Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923

8/10/2019 Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923

1/6

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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1234 I N D U S T R I A L A N D E N G IN E E R IN G C H E M I S T R Y Vol. 15,

No.

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


3/6

December, 1923

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


4/6

1236

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


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


6/6

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.

Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923

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Transcript of Paper_-_The Lubricant and Asphaltic Hydrocarbons in Petroleum_-_Mabery 1923