heavy
hydrocarbons, gave much trouble. Of the common solvents
benzene alone a t the boiling point was applicable, and this
was reliable only with the lower members of the Appalachian
oils. Stearic acid a t 50 C. proved to be more satisfactory.
A
weight of oil from 0.3 to
1.5
grams, depending upon the
specific gravity of the oil, gave a depression of from
0.150
t o
0.400 C. on the Beckman scale. The limitations of the
method and the accuracy required for concordant readings
are shown by the fact that for molecular weights above 1000,
a depression of 0.001
C.
corresponds to nearly
a
difference of
the increment, CH2,but below
500
to a difference of only
2
to 4
units. Occasionally, stearic acid gives abnormally high read-
ings, doubtless caused by irregularity in the initial separation
of crystals, which resisted all at tempts toward correction by
variation in stirring
or
other manipulation; but several, usu-
ally not more than three repetitions, readily revealed by con-
cordant values, could be relied upon for the desired results.
In the extremely high values, 1600
or
more, that define the hy-
drocarbons with the largest molecular weights, the observa-
tions were as closely concordant
as
with the oils having a mo-
lecular weight of 300. The commercial acid dried a t 100 C. is
sufficiently pure; different lots showed small variations in
th e constant-for example, (1) 4.431, (2) 4.467; Bernstein
gives for this constant, 4.5. Particular attention was neces-
sary in getting complete solution of the heavy oils, and these
required large weights for sufficient depression.
To yield the small differences in percentages of carbon and
hydrogen necessary to distinguish between the different
series, the gases from the asphaltic oils require the highest
temperature for complete combustion t hat the most infusible
glass will stand wi th
a
stream of oxygen on the copper oxide
in front of the oil. Much time was saved by weighing the
bulbs filled with oxygen. Although a 50 per cent solution of
potassium hydroxide was used, with solid potassium hydrox-
ide or soda lime and phosphorous pentoxide in the safe
tube of the Geissler bulb, a horizontal tube in front with so
lime and phosphorous pentoxide invariably showed fro
0.0005 to 0.0020 gram increase in weight, sufficient, if lo
to spoil th e analysis.
VARIETIES
F PETROLEUM
NVESTIQATE
General application of the method herein described to th
petroleum fields of th e world should doubtless involve th
study of more than one hundred representativc varietie
In this paper is included the separation of the constitue
hydrocarbons from the following five typical crude oils:
TABLE
Cabin Creek, W. Va.
1st sample
1700
0.8100 25
8683
2nd sample
1700 0.7850 20 8638
Rosenbury, Emblen-
ton, Pa. Rosenburysandoose sand
1240 0.5080 35 8852
150 0.9023 80 9076
ecca, Ohio
Loose sand
2000 0.9333 40 9580
our Lake, Texas
Baku,
Russfa
Loose sand Shallow
0.8650 35 9270
Lowest Berea grit
The Cabin Creek and Rosenbury oils are regarded as th
best varieties of Appalachian petroleum, and known in th
trade as paraffin-base oils. They contain large proportio
of the gasoline, kerosene, and solid paraffin hydrocarbon
leaving residues solid wit& paraffin at 300 C., 30 mm. Au
thentic specimens of these oils, pale yellow in color, were pro
cured for this examination from 0. C. Dunn, Marietta, Ohi
The Sour Lake oil, procured from
a
reliable source, is
typical heavy Southern crude, containing no CnHm+
hydrocarbons; the crystalline hydrocarbons occasionally o
served in some distillates are probably of a heavier serie
That the less volatile portions of the Texas oils are compose
to a large extent of t he bes t lubricant hydrocarbons cann
be doubted, and while the balance of t he Nor thern crude
are of the lighter series, a large proportion in th e basic South
ern crudes are of the so-called asphaltic hydrocarbons whic
impart high viscosity to the lubricants containing them
How
far t he higher specific gravity and viscosity indicat
superior lubricant quality depends, of course, on the inheren
wearing quality of the asphaltic hydrocarbons, and this ha
never been precisely defined. I n the early development o
Texas oil territory
it
was the synonym for high sulfur petro
leum. Intimately associated with beds of sulfur, the
sulfu
was dissolved t o t he limit of satura tion, and the resultin
chemical changes eliminated hydrogen as hydrogen sulfid
with the formation of the heavy hydrocarbons. In the for
mation of such heavy crudes as the Sour Lake, evidentl
sulfur has
been B determining element. With continue
production the original proportions of sulfur in these oil
1
to
3
per cent, have been greatly reduced.
The Russian oil is a par t of two barrels brought for th
author's
use twenty-five years ago from Baku. It is les
stable than American oils and care
is
necessary to avoid de
composition, even under reduced pressure. Like all Russia
crudes, the distillable portion is composed of the naphthen
hydrocarbons that make superior luminants, and the remain
der has
a
smaller proportion of lubricants tha n America
petroleum, but considerable asphaltic constituents. Th
great body of the midcontinental fields yields oils with mixe
Constituents; they are usually referred to as oils with
a
mixe
base, paraffin and asphaltic, and the lubricants made Jrom
them possess a peculiar composition and quality quite differ
ent from those of the Appalachian o r the Southern crudes
From the general composition of these varieties of petroleum
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I N D U X T R I A L A N D E N G I N EE R I N G C H E M I S T R Y
1235
Fraction
c.
120-121
130-131
138-141
160-152
168-170
182-184
194-196
213-214
237-238
244-246
Specific
Gravity
0.8600
0.8631
0.8648
0.8692
0.8696
0.8722
0.8730
0.8750
0.8834
0.8840
0.8837
0.8847
TABLE
1-DISTILLABLE
C H
Mol.
Wt. %
%
--DBTERMINATIONS-
177
190
204
21s
226
244
258
270
334
348
86.61
86 .67
86 .62
87.10
86.87
87.08
86 .95
8 6 . 9 0
86.65
86.73
13.26
13 .23
13 .33
12.75
12 .85
12.82
13 .12
12 .95
13 .24
13.21
Light Hydrocarbc
343 86.62 13.25
389 86.7 0 13.2 5
CONSTITUENTS
O F
ME CCA STROLEUM
-RBQU_IRSD--
- ,
Hydrocarbon
Mol.
Wt.
c
%
86.66
86 .60
86.54
87.28
87.18
87.10
87.03
86.96
86.75
346 86.70
m s rom
Mecca Vacuum esidue
180
194
208
220
234
248
262
276
332
n
%
13.34
13.40
13.46
12 .72
12 .82
1 2 . 9 0
12.97
13.04
13.25
13.30
they seemed especially well adapted for this investigation,
as representing the principal fields.
Mecca petroleum, specific gravity 0.9023, known as a
natural lubricant since the beginning of the petroleum indus-
try, is typical of occasionally occurring small pockets or sec-
tions a t shallow depths where the original oil has been par-
tially refined by natural agencies, leaving only hydrocarbons
with large molecular weights, containing no gasoline, kerosene,
or paraffin hydrocarbons and a very small amount of the
asphaltic hydrocarbons, All but
12
per cent of the lighter end
form the best lubricants.
DISTILLABLEONSTITUENTSF MECCA ETROLEUM
On account of its peculiar composition, and since there is
an opportunity, for the first time, to give
a
description of the
undecomposed hydrocarbons in a crude oil from beginning
to end, it seemed of interest to make the separation of Mecca
oil complete from th e first distillate. The lower constituents
were, therefore, separated by several distillations in
VUCUO
refined, and the values obtained for specific gravity, molec-
ular weight, and percentage composition are given in Table
11. The peculiar disagreeable odor of some of the distillates
indicates that the crude oil is not so far removed from its
original organic source as the Appalachian oils.
These determinations of refractive index increase with
increase in specific gravity and in molecular weight the op-
posite of the hydrocarbons in the Appalachian oils, and, as
will appear later, even in the Mecca hydrocarbons of higher
molecular weight in the vacuum residue. The distillate
244 to 246
C.,
specific gravity 0.8840, treated as in the
separation of the
D
and H series, gave a D hydrocarbon,
specific gravity 0.8850, refractive index 1.4865;and an
H
hy-
drocai*bon, specific gravity 0.8835, a lower refractive index,
1.4765, both indicating more than one series,
as
in the higher
hydrocarbons. Some of the Mecca vacuum residue that can
be distilled at 300 to 320 O C. without decomposition, and
th at has been refined for use as a lubricant on fine watch and
clock bearings, was separa ted by the solvent into the following
fractions
Specific Index
of
Fraction Gravity Refraction
1-0 0.8837
1.4 835 The molecular weight and analysisgave
1-H 0.8780 1.4 805 the following formulas for the
D
group,
2-0 0.8789
1.4 815 indicating the series CnHzn-i:
2-H 0. 87 10 1.4 765 CziHaa
3-0 0. 87 05 1. 48 15 CZZH40
3-H 0. 86 82 1. 47 55 Ci4H44
4-0
0. 87 45 1. 47 85 CzrH4s
4-
H
0. 86 80 1.4 760 CisHrx
5 0
0.8750
. . . .
,
These hydrocarbons form the connecting link in the series
between those that can and those that cannot be distilled.
The dat a of this examination indicate more than one series.
S ~ R I E BKD HOMOLOQ
YDROCARBONSN
PETROLEUM
Investigations carried on in this laboratory and elsewhere
have shown that petroleum is chiefly composed in variable
proportions of the series CnHzn + f gasoline, kerosene, and
ClkH4e
348 86.70 13.30
CzaHrz
388 86.60 13.40
Refractive
Series Index
CnHzn-2 1.4605
CnHzn-
2
1.4625
CnHzn-2 1,4650
CnHzn-4 1.4665
CnHzn-4 1.4715
CnHan-i 1.4710
CnHPn-4 1.4726
CnHzn-r 1.4750
CnHzn-4 1,4785
CnHzn-4 1.4815
CnHm-r
CnHzn-i
paraffin hydrocarbons; the series CnHzs - , the light lu-
bricants, especially
of
Appalachian petroleum; the series
C.HZn-
and
CnH2,-
8, the heavier lubricants, the
aromatic derivatives of benzene; and heavier series still
poorer in hydrogen to CnHPr- 20 t,han appear in this paper
are reported as present in European petroleum. The homo-
logs of the heavier series above 300 C.
vacuo
appear to in-
crease in regular increments similar to the distillable series-
the D hydrocarbons, lubricants to t he final heavy ends, except
in the asphaltic crudes, and the H hydrocarbons, asphaltic
in the heavy ends-in all except the Appalachian petroleum.
In the upper ends of the series first separated of all the oils
examined, the specific gravity of the fractions increased very
materially, some even higher than those of the lower ends.
This was found to be caused by carboxylic acids or ethers
more soluble than the hydrocarbons themselves. By further
treatment of the upper fractions, the soluble oils were re-
moved, leaving the hydrocarbons in Table
111.
The first
ten to fifteen D and
H
homologs separated in each crude oil
were given two or more extractions and collected in t he
smaller groups presented in this table. Much time was lost in
this work before it was learned that the crude oils contained
more than one series
of
lubricants, and tha t the series as well
as the individual homologs differed materially in solubility.
While the formulas and series represent the definite compo-
sition of the fractions separated, it should require the manip-
ulation of much larger quantities
of
the crude oils thanis
possible in the ordinary chemical laboratory, and, as in frac-
tional distillation,
a
greatly prolonged treatment to isolate
with closer approximation the individual hydrocarbons.
To avoid serious loss in watch-glass transference, the fractions
were kept in bottles saturated with the solvent and small lots
were dried at 120 O C. for examination.
For the purpose of showing a t
a
glance the consistency of
the hydrocarbons described in the preceding table as they
appear spread out on watch glasses, in Table
I V
is given a
brief description of the first and last members
of
each series
from all the crude oils.
In the destructive distillation of Appalachian petroleum
by the common method of refining, the most valuable lubri-
cants of the heavy ends, such as the last D and H fractions in
the Cabin Creek, Rosenbury, and Mecca (Table 111), the best
lubricants in any petroleum, are lost in coking. This is of
less consequence in the asphaltic oils, for the lubricants in
these crudes are for the most part carried over in the steam
distillates, leaving only asphaltic residues.
On account of the less solubiliky of the lower members of
each series and the separation of homologs in only one direc-
tion,
it
was possible to remove very completely the higher
homologs, and, therefore, to obtain data for the calculation
of the formulas of the lowest residual hydrocarbons as re-
liable as the methods of definition are capable of yielding.
These last hydrocarbons were, therefore, carefully purified for
the comparison of physical properties an d lubricant value.
Those from the heavier oils have the intensified qualities of
the commercial asphalts; black in color, they may be drawn
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I N D U S T R I A L A N D E N G I NE E R IN G C H E M I S T R Y
Vol. 15,
No.
TABLE
11
r __ALCULATED---
FORMULA
Mol. Wt. Per
cent Per cent
H REIIRACTIV
SERIES INDEX
Cabin Creek
_. DETE_RMINED-----
H
PECIFIC
GRAVITY
c
Per cent
RACTION
Mol. Wt.
Per cent
D Series
1
2
3
0.8755
0.8764
0.8815
0.8882
0.8829
0.8832
0,8835
0.8855
309
327
428
452
488
585
717
803
86.76
86.76
86.56
86.45
86.32
86.35
86.10
86.27
13.21
13.18
13.34
13.44
13.48
13.59
13.79
13.73
12.70
12.64
12.86
13.51
13.22
13.42
13.43
13.40
13.24
13.39
13.71
12.85
13.16
13.25
13.30
13.29
13.37
13.52
13.28
13.35
12.61
12.70
13.10
13.20
13.22
13.50
13.47
13.42
12.37
12.48
12.82
12.76
12.73
12.75
12.56
11.91
11.81
12.15
12.30
13.32
13.18
12.05
12.45
12.35
12.25
12 25
12.24
12.35
12.27
12.53
11.93
12.53
13.03
12.68
11.96
12.01
12.53
12.60
12.66
13.21
13.30
12.68
C22H4O
304 86.84 13.16
CnHzn-4
1.4920
C24H44
332 86.75
13.25 CnHzn-4 . . . .
CaiHss
430 86.50
13.50
CnHzn-4
. . . .
C83H62
458 86.46
13.54
CnHan-4 . . . .
CssHe6
486 86.42
13.58
CnHzn-4
....
CaHso
584 86.30
13.70 CnHzn-4
. . . .
CszHioo
724 86.20
13.80
CnHzn-4
1.4880
CS3H112
808 86.14 13.86
CnHzn-4
1.4810
CaaHsa
454 87.22
12.78
CnHzn-
1.4880
CS4H60
468 87.20
12.80
CnHzn- I . . . .
C36H64
496 87.10
12.90 CnHzn-a . . . .
C46H8P
636 86.79
13.21
CnHzn-
8
. . . .
CasHioa 762 86.60 13.40 CnHzn-
s
. . . .
4H100
748 86.64
13.36
CnHzn-
1.4870
CizzHzsa
1700
86.32
13.68
CnHzn-la
1.4810
4
5
6
7
8
eries
1
2
3
0.8721
0.8725
0.8729
0,8819
0.8863
0,8873
0,9063
459
476
490
635
87.21
87.20
87.02
86.52
86.72
86.72
86.50
4
5
6
7
D
Series
760
769
1696
Rosenbury
0.8796
0.8816
0.8822
0.8836
384
438
481
518
86.13
86.68
86.42
86.15
CzaHsn
388 86.60
13.40 CnHzn- a
1.4930
C8ZH60
444 86.48
13.52 CnHzn-
1.4890
Cs7H7o
514 86.38
13.62 CnHzn-
1.4880
C3SH66
486 86.42 13.58
CnHnn-
8
2
3
4
Series
1
2
3
4
5
6
7
8
9
0.8742
0.876.5
0.8812
0,8850
0.8848
0.8865
0.8950
0,8998
0.9079
549
87.08
86.78
86.65
86.60
86.59
86.63
86.49
86.69
86.58
552
622
636
664
720
804
832
954
1734
86.96
86.82
86.78
86.74
86.68
86.56
86.54
86.80
86.50
13.04
13,18
13.22
13.26
13.32
13.44
13 46
13.20
13.50
CnHzn-a
CnHzn- s
CnHzn-
CnHzn-a
CnHzn- s
CnHzn-
s
CnHzn-
CnHzn-iznHzn- 16
1.4920
....
. . . .
. . . .
. . . .
1.4870
1.4870
. . . .
. . . .
6 i 5
639
666
727
805
830
980
1730
Mecca
D Series
1
2
3
4
5
6
7
8
H
eries
1
2
3
0.8945
0.8950
0.8960
0.8962
0,8966
0.8982
0,.8998
0.9171
465
500
631
662
728
770
832
1080
87.37
87.13
86.87
86.60
86.62
86.41
86.45
86.68
468
496
636
664
734
776
832
1084
87.20
87.10
86.78
86.75
86.66
86.60
86.54
86.34
12.80
12.90
13.22
13.25
13.34
13.40
13.46
13.66
CnHm- 8
CnHzn-
CnHzn- 8
CnHzn-
s
CnHzn-
s
CnHzn-s
CnHzn-
a
CnHzn-
CnHzn-12
CnHzn-iz
CnHzn-iz
CnHzn-a
CnHzn- 12
CnHzn-la
CnHzn-zo
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
....
. . . .
. . . .
....
....
0.9058
0.9072
0.9018
0 9022
0.9052
0.9065
0.9600
477
550
684
725
823
992
1662
87.65
87,57
87.06
87.16
87.12
87.22
87.34
478
548
688
688
828
992
1668
87.87
87.59
87.21
87.16
86.96
87.10
87.23
12.13
12.41
12.79
12.76
13.04
12.90
12.77
4
5
6
7
S o u r L a k e , T e x a s
0.9408
0.9467
0.9482
0.9535
0.9595
0.9643
450
462
503
531
554
849
87.93
88,09
87.82
87.58
87.62
86.80
450
464
506
534
562
856
88.00
87.93
87.74
87.64
87.54
86.92
12.08
12.07
12.26
12.36
12.46
13.08
CnHzn- 12
CnHzn-in
CnHm-la
CnHzn-ia
CnHzn-12
CnHm-iz
CnHzn-is
CnHan-16
CnHzn-16
CnHan-1s
CnHzn-zo
CnHzn-zo
CnHzn-no
CnHan-80
1.4980
. . . .
1.4960
1.4940
1.4970
. . . .
600
632
684
712
785
848
988
1240
88.12
87.62
87.72
87.64
87.88
87.74
87.45
87.98
12.00
12.38
12.28
12.36
12.12
12.26
12.55
12.02
0.9470
0.9497
0.9559
0.9643
0.9700
0.9714
0.9720
1.0230
602
630
680
716
792
854
98
1239
87.90
87.60
87.55
87.58
87.66
87.50
87.65
87.60
. . . .
1,4940
. . . .
. . . .
B a k u , R u s s i a
D
Series
308 88.05 11.95
CnHzn-lo
1.4920
396 87.88 12.12 CnHzn-io
494 87.47 12.53
CnHzn-io
. . . .
634 87.06 12.94
CnHzn-io
. . . .
1026 86.55 13.45
CnHzn-io
. . . .
0,9186
0.9251
0,9254
0.9262
0.9288
381
402
494
640
1022
300
334
378
420
460
661
847
1098
87.42
87.75
87.46
86.91
87.29
1
2
3
4
5
H
Series
1
2
3
4
5
6
7
8
0.9025
0.9160
0.9167
0.9150
0.9162
0,9242
0.9360
0.9402
87.95
87.98
87.36
87.28
87.29
86.72
86.63
98.31
300 88.00
12.00
CnHzn- s , . . .
328 87.80 12.20 CnHzn-a . .
384 87.50 12.50
CnHzn- s
. . . .
426 87.32 12.68
CnHzn- . . . .
454 87.22 12.78
CnHzn- s
. . . .
664 86.75
13.25
CnHzn- s . . . .
846 86.52 13.48
CnHzn-
8
. . . .
1100
87.28 12,72
CnHm-zo
1,4910
out to a considerable length in very fine threads, and possess
great adhesiveness. The residual lubricants from th e Ap-
palachian crudes, amber in color, greasy in feel, and of high
viscosity, differ in appearance from the gray basic stocks of
th e midcontinental lubricants, which are doubtless to some
extent mixtures with asphaltic bases.
On account of the limits of accuracy in the determinations
of molecular weights mentioned above, the fractions with
higher values, such as the Rosenbury fraction CI25H2 4,may
be incorrect by one or more increments CH2, but by the de-
terminations upon which it is based
it
must have a high value,
for the fraction
9-H,
specific gravity
0.8933,
gave in two
molecular weight determinations (1) 1722, (2) 1718; furth
fractioned with specific gravity 0.8943 it gave 1728; and sti
further fractioned with specific gravity 0.9079
it
gave 173
There appears, therefore,
t o
be no doubt as to it s high mole
ular composition.
So
d s o the molecular weight
1696
o
the Cabin Creek 7-27 fraction, specific gravity 0.9063, wit
the next largest value, appears t o be correct, since it wa
separated from both specimens of t he crude oil which gav
fractions with the molecular weights (1) 1685, (2) 1690, an
with analysis corresponding to the formula
C123H232
There
fore, with methane as the first gaseous hydrocarbon an
pentane as the
first
liquid, under ordinary pressure, passin
-
8/10/2019 Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923
5/6
December, 1923
I N D U S T R I A L A N D E NG I N E E RI N G C H E M I S T R Y
1237
TABLE V-CONSISTENCY
OF D AND H
CABINCREEK ROSENBURY MECCA
D Ser i es
1)
Ligh?amber;f ine,l ight
1)
Light amber: fine
(1)
Light amber;
fine
lubricant light lubricant lubricant
(8) Dark. amber; flows (8) Dark amber: thick
7)
Dark amber: thick
readily; heavy lubri- flow; heavy lubricant flow: heavy lubricant
cant
H
S e r i e s
(1)
Light amber; like
1-D
(1) Thi n flow; light lubri-
(1) Light amb er; thicker
cant than Cabin Creek and
8 )
Dark amber; thick, (8) Dark amber:
slow
flow
(7)
Black, sticky, tarry oil
Rcsenbury
solid
HYDROCARBONS
SOUR AKS
1)
Dark amber: just
1)
(7) Black, sticky ta r; no
8)
flows; good lubr ican t
lubricant
(1) Dark amber: just 1)
flows; good lubricant
8)
Black,
asphalt
brittle, solid
R
u
A
N
Dark
amber: slow
flow; good lubricant
Black, sticky, asphalt,
oil;
no
lubricant
Dark amber: thick
flow;
heavy lubricant
Thick, black asphalt
011
through the several series of light and heavy liquids, through
viscous lubricants and solid paraffin, the final lower end is
reached in these oils, so viscous they will not flow a t common
temperatures, the heaviest lubricant hydrocarbons in Appa-
lachian petroleum.
Although the Mecca
H
group is composed in general of
much heavier hydrocarbons than those from the Appalachian
oils, the lubricants in the lower end of its series are not very
different from the others. The last H hydrocarbon, ClzzHz~,
specific gravity 0.9600,
is
not a lubricant but an asphalt. The
last D hydrocarbon,
Cr8H148
specific gravity 0.9171, is a true
lubricant, viscosity 5461 seconds; and the last Rosenbury,
9-H,
specific gravity 0.9079, viscosity 5248 seconds, water
standard 2.4 seconds at
50' C.,
probably the highest viscosity
of any petroleum hydrocarbons, not only indicates tha t lower
specific gravity is characteristic of the best lubricants, but
it
defines the difference in lubricant quality between the
hydrocarbons of the Appalachian and those of the heavy
asphaltic crude oils, with the higher specific gravity of the
latter. Furthermore , this Mecca asphaltic oil, 7-H, has
nearly the same high specific gravity, 0.9600, as the Sour
Lake
D
asphaltic oil, specific gravity 0.9643, which resembles
all the others with which
it
is associated, except the higher
homologs, which are lubricants. The las t Sour Lake oil,
H, specific gravity 1.0230, C ~ O H I ~ O ,s a brittle asphalt, for
which no lubricant quality can be claimed.
The predominating asphaltic nature of the Baku oil is
equall-ywell defined, although with smaller values in specific
gravity than the Sour Lake. The last
H
hydrocarbon is a
black, sticky asphalt, a little higher in viscosity than the
Sour Lake, but the last
5-D,
C74H138, also a black st icky oil,
has a higher viscosity than any other in this or the Sour
Lake groups. In the Baku oil, unlike the others, the
D
series, CnHzn-lo, seems to be poorer in hydrogen and heav-
ier t h m the I-I series. The latte r appears to be composed of
a large number of low molecular weight hydrocarbons, the
upper lubricants, the lower asphalts. As in the Sour Lake
oil, the asphaltic hydrocarbons, in part lubricants, appear to
predominate; even the last
D
oils are asphaltic.
The halogens react with these hydrocarbons as readily as
with those of lower molecular weights, and with the same brisk
evolution of the haloid acid. At about 70 C. the action
proceeds most satisfactorily, with complete solution of the oil
in 4 or 5 hours. At higher temperatures complete solution
may take place in 1 hour. There is a marked difference in
the appearance of the products from the
D
and
H
hydro-
carbons. On pouring into a large volume of water, all the
nitro derivatives from the
D
hydrocarbons separate in a
flocculent, finally crystalline form, those from the heavy
H
hydrocarbons, as sticky oils. The reactions of these bodies
show them to be nitrocarboxylic acids. With the ammonium
salt formed by solution in ammonium hydroxide silver
nitrate precipitates the silver salt readily soluble in nitric
acid. With tin and hydrochloric acid the nitro compound
i x
reduced to the amino acid.
Barium and lead salts are
readily formed. Analysis showed a much lower molecular
weight than that of the original oil. While the action of
solvents indicated complex mixtures, it seemed possible by
proper fractionation to separate individual constituents. A
study of these derivatives will be continued.
A summation
of
the facts relating to the na ture of these
hydrocarbons that make up from 25 to 35 per cent of petro-
leum seems to present a well-defined distinction between the
lubricant and the asphaltic hydrocarbons, and appears to
support the view that the higher specific gravity of the Sour
Lake and Russian lubricant hydrocarbons is due to their
inherent structure, which is altogether different from the
lubricant structure of the Appalachian oils. In further study
now in progress of petroleum lubricants in general, including
the midcontinental oils, the relation of high specific gravity
and viscosity to wearing quality will receive attention.
SULFURS SOURLAKE,RCSSIAN, ND APPALACHIANYDRO
All determinations of sulfur were made by combustion in
oxygen, the most accurate and expeditious method for sulfur
in oils, tars, and asphalts. The variation in the percentage
of sulfur indicates that the solvent differentiates in the sulfur
derivatives as in that of th e hydrocarbons, the greater part
appearing in the
H
series.
CARBONS
TABLE
V-PER CENT SULFUR
N HYDROCARBONS
H FRACTIONS
Crudeer centil
FRACTIONS
1 3 6 1 4 8
Sour Lake
0
3 3 0
27 0 57 0
67
0 48 0
66
0 .59
Cabin Creek
0
5
Rosenbury 0 01
Mecca 0 08
Russian
0 15
CARBOXYLERIVATIVES
N
AMERICAN
ETROLEUM
All previous records of individual fractions from the differ-
ent varieties of heavy petroleum-Ohio, California, Texas,
Russia, etc.-have shown wide variation and abnormally
high values in specific gravi ty.
So
the different series from
the heavy crudes described in this paper show similar varia-
tions. These observations indicate that t he carboxyl acids,
or
more probably esters, are present in all varieties of American
petroleum, but i n variable amounts, from the traces detected
in the Appalachian oils to 2 per cent indicated by com-
bustions of the fractions in the Sour Lake asphaltic oil. I n
fur ther testing for the presence of carboxylic acids, the upper
D Sour Lake fractions, dissolved in ether and extracted with
potassium hydroxide, the aqueous solution acidified and again
extracted with ether, leaves on evaporation a considerable
amount of the oily acid residue. The specific gravity of the
hydrocarbon oil before and after the extraction of
4-0
raction
was, respectively, 0.9642 and
0.9575.
The action of t he sol-
vent in carrying up the carboxyl derivatives in the fractions
of the Russian oil is plainly evident in the high specific grav-
ity, 1.1050, of the oil extracted from the upper D fraction, and
the composition of this fraction C, 86.83; H, 10.41) as
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1238 I N D U S T R I A L A N D E N G I NE E R I N G C H E M I S T R Y
Vol.
15, No. 1
compared with a frac tion in the middle of the series (C, 87.58;
H,
12.45) , viscosity
of
the first oil a t
50
C. 317 seconds and
of the second oil 2005 seconds, water equivalent 2.8 seconds.
The carboxyl oil dissolved out from Mecca 1-D fraction,
specific gravity
1.0105,
gave by combustion
86.70
per cent C,
and
12.41
per cent
H,
with a difference of
0.89
per cent for
0 2
The viscosity of this oil was 468 seconds as compared with
the hydrocarbon C120H220, pecific gravity
0.9171
at the lower
end of the same series, viscosity 1073 seconds a t 50
C.,
water
equivalent 2.8 seconds.
It
would be of interest to isolate
larger quanti ties of these oils and ascertain their composition.
UNSATURATIONS SnowN
BY
IODINEUMBERS
Of the two forms of unsaturation, open chain and the ring,
evidently only the latter applies to the lubricant hydrocarbons
and
it
has received much attention with respect to this con-
dition
as
shown by the iodine numbers. Iodine reacts in-
discriminately on the D and
H
hydrocarbons without showing
any consistent relation or differences, but with results much
like those observed in distillates. Tria l of the Johansen
method that appears to reveal what has been regarded as
addition is really substitution, not only disproved additio
but gave negative numbers to the extent of two to four unit
FORMALITE
EACTION
The D hydrocarbons described in this paper do not ent
into this reaction as applied by the Marcusson method fre
quently quoted in works on lubrication, and the H hydro
carbons of the Texas and Russian oils give variable mixture
with an indefinite composition. The Rosenbury fractio
3-H,
specific gravity 0.8512, gave after the reaction, 0.882
and the Russian fraction 4-0 specific gravity 0.9262, aft
the reaction, 0.9291. I n no case coud the reaction procee
unless the resulting increase in temperature was unchecked
No
naphthene, C,Hh, lubricant hydrocarbons have appeare
and cont rary to the statement of Marcusson, the hydro
carbons from American petroleum have shown a superiori
in lubricant quality over those from the Russian oil.
Acx
NO
WLED
GME NT
The writer wishes to acknowledge the efficient aid whic
he has received in th is work from his assistants, R.
C.
Knap
and George Grossman.
The Value of Sweet Po ta to Flour in Bread-Making'
By H. .
Gore
BUREAU
F
CHEMISTRY,WASHINGTON, . C.
T
WAS recently shown2 th at two widely grown com-
mercial varieties of sweet potatoes, Nancy Hall and
Porto Rico, are rich in diastase and that they retain
their diastatic power when sliced, dried, and ground into
flour. The diastatic power ranges from 200 to 500 Lintner.
That in the southern sweet potato we have a source
of
dia-
stase capable of competing with the cereal sources of this
impor tant enzyme is shown from a study of the economics
of
sweet potato production.
The present cost of growing sweet potatoes on southern
farms is shown by Haskel13 o range from 22 cents per bushel
upward, depending on the yields, the higher yields (160
bushels per acre) being produced a t the lower uni t cost.
Sweet potatoes are
a
sure crop, respond well to fertilizers,
and their cultivation is well understood. The entire crop
or any portion of it can be used as raw material for the pro-
duction of sweet potato flour. In a normal season about
40
per cent of the crop overgrows-that is, the roots become
so large (greater than 3.5 inches in diameter) that they are
not in demand for table use. They are, however, acceptable
for technical uses.
I n preparing sweet potato flour the process required is
very simple.
It
is not necessary to peel the potatoes; they
should, however, be washed in order to remove adhering
soil. They are then sliced and dried. In drying, an u p
draft drier has been found to give satisfactory results. The
temperature employed should not exceed 50 C. The yield
is one-third the weight of the potatoes taken.
Sweet potato flour imparts but little flavor to the mash.
It
does not liquefy s tarch
so
rapidly as barley malt.
It
has,
however, much greater saccharifying power. I ts uses in
I
1
Presented before the Division
of
Agricultural and Food Chemistry
at
the 05th Meeting
of
the American Chemical Society, New Haven, Conn.,
April 2 to 7, 1923.
J . Bi d .
Ch e m. ,
44, 19
1920).
8
U . Deal. Agr. , Bull. 648.
industry remain to be worked out. The most interestin
development which has occurred thus far is the discovery o
the fact that sweet potato
flour
can be used as a bread im
p r ~ v e r . ~
A large number of experiments were run in which a seri
of mixtures with varying percentages of sweet po tato flo
with hard wheat flour was tested. The different percentage
of sweet potato flour used were based on the weight of flou
taken. The baking tests were made by the straight doug
method, with the following formula:
GRAMS
PER BATCH
Flour 46
Salt 7
Sugar 16
Yeast 10
Water
Sufficient to produce a dough
of
proper consistency
The sweet potato flour was mixed with the liquid ingre
dients before the wheat flour was added. Before panning
170 grams of dough were removed for expansion tests, th
remainder being panned for baking.
It
was found tha t a substantia l increase in volume occurre
when sweet potato flour was used. One and one-half pe
cent of sweet pota to flour appeared to give the best result
In one test , which may be considered as typical, t he volum
of the control loaf was 2250 cc., whereas tha t of t he loa
prepared from the mixture containing
1.5
per cent swe
potato flour was 2425 cc. The texture of the bread and it
color and flavor remained fully up to the standard. Thes
results have been confirmed by independent tests made i
three commercial baking laboratories. There is, therefor
no doubt of the fact tha t sweet potato flour does give a sub
stantial increase in volume when used as a bread improve
4
The baking tests herein repo rted were made by I,. H. Bailey, of th
Bureau of Chemistry, and
Miss
R. Leone Rutledge, formerly of the B urea
of
Chemistry.