Transcript of Record — Standard Oil Co. (Indiana) v. United States

Supreme Court brief1931

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Ri feia PATENT EXHIBITS

—— —

—

Supreme Court of ve fenton States

OCTOBER’ TERM, 1930... mihi ae

No.378

vit goed 4 . .

STANDARD OIL obupany (INDIANA), STANDARD

OIL COMPANY (NEW JERSEY), STANDARD DE-

VELOPMENT oe ET Al, J vais amin

a OO vs. he wea

THE UNITED STATES sich AMERICA

(35, 300)

: Q SUPREME COURT OF THE UNITED stares,

og OCTOBER TERM, 1930 ae

“STANDARD OIL COMPANY (INDIANA), STANDARD

“OIL COMPANY (NEW JERSEY), STANDARD DE- ~

VELOPMENT COMPANY, ET AL., APPELLANTS, —

“WS.

THE ae STATES OF AMERICA -

_ APPEAL FROM THE DISTRICT COURT OF THE UNrrED STATES

">? KOR THD mee DISTRICT OF ILLINOIS

ie ‘nes BO SEAS SEP PE ED re Ne

~ 3899

No, 80—Letters patent No. 28,448............. 693. 3899

-_ : $1-—Letters patent No. 340,878......-. ‘++, 697 3906

t=. _—s—__".. 98--Britisl patent No. 8345.............. 704 3916-

+. > > S4-96-—Proceedings of Royal Society “of APS

Ea 3 EMO SEAT ss nct ese nee ns es ems . 706 3919

| 97—German patent No. pair ites 784 > 8948

98-102—Laboratory reports..,............ 737 3951

Meee) yale 103—Letters patent No. 419,981......... ». TT. Be

a, oe _ 104—Letters’ patent No. aaa 770 «= 8986 —

ae 105—Letters patent No. 488,767... | 3989

3994

Toop & Derwemra (Inc.), Parma, WastcneroH, D. C, Ootoam 6 1930

107—Treatise on: petroleum ..

108—Letters patent No. 107,784..

109—Letters Patent No. 58,054:. gs

110—Letters patent No. 65,866 SPST eae

111—Letters patent No. 972,958...........

ae: Exoerpts .from Chemical Publiva-

_.117—French patent No. 329,076

118—Excerpt from “Detructive Distillation

in Mineral Oil Industry”......... enace

119—Excerpt from “Journal of The Chem-

120—Russian patent No, 4584...... se eene

121—Letters. patent No. 659,076..

- 122—Letters patent No. 1,131,809. . oop

123—French patent No, 328,051. ire a

124—French patent No. 380,282...:...... He

' 125—Addition to French patent No, $22,265.

126—Letters patent No. 110,806. .

" 127—British patent No. banat VETTES 7

-128—Letters patent No; 1,110,924....

129—Russian patent No. 12,926.

_180—German patent No. 166,723

131—French patent No. 417,582

132—Letters patent. No: ‘1,046,683. .

- 188—British patent No. 1308. .

134—Letters patent No. 477,158...

- 135—Letters patent No. 954,575...

136—French patent No. 822,265...

_ . '18%—French patent No. 399,722.

*.. 188—French patent No. 434,677.

189—French patent No.. 390,558

140—British patent No. 27,005..... me hmboce

141—Letters patent No. 836,782............,

142—Letters patent No. 1,170,884. ........

- 148—Letters patent No. 619,598............

144—British patent No. 25,510...

i45—Letters patent No. 971,468............

146—British patent No. 13,675

147—British patent No. 16,881............

148—Excerpt from chemical report

- -149—Letters patent No. 755,800.......

- 160—Letters patent No. 342,564...

151—Excerpt from Chemiker Zeitung, 1895.

152—Excerpt from Engler-Hofer-Das Rrdel,

Vol. Roviscavcccees eeeeeeeeseeeee eseeeeveeee

-—-189—Brcerpt from Jourial of American.

Chem. Society, Vol. XV, 1898. eee seeee

Taos

INDEX.

“'155—Excerpt) from Chemiker Zettang Re-.

pertorium ......../.. esecsies osecsevoceer

156—French patent No. $43,890............

157—French patent ‘No. 108,214...........

158—Excerpt from Dingler’s Polytechnische

Journal, 1878, Ce eeeeeseewees Pee eereeeeee

159—Answers to interrogatories re patents. -

160—Answers to interrogatories re fener

170—Letters patent No, 1,318,060. . eee

171—Letters patent No. 1,167,884:........

174—Letters patent No. 1,105,961..........

175—Letters patent, No. 1,818,061..........

176-—Letters patent No. 1,049,667...... er

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(fol. 693]

PETITIONER'S EXHIBIT 80

or L. ATWOOD.

Oil Still.

No. 28,448,

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[fol..694] | - United States’ Patent Office

| Luther Atwood, of New. York, N. Y.

P Improv ement in ‘the Manufacture of Oils Obtained from

! | Coal

ie Specification ebaiae Part of Letters Patent No. 28,448,

3 Dated May 29, 1860 :

To all whom it may comgern: ty

Be it, known that I, Luther Atwood, of the city and pee a

of*New York, and State of New. York, have invented certain

‘new and useful Improvements in the Manufacture of Hy-

‘ drocarbon Tluminating-Oils ; and I do.hereby declare that.

the following is-a full and exact description - ‘thereof, refer-

. > ence: being had to the annexed drawings, making a part: of

this specification, and to the letters of reference thereon. —

‘Thin hydrocarbon oils suitable for illuminating purposes,

and-such as are now burned in the ‘‘Deitz,’’ and similar

chimney lamps, are usually obtained from,petroleums or .

natural oils, and crude oils obtained by distilling at com-

paratively low temperatures bituminous coals, bitumineus

_—ghales, bituminous schists, ‘peat asphaltums, rosin, and the .

. tarry or pitchy residue remaining in the process of manu-

facturing adamantine or stearine candles. These natural |

oils and the crude oils, distillates of the above-mentioned -

‘and similar substances, it has heretofore been the practice .

to distill over in g cast-iron still suitable for such pur-

‘poses, and to separate and set aside the first. or lighter ©

portion of the distillate, or such portion as comes over until

the temperature in the still rises to about 600° Fahrenheit,

.. for the purpose of manufacturing into illuminating-oil, with — ‘

the exception, sometimes, of such exceedingly volatile part _

as can be steamed off during the process of manufacture.

The latter portion of the distillate, which comes over at eee

increased temperature, is termed ‘‘heavy oil.’’” It gener- -

ally contains visible crystals of paraffine, and has hereto-

> fore been generally manufactured into lubricating-oils and

_. eandles.. By repeated simple distillations of the heavy oil ——

- a further quantity. of thin oil has: been _—— BAN dit, ae

3900

.oif remaining containing larger proportionate quantities of

paraffine.- I mention this’in_ order that it may not be con-

founded with my proces6.

My said inyention cénsists in a swnethod of senile ‘hiss

heavy oils, paraffine, fatty oils and acids, or the crude oils

‘ and natural oiJs fyom which the heavy oils are produced,

as above mentioyed, so that the whole or as much as de- .

‘sired may be vo verted into thin oil suitable, when purified,

sisa oractiaal development, snabiodinih and

combination of two operations peculiar to these bodies i ina |

process of continuous distillation—viz: first, a gradual and

continudus: application of sufficient heat to. the substance

acted /on to initiate chemical changes which result in. the

decomposition or ‘breaking u up of the heavy bodies and the |

_ formation of light and heavy oil-vapors,; and comparatively

ee amount of fixed gases accompanied with deposition.

of carbon in the still; second, a continuous separation of

~ the light thin oikvapors and fixed gases from the heavier

. Oil-vapors, and continuous condensation and. return of ‘the

latter to the sphere of action of the heat until the whole

is*broken: up, or nearly so, or'as much as desired, by expos-. -

ing the eliminated vapors in a chamber or. receiver of con- —

siderable capacity situate between the point of forming ~

the wapor and the condenser to a temperature about the

_boiling-point of the lighter vapors -and below -the boiling-

point of the heavier vapors, so that the heavy vapors grad- -

ually liquefy and return to’be broken up by further action

- of the heat, while aie light product passes over to .

the condenser, where iti liquefied ‘and separated from the —

_ fixed gases. NG &. |

‘It will be observed that, ywing to the fact of the return

to the action of the heat of the heavy oil when it is.nearly - .

“at the boiling-point, a comparatively small increase of temi-

_ perature is necessary to break it up. This gives my process

a great economical advantage over the former. practice of =

_ successive plain redistillations, by which a further portion

_ of thin oil has heretofore been obtained from’ ‘heavy oils, a

“Spa dadecibad i the boginaing of this specification fs age al

§. Theapparatus I prefer to use is figured in the annexed

Feit os No. gas rane Fig. ‘No. 2, ° |

3901:

a front elevation; Fig. Nq. 3, horizontal section through ~

dotted line x a, Fig. No. 2; Fig. No. 4, horizontal section

Pthrough dotted line y y, Fig. No. 2; Fig. No. 5, transverse

séction through dotted: line # #. Fig. No. 1; No. 6, ver:

tiggl longitudinal section through dotted line y y, Fig. No, 1.

Letter A represents a cast-iron still constructed with a

removable lower section for the punpose of convenient re-

pair. The bottom of the still is heated by products of com-

{fot 695] bustion supplied to the chamber B from the —

‘box E, the arch E’, with its piers and passages, serving to

~ divide and distribute the products. of combustion, equally

. within the.chamber B. B’ is.a short horizontal passage con-

necting the chamber B with the flue B*, which is furnished ©

_ with a damper, B’, and connects with the chimney C. ~~ -

_ Dis an uptake opening out of the passage B and leading ©

up to the flue D’, which, passing around the sides of the still,

eonnects' with the chimney C by the passage D*, whichis -

furnished with a damper, D*. When the damper B* is ¢losed .

and the damper D* open, the products of combustion from

. ~ the chamber B are forced to pass through the flue D’, heat-

. ing the sides of the still on their way to the chimney. I use

the flue D’ in this manner in commencing a distillation. ©

After the distillation has commenced, I shut the damper is

- and open the damper B® in the passage B*, which connects ©

_ the chamber B directly with the chimney. \ x

~~ Letters F F are two man-holes for removal of residue,

~ provided with the’covers and fastenings. . PN HEE ie

Letter G is a filling-pipe provided with a’ stop-cock, _

(shown broken off,) but must be connected with a‘feservoir .

ot walneal da ee ee

Letter H is a funnel-pipe provided with a stop-cock, used.

also for filling the still. ae ee SRG Reith

Letter I is a weighted safety-valve on the dome of the

still, through which vapors can escape when, from any

~ -eause, the worm’ becomes choked, The stem of the. valve is

_ fitted to receive a slotted weight, and terminates in a ring-

handle, by which it may be raised up and hooked: on the.

hook I’-when necessary to keep the passage. open. Lon.

_ Letter:J is a main or condensing pi connected with the —

_ safety-valve by the blow-off pipe J’. The condensable . ss

| products escaping through the safety-valve and saved inthe

, main J flow out through‘the small pipe J* into any suitable —

3 Bat Het ae is so at SY, pe oy

3902 fee igy ene ,

‘receivér, the fixed gases and vapors not condensed escaping

‘through the discharge-pipe J*, (shown broken off,) but to

be carried up through the roof ef the-building, or in any

suitable manner away from the vicinity of the still.

Letter K is a pipe connecting the worm-condenser with ,

the still through the angle-valve L.

Letter M.repregents a vertical cast-iron chamber of cylin-

drical form, standing on the top of the brick-work casing

of the still and near the still. This chamber I call a “‘sepa-

-rating’’ chamber. It connects with the still by the superior

pipe N through the angle-valve O, also by the inferior pipe

P, which is furnished -with a ‘stop cock. The pipe Q, pro-

vided with a stop-cock, connects the top part of the: sepa-

J galeebeae with the worm-condenser through the pipe-

_ K._ The separator is made in sections conneéted by flanges

~ and serew-bolts for the purpose of convéniently increasing _

or diminishing its capacity. The worm-condefiser is situ-

‘ated in a water-tub, R, supplied with cool water from’ a

force-pump or a reservoir, by the inflow-pipe S, the surplus Se

flowing out through the pipe T. The'worm terminates in a

* small chamber, U, from the bottom of which the liquid prod-

ucts escape through. the sealed siphon-pipe V, the fixed gases

passing up through the gas-pipe W, (shown’ broken off .) but ©

to be carried up through the roof or away from the vicinity.

. of the still. The gas-pipe W is furnished with a stop-cock,

to be eloseds when necessary, to-blow steam through. the

chamber U and siphon V for the purpose of removing ob-

structions.or to cleanse them.

Letters a, b, and ¢ are steam-pipes, ach provided with a . -

’ guitable valve or stop-cock, connecting, respectively, with .

the dome of the still, the pipe K, and the pipe N, and. by a

branch coupling with a steam-pipe, d (shown broken Off »).

but which must be connected with a steamboiler.

Letter e is a.draw-cock used for the. purpose of discharg-

ing condensed steam from tlie steam-pipe.

The steam-pipe a is used in Combination with the safety-

valve outlet when open, the other openings in the still being —

(Spans Mi Bele: teoteladoa fa Gk gill of the eomplodion of

Vapors and gases re still at the completion of > —

re eal aia after removal of ¢he residue, to pre-

_ pare the still, when ab a or the safe reception of a charge of L

oil by foreing steam eee eens smnetiey te %

>. ehiemical changes, which results in breaking

. jing the substarice acted on, forming ight and heavy oil: -

_ Vapors, with comparatively: small quanti oe

. y - 8903

displace atmospheric air, as described in other Letters

Patent of the United States to me.

When the angle-valve L is shut and the stop-ccck 4 in the -

pipe Q, which connects the separating-chamber with the pipe

K, is closed, steam may be blown through’ the worm-con-

denser f roin the steam-pipe b, for the purpose of removing |

obstructions and cleansing the condenser. When the angle

valve O is shut ahd the stop-cock closed in pipe P and the

pipe Q open, steam may be blown through the separating-

chamber and condenser from the steam-pipe C..

For'the purpose of the.process herein described, the di-

rect connection from the still to the worm-condenser through ~

the angle-valve L is. kept closed, t6 be opened wheri desirable

to interrupt the process of obtaining light thin oil from

heavy oil, and to-run over heavy oil. In that case the con- —

>, nections to and from the separating-chamber are to be closed.

The operation of my process is as follows: The apparatus —

having been arranged for the operation above described;

I place the substance to be acted on in the still and gradually -

and continuously apply sufficient heat externally to initiate -

gases, and with accompanying deposition of carbon in the

| [fol. 696] still. The vapors and gases pass through the..

‘superior pipe N upward into the separating-chamber M.

The separating-chamber being exposed externally. to the

cooling influence of the atmosphere of the still-room,. and’

heated only by the radiated heat from the top of the still ae

the incoming vapors and gases, a temperature confpa

’ higher or lower in proportion to the relative quantity of i ni

coming vapor, but sufficiently below the boiling; of the:

major portion of-the heavier ‘or ‘higher boiling-point vapors

to gradually liquefy them is maintained internally, and as

. ‘they liquefy and fall to the bottom of the. separating-cham-

. ber they are continuously returned to the still through the

inferior pipe P, The lighter vapors and permanent chai

gradually rise to the top of the separator and pa#sson through ~

the pipe Q to raplneibicrarpelr the liquid pro products pass-

‘ ing out at V, the gases esca ecnning wre through the pipe W.

; see ere main as ee ee

‘

o* Baise ae om 3 . £ ozs es . Xs

’

ca operation i is conducted within such limita a as ite can be carried oe

~~ on at all in the above-described apparatus, If vapors are -

not formed with sufficient rapidity and in sufficient quantity

_. * to keep the internal temperature of the separator up toa. --

’. point about the boiling-point of the lighter vapors, they will,

of course, all condense and fall back in the still. If heat is,

‘applied so actively as to form vapors rapidly enough to keep

_the temperature nearly up to about the boiling-point, of the

heavy vapors, a portion of them willbe forced over and con-..

densed with the lighter vapors. Therefore the particular

degree of change resulting from any one operation will. be

governed by the ‘relative quantity and degre¢: -of heat ap ee

plied. ;

. It.is not: sataela j in the practical working of my process oe

-.. t6 effect the desired. change in one operation, neither is it ~

_ generally convenient or practical to do so; but within the —

- limits abpve mentioned the slower the operation is con-

* ducted tie eee wil be the change effected by one distilla-

tion. ¢ :

| During the necessary ‘end corimonly practiced processes |

.. of purifying hydrocarbon illuminating-oils by treating them —

-Tepeatedly with acids arid caustic alkalies, they are subjected

- to redistillation, which may be performed by my process, -

_. and the operation of converting heavy oil into light oil go on’

: reg the purification process, with which * does not inter-

ere.

‘When carrying on my process in this- ‘manner, alter the

“a purification i is completed I prefer to: distill over such. portion .

6f the purified oil as will go over at below-about 600° Fah-

renheit, with the still arranged so.a8 to have direct eommu-

‘nication with the condenser through the angle-valve XL, and

with the separating-chamber cut off. This portion is then

_.. fit for use.. The remaining contents of the. are then run

~ over through the separator, -— for reasons not necessary __

to mention here, being obvinws to those skilled. in the art, nee

; to {et treatment. ._— :

_ When crude subjected directly to my process the - |

ight: génerated simultaneously with the frost 4

ai in the original production of the ernde oil by ee

__ ing coal or other substances, passes over until the tempera- i

ture of the still rises above about 800° Fahrenheit, when.

ecm The =

~ relative height of the separating-chamber is an important i

element in its proportion, because. it favors separation of

_ the vapor by difference of specific gravity. oa

-* (he proportion, situation, and arrangement of the sepa- _

' yating-chamber as figured in the drawings I consider best ©.

~ for a still. such as.shown with a body or boiler -of about ..

- not djffer materially from them in color. or mobility; ‘but ©

seven feet in diameter.) In a still of such dimensions I carry — :

.on the operation at the rate of ten gallons per hour. —

Although I prefer the apparatus herein described and

. figured; and consider it best adapted to carry on my process)

rapidly and profitably, I will nevertheless use any form of

‘apparatus or still in which I can practically’carry on my

process. %

“he illuminating-oils resulting from my process, when

purified and finished as usual — iHuminating-oils heréto-

fore manufactur- from the lighter parts of the crude oils, do |

- owing, perhaps, to the greater proportionate “quantity: of.

oe paraffine in the source from which they are immediately de-

~ zived, they possess greater illuminating-power. Inthe prac- _

- tical manufacture of these oils they may be beneficially ©

mixed with other light oils; or when operating on crude oil

the distillate of both light and- heavy parts may be suffered

- to run into the same cistern or other receiver:

By the. use of: my process above described the manu-

- facturer can, by a comparatively small number of distilla- —

-” . tions, break up or convert the: whole heavy liquid and solid

portions of the crude oil into light thin illuminating-oil ~

‘whenever it is desirable to do s0.

_ What I claim as my invention and improvement in the

manufacture of hydrocarbon illuminating-oils is— =

-*. The production of thin oils suitable to. he matiufactured:

into illuminating-oils from the heavier parts“of the crude _

and fixed oils and other substanves. within’ mentioned by

treating them in manner substantially as-hereinbefore-de-

scribed during one or several cdntinuous distillations. _

: Ce eg eo 2) ae ee

Witnesses: Braind. G. Latimer, F. C. Treadwell, Jr. ee

re ,

fol. 607) ee ae See bY oo ee

| PETITIONER'S EXHIBIT Rae a ee

Go Model.) : ae Sheets—Sheet 1,

; NM. HENDERSON «. ae

APPARATUS POR DISTILLING OR REFINING MINERAL OILS.

‘Bo. 340, 878. .. 1, ) * Patented Apr. 27, 1886. oe

So meee,

iz ee *

,¢

/ ee AR

WrsRecase?

[fol. 698] |

- tente—sent &

ae my UE SENDERSON. . ; :

» APPARATUS FOR DISTILLING. OR’ /REFINING wureRas. ‘o1Ls.

fle, RAD B18. er _ Patented Apr. 27, 186.

ee 2 ay,

Gr’

2 .

2 Jue

+ (lo Model.) he - M. HENDERSON. c « Sheets—shoet 2

APRARATUS FoR DISTILLING OR RE RAL OILS.

“No. again - Paten ed wed 27, 1886.

KS ae

a ene yee

[fol 700) i Pe saree eee

lo Model.) | cree ren |

: : N. M. HENDERSON. :

' APPARATUS FOR. DISTILLING OR REFINING MINERAL OIL8.

No, 340,878 - Patented Apr. 27, 1896. ous

Fie Ss

fies:

__[fol. 701] United States Patent Office

-. ~,

MOEN pend aay,

| , Sey |

Norman M, Henderson, of Broxburn, County’ of Linlithgow,

ieee Sag ae tae

. Apparatus for Distilling or Refining Mineral Oils ~

Specification Forming Part of Letters Patent No. 340,878, |

Zak 3 _ Dated April 27, 1886

Application filed June 11, 1885. Serial No. 168,344. (No ‘

model.) Patented in England, February 1, 1883, No. 540 ©

_ To all whom it may concern:

Rey ae

Be it known that I, Norman Macfarlane Henderson, a

subject of ‘the Queen of Great Britain and Ireland, and a

resident of \Broxburn, in-the county of Linlithgow, Scot-

~ land, have invented certain Improvements in Apparatus

‘for Distilling or Refining Mineral: Oils, (for. which I ‘have.

obtained ja British Patent dated February 1, 1883, No. 540,)

_ of which the following is a specification. a |

‘My said invention relates to the distillatory processes

employed in refining mineral oils; and its object is to sim-

plify and improve the processes and apparatus and to ren- -

_der the operations more continuous and more uniform in

their results than as hitherto conducted. tole

My improved *processes and apparatus also reduce the

cost of plant, fuel, and labor. - pe obs

- My invention may be applied in.the treatment of va- -

rious kinds of mineral oils and ‘at various stages of the. re-~..

‘fining operations, © = ts :

"ir one arrangement’ of my improved apparatus suitable

or treating shale or coal oil after it has undergone one

distillation, subsequent to its‘aftainment by destructive dis-

tillation from the shale or coal; there are arranged in con-

nection four horizontal cylindrical: stills placed near to-

gether and heated by ordinary furnaces. Oil is continu: .

ously fed into the first still, and portions of the oil con-

tinuously flow. from’the first still into the second, from the

‘second into either the third or fourth, and'from the third

or fourth into one or more residue-stills, and’ in each still ~~

the inlet‘is kept as far separated'as*possible from: the’ont- =

—

7 ; . APOE nn a eat j iy ; y e

let leading to the next still. The inlets are also placed at. —

‘higher levels than the outlets, and both inlets and out- —

léts are provided with special safety-valves hereinafter-par-

ticularly, described. Each still is formed with the usual _.,

dome or vapor-chest, into which the volatilized oil rises,

and from which it passes by a curved branch into’ a lon g ‘

horizontal cylinder or pipe, wherein its heat is utilized in~

raising the temperature of the oil which is being continu-

ously fed into the first of the three stills. These feed-heat-

--ing eylinders are of special construction, hereinafter par- -

~ ticularly described, and which is such as to render im-

possible the mixing of: any of the comparatively crude

feed-oil with the newly-distilled oil. The oil supplied tothe

first still is passed through the feed-heaters of all the three

stills, and the distillation proceeds continuously, the tem-

‘perature, maintained in the second still being higher than

‘ in the first, and that in the ges or fourth higher than in

», the second. Consequently the oils vaporized in the several

stills are of different specific gravitiés; but the oil vapor-

ized in or distilled over from each still is always of one’

‘quality or specific gravity so long as the feed and the heats

~ applied to the several stills are suitably regulated. In each

still the lighter or more volatile constituents of the oil rise

and are vaporized, while the heavier constituents draw to —

the bottom, and are transferred thence, to the next still in

order. The third and fourth stills are both for the third

distillatory stage, one being in action while the other is be-

ing cleaned. In the third and fourth stills, where there is

a tendency for coke or adhesive carbonaceous matter to

separate from the oil, there are fitted inside of the. stills '

certain plates or dishes, to promote the citculation: of the

‘oil, and to form receptacles for the coke, so that it may: not |

adhere to the bottoms of the stills. These dishes or cir- ;

culating-plates extend along: each still on each side of its

longitudinal central plane with a middle space between —

them.’ Their bottoms are shaped so as to be nearly par--

- allel to. or concentric with the: bottom shell of the still, and

the oil in circulating passes from the middle under the

ae dishes or plates and up the sides of: the still, returning -

_ downward from the sides toward the middle, and this cit

culation is assisted and insured by jets of steam issuing

from perforations in the sides of a’ pipe extending. along:

the's still near thes middle of the Yeticas. i found necessary

or desirable, the, circulating plates or dishes may be applied

to the second still) and even to the first. ‘Two or more

‘residue-stills are, .by preference; : provided in eee).

with each set of three‘ connected. stills, in order that while.

one of the residue-stills\is being cleaned otit there may be |

no int iption in the continuous action of the three stills,

Instead of heating the dil supplied to the first still by

means of the vapor-feed heaters, as hereinbefore described,

[fol. 702] or in addition to: that means of heating, it may be:

_ heated by \being’ passed -through.a coil of piping in the

.B third still; or the feed-oil may be. heated i in any other con-

venient way...

. Figure 1 on Sheet 1 of the accompanying drawings is &

plan, and Fig) 2 on Sheet 2 is a back:elevation, of ‘a set of

..four-stills with oné-of the residue-stills. Fig. 3'on Sheet 3

. is a front elevation partly in section. Figs. ‘4 and 5 on

Sheet 4 are enlarged longitudinal and transverse vertical

. sections representing the third and fourth stills, and Fig.

6 is an enlarged longitudinal section of one: of the feed-

heaters. In these drawings the same reference-numerals. .

\ are used-to mark the same or like parts wherever ass are

‘repeated. |

In the arrangement shown | in. ths drawings sig are four

. horizontal cylindrical stills, 11 12 13 13’, placed near to-

. gether in. a suitable building and heated by ordinary fur-

maces, 14, a convenient size for these stills being seven feet —

in diameter by about ninetgen feet in length. The fire-place_

of each furnace, or the s immediately over the grate, is\

arched over, and the fire-gases pass through lateral open- \.

- ings'15, Fig. 3 into a heating chamber, 16; in which they act - :

directly on the still,:4nd from one end of which they pass ~

‘off downward by lateral flues 17 (indicated by dotted lines ;

5s Fig. 9) to again underground : ai leading to the. chim- a

: Bach still is fitted with an otitiet or : didtharge pipe, 18, in.

. the bottom at one end, and in the second, third, and fourth

stills, 12 13°13’, an inlet-pipe, 19, enters the same end : “a 3

higher level, but is continued inside the still, to the ase

80 that the actual inlet may be as far ap possible from ae)

outlet. The side the stills of both the inlet ss

or let pipes 19 18 open or face upward, and plug-valves Som

“provided ‘ayes yuan cllokd sen Singuatiiatae: @

3913 -

necessary, these valves. 20. consisting of conical loaded

- valves attached to vertical rods 21, which pass out through *

stuffing-hoxes in the tops of the stills and are ordinarily ”

_ held up by any simple appliance which can be disconnected

at a moment’s notice to allow the valves to. close. . This in _

‘the event of the external. stop-cocks, 29 23, or any pipe con- ..

‘ nections or. joints getting out of order the safety-valves 20°

- can be instantly closed, so as to prevent. leakage of the oil. —

Each still is formed with the usual dome or vapor-chest,

24,‘into which the volatilized oil rises,: 1and from which it

_ passes by a curved branch, 25,.into a long, horizontal eylin- -.

''. der or pipe, 26, wherein its heat: j is utilized in raising the —

_ temperature of ‘the oil which is being continuously, fed into

the first,-11, of the stills.. 7

As shown in Fig. 6, each feed:heating cylinder 26 is a

cylindrical pipe with langed ends, with an inlet, 25, at on

end for the vapor, and with an outlet, 27, for the same af .~

the side near the othér end, this outlet 27 being i in a curv

' branch communicating with the pipe 28, which leads e :

-vapor to the condenser. Within the éuter pipé, 26, there ie. {

_ fixed an inner pipe, 29, the inner end of which is closed,

while its outer end is formed with or has tightly fixed. to it <

. by screwing, a flange, — by means of which a tight. joint 1 is

-- formed with the flange at the outlet end of thé.onter pipe,

26. The outer end of the inner pipe, 29, is closed By a, plate,

31, which has fixed through it a ‘short pipe, 32, extending |

: only a short distance inw a and a longer pipe, 33, ‘which. -

+ extends almost to the imer end, andthe feed oil is admitted ee

_-by the shorter pipe 32, and passes off by the longer one 38,

. after being subjected to the heating action of the vapor’

- - passing between the outer cylindrical pipe, 26, and the in- ©

ner one, 29.; The feed-oil passes through the. heaters 26 of -

all the stills, being led from one to the other through pipes _—

34 34’ 35 36, anid y passing by a pipe, 37, into the first

still, 11, the pipe dipping a short distance below the surface __

\. ‘of the oil i in that still. “While the distillation is proceeding

oX\ continuously in the stills 11, 12, 13, or 13’, there isa continu- “

' \qus transference of oil from the first still, ti, to the second

ill, 12, by a pipe, 38, connecting the outlet-pipe 18 of the _

ee still to the inlet-pipe 19 of the second still. Similarly, —

- there\is a continuous transference of oil from the second —

ae . Aree © Ee RRS 13, or to ;

. quality of shale-oil with stills of the size shownin the draw- |

3014 . ae

_ the fourth still, 13’, and from the third or fourth still, 13 or

13’, by a pipe, 40. or 40’, to one or mere residue-stills, 41. 0

- As the.specific gravity of the oil varies fn the stills-11, 12, |

18 or 13’, the surface-levels of the oil-will be — correspond-" —

ingly different levels, When operating upon an’ average

ings—that is, of seven feet diameter, I believe the best

working-levels are five feet, four and one-half feet, and

four feet, respectively, in the stills 11, 12, 13, or 13’. As

there is a.tendency for coke or carbonaceous adhesive mat-

ter to separate in the third still, 13, a fourth still, 19’, and

connections are provided to allow of either still 13 or 13’

. being cleaned, thus enabling the apparatus to work without" .

interruption. If the still 13 is in use, the stopeocks 22’ 23°

are closed, and the. oil is transferted through the pipes 40

40’ to the residue-stills 41; but: when the still 13° is in use

the stop-cocks 22 23 are closed and the stop-cocks 22’ 23’

opened, the oil being then transferred directly from the

still 12 through the pipe 39’ to the still 13’, from which it

passes through the stop-cock 22’ and pipe 40° to the residue-

still 41. - | : Be :

: The residue-still 41 is at a lower level than the other

_ stills, and’ the stop-cocks on the pipes 40 40’, leading to it; .

are.in practice to be adjusted to allow of such a flow from :

either of the third-stage stills 13 or 13’ as will cause the

levels mentioned to be maintained without much variation.

The heats applied to the several stills must also be regu- 3

lated to suit.the different qualities or specific gravities of }

oil which is found is practice to be most advantageously —

' yvolatilized: in’ each still. It will, however, be obvious to

[fol, 703] those conversant with the refining of mineral oils

that the rates of feed and of flow of the oil through the .

- gtills, the levels in the several stills, and the heats applied °

- -will in practice have to be adjusted to suit the particular

oil operated:upon in each case.

The dishes or plates 42, for promoting circulation and =~

olécting coke, and which will in general be applied to

and. fourth stills,.13 13’, are shown jn Figs. 4 and

Sheet 4: There are two dishes, 42, in each still, each

. beitig made with a curved bottom nearly concentric with

the‘bottom ‘of the still, while there are vertical ends and a

eens Mich ‘sega cs iain R ra es :

nieustvertboal side along ie. iffmer part) of ‘ae there

being a middle space, 48, ‘between the two

. dishes 42 are jointed to straps or hinges 44, riveted to the

sides: of the still, and are supported by feet 45, rings or

shackles. being'jointed to. them for the attachment of chains

by which the dishes can be turned up for cleaning purposes#* eos

At the lower part of the middle space, 43, between the ©

dishes 42, theyé is:a longitudinal steam-pipe, "46, ‘which has ,

ree perforation made along the lower part of each. side, Th oh

oil in circuyating passes down the middle space, 43, bet

the dishes 42, and being aided by the stefin-jets fro

pipe 46, passes under the dishes 42 and up the sid of the ”

still, the non-volatilized portions réturning- ‘downward’

_ above the dishes 42° and toward the middle space, 43, As -

_ the circulating currents are at their slo est while passi Ck

’ over the dishes 42, the coke which séparates from the oil .

tends to be deposited i in the dishes instead of on the bottom ~

of the still, and it can be removed from, the dishes “eulare

ically.

As hereinbefore mentioned, the oil fed or supplied to the ©

first still, 11, or some of that oil, instead of being heated by _,

the feed-heaters 26-may be heated by passing through a

pipe, 47, led through the third or fourth stills, 13 or 13’, in

_ which still it is arranged in a number pf lengths or coils, ,

On leaving the third dr fourth still, 13 or 13’, the pipe 47 is

represented as passing directly to the first still,. 11; but it

might also be led through the second still, 12, if found

desirable. = § ~~ | ‘

What I claim as my invention i ORE ston

1. The combination of the still and its ‘inlet pee outlet

pipes, having the usual stop-cocks outside the ‘still, with ©

weighted ‘valves 20, applied to the said pipes within the —

still, and having handles extending to the outside, oat sub- aS

- stantially as specified. — . |

2, In combination with the: set of three deat ne: 3

‘ working at graduated . temperatures, the feed-heaters con-.

sisting each of an outer pipé, through which the vapor from

Se a te a ee

closed inner ‘end and fixed by its outer end, :

| ott end net aod outlet pipes Tor te tat pare in |

Sega ep peg as hereinbefore deseri ha

- ae

3: The dishés or ‘sliie 42, arrang> ed to saimele eireula- oe

tion in the still, and also to receive the coke, the said dishes ‘

being hinged at their outer sides, and having a space be-.

tween each and the bottom of the still and also a central

‘longitudinal space between the two dishes, substantially as *

and for the purposes hereinbefore described...

ae The combination of the still’ ‘with dia or ae

therein to receive the coke, and having @ longitudinal. space

between them, and a perforated steam-pipe to promote cir-

culation around said dishes, substantially. as set forth.

In testimony whereof I have-signed my nanie to this

specification i in. the presence of two. Binge witnesses,

\N. M. Henderson..

- Witnesses : Eamon, David 1 Ferguson, ee

: [fol. 704] . Perrriowzn’ ~ Exprerr-93

‘British Patent No. 3345, ry D, 1865.

Specification i in Pursuanee of the Conditions of the Letters

Patent Filed by the said James Young in the Great Seal

Patent: Office on the 26th June 1866

To all to whom these presents shall come, s James ee

. Junior, of Limefield,.in the :County of Mid Lothian,

North Britain, Gentleman, send Greeting.

| . Whereas Her most Excellent Majesty: ‘Queen Victoria, b3 a

Her Letters Patent, bearing date the 27th day of Dece “44

in the year of our Lord One thousand eight hun sha Ge

sixty-five, in the 29th year of Her reign, did, for Herself,.

_ Her heirs and successors, give and grant unto me, the said ©

James Young, junior, Her special license that I, the said

- James Young, junior, my executors, administrators, and as- |

__ signs, or such other's as I, the said James Young, junior, my.

executors, administrators, or. assigns, should-at any time ~~.

- agree ‘with; and no others, from time to time and at. all.

_ times thereafter during the term therein expressed, should

and lawfully might make, use, exercise, and-vend, within the

: ‘United iagdom of Great Britain and haan the Channel —

Talands, and Isle of Man, a an ‘Tavention for <Tinppovesientas ‘

De oie ‘Treating Hydrocarbon Oils,” upon the condition

_ (amongst others) that I, the said James Young, junior, my

‘executors or administrators, by: an instrument in writing _ .

under my hand and seal, should particularly describe and

ascertain the nature of the said Invention, and in what man-

” ner'the same was to be performed, and cause the same tobe ~

_ filed in the Great Seal Patent Office within six: calendar

. months next and immediately after the date of the said Let- .

ters Patent. faced o

Now Know Ye, that I, the said J ames Young, junior, do

3 ‘ hereby. declare the. nature of my. said Invention, and in

what manner the same is to.be performed, to be particularly

- des¢ribed and ascertained ‘in and by the following state-

_ ment; that is to say:

This Inyention relates to the toeatinint of certain hydro-

-. earbon oils, such as those obtained from the distillation of _

coal or shale at a. comparatively low temperature, and »

knowr as paraffin oils, or such as petroleum, either crude or

more or less refined, with a view to the reduction of the

specific gravity of such oils, and otherwise to the beneficial -

alteration of their properties:. In the preparation of these

oils it is desirable for commercial purposes that’ the: pro-_

portion of heavy oils to the lighter or burning ojls should

be as small as possible on account of the greater demand

‘[fol.. 705] fer burning oils, but inthe processes hitherto

employed the production of heavy oils has been. unavoid-.

' ably large, to the great detriment of the manufacturer.

My invention applies both to the heavy and light oils,

rendering both lighter and improving their quality, but

-its importance i is greater as applied-to the heavy oils. .

In carrying out my Invention I take the hydrocarbon oil

to be operated upon and run it into any tonvenient boiler :

or distilling vessel, which to.ensure safety should be made

' -of ‘sufficient strength to resist.a pressure of at least one

“hundred pounds, to the square inch, the heat being applied

thereto in the usual manner. The oil contajned therein is

is thereby converted into vapour, which may be allowed to

i : toe

pass to the condenser under any desired pressure, and such

—

_ pressure may be regulated by means of a valve loaded to...

~ the ‘extent of Tet of | réquired. The compressed vapour

or volatile — t of distillation may be allowed either to

BIB | :

S pass POAE? such dee or thoonake a seiiteke tube with

regulating stop cock to the refrigeratory.or condensing ap- .

' paratus, where. the products are collected in the usual man-

ner. An ordinaty steam pressure giage may be employed —

for the purpose of indicating the pressure. The result.

_ of my process is that a large proportion of the oils origi- ©

nally operated upon are converted into oils of lower specific

- - gravity.- I have found in practice that a pressure of about .

- twenty pounds to the square inch in the boiler or vapour.

- generating vessel is suitable for the treatment of heavy

hydrocarbon oils obtained from coal or shale, but such ©

_ pressure may be varied'to some extent. Th “apparatus

employed may be-of various forms, but I have found that

an ordinary steam boiler, not tubular, answers the pur-

pose efficiently; the more capable it is of being easily.

cleaned the better, as the. heavy deposits should be ‘re-

moved therefrom at intervals, such deposit, if allowed to

remain, seriously interfering with the process of distilla-— 7

tion. - The vaporization or distillation under pressure May

also be applied to the before-mentioned hydrocarbon oils

in various stages of rectification; for instance, the crude ~

oil or first product of distillation may. be at once treated,

or the erude.oil may be first distilled in the usual manner,

and the products of such redistillation, may be treated ac-

cording to my: Invention; or the ~~ ~— of distillation

may be separated into two portions, and the heavier

‘- portions may, be treated according to my Inven-

tion, but it will be all cases that the result of my .

process is to convert the hydro- . —«—inwhatever state

they are. operated upon into .

‘(Last 4 lines unreadable.)

_ oils of a ligther natare. I do not claim any particalar form

- [fol. 706] of apparatus employed, but what I claim is, the

distillation of paraffin oils and. petroleum under presente, 4

thus obtaining improved products therefrom.

In witness. whereof, I, the said James Young, junior,

have hereunto set my hand and seal, this Twenty-fifth day -

eae S une, One thousand eight hundred and sixty-six.

James Young, Junior. (L. Ss. ) 4 |

- London: Printed by ‘George Edward Eyre and William

Rpattiowonte, Printers to the veel 8 most Excellent Ma- ;

: PerrriowEr’s Exuisrr No. 94 :

: Proceedings of the Royal Society of London From June ie

ee : ~ 16,1870, to June 15, 1871 . :

Vol. XIX

50.968 ee

(Filed U. 8. Patent Office, May 23, 1885) -

London :

Printed by Taylor and Francis, Red Lion Court, :

oS) . ' Fleet Street Eeae

MDCCCLXXI. :

(Pages 370-371) > ee.

TI. “Preliminary Notice on the Production of the Olefines

‘from Paraffin by Distillation - under Pressure.’? . By

\T. E. Thorpe, Ph. D., Professor. of Chemistry in Ander-

son’s University,,Glasgow, and: John Young. Communi-

cated by Professor. Roscoe, F. R. 8. Received February. ~

$16... Cree = saat

When paraffin is win deg to a high temperature in a ~

. ’ closed/ vessel, it is alnfost completely resolved, with the

* * evolution of but little gas, into hydrocarbons which remain

liquid at the ordinary temperature. ce: oes

-. This reaction will undoubtedky afford.the most important |

insight into the constitution of this body; . ~— te ‘

Accordingly we have repeated this conversion on e large .

scale, and from about 34 kilograms. of paraffin melting wa.

- 44°5C. (prepared from shale) we have obtained n¢arly

_ ‘[fol. 707] four litres of liquid hydroggrbons. ‘This mixture ©

of hydrocarbons commences to boil at about 18° C., but the .

~ quantity coming over below 100° C. is comparativley small;

by far the greater portion -boils between,200° and 300°,

A preliminary separation shows. that the four litres are

5 made up of hydrocarbons boiling :

~ - . :

— $920 ee >

Between 200° and 300°: 0.1... .6. vee e eee aera a at a

at. 08? and FOr is ce hea iw ks eae eae

> Below... IMME DESL es WN GA Rae bs ete a ee

a *

Up to the present we have principally occupied ourselves

with the investigation of the fraction boiling below- 100°,

in considerable q

and have obtained conclusive evidencé that it is mainly com-

posed of olefines, the proportion of members of the’Ca Hu

+2 series being but small. By repeated fractionations over

sodium. we obtained perfectly. colourless, liquids. boiling

about 35° and 65°, which were attacked by bromine in the -

cold with the greatest energy. On adding the bromine ~

_. slowly: and in minute drops, and carefully cooling the

hydrocarbon by a mixture of snow and salt, . searcely a

trace of hydrobromic acid was produced. - The portion

boiling at 36° may: be either amylhydride or amylene, or a

mixture of both;\the avidity with which the bromine com-

"pines with it shows that the latter body must be present |

tity. -As soon as the drops of bromine

permanently coloure lis

--tillation, Only a'small portion:came over below 40° ; the |

thermometer rose rapidly to 180°, and nearly the whole-of -

the bromine-compound distilled at 184° to 188°. This sub-—

* stance is amylene bromide, C, Hio Br.; Wurtz gives the *—

- boiling-point of this body ‘at about 180°. The portion there-

' fore boiling at 35° is mainly amylene. ~ iS

- Exactly similar results were obtained from the portion

. _ boiling at 65° to 70°. This, f

either C, H,. or C. His, or a mixture-of both. Bromine dis-

’ appears instantly on adding it to the carefully cooled liquid,

* gnd‘on distillation by far the greater portion is found to

the liquid, it was submitted to dis-

om its’boiling peint may be

‘have combined with the halogen. The: bromine thus ob-:

. tained distils with slight decomposition about 195°. Pelouze .

and Cahours’ found that .hexyletie bromide, C. Hi Br:,

Sedied MP Tee RS Se

| ‘We are at present engaged in the further investigation of _

this subject, and hope shortly to lay our results before the

Pe ee ee |

— —————————————————————e

ce (fo. 708) ‘Perrtionen’s Exum No.9,

~ Proceedings of the Royal Society of Gosden feu ;

+ November 16, 1871, to June 20;1872. te che

pad

(Filed U. Ss: Patent mee May 22, we)’

| EOS Vol. Xx

bie a eae

Be nia 50. 969 |

London:

Printed by Taylor andl Francis, Red Lion Lion, Court,

| Fleet Street

-MDCCCLEXXI |

(Pages 488 to 491)

XVI. “Ont the Combined ‘Action of -Heat and Pressure

upon the Paraffins.’’. By T: E. Thorpe and John Young, .

of the Andersonion University, Glasgow. Communicated |

by Prof. Ree F. R. 8. / Received. June 5,1872

* (Abstract)-

The authors first duller to their. srelinlegee eommunica- :

- “ tton.read before the Royal Society on, March 9, 1871, in .

-. which they described the combined effect of heat and pres-_

-gure upon the solid paraffins. They showed that -when _

these substances are exposed to a high temperature in a —

closed vessel, they are almost. completely resolved, with the

‘evolution of ‘but little gas, into hydrocarbons which remain

-. liquid at the ordinarytemperature. In the present com-

munication they describe-how this transformation may be

easily effected on thé small scale...A few grams of ordinary

’ paraffin: are s

_ tubing, bent i

surroun sd

up in a piece of ‘strong combustion-

the form of the letter V; the tube is securely

by strong wire’ gauze, and the limb containing

' the paraffin is gently heated along its entire length in a —

- gas combustion-furnace. If the heat is properly regulated, —

. the paraffin rapidly distils over and solidifies in the cold —

- [fol. 709] antag of the tube. The sasoennent are ase: |

~246—378

et: -

~ turned. down, the tube reversed, and the paraffin again Ma 4

tilled. After a few repetitions of this process the pataffin. ~

acquires the consistency of butter, and the warmth of the _

hand is sufficient to liquefy it; and after about a dozen dis-

tillations, the greater portion of the substance remains per- —

~ ‘manently liquid. It seems to de absolutely: necessary that

thé paraffin should thus be distilled over and condensed;

by merely heating it in the tube in sich a. manner that the

- condensed vapours flow back again upon the heated portion,

the liquefaction is never accomplished. ‘It appears that -

only paraffins boiling at an extremely high temperature,

and those usually solid under ordinary conditions; are thus —

susceptible of decomposition, The readiness with which

_ they yield liquid hydrocarbons appears to depend upon the _

complzxity of their constitution. . =

-The authors have not determined with certainty the

limits of the decomposition, but they find that the mixed

paraffin and olefine, boiling at about 255°, may be re-.

peatedly distilled backwards and forwards in a sealed V- _

tube without.suffering the slightest change.

_ The authors have repeated the process of conversion of

-golid paraffin into liquid products upon a large scale, in the — 2

hope of .obtaiping an insight into the constitution of the —

_ higher members of the Co» Hm + 2 series of hydrocarbons. ©

The paraffin.employed was obtained ‘from shale; it melted -

at 46°, and hada specific gravity (when solidified under’

pressure) of 0.906 at 13°, Its compositionwas: :

Carbon Pie SAE EER 8 ORS oo FE AES mx pune cet pwr 8414

Hydrogen .-..4...-) 65.650. eee ate ae

§ ‘The apparatus employed is fully described in the original

“gaemoir. 3% kilograms of paraffin yielded abont 4 litres

of liquid made up of hydrocarbons boiling, _ Nes

ee ee Littes

OS EEL SRI Dee ee 08

From 100-200° ....... IaES EEE SA Cre eee a eter 1-0

‘From 200-300° ....... i Sua Lia oa Len 27

‘position was: =“

“3

A considerable quantity of substance which could not be

distilled within the range of the mercurial thermometer te-

[fol..710] mained in the retort, and ‘solidified on cooling. —

By repeated recrystallization from ether, this ‘substance —

was obtained of a constant melting-point (41°). Its com- as

" ‘The action of bromine upon this body showed that it’ was

a.member of the Ca Hn + 2 series.. Heated in a sealed tube |

in the manner above described, it was readily split up into

_ liquid hydrocarbons, which were shown. to be mixtures of:

. hydrides and olefines. «= es An Wiss

The four litres of. liquid were submitted to a systematic 2:

fractiorial distillation over sodium; the greater portion of

the operation was effected in an apparatus after Warren’s

. design. The following fractions were thus isolated (boil-

ing-points uncorrected) : Be

--(1) at 35-37. (7) at 193-195 —

(2) 65 =. (8) ~~ «212-915

| BY SEM, 39) Se

. (4) 192195 (10)—252-255

. "@\ 1ebade 1) BB

(6) ANAT] 09) 0

By means of bromine all these fractions were shown tobe

mixtures of hydrides and olefines; and an attempt was —

- made im each to determine, by means of this reagent, the ©

relative quantities of the two:series of hydrocarbons. ‘The ~

method by which this was accomplished is: detailed in: the ce

_ original memoir. It was shown that in the lower frpgétions —

(up to 200°) the amount of hydride was sensibly dual to

that of the olefine. Thuis the fraction boiling,at 65-70° was

* shown to be-a mixture of hexane and hexylene in equal pro- ~

portions; the fraction at 94-97°: was also made up of hep-

tae and heptylene in equivalent amounts: In the higher —

. . fractions, however, there is a decided increase in the amourt

of the hydride present. _

3 "After the treatment with bromine the’ hydrides sould be é

“isolated in ™ pure seat Tlie authors obtained: |

- fluence of heat, these groups

. vA

[fol 1) a hate Sa sal orn * Bolting-point ‘Sp. ae

Nat eee EER He Bg « aoe Ces :

_. Hexane .........:.../-....:.. 6% 68 06681 at 18 C.

-/HMeptane ...)...:.. dissny wpe, Bie 90. DOOR 385 -

Ce MMM Vadis eae h esa. dios . 122-125 0-7165; ‘* 156

: Nonane 2.20.0... 5.065. ..555/ AAT-148 07279 ** 35

__. From their specific gravities, and. oiling-points these in

drides in all plagevesed belong ‘the series of normal par-

: affins, ao a ve

ee The authors have established| ithe existence of the olefines:

* “not only by the action of bromine, but also by the preparation:

of a ‘number of brominated ene They’ have obtained S

: lester ‘ie °% ES eee Ce aa es 208-212

‘They have also prepared a few ecitai from the bog

| drides, and studied the action of oe tetroxide upon' the |

BS ‘mixture boiling at 122-125°. mee

- The mode of decomposition of the patito len tet in-

. fluence. of heat and pressure appears to be general for the

higher terms of the series of normal hydrocarbons.

_If the.paraffins be represented iyationally, by linking.

loosening of the affinities of the CH, groups. Under the in-

. combine to form saturated hydrocarbons. Assuming, for the

— of. saree fat that this decom sition Tr occur 80 low <

me disassociated, and re- —

ewe =

oe tas Sey -point re 8p. gr.

: si! ‘ ee ° ; 3 at

. C.HiBr, Pe ab we a ee eee aise : 3 - a “

on eee ere ea 195-200 - 18967 at 20.

| hiebtaaes 2.5 33 1 ees... Gecomposes © 15146 at 185

C.H,.Br Haas wee en ae ee 185-190. Ree is :

WR Ms hbo es os about 235° with decomposition.

_ together the carbon atoms in a single chain, the simultaneous —~

formation of hydride and olefine obviously arises from the _

. ; } i:

o ; 3925 y

ue .

down in the series as in the case of butane, it might be thus

-. represented :— - eee BONY | bag ap

H :

a aC a am, b jee i

ee it n ; y 2 <a

- ffol. 712] The authors have but little. direct evidence: to

offer as to the exact manner of this decomposition hether

- it is attended by the gradual elimination of ethylene,\a hy-

dride cntaining greater number of carbon atoms ing

left behind, or whether the paraffin is at once split up into

hydride and olefine containing an equal number of carbon

atoms ag in the ‘above equation. Neither supposition. is \.

‘exactly substantiated by experiment. If the action of heat \

gave rise to the former mode of decomposition, we ought to. ‘

obtain a larger quantity of ethylene after prolonged heat-

Gng, especially when the liquefied portion is rich in hydro-

~ earbons.of\ low molecular weight; but it has already been

_ pointed out that the process of liquefaction is accompanied -

with the production of comparatively li / On the

other hand, an examination of :the amounts of bromine re-_

- quired-to render the hydrocarbons boiling above 200° perma-

~ néntly red, slows that the proportion of hydride to olefine

in the several mixtures becomes. gradually larger as the

molecular weight increases. = i

‘It would doubless have been interesting to have deter-

_ mined the relative amounts of the twelve fractions isolated

from the decomposed paraffin; but when it is considered that |

’ their separation was only effected after several thousand :

* distillations, ste be evident that the quantities obtained

after/such prolonged treatment can afford no real indication -

‘of the amounts present in the original liquid. It appears, —

‘however,«that the amounts of liquid -boiling at 94-97°- and

_- 122-125° mere but slightly, if at all, less than the quantities *

boiling at 252-255° and 273-276", : ee

es Rie

a Beat |

Undersdgelser, med serligt Hensyn til isomorfe Stoffer. ~~

[fol. 713) Prrrriowen’s Exuysrr No. 96

Proceedings of the Royal Society of London from. November.

21, 1872, to November 27, 1873

Vol, XXI :

ae 970

’ (Piled U.S. Patent Office ‘May 22, 1885).

London:

: | Printed by Taylor “and Francis, Red Sion Court, Fleet Street

MDCCCLXXIII

(Pages 184 to 200) ©

.¢,

Transactions-( continued). i ees

Vienna :—Anthropologische \Genclischaft:. _“Mittheilungen.

Band Il. “nr. 3-5, 7, 8. 8vo. Wien 1872, ‘The Society.

Adams (John R.) Dulwich College and the Endowed Schools.

Commissioners. . A Se dead for the emo, ‘8vo: London

be ISIB es es ~The Author,

Dumas (J. B.), For. Men: R. 8. Bloge Historique de Isidore:

Geoffroy Saint-Hilaire. 4to. Paris 1872. ~ The Author.

- Rogers (H. D.), The Geology of Pumsistvanis, a Government

Survey, with a General View of the Geology of the United ~

State. 2 vols. in 3; ‘and volume of Maps. 4to. Edinbufgh

1858. eee eek Professor Huxley, Sec, B.S.

og C. Christiansen. ‘Krystallografisk-optiske :

‘4to. _Kjobenhavn LS ae at : _ Thre Authors.

( {fol. 71: ] “On the Combined etion of. Heat and Pressure

Upon é Paraffins.”’ ‘By T. E. Thorpe and John Young, of

__ the Andersonian University, Glasgow, Communicated by— .._

Prof H. E. Roscoe, F.RS, Received June 5,, 1872*.

ve 4; Ina preliminary edkaminhioation read before the Royal 4

Spur on apie shin lei we. described the ere o

eT « Aree

7 ead Jane 20; 1872, See abstract, vol. x: 488.

ee oe 370. a

hie *

M4 ’

Pane * hs = . 8927 .

! a. : b sy

. _ fect of heat and pressure upon the solid paraffins: We

showed that when these substances are exposed to a high.

temperature in a closed vessel they are almost completely re-

solved, with the evolution of but little gas, into hydrocarbons,,

which remain liquid at the ordinary temperature. This —

transformation may be easily effected on the small scale. A

few grms. of ordinary paraffin-are sealed up in a piece of

_ strong combustion-tubing bent in the form of the letter V: a

the tube is securely surrounded by stout wire gauze, and the

limb containing the paraffin is gently heated along its entire

‘ length in a gas combustion-furnace. If the heat is properly —

‘regulated, the paraffin rapidly: ‘distils over and solidifies in —

__. -the cold portion of the tube. The gas-flames are then turned

- . down, ‘the tube reversed, and the paraffin again distilled. .

_ > After a very few repetitions of this process the paraffin |

- aequires the consistency of butter, and the warmth of the .

. hand is sufficient to liquefy it, and after about a dozen dis-. -

tillations it remains .permanently liquid.. Although there is

no difficulty in thus ultimately effecting the resolution of the

_. solid paraffin into liquid products, the rapidity of the trans-_.’

- formation seems to be dependent upon conditions which we. -

-eannot yet say we haye satisfactgrily determined. On one .

oceasion, after all the-paraffin had been distilled over and_-

had solidified in the colder limb of the tube, the empty por- —

- tion in contact with the flame became softened and blew out,

_ when ce it on the removal of the pressure, the solid mat- -

ter becafne liquid, and slightly effervesced as.if gas had beer .

:~_-/ eondensed in the substance by the pressure to which it had -—

“Y heen subjected. It seems to be absolutely necessary that .

-the paraffin should be thus distilled over and condensed ; by.

merely heating it in the tube in such a manner that the con-. es

densed vapours flow back again upon the heated portion, the ~

liquefaction of the paraffin is never accomplished. About 6 —

- grras, of a pure paraffin, melting at 41°-5 C. (see section 12),

_ * were heated in a sealed tube to about 200° for twelve hours,

“. {f0l.715] but the melting-point ‘remained. unchanged. — The |

same portion of paraffin was then transferred to a V-tube |

surrounded by wire gauze, and distilled backwatds and for-__

~~ + wards in the combustion-furnace. After si distillations it

- "was rendered completely liquid. The total q antity of liquid °.

obtained was about 6 cub. centims.. On gently warming it, .

‘ gubbles of gas were evolyed, ahd the liquid was in full ebul-

ition at 40°, but only about-one sixth came over below 100°;

ees

~ about’ 21% ee centims. distilled ‘ening 100° and 200°, iat

‘nearly the whole of the remainder\below 300° ;- the small

quantity remaining solidified when the bulb’ was lunged’

_ into cold -water,

2. It appears that only paraffing. boiling at an itesmily

_ high temperature, and those usually solid under ordinary ©

conditions, are thus susceptible‘ of decom ition. The

_ readiness with which they. yield liquid hydroe, rbons ap-

-pears to depend-upon the complexity of their constitution.

- We have not determined with certainty the limi

< aparanaaettih but.we find that the. paraffin (and

boiling at about 255°. (see: section 11) may be re

__ distilled-backwards and forwards in a sealed V-tube

out suffering the slightest change. 6-7 grms. of the

_ ture of hydrocarbons were distilled bach ards and for-

wards, twenty-one times; but on opening the tube no’ gas _

was evolved, and the boiling-point (252°-255° uncorrected)

* remained unaltered. A further proof, of its unalterability\

on. repeated distillation under ‘pressure is afforded ah its;

‘reaction with bromine (see section 5). ; \

_ Al, 938 grms. of the mixed hydrocarbons before distilla-. |

“tion required 295 grms. of bromine before the liquid be- >

~. came permanently. teddened ; 100 - ‘parts by. weight a

require 31-4.”

. IL 8605-grms. hydrocarbor before distillation ‘requir ed

-. 2672 grms. of bromine, or 100 grms. would require 31 of

bromine. ‘Mean. amount of bromine needed 31:2 per cent.

- ITE. 513 grms. of the hydrocarbon after repeated distil-

lation (21 times) required 1:54 gms. of bromine, or 100 -

__grms. would require 30 grms. :

3. In the hope of throwing some light upon the constite:

_ tion of the solid paraffins, we have repeated this process of

transformation into liquid products upon. a large scale.

The paraffin employed was obtained from shale; it melted

at 46° and solidified at 43°, and had a specific gravity -

0906 at 13°, when solidified under an qe pressure of ~

, Efol, ld 0-75 millim. of mercury”.

ae Considerable . ae exist in the statements by —

_ various observers. of the specific gravities of the solid par- .

wine. These ees are doubless due more to _ dif-

be]

a It was burnt with copper oxide in a stream of oxygen, a

with the following results: pa Rr

1, 02980 grm. paraffin gave.09293 grm. carbon dioxide ©

__. and 03980 grm. water. hal | ae

‘II. An unknown quantity gave seas grm. carbon diox- | =

ide ard 06060 grm. water.

re ave 4.52322 3

ee BERS ee 8505 8523 . 8514

"9989 10000 ~ 9995

ficulty of obtaining the bodies perfectly homogenous after

-melting than to any great variations in their true specific —

gravity. "When a piece of ordinary paraffin is examined,

it is seen to be made up of an infinite number of small cavi- -

ties; and however carefully it may he cooled after melting,

- the interstices‘ are invariably present.. From this cireum-

_ stance it is obvious that. ahy attempt determine the real

specific gravity of this body would give too low a result.

By sdlidifying the paraffin under pressure, the formation

of the cavities may be, to a great extent, obviated. .:We

have effected the solidification ifi the,apparatus figured in’ -

the margin. Mercury was first poured into the tube: up: to.

the level A B, the bottom end of the tube being securely —

, \ plugged by a cork C. The.wider portion D of the tube was

_ --then filled with the melted paraffin, and a wellitting caout--

choue cork fastened down by wire into the opening, care —

being taken to exclude all bubbles of air. Mercury was —

now quickly: poured into the longer limb of the tube until

it stood about 0:8 m. above the level of. the metal in the

wider tube, and under the pressure of this mercury the .

» paraffin was allowed to soliflify slowly. By, withdrawing

the cork C, the mercury could flow out, and on warming the

sides of the tube the plug of pa: affin was easily detached. _

Thus solidified, the body was almost entirely free- from

cavities, and portions perfectly homegeneous were “easily

found; these‘had a specific gravity of 0-906 at 13°:

—

- 83930 Cee Oa, - |

| | (Cut unproducible)

[fol. 717] These numbers agree perfectly with those ob-

- tained by Anderson many years ago” from analysis of a

paraffin. identica] in origin and melting-point (45°°5) with ©

that employed by us. Dr. Anderson found for the.sub- ~~

_ stance the spcn acces |

I gee ee Fer LENS a ik ve oo kn ce ES 85:1

NS OEP R eee es PE er ee ee 1.

_ 1038

A ols of — from peat, melting at 46°: 7 gave:

bi foe oe alee

Cathe o.2, 8495 8523-85-09

yee ere ... 1505 1516; «1510

7 ~, ee a —

10000 10039. 10019

In the process of conversion we ‘replaced the. bent glass

- tube above described by an apparatus consisting of two cast-

. iron mercury - bottles connected together by’.a ‘bent iron

"= pipe, in which were fixed a stopcock and pressure-gauge.

One of the bottles was charged with the paraffin, and was

- heated over an ordinary coal fire, the heat being so regu- ©

. Jated'that a pressure of 20 to 25 lbs. was maintained in the

apparatus throughout the operation. The volatilized prod-

ucts distilled over into the second bottle, which actelasa -

condenser. In about four or five hours the operation was. -

concluded, and the distillate had the appearance ofa .

magma of oil, and of apparently unaltered paraffin. This —

- qnixture. melted at’ a comparatively low temperature, the -_ .

- warmth of the hand pie iad sufficient to. render, it way ae

liquid. - ae

- Three and a half iilograma of the paraffin yielded about -

4 litres of liquid hydrocarbons. On distillation the mixture

= eommenced to boil at 18°, but the quantity coming over

below 100° was comparatively small; by far the greater

portion boiled. between 200° and = A reasana'd

——————————

=} : : ‘ : ; + ee ae 7

‘separation. showed that the 4 Lities ‘were approximately :

made up of hydrocarbons boiling: ony

ae Below 1 | lates Ste bye Rene Sy! > ape es

Tis: Prom 100-2008 33 SG See occas 10.

- TIL. From 200-300°"*......... Pe ee or ck

| 40: ;

(fol. 718] A considerable ieee of vilteales: which ; :

could not be distilled within the range of the. mercurial

_ thermometer, remained in the retort, and solidified on cool- |

‘ing (see section 12). Each of the portions was then sub- ae

mitted to a systematic | fractional distillation. °

__ +4. Fraction boiling below 100° —After repeated distitia:

'. tions .over sodium this portion was almost completely re-

solved into three fractions, boiling constantly at (1) 32-38°,

— (2) 65-70°, and (3) 94-97°. The quantity of liquid boiling

«below 30° did, not amount to 5-cub. centims. Although the

* distillation was. conducted i in winter, and freezing-mixtures

- of snow arid salt were employed for the condensation, the -

greater portion of the product boiling at 32-38° came over.

: ‘at about 35°; this boiling-point would indicate that the ©

liquid is probably either quintane or amylene, or a mix-

ture of these hydrocarbons. -In. order to decide the point,

the distillate was treated with bromine. The liquid was

violently attacked; and each drop of bromine combined,

with the hydrocarbon with a hissing noise; so energetic

- was the. reaction, that, in order to: moderate it; it was neces- —

sary to immerse. the. hydrocarbon in a freezing-mixture.

When proper care was taken to cool the liquid, séarcely a

trace of hydrobromic acid was evolved. In order to pre-

vent the possible formation of higher brominated products,

the addition of the bromine was frorn time tc time inter- -

rupted, and the liquid’ submitted to distillation; it invari- -

ably commenced ‘to boil at about 32°, and the- distillation

was maintained until the thermometer stood at 50°.- The -

ee. - distillate was again treated with bromine in the cold, and

again distilled, the process- being repeated ‘until it was

without visible action upon the hydrocarbon,—that'is, until

the liquid was permanently reddened. . It was then washed

with dilute site solution, and rectified © ever * pallens it

boiled constantly at 35-37°; the liquid was evidently quin-

‘tane; ‘and -in all probability normal quintane, the boiling- —

point of which is given by Schorlemmer at 37-39°, and by ~ |

Warren at 37°. The amount was.far too small to attempt .

the preparation of any.-derivatives from it. The bromi- -

- fated portion boiling above 50° wag then distilled; the

thermometer rose rapidly to 180°,\and the whole of the.

liquid came over below 200°. After renewed distillation |

. the liquid was found to boil constantly, but with slight de* _

. eompositios? at 184-188°; this compound is amylene dibro-

_- [fol. 719] mide, - the. boiling-point of which, according _

’ Wurtz is in the-neighborhood of 180°. wt

06515 grm: bromide gave 19125 ‘grm. Ag r and 0:235

‘ erm, reduced silver. kee

: ; Calculated ~ | Found : -

Bel igith te ei COB 5 oh 688

5 The fraction’ boiling between 65° and 70°, which was at ~ :

‘aie fifty times greater than that boiling at 32-38°,-was then, -

. treated with bromine; the bromine was ‘absorbed: with the

same avidity as in the preceding case; and it was equally :

‘ necessary to cool the hydrocarbon in order to moderate the

reaction As soon as the liquid appeared permanently red--

dened, it was distilled. The portion boiling below 80° was

-no longer instantly attacked. by bromine; it was accord-

_ ingly free from the accompanying lefine. The: distillate

was then treated with aqueous potash to’remove the free ©

. bromine, and when colourless the hydrocarbon was decant-

ed, dried, and distilled over sodium; it boiled almost en-

tirely between 65° and 70°, by far the: greater portion

coming over at 67-68°. It was analyzed with the follow-

ing results: | —

0-1440 grm. hydrocarbon gave 0:2095 grm. water the car: z

- bon determination was lost.

* Calculated s Found -

Poke eck cen eee

of different, bottles gave:

-. Two determinations of its spécific gravity made by means

-~ (4) 06620 at 19°5, and —

(2) 06641 at 18°.

= E Compared with water at the same temperature, Pelouze as

and Cahours found 0-669 at 16° for the hexane boiling at 68° -

obtained from American petroleum. Hexane from suberic

acid, boiling at 69°-5, according to Dale, has a specific grav- -

ity. of 06617 at-17°5; this agrees with that of B hexane ob-_ -

tained from mannite, viz. 06645 at 16°5. Schorlemmer ~

found 0678 at 15°.5 for the hydride from cannel coal, which

agrees perfectly with that obtained by Williams for the

same hydride prepared from boghead coal, viz. 06745 at

18°. On the other hand, Schorlemmer has found that the -

hexane prepared from mannite is probably identical with —

= [fol. 720]. that obtained for. secondary hexyl iodide by the. —

action-of zinc and hydrochloric acid, and with the dipropyl

obtained from primary hexyl iodide, for which he found the. ;

specific gravity Q-6630 at 17°; and these are probably iden- —

- tieal with the hexane of Pelouze and Cahours obtained from -

_ petroleum, and with the hydride found by Schorlemmer in -

- cannel oil, all being normal hydrocarbons with the consti- _

tution ~ Se ae Bi

CH,—CH,—CH;—CH,— CH,—CH, : x

- . The brominated hydrocarbon left in the flask after re-

- moving the hexane was then distilled: it commenced to boil

at about 190°; the thermomenter gradually rose to 195°, and

nearly the whole of the liquid distilled over below 205°. As

- the compound showed signs of decomposition on boiling, hy-

‘in the flask, it was impossible to fractionate it,further. It.

drobromic acid being continuously evolved during the dis-

tillation, a considerable amount of tarry matter remaining

- ‘was purified, however, by distillation in a current of steam;

‘it was nearly colourless, and on analysis. yielded numbers’

agreeing with the formula C. Hi: Bre - ~ tae ae

, z

+0:8950 grm. of. the bromide gave 1:3570 grm. silver bro- -

mide and 00090 grm. reduced silver. ages

geo See ee,

/. Calculated "Found

15975 at 18°. Pelouze and Cahours found the, -boiling-point —

had probably been slightly decomposed by ~distillation.

2 flash, and well cooled by a mixture of ice and salt; ‘bromine

Be éaoutchouc bail about.5 cub. centims. in diameter, which

ae The tollbeine' are the data obtained: in x the determination |

~~ of its specific gravity: . . ee eel a gem

Weight of bottle 2000/2 oo 680 em.

-- Bottle + water at 20°...... De eet 1988 erm

Bottle + bromide at 20°. So Ae nee AOCMRO FE

oo frat which 1. 5967 is obtained as “the ‘peel piavity: ‘of 4

-hexylene dibromide at 20° compared with water at the same

‘temperature. - —

A second detérmination with a ‘mihaller ‘quantity gave eee

of this body. to be 192-198°, and its specific gravity 1582

at 19°.” These numbers are ‘certainly too low;. the bromide

We have attempted to determine the relative amounts of

hydride and olefine in‘’the fraction boiling at 65-68° by :

means of the reaction with bromine. *.

-. The hydrocarbon was weiglied out in a small. distillation- :

‘[fol. 721] was then slowly added, and i in minute drops, by. |

means of the. little apparatus seen in the figure—a small

ean be compressed bythe plate movable along the rods by

means of the milled head-screw.. The mode of working the |

- instrument is obvious; by means of it the.bromine can be'

easily transferred from the bottle in which it is preserved __

- to the hydrocarbon, and the amount added.can be regulated.

~ with great nicety. The bromine was added until the liquid sae

owas permanently reddened, when the flask was again

‘weighed to determine the amount of bromine employed...

~ “13:30 grms. of the mixed hydrocarbons boiling- at 65-70° *

- yequired 13:16 grms. bromine before the red colour was

“persistent: This amount of bromine is equivalent to. 69

grms. of hexylene, and 133—69=§4 as the amount of .

_ hexane. present. - The mixture was now distilled,and all

- passing over below 110° (at which point the: Nignigh in: ihe.

. flask commenced to blacken) ‘collected in a weighed test-

- tube. The weight, of the distillate was 618 grms. From

~ these nurabers it would appéar that the produet boiling at”

- 65-68° is a: ure of: hexane vai cig Soar in val ae he

. proportions. | ey,

\ ee

4 ; * oe aS xs Att Bere =

“ ; “ eee ee te een ee ah oe os

. = oO eae

\ : - . vee

t Pee

6. The fracffon boiling at 94-97° was next treated with —

promine-in the cold until:the liquid was reddened. The

termination. of the reaction was not so easily seen in this

é kes the mixture blackened slightly, and more hydrobromic __

‘acid was evolved, although the hydrocarbon was: carefully

— gooled by ice and salt. The brominated mixture on distilla- ;

~ tion commenced to boil about 95°, and it was heated to 130°,

--when the liquid in.the flask commenced to decompose; at

_ this point, therefore, the distillation was interrupted. The

following-are the details of a quantitative ‘determination: =

. Weight of mixed hydrocarbons.............- 1421 grms.

- Weight of bromine added..............:-..-. 198

' Equivalent to heptylene ...... i bi A ee ee

~~ Equivalent to heptane ........ Syeeay ee pn bo ee

- Amount of:heptane actually obtained... :...:.° 616 ae

” From this experiment it would appear that the amount of ~~

- olefine is slightly greater than that of the hydride in the —

. fraction boiling at 94-97°;- but, from the circumstances of

the experiment, we have reason to believe that the amount —

~. . of heptylene thus indicated is slightly above the ‘truth. It —

“was difficult to determine the final point of the reaction; the _

_ hydride was not altogether unacted on by the ‘bromine, and |

. [fol. 722] small quantities of-hydrobromic acid’ were cop-

tinuously disengaged during the process; these cireum- __

. stances would tend to increase the weight of bromine used,

‘ and consequently the apparent weight of the olefine pres-

_. ent. In extending our research to the determination of the

_ constitution of these hydrocarbons, we have had occasion — <

- to répeat this experiment on a far larger scale and under.

- . more favourable conditions. = 83 ie

_ 900’ grms. of the mixed heptane and heptylene required _

_. 716 grnis. of bromine; this would be equivalent to 439 grins. °

| > of heptylene. 900 grms. of a mixture of heptane and hep-

tylene in equivalent proportions would contain 444 grms.'

a7 oF nentyiond, ee

Tlie -heptylene bromide could not be redistilled under

' the ordinary ‘atmospheric pressure without decomposition; ,

it commenced to blacken at-about 150°, and dense fumes of —

hydrobromic acid were evolved. When distilled in a cur-

rent of steam, it was obtained nearly colourless. © =

> .

ae drying, and. rectification over sodium, boiled constantly at.

and 02460 grm. water. wont pas e:

® Vis

By : eo z tee

Sy A By ste bos “4 ay >

4 * bh oP oe F s aes 2

f ge) Aals . . > x" <

. E * . : ¢

It cannot be preserved, however, without slight decom-

_ position; when exposed to light, it. slowly darkens in aA

colour and: evolves hydrobromic acid gas, .- a

_ It was analyzéd with the following results: oe ae

- 0-7470-grm: gave 10210 grm.. Ag. Br and 1.0035 grm, re- e

"duced weer % : | :

Soe .

7 cibilinl Jas oe al

e fs ; erent ae - for Br, Found «|

: : 5 Sey . 2 ee >

BR ee a ee a

The specific gravity of this compound was found to be ~

15146 at 18°-5, water at whe same temperature being taken

/a8 unity. ie

The heptane, after euhine with dilute potsish adiation.: ae

97-99°.. Its specific gravity was found from two experi-

‘ments to be (1) 06910 at 19°, and (2) 06915 at 18°. War-° .

yen and Storer found for the same hydrécarbon from Men- Be

_hadden oil the specific gravity of 06942 at 1°5 aa

or Burnt with copper oxide in a vadeaaet of oxygen, it piceeas ee

~. the following numbers : Pr Be

1. 01695 grm. hydride gave 05240 He . earbon dioxide ;

-TL.-0-2688 erm. hydride gave ogii9 grm. carbon ior :

and 03733 grm. water. — is

TEE des unknown gunniity ave 05015 ; ‘rm. carbon ai: @

ie éxide and 02318 grm. mater | =

bass 723) a De o Pee .

ee Caleulated- (oe oe ee

OSS e 8 ee eee eee eet

SE anes Ree eens 16:00 1613. 15 73 3 a 2

ae “ 10000 _ toy'e a \> 9967 100-00 0

| These six: bodies, quintene and amylene, atid: ae a

hexylene, heptane and heptylene, are the only liquids we

-have been able to isolate from the fraction boiling: below

- 100°. Careful search was made for the other hydrocar-

: bewsa, hartionioniy,£ for mengoh and for she. a. of Cav- :

a a Oe NN er TE ren meena - —

entou, boiling about 80°, but without success. The frac--

tions intermediate between 70° and: 90° could be resolved AM

' by repeated distillations into products boiling at 65-70° — 3

and 90-100°. The amount coming over in the neighbour- =”

"hood of 80° was very small; in fact the entire quantity

- pate, could any solid promide (C. H.: Br.) be obtained. —

Hence ‘we infer the absence of members of the C. Hm-.*and —

C, Hon-. groups in the liquid hydrocarbons obtained by the

-decomposition. of solid paraffins, - =

. 9. Fraction boiling between 100° and 300°.—As this por- .

tion amounted to about a litre, it was thought worth while _

to‘attempt 4 more rigorous separation of the hydrocarbons —

than is possible by the ordinary method of fractionation;

.for this purpose a small condensing arrangement on War-".

ren’s principle was constructed, and by means of it. the

hydrocarbons were. separated. at first at intervals of 10°,

’ eventually obtained between’70° and 90° amounted to only ~—.

..a few grams. About a gram of the small portion-boiling —-

at 80-82° -was treated with strong nitric acid; ‘the liquid _

__ was very slowly acted upon, and when treated with alcohol,

zine, and hydrochiorie acid, after washing and solution in©

ether, it failed to give the characteristic reaction for ami- ~

line; nor on treating thg remainder of the hydrocarbon —

with excess of bromine, and allowing the mixture to evapo-

afterwards into portions boiling between 5°, and eventually =

into portions boiling between 2°. ‘The hydrocarbons were.

distilled over sodium, and the temperature. of the worm —

was maintained about 20° lower than that of the vapour —

-° Gn the flask. .A considerable quantity of liquid was ob-

.. tained boiling below 100°; and this’could be resolved into —

hexane and hexylene, heptane and heptylene. The amount ©

-of liquid eventually obtained between 100° and 120° was

very small. fete : a Age ee

About 120 grms. of liquid-were found to boil constantly _

- fol. 724] between 122° and 125°., Bromine was eagerly _

absorbed by this fraction, indicating the. probable presence

. of octylene, the boiling-point of which is given Dy Bouis

at 125°, and by Pelonze and Cahours at 118120°. The

- yeaction with bromine yielded the following data: = =.

Amount of hydrocarbon taken ~

Amount of bromine needed ........... Sia

Equivalent of octylene:...........2..06..05.., 941 $6

47878

. ~ ;

fs ign ts *

aa . e ‘ " ; m,- -

i , Z wete oi ad

: 3938 . ee

. . : ‘ d ° 5

. : :

cd rity

On addition of bromine the Nodciantici darkened rap-

‘aly in colour, and-a. stnall quantity of tarry.matter col-

- lected at the bottom of the flask. As it was impossible to ©

. distil the mixture under the ordinary atmospheric ‘pres- |

| sure, the bromide being decomposed by a very slight eleva- ;

tion of temperature, it was treated with alcoholic potash,

and distilled per ascensum for sdme hours. until a few

drops thrown into water floated upon its surface. Water .

-was then added, the lighted portion separated, dried, and —~

: fractionated. The largest.amount came over between 120°. -

and 140°, the next fraction from 140-160° being much

.. smaller’in quantity, whilst | scarcely any liquid distilled over

between 160° and 180°; After this point the thermometer -

. became more stationary, and a fraction almost. as large .

as that at 120-140° came over between 180° ard 200°. >

_ This, .on renewed distillation, boiled at 185-190°; it. had a

‘feeble garlic smell; and was heavier than water. Analysis

. abe that it had eupreranately. the oe | C, His:

ry T BAAS

0-4755 grm. aks, gave 04165 grm. silver bromide

and 0180 grm. reduced silver. -.

IE. 04600 grm. bromide gave 04100 om silver bromide ;

and 00150 erp. reduced silver. - ey

| Pound Ss

ak eee ee ae eee

BE yl Oe ae 401 40-7.

as ‘homsetiing to Rubien® , by whom this ; com

: described, its boiling-point i is 185°

The fraction” ‘boiling between 120° and 1 Pon repeniad

: distillation was separated into octane, boiling at. 122-125°,

and a liquid of an alliaceous odour boiling constantly at a

- 130-135°, which absorbed bromine with -avidity. This in |

all probability’ was caprylidene, the boiling-point of which

has already been found by Rubien (loe. cit.) to be 133-134° ;.

} big was first

[fol. 725] its formation was doubtless due ‘to the prolonged a

action of the holic potash on the C, H., Br.

Action of orine on mixed hydrocarbons boiling at 122-— 3

125° —34 grms. of the qlanconeve were Ang out into -

“Amn, Ch. Pharm, vol oxi p. 294,

> , i ae aay ,

4 s a . ‘ ae $9: * , 1

: y yz ¢

wr . a bed 3 é

> ~ galt/and a gentle stream of chlorine sent through the liquid

‘

‘ darkened considerably.

The chlorinated liquid was then distilled in a current of |

steam; as soon as the distillate appeared to be, heavier than _

& inthe dark. The chlorine was_rapidly absorbed, and for.

the first hour but little hydrochloric acid was disengaged;

‘ “during the second hour and to the close of the operation,

<. the evolution of this gas increased largely, and the mixture =

oad

‘a small distillation-flash, immersed in a mixture of jive and a

rated, dried, and distilled. It commenced to boil at about. _

: - “water the receiver was changed, and the heavy liquid sepa-

- 920°, but.showed no constant boiling-point; but. the greater —

- | ‘portion came over between 230° and 240°. At this high.

“terperature the product suffered rapid decomposition.

The portion boiling at.230-240° was redistilled ina current — ;

- of steam. After drying over calcium chloride it was nearly

colourless, heavier than water, and of a pleasant aromatic

ee _ odour. Analysis showed that it was octylene dichloride.

02760 grm. chloride gave.0-4225 grms, silver chloride and 5

0.0100 grms, reduved silver -

“he portions of ‘octéine obtained aft

€: .

- distilled over sodium. The mixed liquid commencéd to boil —

at 118°, and about two fifths came over ‘below 122°, the

S , a Calculated " Found *

Sees nee ene SS ener A unokes ee eee

| i + treatment with. -

- chlorine and‘with bromine were then-mixed and repeatedly —

- " s pemainder distilling bétween 122° and 125°. Both frac- oY

tions were immediately reddened by bromine vapour. The.

+. 122-125° fraction was analyzed with the following results:

0:2970 grm. hydrocarbon: gave 09170 carbon dioxide: atid

; 04095 grm. water.

? oe SA es or Cala aoa,

ae AB ccc sees goes Scns enemas 8422 . 8420 —

a ee ee

10000 ° 9952

“The specific gravity of this fraction was found to: be

[fol-726] 0:7207 at 15° 5; the fraction 118-122° had the spe-

eifie gravity 0:7165 at 15° 6. Zincke found 0-7124 at 16° —

for normal octane*.

oe ‘ Ee ‘*Ann, Chem. Pharm. vol. elxi. kee Ibid. p. 281.

* 3940. .

ass ee eee 8 , diteityi, which boils at 193. 125°, has the -

_ specific gravity 07032 at.17°¢.

_. Action of * nitrogen tetroxide upon the octane and octy-

lene boiling . at °122-125° ——Many years ago Guthrie de-

“gseribed a solid crystalline compounded of amylene and —

nitrogen. tetroxide, C; Hio (NO2)2. So easily is this com-

pound formed that the, reaction ‘of the gas upon amyleme

constitutes.a, very good test for the presence of the olefine,

and ‘comparatively-small quantities of amylene may, by |

means of nitrogen tetroxide, be discovered and. ve er atone

from considerable quantities of quintane.

‘We have studied the reaction of nitrogen tetroxide: upon

a mixture of octane and octylene i in the hope of discovering:

- an-easier method of separating the two hydrocarbons. No.

solid nitro-compound, however, ‘was obtained. On passing

the gas info a mixture of-the hydrocarbons it was rapidly.

absorbed and a heavy oil separated out; this had an, odour”

resembling’ that of eaatie:olls but the substance could only

_ be preserved in the freezing mixture, and on- distillation,

even in steam, it was immediately decomposed.

. 8. The next well-defined fraction of the original liquid:

boiling between 100° and 200° distilled constantly at 145-

148°. It-was remarked that as this fraction increased in °

bulk, and the neighbouring ones became more free from oc- ©

‘tane and octylene, they gradually acquired a very charav-

‘teristic and unpleasant ‘smell, quite different from the:

' fraction boiling at 122- 125°,' A portion ofthe mixed hy-

- drocarbons’ was treated with bromine ‘in the cold. The

same.darkening was observed as in the case of fhe 122-125°

fraction; but it was by.no.means so niarked as in that in-

stance, and there was no difficulty in perceiving when a

decided excess of bromine had been added.. The following

are the détails of the experiment:

| Hydrocarbon ‘employed ;

' Bromine needed ......... aera ys Rete Oe ae ‘s

or to perme: |

ut. at the same ‘time gene oct ad

. the bicentins somone the liquid was treated with alco-

Tfol, 727] holie — and nee i ate for somé tire.

tion.

0.2820 grm. water. :

| ae

Water was then added, the dark iain oil separated, dried,

. and distilled; it commenced to boil at 150°, and fractions

were collected between every. 10°... The largest fractions

came over at 160-170° and 200-218°,

‘The. portion boiling between 200- 218° on repeated dis-

tillation boiled almost entirely between 208° and 212°, and -

_had approximately the composition C, H,, Bre

.0'4165 grm. bromide gave 0:3370 grm. silver bromide abd ay

| 00105 grm.' reduced silver,

Sine Calculated, | Found

BS ee $90." 363

"The quantity vbtained. was too. small to admit-of -parifica- At

A second yortion of the BGR re betweeii 145° and...

148°, was treated with fuming sulphuric acid. A conside¥-

able rise of temperature was observed, 80 that it was neces-

sary to coo! the mixture in order to prevent, as far as possi- ’

ble, the polymerizing action of the strong acid. -The super- *

natant oil was then decanted, washed with dilute soda solu-_

tion, dried, and -distilled over sodium. About half the

liquid camd over below 170°, after which the thermometer. g :

rose very rapidly to above 340°, when ‘the distillation was

stopped. On cooling, the dense. oily liquid in. the retort:

solidified. ‘The fraction boiling below 170° was redistilled

over sodium; it: boiled almost entirely between 145° and.

150°. It was then mixed with the hydride obtained. after |

treatment with: bromine (see preceding section), and -the

mixed liquids were again distilled over sodium. The boil-:

ing-point was unchanged, the greater portion of the liquid

} distilling at 147-148°. This liquid is nonans, as the follow-

ing analysis shows: — :

0:1970 grm. hydride gave 06080 ere, carbon dioxide and

Cenitiaen Found? .

Pe esa a ate, a

ETS take + ee Laie ts» 25 aca , 1563. 1592

10000 - 10008

* ae ee ee

A determination of its vapour- density afforded the fol- ~

lowing data: .° §-./, , . | Re

[fol. 728] Balloon with BIT. ok eee ts | (L3B050 germs.

. Temperature of air./.....°....- +>. st | ia, a naan

Balloo with vapour..........:..,.... , 140525 grms.

. Temperature on Wemling eee «209° ’

ge ES Se fe eg en ree Se raat tie ee gees

te PaERy: of balloon. °.......°: pres t et JI 168 cub. centims.

saga « Vapour- ‘dauatiy calcolnted |

hogs ior Oe “Hag (H=1). in Found.

~ 640 ine SVE ca ane

ee die

Its specific gravity was s 0:7279 ‘at 13° 9, compared with

water at the same temperature.

- It should be remarked. that no liquid boiling at about

145: 148° was discovered by Pelouze and Cahours in Ameri-.

can petroleum. The nonyl hydride isolated by these. -

chemists had the boiling- point 136-138°. -We have’ assured

ourselves that there is no liquid boiling at -abor 5 tem-

‘perature in the products obtained from solid paraffin. sa ell

«The boiling-point of the nonane iselated: by us. agrees.

perfectly with that caleulated on the assumption that the .

differences in the boiling-points of the simpler members —

of the Cn Hiss become continually: less by 4°, until the well, 9

nown difference of 19° is obtained.’ ( Schorlémmer. eS

Calculated boiling-point of Cy Hz» 146°. Found 147-148°.

Action of chlorine upon nonane.—About 15-20 grms. of

“the purified hydrocarbon were heated i in-a small flash fitted —*

to an upright condenser, and a current of well-dried chlorine .

was sent through the liquid. The apparatus was placed i in

~ direct sunlight. The action appeared to commence im-

mediately, the liquid darkened slightly in colour, and a

large quantity. of hydrochloric acid was evolved. The —

\ chlorine on ‘passing into the heated liquid appeared to burn,

‘a flash of light appearing at the end of the delivery-tube °

as each successive bubble of gas passed into the .hydro-

: earbons In order to prevent as far as possible-the forma-

tion high chlorinated products, the passage’ of the -

_ chlorine was occasionally interrupted and the liquid. dis-

_ tilled; the portion boiling below 200° was set aside, and-that .

is which came’ over below this: 2 Ss was submitted to the. —

3943

tion of the liquid was found to boil between 200° and 230°,

- . .about.2/5. boiling above this point. By repeate distilla-_ es

tion the former portion was divided into two portiotis—one

boiling at’ 190-198°, and the other boiling constantly at

{fol..729] 240-245°. The first frdetion on. analysis gave

numbers agreeing’ with the composition of nony] chloride.

1 Us 6670 grm. chloride gave 0. 5937 grm. a chloride

: further’ action of the chlorine. Ultimately the a3 por- i

and 0. 0100 grm., metallic silver.

IL. 05195: grm. chloride gave. 04930 grm.’ silve

. chloride AS

and 00080 grm. metallic silver. | Me

und |

‘Canalaoiae: I

ic eae ae en “928 "

ye P

The pa gravity of the nonyl, cioride: was found: to be

: 08962 at 14°. Pelouze and Cahours found the ‘so-called

pelargyle chloride to boil at 196°; its specific

~-0:899 at,16°. It is highly probable, however, in spite of the

_- concordance of these results, that the liquid 6btained by us.

was a mixture of primary and secondary chlorides; and the

_ ' game remarky i is probably applicable to the ‘produet ‘ob-

- tained by Pelouze-and Cahours. The fraction boiling at, |

about 245°. was in all probability Cy His Cl:, produced by |

. the further action of the chlorine upon the hydride; the

quantity, however, was insufficient to purify it for wens. Se |

9. The next well-defined fraction distilling ata constant

temperature boiled at 170-172°.. It was. treated with

bromine, with the following results: © i ras

| Weight of liquid taken ..... See ta ae woke ae aN 480 grms.

a Bromine needed.:............... oe SBE

Equivalent to decylene ........, Pies d ee pnt ee eg

The liquid was ‘too strongly sotlouah oe the bromine; it

was evident that too great an excess had been added. This

ee _-would make the amount of olefine too large. The quantity. 3

of hydrocarbon taken was too small; the experiment should —

have béen repeated on a larger scale. Our object, however, .

was to economize our material, as we could find no ready

method of “separating the brominated compound from the. -

ga N ;

3944 - | :

‘anattacked hydride without deopmipoajtion. Boiling with: ,

alcoholic potash gave.a very indefinite Tesult.

About 37 grms. of the mixed hydrocarbons were cauti:

ously treated with nitric and sulphuric acids, and the mix-

ture cooled to moderate the reaction. After standing about

17 hours the clear amber-coloured oil was separated, re-

peatedly washed, and distilled in a current of steam. When

about 1 of the liquid had passed over, the remainder in the

flash suddenly decomposed, becoming almost solid, and

' fumes of oxides of ‘nitrogen were abundantly: disengaged.

[fol. 730] The distillate, which floated on water, was dried

and distilled; it commenced to hoil at 169°, and all came

over ‘below 175°, after repeated distillation over sodium,,.

until the metal was no longer attacked ; it boiled PY

at 166-168°.

It was analyzed as under: Rs aa

02090 grm: hydride gave 06460 grm. tarbon-dioxide and J

‘ 0-2950 germ. water

\ Calculated Found

Tes ROA papi te elf ee EHO ee 2.1 8445 8430

Aes . Naaseatine eS back Baro" oie PEERY (1555 15°69 ©

Sah ARLES cna RCa 49000. , | 99:99

Its _speeifie-gravity. was 0-7394 at 13°: 5,’ compared with

water at the same temperature. Schorlemmer’s amyl (de- f;

- esityl hydride), obtained by the action of sodium on amyl

iodide, boiled at 158-159°, and had the, specific gravity a

07275 at 14°. It is very probable that this hydrocarbon is -

not the normal hydride, but #tands to the decatyl hydride.

boiling at 168° im the same relation that the amyl hydride

boiling at 30° does to the isomer boiling at :39°, or as the

. ethyl amy! boiling at 90° (sp. gr. 06819 at 18°-5) does to .

- the normal heptane boiling at 99° (sp. gr. 06915 at 18°). °

The normal decatyl hydride obtained by Pelouze and

- Cahours’ from petroleum had the specific gravity 0-735 at

"15°; the hydride found by Greville Wifliams i in the oil from

boghead coal had the specific gravity 0. at 18°." ag

A determination of the vapour-density thedeoatyl. :

bs et from naa gave the acecteaty seme a

Relloon: Wik abt eck ls oe _. 139745 grms.

Temperature of air..../........... 2.4 128

Balloon with vapour................ “* 14-9915 grms.

Temperature on sealing...::........... 222° ° iy heh

Residual air........ MSC rO RT re se Cr 0-2 cub. centims. _

‘Capacity of balléon....... Shona pelea . 1055 eub. centims.

Vapour-Density. Calculated for Cro. Hes (H=1)¢

, 3 ; | _. Found ‘

SUA ionig do SS Se 4 ae enh cued pela oe 72%

rar (2° The next fraction of the liquid boiling below 200° dis: .

tilled constantly between 192° and 197°, the greater por-

tion of thé liquid coming over at about 193-195°. The frac-

tion boiling at 193- 195° was treated with bromine, with the

_following results: . '

-[fol. 731] ° : ha

(1) 763 grms. required 476 grms. bromine. a

(2) 718-4. $8 hd ee os ene bce

* Mean..7405 =. $5 | |

- The fraction. boiling. at 195-197° was also treated. a

. 704 grms. hydrocarbon required $85 grms. bromine.

Assuming that the fractions are mixtures ef undecane

and undecylene, 4425 grms. of bromine would be‘equiva-. |

lent to 378 grms. of the olefine, leaving 3625 grms. of the -

hydride, or the fraction is a mixture of undecane and the

undecylene in equal proportions.

A determination of the vapour-density of the 180-106"

‘fraction gave the following data: | 9)

‘Batloba with On RT JAAS Lise he's +» 132640 grms.

- Temperature of air........... Lek 5 26 ae ae Woe:

Balloon with vapour........ a ave si kin erme.

_ 'Pemperature on sealing.:............. 261° —

Residual air... esha eu? an Ch PR oh

7 | Found. path: 811 Calelated 71s.

‘

‘=

s ~

po”

OTRAS gpa DE Nah

tne * °& Fraction boiling between 200° and, 300°.—By long-

, continued distillation ,over sodium the 2% litres boiling

—riginally between these limits were resolved gato the fol-

lowing fractions: Pe RE - cae

(1), 212-215°° He cp Mon

(2) '230-235° solidifies at —14°5t

, (3). 952-255°- St 6°5

(4). 278-2762 8, 290.

| # 5) (5) 200-2968 hen

"The portion boiling at 300° (in the neighbourhood of

315°) is solid at ordinary.temperatures. Lasoo t) saad

following details of the bromination , experiments

that the fractions were invariably mixtures of ole-

es and: hydrides:

Fraction 212-215°:

_ 448 grms. required 2:65 grms. of bromine.

_: Fraction 230-235°: a

art 423 grms. required 1:92 grm. of bromide. —

[fol. 732] . Fraction 252-225°:. .

(1) 938 grms. required 295 grms. of bromine... -°*"

(2) 8605 grms: required 267.grms. of bromine.

| . (3) 513 grms. required 1:54 grm. of bromine.

_.. Fraetion 273-276° : Fg iN

. + 789. grms. hydrodarbon reguired 2:04 grms. of -bro-

mine. tag | rages Mia oti ate Ph eae <

42 It has already been mentioned that, on the first dis-

- tillation of the oils obtained by. splitting up the 34% kilogs.

of paraffin, a considerable amount of | ubstance (which

could not: be distilled within the range of ca thermometer) ©

remained in the retort and solidified on cgoling. This sub-

_ stance: in its erude condition melted at 31°, but on recrys- |

tallization from ether the melting-point became higher.

‘The whole of the substance was therefore cut up ‘into small

fragments, and spréad upon filter-paper to remove adher-

ing oil as far as possible, -and repeatedly recrystallized

from éther until the meltizig-point was unaltered. — Ses

PR , ‘. pati ; rs | . , ‘Wig bial .) ae

‘ . ‘er ‘ +. 8 ; ‘ ie ‘ , - sa! . ‘ ; “ ; , 7 ? eet

_ * These boili>g-points are uncorrected. a

ts of solidification are only approximative.

riba PRS Faget: oot

i 7 eae, hats

It meltéd invariably at 41°5.and solidified at 40°-5; it

could not be distilled within the range -of the merenial, ”

» . thermometer. athe: Re agar ties © ih ‘,

‘-- Tt erystallized from’ either in beautifully white satiny _.

- seales, and gave the following numbers when burnt with. —

oxide of copper in a stream of oxygen: ys pet

03035 grm. gave 09590, grm. carbon dioxide and 0-419.

gym. water... |

Chg cor ck Sect hips we lateral Geen

_ Hydrogen He Het Deak mamta ine ger nee y hee Nos Fe

Action of Bromine Upon the Solid Paraffin Melting at

“41°5.—A few grams of the substance were dissolved in bi-. -

sulphide of earbon, and four minute drops of bromine

_ added ; this’ small quantity of bromine sufficed to colour the

liquid strongly. On standing from 12 to 15 hovrs, the

colour appeared unaltered, and, the solution was not de-

colorized after heating from 60-70° for 12 hours. ‘On heat-

ing ‘the liquid to.150°, the. colour disappeared after a few —

- hours; and on opening the ‘tube hydrobromic acid was ©

evolved. About 10 drops of bromine were again added,

and the liquid reheated to 150°; but.no diminution;in the~

red‘ colour of the solution was perceptible, although on |

-opening:the tube dydrobromic acid fumes were abundantly

disengaged. This observation would .appear to indicate

[fol. 733] that the hydrocarbon melting at 41°5 is a mem-*

ber of the Cn Hens series. iti ke cin went

Action. of heat upon 41°5° paraffin,—Repeated crystal-.

lization from ether having failed to alter the melting-point

». of this substance, and the behaviour with bromine evidently

indicating that it belonged to the mnarsh-gas series, we con-

sidered that it would be interesting to study the :combined |

action of ‘heat, and pressure upon it. The details of the

‘experiment have been algeady.given in section 1:. After six .

distillations it. was rendered completely liquid: It began

to. boil at about 40°, and’ about one sixth came over below: -

100°, about one “third between 100° and 200°; and-the _

- greater portion of the remainder ‘below 300°;. the small

_ quantity remaining in the retort solidified on.cooling. .

» Ha

Mend

ad @ .

908 Ca Pin ek ge a

Ina seegnd experiment (He action of bromine upon the’ a

__ liquid’ hydrocarbons was quantitatively determined :

wag of liquid hydrocarbon taken: :~.:. 598 grms.

GMs bromine required before the liquid. |

was » reddened . na nay) PER oa eat EB 307. ‘

The action of the ikouitas was very energetic, and it was

hecessary to moderate the reaction by cooling the liquid.

It is evident from these experiments that the solid par-

affin (a Cn Hy.) had been split up by heat.and pressure ;

into a mixture of hydrides and-olefines.

. ®

(fol. 734] TRANSLATION OF Perrrioxzn’s xesrr No. 97

Berman Patent No. 37,728

Class 23: Pat Industry Kj Piath,

Salle

‘opis for Sapstantie off Light Hydrocarbons and Ob-

_taining Viscous or. Asphalt-like Qils from Paraffin Oils,

ete., by Distillation under Relatively High. Pressure

Patented in German Empire from, Febranry 28, 1886. Is-

"sued December 17; 1886

“The process heretofore employed for the distillation of.

heavy dark paraffin oils (brown coal tar oils), crude petro-

leum or residues from the refinement of the latter, or of the

tars obtained in the preparation of oil gas from paraffin oil

‘ or petroleum residues, are al] subject to the objection that —

‘the yield in light oils, such as benzine and illuminating oils, |

is relatively small and that the tigh-boiling ingredients,

ft behind are in many cases of inferior value as lubricants.

/and for other purposes. Thus, for cedphiis the heavy dark

.“paretin oils {brown coal tar ols) have heretofore -been

used only for the ee ek or the production’ —

of ierarede lubricants (anxle grease). The possibility of

sites braces ects meals, i iad ae

he} |

3049

e tion of- oil gas from petroleum residues has heretofore also_

been precluded.

- Numerous experiments on a large scale to subject such |

oils,. residues, .ete., to distillation under pressure, in the -

. course of which extenbive decompositions. take place, have

_ shown that vt such a process the yield in excellent light oils -

» (benzine -and illuminating oils) is considerably ‘increased

. and that the immediate residues obtained. find a reddy mar~

_’ ket as vety good lubricating oils and asphalt oils::

. /The most advantageous pressure for the decomposition

of the oils is quite definite for each kind, the yield in the /

different products and the lossés due to gasification de-

pending qualitatively , and quantitatively on the degree of -

pressure, Experience has shown that for heavy paraffin ~

' oils (brown coal tar ojls) -the most suitable’ pressure is 3

(fol. 735] to 6 atmospheres scnocding to the nature of such

oils, for crude. petroleum and. its residues 2 to 4 _atmos-

pheres, and for ojlgas tar 4 to 6 atmospheres. |

The apparatus ‘wsed for the distillation prider pressure

of the materials referred to consists of a distilling vessel

fitted with a safety valve, inlet pipe, ete., a. condensing coil

and a valve, . The distilling vessel is made of cast steel and

has, genérally —? the shape of the distilling vessels

commonly used in the brown ‘coal tar industry. When the

parts swept by‘ the fire are heated to a red glow, the vessel

. must continue to be impervious to the contents heated to.

about 400° ‘at a pressure of 10 atmospheres. The' tube of .

+ the condensing coil connected with the distilling vessel may ,

. be of-less diameter than for distillation in a vacuuin or’ un-

der, norma] pressure.

“The valve interposed between the distilling vessel. and

eidaiaiue coil is so arranged that it will o mae

cally and establish communication between the distill

vessels and condensing coil as soon as the pressure desir

for decomposition is attained. « |

__. . When fire is first started under the distilling véevel the*

om 9 a Pig geo between the distilling vessel and the condenser

Von f. eft open by putting. the valve in the Praber position, .

teehee il all the-air has been displaced by oil apure.qnd tis.

ae fp ecting pipe begins to heat. ‘The valve is then adjusted

- ee or the required pressure ‘and, the distilling ‘vessel ‘more, ¥

‘ ~inténsely heated. Woes the Somieee sence ae at-

WEY, eo

“3980 fe ae F

tained it lifts the vabeks allowing the * vapors. to enter the :

condensing coils, in which they are condensed.

The effects of the above described distillation under. pres-

.stfre may be illustrated by the following results obtained ) in

“b distillation on & large scale. ?;

_A dark heavy paraffin oil of 0.912 apevific gravity at 17. 5°

-canda viscosity. (according to Engler) of 2.5 was distilled. =

: 15%: ‘(by volume) passed up to 300°, the remainder at a -- |

higher temperature. The distillations under a pressure of

about’3 atmospheres showed that. the decomposition prod-

uct distilling over does not vary essentially whether taken >

off from the contents of the distilling vessel in amounts of

80% or of 80%. It forms a brown very mobile fluid.of .

* 0.820 spee. grav. at 17.5° C.- This decomposition, product . -

is absolutely equivalent to the crude illuminating oil of — .

-. brown coal tar, and when treated with chemicals and dis- .

. filled in the usual manner it yields a water white illuminat-

[fol. 736) ing oil of 0.815 to 0.820 spec. grav., a f flashing *

. point of:about 30° ¢. and of great illuminating power.

}+ When 25 to 30% of distillate is drawn off there remains »

ie residue having a viscosity of 7 to 10,\a spec. grav. of

. 0.930 to 0.950 and forming a profitable ‘lubricating oil of

good quality.: When moré than 30% is drawn off the resi-

- due becomes more and more asphalt-like, so. that, whert

50% of distillate is drawn off, there is left behind a black.

lustrous asphalt oil of 1.005 spec. grav. When 80% of de--

‘composition distillate is drawn off the residue hardens into

-.a coky asphalt. —

For distillation under a pressure of. 3 atmospheres the-

loss dué to gasification, with 25 to 30%. distillate drawn off,

amounts to 4% (hence not much more than at normal pres-

- gure) ;-with about 50% of distillate drawn. off to 7 Ze; ; and

. with about 80% of distillate drawn off to 15 to 18%. | ae

- When the process of distillation under pressure is ap->.

- plied. to shate oil and petroleum, the best method is: to ab-

- gtract from thé crude oils, by ordinary distillation, the light

oils up.to 70 or 15% residue and then to decompose the ,-

‘residue under pressure, drawing off about 50% of distillate.

An Alsatian petroleum (Pechelbronn) of 0.880: spec. grav.

' treated-in this manner yielded 15.32% more illuminating’ __

oils than with the usual distillation, being about one-half

-more 6 than the uenal yield... The residue 4s ugar to that “5

ee. a eae Ne a mgt es * S081 -

a obtained from the method of épentantnt heretofore em-_

» ployed | and may be used in the preparation of.asphalt or, — .

|.‘ when. redistilled with super-heated steam, it can. be made

, . into lubricating oils.

When the distillation under pressure is applied ‘e: the

- tars left behind in the manufacture of oil gas, similar re- _

_ sults aré obtained. The yield in low- boiling oils amounts to .

‘about 2% times the yield: obtained with ordinary distilla-

tion, with a thickened residue, and without the formation of, - _

‘. .the usually obtained. intermediate oils of 0. 950 specific :

: gravity. eat

Claim

: Process. for senda by distillation ander a pressure |

- of at least 2 atmospheres, light hydrocarbons (benzine and

s' illuminating oils) and simultaneously viscous lubricating ©

‘oils or asphalt-like oils from heavy’ dark or light-colored —

paraffin oils (brown tar oils), crude shale’ oils and petro-

leum, residues from the refining of crude naphthas, from.

the tars resulting from the preparation, of oil gas from

"| paraffin oil or petroleum residues, and” from all other .-

mineral oils. }. 2:

Nak ak 2a!

53-15. Re 4

6-28-15 (8506), eee

[fol, 737] ‘TRANSLATION. OF PrririonER’s Exutsrr No. 98 :

| Berichte der Deutschen Chemischen Gesselechait

Vol. 30, Pages 2919-2920

| This result i is confirmed biy the apec: gr. compared with

__ . the light refraction index of the different fractions before,

ie meroteeald removal of the olefine, the benzins, and the

- naph es, and in this respect exhaustive determinations | .

_ were made ‘(see: Gruening, phere ce Switeerland; disserta-

tion). Pe ee Se

_/ > Hence, apart from. ‘paraffins’ end vihylense 3 in the main,

_. also. ne. phthenes and benzin hydrocarbons are formed at

ae comy paratively low temaperasares by _ a process. |

| ee

: 3952

te Dissociation Oils Resulting from High-pressure Distilla-

tion of Heavy Mineral Oils

, (With the collaboration of C..Schneider)

The distillates which are obtained, by’ the Krey process

~ (G. P. No. 37728) as products of the dissociation of high

molecular hydrocarbons deserve particular interest. Both

from the petroleum oils with high boiling point as well as

from heavy lignite, oils, such as paraffin oil, etc., it is pos-

_ sible to produce light oils by high-pressure distillation, sim-

. ilarly as by the method of Thorpe and. Young, and these

light oils are useful as burning oils.’ 'Fhe oil which: Mr.

_ _Krey was kind enough: to place at our disposal had_ been -

‘obtained from heavy lignite oils by’ pressure distillation, the

pressure being as high as 6 atm. approximately, and the

yield of this distillation process ranged: between 30. and

’ 60% of the raw material, -according to how og) the distilla-

This: pressure distillate - constitutes a sates mobile .

- (fluid) liquid of a reddish-brown color exhibiting weak’

fluorescence, and giving off a disagreeable smell. Its spec. -

gr. was. 0.8301. Elementary composition : C-84.67 and. 84. 83; .

. H = = 13.93 and 14. 30;S=0. 80%, Boiling point:

Below 100° 100/120° 120/140° 140/160° 160/180" 180/200° 200/200°

* 220/240° 240/260° | 260/280° 280/300° Over 300°

11.5 12.6: 422.8 8.6 8.0% by volume.

[fol. 738] Only the normal paraffins 7 were isolated ; but it

is probable that also sécondary and tertiary paraffins were

‘present.. From the different main fractions (whose boiling

__: pionts were concentrated by the aid of dephlegamators) the |

olefines were combined with bromin, whereupon ‘the non-

bromated portions were distilled off; next the ‘substances

were treated with fuming sulfuric acid in order to elimi-

nate the naphtheries as far as feasible, and they were finally

fractionated repeatedly to obtain definite boiling igen In |

- - this way there were obtained:

‘Pentane: boiling point 37-39°, spec. Br 0.6251 (20°). Se

Found C 83.50, H 16.61. Calculated C (8. 33, H 16.67.

3 d=2.51 (calculated 2.49). es ee

| LO

: 4 ae a pie

Hexane: boiling point 68-69°, spec. gr. 0.6670. Found C ~;

83.55 H 16.12.. Calculated C 83. 12, H 16. 6.28, d==2.94 (caleu-

lated 2.98). .

Heptane: boiling point 97, 5-98.5°, spec. “gr. 0.69-24.

d=3.44 (calculated B47) 20%

Octane: boiling point 124-125°, spec. gr. 0.7124. Found

C 84. 20,H 15.58. Calculated C 84. 21,H 15.79. d=3.90 amel |

culated 3.95). |

Nonane: ‘hoiling point 148.5-149.5°, spec. gr. 0. 7296.

d=4.55 (calculated 4.43),

The proof of olefins was carried out with sulfuric acid) -

and bromin substantially in the same manner as previously —

described. Ordinary concentrated sulfuric .acid absorbs:

from.the crude distillate from.34 to 35% by volume;. hence, |

the same consists approximately 2/3 by volume tf etl |

rated, and 1/3 of non-saturated hydrocarbons. |

In the several fractions there were found: Ae rate

ee Fraction 35-40° 8.25 grams consume 8.13 gr. bromine cor-

fe _ responding to 44% amylene. -

Fraction 67- 70°: 11.52 grams consume 9.61 gr. bromine cor-

ay responding t6°41% hexylene. BP Ye

Fraction 96-99° ;.13. 93 grams consume 9.80 gr. bromine zor- -

: responding to 43% heptylene.

sa “The presence’ of. natththenes may be taken to’ ‘be ex- =

tremely probab-e, judging from the change in spec. gr. and

in the light refraction index of the different fractions of the

-0il prior to, and after, treatment with concentrated followed -

[fol. 739] by. a. treatment with fuming sulfuric acid. (For

_further details see C. Schneider, Giessen thesis. )

. As regards benzol hydrocarbons, it was possible to dem.

onstrate the. presence of benzol in the form of nitrobenzol. ”

__and by the fuchsin reaction in the fraction-75-96° and the _.

esénce of mesitylene and pseudocumene i in the. fraction :

3 160/180° in the. shape of the typi¢al trinitromixture. having

a melting point ranging between 166-167°. By. re-erystal- A

lization from benzol, the mixture could be separated into _

. . trinitromesitylene (fusion’ point 232°) and ane trinitro-

psendocumene (fusion point 185°), :

8378 (OT Mee ee a

'- Also in the dissociation process by distillation of heavy

lignite oils in the presence of high pressure, aceording to

‘the findings obtained, the formation of paraffin-like hydro-

carbons from hydrocarbons poorer in hydrogen must' be as-,

sumed. ~

' Karlsruhe Chemical Laboratory. . :

: .)

[fol. 740] TRANSLATION or Petrrioner’s ExHerr NO. 99

Translation ‘ from Berichts ‘Deutsche Chemische Gesell-

thes schaft, Vol. 21, pp. 1816-1827

331, C. Engler: Concerning the Formation of Petroleum

(Reoeived May 28, ‘Presented at the Meeting by W. Will

oe his excellent Wak on “Petroleuny -

and related substances came to the conclusion on geological —

‘grounds that petroleum must be of animal origin and ‘that

for its formation the remains of animals of earlier geologi- |

cal epochs, especially fish, gaurians, coral animals,.ink fish,

. Mussels and other ‘molluses have contributed. It is well.

_., known that this hypothesis is not new as even ten years .-

_ago, the statement'‘of Hoefer found its followers in Leopold

-y. buch,.Bertels; Fraas, K. Muller and others and later in

: geologists who have been concerned with the apeparance of

bitumen or petroleum in America, as Wrigley Whitney,

Hunts and others, moreover.in Ch. Knar, Credner, Eck,

Zinken, Paul, Tietze, Uhlig, Piedbeué; and holding first

is the fatty substances developing in enormous masses

[fok 41] in the marine life of every-animal are used as”

| raw iterial for the formation of petroleum.

: especially interested me in the conclusions of Hoe.

__ fer, who on account of his own rich experience is instructed —

_as few others concerning the conditions under which petro-

- leum is found in its numerous fields, was the proposition |

“that from geological reasons—similar to those G. Kramer

derived from the chemical point of view—petroleum could

7 patie resulted only with high pressure and not too high -

_ temperature , since this statement happened to be in agree-

~ ment with the experiments that I intended to: make relating’

fo - — of animal fats under great _— :

I. am giving here a short account of the rebated of my ex-

’ - periments up to the present, as they ‘are perhaps capable of -

assisting in filling up a gap in the theory of the formation —

of petroleum from animal remains. ce

Dr. Krey, Director of the Riebeck Mining Co., of. Webau, |

Saxony was kind enough to permit me t ake. my experi- —~

ments with the aid of the apparatus paténted by him (Ger- .

man patent 37728) which made possible the distillation. at /

a pressure of up to 10 atm., for which I wish to offer hiny As

my thanks.

492 kilograms of brown North American train oil. (from

Menhaden, Clupea tyronn., caught on the west coast of

_ North America, 1-1.5 kg. heavy) of sp. gr. 0.930 were/sub- |

“jected to distillation in the apparatus. With an original

. . pressure of about 10 atm: which however, descended to

| - temperature of 320°, towards the end somewhat above 400° .

C., besides ‘combustible gases a distillate passed over which

separated into a lower hydrous and an upper oily layer.

The latter was collected in fractions and those which th:

testing showed a still considerable portion of unsaturdted.

fats or fatty acids (in all 217 kg. of the distillate) were ‘sub

_ jected to another pressure distillation. In all 299 ke. of |

oily distillate was obtained which corresponded te“an ae

_. put of about 60%. About 20 kg. hydrous distillate was col-

+ lected but unfortunately. it was impossible to prevent con- Me

*. giderable amounts of steam and: light boiling oils to be —

- earried-along’ by the gas current which’ was at times very

. powerful. Still-the condensation was ‘80 efficicht thatthe

oil after surface purification began to boil even at 34°. °°

-[fol: 742] The erude oil distillate is of a brownish color,

| transparent in thin layers,- with very green fluorescence |

and withont unpleasant odor; the pungent odor of acrolein

_ig Jacking. Sp. gr. 0. 8105. | Upon agitating, it gives: —

Mo. water’ ....00.-..0 soe ah vals aie ey 0.4% Vol. Pee

Ria potassium Wye n-ne ewves snow 48%

sig . Mixture of Engl. & fuming sulfuric acid: apa

oe. A fractionated distillation of 100 com.—8i gr ; of the’

ae erude. oil according to the method | described Fg me ‘else-

ae ernie 2 cata: ce tae :

') Mo 125° 125-150 150-175 178-200 200-22 225-250 2502275

* Ged: MBBO8 10. 6 9.5 10.5 11

gr: aha Sade 15.5 5.5 . 7.5 - 5 s | 9 9

bpaeess “88. . Es (reldag plus 188)

Under 150" 150-300 Over 300

‘i sansa cibetaapeda's pee camecenet es 2.5 *\ 87.6 - °12 |

POMBE ccctccccrccccwoscces reseoceveccces 25.9 58.0 16.1

¢ 7 > eee ererer eee eer een eeeeeeeee e eeeeeeeveae nines 0. 817.

: First, the ‘att bailing’ under . 150° was subjected * a

- more. thorough examination. For purifying, I treated it

successively, and occasionally with: repetition, with con-

eentrated sulfuric acid, then a mixture of 2 parts English

' and 1 part fuming sulfuric acid and finally with sodium

. lye and water. 37% volume disappeared by agitating with

‘sulfuric acid which as.the fatty acids boiling under 150°

‘must be found. mainly in the hydrous distillate, gives an :

approximate basis for the mixture proportions of the hy-

drocarbons (saturated and unsaturated) contained i in ‘this

oil fraction. During the examination of the latter (as well

- fi other parts of the work) 1 first of all separated the

former, present in different main amounts, by fractional

distillation, as possible, and in this way isolated the » follow-

- ing hydrocarbons. —

A pig i pentane with boiling point 36-38°, sp. gr. 0. 622,

'. vapor density 2.51, carbon 82.81, hydrocarbon 17, 10, ( calen-

lated 83.3 or 16.7) % which valnes correspond satisfactorily

to those given heretofore for pentane. Neither. bromine nor

hot fuming nitric acid act on the‘hydrocarbon so that its

- identity is established indubitably. .

[fol. 743] Normal hexane, boiling point 68-70°, ‘sp. gr. .

: 0,664, vapor density 2.876, carbon 83.40, hydrogen 16.58%

(calculated 83.72 or 16.28%). ‘On this: hydrocarbon as well

as on the following, there is. no action of bromine. and:

a yee heated nitric acid. - a

: - Normal heptane, boiling point 97-99°, sp. gr. 0.688, vapor.

3.35, carbon 83. 19%, bydrogen, 16. 29% (Calculated

84.0 or 16.0%).

~The hydrocarbons octane and nonane of. the normal ~ bb:

o me « are likewise ade known seesaue ita to. their ssi ‘ i

fn @

\ 3957 i

ing sont inl sp. gr. but have not been examined in detail.

_ Moreover, the behavior: during the distillation leaves me

_ no doubt that hydrocarbons of the secondary series are

.rial which is called the ‘‘inextricable mixture”? of ayaeb-

carbons of petroleum byeSchorlemer.

As train oil is a mixture of triglycerides, mainly slete

acid and moreover palmitié acid,: stearic acid and fatty

. acids peor in carbon, it must he of interest to learn the be-

havior of the diff€rent glycerides in pure state under like *

‘conditions. Therefore, I have first- subjected tri-olein and

tri-stearine to a pressure distillation in small amounts.

_ The glyeerides:- were.made artificially and purified as pure |

' oleic acid or stearic acid with pure glycerin according to _

- the Berthelot method. As apparatus I u Theat glass tubes

. bent at. an. obtuse angleeach-charged with about 30 gr. of .

the stibstance, then fused shut and inserted in a digester”

_. so that the empty leg, bent downwards, projected outside.

_ . After heating for about four hours at about’ 350 deg., the

tubes were rerhoved, the gases let out and this operation

repeated (on an average 4 times) until upon formation of

ended. Preliminary tests with train oil had shown that the -

reaction is exactly similar, to that with’ the pressure te

_ | Pricolein gives besides water a light oily product whieh oe

~. develops gas even at ordinary temperatures, begins to .

boil perceptibly at about 300° and contains about 50% in

weight of pafts boiling under 300°. The residue from the

_ distillation upon repeated treatment in the’ closed tubes

then gives moré volatile oils so that by repeated treatment, —

the tri-olein can be changed -almost completely into prod-

ucts of dry distillation. It shouldbe mentioned here that

in certain tubes only a, very small amount of residue re-

. [fol. 744] mained after repeated heating of the olein under —

_ ’ pressure, the olein thus under certain conditions changing -

nearly entirely into volatile distillate and gases: without

_ removal of parts of the distillation products. svcd

- Tri-stearine, treated in the same way, gives about 60%

- of oils boiling under 300°. Othérwise, the behavior is the

same as with the olein, only great’ quantities ofestearic acid

‘gaa at. the — in the cold _— ‘of. the ——

“3958 |

Although it can be Assumed from general reasons that

the fatty acids participate alone in the formation of vola-

-tile hydrocarbons, jt still appears importaiit to verify by

some direct ‘experiments of heating free fatty acids alone

.. the analogy of the course of the process. Pertinent obser-

vations are to Some extent available without however offer-

ing a satisfactory answer to. the question, as is evident

from the gontradictory statements. in our textbooks and

handbookg. Gottlieb (2) in 1846 called attention to the

hydrocarbon occurring with other products in the distilla-.

tion of/oleic acid, likewise W. Heintz (3) in 1855 observed °

ie fematn of small amounts of hydrocarbons of the

ethylene series in the distillation of stearic acid in a hydro-

n current and Fremy. and especially Berthelot, (4) no-

Aiced. the occurrence ‘of ethylene hydrocarbons among other.

/ products in heating oleic acid alone’ or with alkaline bases.

: Bolley and Bergmann (5) ‘obtained a like result upon heat- -

/ing oleic acid to 320°. Cahours and Demarcay (6) more- -

/ over isolated liquid fatty acids with low carbon content’

(baldrianic acid, capronic acid, etc.) and saturated hydro- .

_ carbons (pentane to nonane) from a by-product which was

* obtained in the Fournier stearine factory from crude fatty —

acid distilled in superheated steam and product of sul-

phuric acid saponification; and finally G. Johnston (Z) sue-

: eeeded in disassociating stearic acid by distillation of solid

_ paraffine under pressure in a way similar to that of Thorpe _.

. and Young (8); i.'e. by,superheating ‘in a tube placed on,

one side in a gag combustion furnace and effecting the .

cracking into water, carbonic acid, paraffine, olefine and

ketone. a eae ue eae Bess Rts aoe eres

Tf the free fetty acids are heated in the above described

_,, way to 350° or a little more, with oleic acid there is ob-

_ ‘tained very soon, besides water, light: hydrocarbon oils:

just as.with olein and train oil and when stearic acidis

heated exactly the same result is given. The last result _

proves the observation of Johnston in contrast with that

‘of Berthelot, the latter stating that th |

by liaise | tho change in the shail: acid can be sstieal :

' “especially no development. of gases, while the formation of |

liquid decomposition products begins at once when a part

of the tube, bending downwards, projects outside so. that

the products of disassociation can condense. . With oleic

acid on the contrary, and likewise with train oil, the de-

composition takes place even tn a pipe heated throughout.

Gases and even.combustible gases, chiefly swamp gas with

“which however there is always mixed a little carbonic acid,

_ likewise water are to be noticed if above ‘all decomposition

or formation of hydrocarbons has taken place.

__ A distillation of the train oil used for the above experi-

ments .in a vacuum shows how different its behavior is |

upon heating at low: temperature. Train oil distills over to.

4/5 of: its weight with generation of combustible gases and -

the distillate stiffens to a light-yellow butter-like mass which

contains only about 10% hydrocarbon, and moreover is coni-

pletely saponifiable: water appears in only exceedingly ae

small amount. ;

‘By the observed behaviour of. animal fat in heating un-

' * der pressure to not too high temperature and especially by-.

the surprising result of obtaining 60% of weight of the fat

in crude oil, which to more than 9/10th consists of hydro- .

carbons, there appears-to me that a new witness to the

truth. of the theory concerning the formation of petroleum ;

from animal remains has been found. oe

If it is considered that there are weighty. arguments

' against the formation of petroleum by: inorganic means as _~

Berthelot, Bryasson, Mendeljew and others have contended, _

- (9), there remains only the assumption that dead plants or

animals have contributed the raw material for.the forma-

~ tion of petroleum. ° If the formation from plant remains is

‘assumed, there must have been a process of dry distillation,

. . even though at low temperatures—as G. Kramer correctly

deduces from thé,chemical properties of petroleum. Then -

however, there would be coal-like. plant: residue in the neigh--

fields—assuming secondary fields, whi -has-not been the

case with all the important oil fields examined up to the —

“present. .On:the other hand it would be expected that in

_. . [fol. 746] coal beds or the neighborhood of the same, liquid

ae bicaaetae or other bitumens should appear .oftener — 3

formation process of petroleum fron animal rere fg |

in larger quantities... However this asiumption is not met

either as where liquid hydrocarbons are inclosed in coal

beds or trickle out of the same, it ts found upon further con-

sideration that they never. appear in the bed itself but that,

the oil occurs rather in other layers, as for instance at the

well-known coal beds in Wombridge, England, in sandstone

or inside coal beds in combination with strata which show

animal remains and it is lacking in the coal districts, above

all in all minéral coai districts.

On the contrary it has ‘been determined that wherever

petroleum is found in primary fields, plant remains are not

seén at all or only in very unimportant amounts but on the

contrary animal remains or undoubted traces of the. same.

are regularly seen. Of special interest from the chemical

point of view are the ortho ceratites in the Trenton lime-

stone at Packenham in Canada, whose living chambers .

sometimes contain up to several Ounces of petroleum, as —

‘demonstrated by T.:St. Hunt, and likewise the occurrence

_ of petroleum observed by Fraas as a kind of exudation of

coral reef now projecting above the. level of the. sea; on the

shore of the Red Sea near Djebel Zeit. Similar observa-

tions have been. made with fossil ¢ordls’ in Canada: with

Carpathian fish schists and even in mussel limestone, small

_ Hoefer calls attention to the fact that all schists which pro--

_ duce large amounts of hudrocarpon oil upon dry distilla- a8

-. tion-are rich in animal remains while. they show relatively

smal] amounts of plant remains, and than minerals con-

taining large amounts of plant remains dre as a rule not -.

bituminous but they usually become bitminous as ‘fhey in- --

clude animal remains. age Se 2 a

That petroleum originates from marine fauna (assum-

ing animal origin), is-corroborated not only by the animal °

remains in geognostical relation to the same, but also by

a whole series of other circumstances, among-which the _

water ‘containing common‘ saJt ‘usually gushing ut or

_ pumped out with the petroleum does not play a minor patt,

_ It is perhaps not untimely to describe more in detail the

a purely chemical standpoint. As ‘chemists and-more

customed to working with plant substances, we are inclined

- t0 consider them as the foundation of the. formation of- »

3961,

petroleum likewise. If however thie paleontologists bint as

[fol. 747] immeasurable amounts of. animal substances at .

our ‘disposal, as is easily done considering the great mass ,

of their fossils; the question of the formation of sovedirrergi

from animal remains—disregarding geognotic relatio

warrants the same claims as that of formation from pl at

remains.

iF proceed from the assumption that the. question put by '

et De er (10) as to “whether different temperature and |

, préssure conditions: govern in the formation of the paraffine

oo and naphthene contained in petroleum, should be answered

in the affirmative according to his'‘own example, that fur- _

~ -..- thermore both from the character: of the substances com- ;

> posing the:petroleum and fram the lack of carbon-like’ resi-

‘ . dué-a distillation process at considerably lower tempera-

‘ture must be assumed and perhaps more probably, that the. ./

‘ “pressure, at, which the hydrocarbons of petroleum: were ,

_ formed from animal remains wa often such that it often \~

“caused the condensation of the produé s formed. In this _

relation, I recal my e eye in whie succeeded in

disassociating train oil for the/ greater part into hydro-

earbon oils, water and by-products by heating. to 350° in -

closed tubes without an extension serving for conden tion ee

of the oils formed. Just asin these closed twhes, it is —

' pogsible that the animal substance of earlier geological

__~ epochs has been subjected to this high pressure surrounded -

_- by impermeable layers and in closed receptacles. An view

’~.. of the sedimentary starta deposited above the ‘petroleum

“fields, we do not lack proof positive .of such pressure,

-Packenham. filled with ‘petroleum are such eceptacles on

a small scale. “It is not impossible that in certain cases the ~

_ -pressure of the sea water above the. starta has’ evoperated,

: the coral banks of Djebel Zeit wi their exudations of pe- |‘

troleum obeetred st Fraas appent 9 me to be proof of. the

fact. :

The lack of'a series of chemical’ ot kenpotusidia: which, as for E

instance acrolein, allyl compounds fatty acids ‘with less. —

carbon content than products of fat dec omposition, it would —

seem should be pres t, is not astonis if.it ig taken —

.\* into account that with thousands of years contact: of the *.

ea ‘ oomaa with water, those subst nces: — in a water A

4 \e

ty gee: eS :

“\ . ae oe > 4

‘ ‘ . - « ~ 3

a2 ob . 4 . *

would long ago have Kean washed out, without considering

that glycerine, as given more in detail below, can have been

‘separated out and carried off even before the formation

of petroleum. Testing of crude petroleum in this relation

[fol. 748] from indubitably ‘primary fields would be of

greatest interest. ,

' On the contrary it seems astonishing a first thought that

nitrogen .is lacking in petroleum. However, this discrep- .

ancy even though not in le same degree would still appear * —

extraordinary if petroleum originated from plant. remains, —

although the latter contain considerably less nitrogen, since

we know that in the products of their dry distillation not.

_ inconsiderable amounts of nitrogen: compounds are present.

Disregarding the bases contained in the true animal, all the

nitrogen of our ammonia and its salts originate. from coal,

thus form such‘plant remains. Nitrogen, however, cannot : -

_ be noted as entirely lacking i in all petroleums, it has rather

been positively detected in a series of such oils, i. e. by

~Peckham in several American oils, by St. Claire-Deville and

_ Boussingault i in Alsacian crude oil, by the latter investiga-

. tor in a petroleum from. China (Ho Tsing) likewise, by |

‘. Delease in mineral tar from Trinidad etc., Feodorowicz |

- noticed ammonia in petroleum froni Siary (Galicia) and

Carnegie observed s. of ammonium -carbonate in- =

- In this connection lowever, one cok should be referred A

_ towhich appears-to me to have received too little considera-

. tion in all former examinations of this question, which how-

ever upon closer inspection appears natural,—that the oc-

-eurrence of nitrogen in crude petroleum i is the exception.

‘While I ami very well acquainted with-the fact that in the

chemical nature of the chemical compounds. composing ani-

mal substance and plant substance there is no very sharp

difference, that plants, for instance, carry substances con-'

taining nitrogen, fats etc., as important constituents for: —

their life and propagation as well as the animals it is how-

ever clear. that in the organit substance of the animal. world —

there is more questiqn of the presence of two. contrasting

show a certain unity"in their main mass, the former con-

sist of concurring parts of nitrogeneous muscle substance

| and fat free cage Paroeet in nesaals main a: error =

: the sea ani als which are chiefly snl cinahdebitlien hore.

The durability of these two substances is however very dif- , — -

ferent; the nitrogenous substances rapidly succumb to rot .

and decomposition, the fats do not. It is certainly to be

assumed not unqualifiedly that in the agglomerated animal

as corpses of prehistoric world the decomposition went on in

two main phases: : that first the nitrogenous substances de-

[fol. 749] composed, thenitrogen being volatilized as such = _

or in the form of ammonia and its compounds or perhaps ‘

_ in still more complicated forms or being carried away by

. water, that the fat remained. behind (it being not:impossi-.

. ble that in egrtain cases the fat was carried to secondary —

beds) and only at a later time was converted to petroleum -

’ by pressure and heat, perhaps chiefly by-the former. In

this relation I recall the-research of Gregory (11) but more

‘especially Wetherill’s (12). The latter found in the fossil -

-bones of the American bison 86.3% fatty acids and some

coloring matter, 10.1% lime with a trace of phosphate salts

and 3.6% ‘‘flaky organic substance”? and i in a great number

of cases of burying corpses, all of fat men, in wet ground

noticed that the decaying process left behind a wax-like sub-

stance ‘‘adipocere”’ or fat-wax, consisting chiefly (97-98%) :

_ of fatty acids. He obtained a similar result with a ‘sheep 3

buried for 10 years. In no case however, did he find am- .

monia in the remaining material. Even before him, Greg- —— -

oe ory found, in the remains‘of a pig buried 15 years before, ia

an adipocere as residue which was one-fourth stearic acid

‘and three-fourths palmatin acid (‘‘margarin acid’? “and

oleic acid, even the bones had in this case already disap- _

pedred. Finally, direct experiments by ‘Wetherill. yielded

that when animal substance (an ox ts maa under- ..

-. goes rotting or decay, the nitrqgenous substance disappears’ —

and only the fat remains beljind in the condition of adi: |

pocere.’ These -cases are sufficient. to prove. the durability

‘of animal fat whether the glycerine is already marian! :

off or not. se.

. If we now imagine sedimentary mineral intoreionie’

. with fatty material of this kind, the remains of decayed.

'_« animal bodies, and subsequently. subjected -to great pres- ff.

gure, or placed i in heat, an explanation of the formation of

ee — is given. It is possible that the ammonia of the _

NGS 2 petmolgum, of Siary and, the ammoniim carbonate of ‘the z

satel gas welle of Pittsburg. are remains of the nitro- ;

genous: substance of prehistoric animals obtained as an,ex-

ception; the presence of nitrogen in petroleum is not a.

necessary result of the formation from animal remains..

The lack of coal-like residue in the petroleum itself or in

genetic relation thereto, could not be made to harmonize

-” with the theory of the formation of petreleum from organic

substances, ‘This eondition however: is a great deal more — -

avorable to the formation from vegetable substances |

_ than from animal jsubstances. If cellulose (C.H,.0,) is -

3 [fol. 750] taken as representative of the former, we have. -

in it 44.4% carbon, 6. 2% hydrogen and 49. 4% oxygen. If .

even only-a small part of these elementary substances are

‘allowed to-eome together as water, there remains a residue

which is’ so poor in hydrogen and so rich in carbon that

without separation of carbon a formation of saturated

_. hydrocarbons or even the series C.H»n can no longer be

thought of. For general reasons however it is probable

that the higher the pressure and the lower the temperature

in comparison, the more water and the less carbonate acid.

is formed during disassociation. The more water that is

‘expelled from the woed substance however, the more car-

-bon must necessarily remain behind. That hydrocarbons =

can: nevertheless be formed from cellulose, remains of

- coursé undisputed, I-only maintain that their formation is’ is

impossible without coal-like or carbonaceous, remains being 4

- Jeft as residue. —

It is entirely different with the animal. fats or ibe fatty

acids resulting therefrom’ by glycerine separation. The

following are obtained :

Tri Trt Tri °. Stearic Palmitic Otel.

Cina hc Stearine Patmitine -Olein - Acid Acid t Acid

45.9 17.4 76:1 «75.0 76.6%

9 8 7 12 8 tet.

308 41.9" 3S. 5 11:3

-Ppain oil likewise hoepa approximately within the above

limits in its elementary composition. If all the oxygen and

the hydrogen necessary for water is eliminated from these ~

_ fats or better fatty acids; carbon and hydrogen remain be-

hind constantly in a ratio (about 87% carbon and 13% nye

: drogen) eceree is not wand not far from the _— composi-

mene

—

aes

. 9065

. > ~

ies of our ‘ender petroleum a ‘iad is ‘astoatabings oe

close... I refer ‘in this connection to the analyses: of Mark- —

: ownikoff and Ogloblin (18) who. found:4 in 1 petroleum from a

Baku: | : | :

BS me : | b wee: Ne ul.

oe: DEO ge PB oI 8 s.cs.e), 86,65. 87.01 86.89%

Te ae say 13.35 13. 22 13.18%

and furthertiore to. the humerous auakpoos of St. ‘Claire De-

- ville (14) who found i in. the, petroleum from:

(fol 751] .

2 eee re ee

Deduallieans aay MSS igh da eats .., 85.7 12.0 2.3%

Schwabweiler (Alsace) ............... , 86.2. 13.3° 0.5:°°

Oedesse (Hannover) ................. 804 12.8 6.

Wietze (Hannover) ......... aig a ks 86.2 114 24 .

Hast Galicia .:......:.... yb cna eg 66.2 121 6.7

Te uate . 853 126 21 ~

West Canada ..... We er ee

West Canada ...:. 2... wcities cscs: Bee dee ee

ee Viren rhawaaeces (8382: 132 36: -

, West Virginia :.......... Prue oe :... 836° 129 3.5

| We a SAS .: s+, 83,0 122° 48

7. Wieamont 3... ae Die as Sees . 864 122 14

-. Zante settee reat ese eens este sete dea oo Om abe BO 2

Burmah .....:... eS es bi ed rere: 83.8 127 3.5

Tf in thiess result of ssiveia account is taken of the oxy- -—

~. gen with the hydrogen necessary for forming water with it.

_ and the remaining carbon and hydrogen is reckoned by per-

centage, numbers which’ are not far from wd carbon and

13% hydrogen are always. obtained. =~ :

|. From these considerations it is likewise explained why |

‘we never find coal-like residue in conenction with the petro- _

_ leum fields. The decomposition of the fats or. fatty acids

, takes place with very high pressure without the formation

in closed tubes under pressure often sonnabed without any |

se considerable formation of carbonaceous residue,” ;

. 8966

Finally I denned concur in the eonception that petroleum’ :

: originates from plant remains even on general gro

is is known that plants play only a ver. inate role i in,

* murine life; they are. met _with on the shores, but the condi-

tions for their existence disappear even at depths. of 30-40

m. and therefore only in. the neighborhood of the coasts

can great accumulations of plant remains be: formed—dis-

regarding those submerged. The: Sargassum-algas. which - ,;

float about on the sea as floating islands oceur’so sporat- .

ically that their appearance must be considered as a dis-

appearing. minority i in contrast to the marine world. .

Karlsruhe, May. Chemical laboratory.

[fol, 752] . (1) Hoefer in Bolley’ 8 Technology “the Min. :

eral Oil: Industry’’ i. Houfer and F. ‘Fischer, 4 edition :

F , p 101.

‘~ (2) ‘ke, Chem. Pbavin, 57, 33.

~ (3). Poggend. Annal. 94, 272

(4) See Compt. rend., 89, 336.

(5) Ding. Polyt: J ourn. 179, 463.

(6) Compt. rend. 80, 1568; 89, 331.

“£0 This Berichte VIII, (1465.

(8). eee OT, 556.

, a see Hoefer, p. 101. : . 3 ae aa

(10) This Berichte XXI, 608. | one ain —

_ ~ (11) Ann, Chem. Pharm. 61, 362.- tg

(12) Jahresber. f.. Chem. 1855, 517. Journ. f. pr. Chem.

68, 26 following. peirerrqin of ‘the American Sl eeiiens sna

Soe: D6 Ee ) | x

(43) This Berichte XVI 1874.

_ (14) Compt. rend. 66, 442; 68, 485 ; 69, 1007. See likewise

' Jahresberichte fir Chemie 1869, 1126. | Le

Te; MMJ. Be of ia hem

6/17/25. ere tece d

m \ r 5 4 ‘4

S . °

Be :

te . rig a

y bs * ad BREN Cs PD

. ° Se eee *

OT e x

a --o* Fae ae ¢ >

——- tee . f ° * rape oe

on)

[fol. 753) TRawanaTion ¢ OF | Perrriowzn’s Exausrt No. 100

Berichte der Deutschen Chemischen Gesetlschaft

Vol. 30, Sheu 2365-2368

: Formation of Olefine, Naphthenes, and “Bensal Byardeas: s

bons sd = Distillation of Fats under High simmennses Ee

._ By. 0, Engler and Th. ‘Yehniann i

"(Received October 13) |

a earlier publications (see this. paper, Vol. 21, -p. - 1816

‘and Vol. 22, p. 592), one of ‘the Authors has demonstrated

that in the pressure ‘distillates of fatty substances there

oe are found a great number of light and heavy hydrocarbons .

- of the ‘paraffin series, among them also.solid paraffin and

ian lubricating oils, and from the further behavior ef Joey’ dis-

' tillates the’ inference could be drawn further that also ole-

file, and apparently also nap thenes, are contained therein.

Now; this assumption has been confined by the following -

investigation; also the presence of benzol hydrocarbons .

could be proved: . (For further details see inaugural disser- * _

- tion of Theod. Lehmann, Freiburg, Switzerland; 1897.) |

The proof of the olefins was effected in the main accord.

ing to the method previously used by Thorpe. and Young.a

- later elaborated by Hensler. The approximtae total quan- .

tity of olefins had. previously been ascertained in the local _

laboratory by absorption with concentrated sulfuric’ acid, >

the quantity in the lighter portions having been det

- to be 37%. Now, since against this method—and qui

'tifiedly so—the objection could be made that p ymeriza-

[fol. 754] tion might take plage'on account of

acid, a fact, that if true, would vitiate the

S results, we repeated .the tests on the portions of fish-oil —

pressure distillates boiling below 75°, those boiling betweén: -

75 and 100°, between 100 and 125°, between 125 and 150°,

and between 150: and 175° by the: application of the broma- |

tion method. ES

| The. different fraction were diluted with a little anhy- Ns

-- drous ether or carbon disulfid, then atonal ‘chilled, and oe

the sdditicne . of FRR dissolved - it ether or sialic

“disulfid from a burette made as long as the color was no- ..

_ _ ticed to disappear rapidly. Whatever extess of free bro-

~ min was left over could easily be removed by ‘means of a |

current of air, whereupon the whole mass was distilled with

_ steam. After the light portions floating on water had been

driven off, the heavy bromides were collected separately,

. the steam distillation being thereupon repeated twice in or-—

_ der to separate off as rapidly as- possible whatever non- .

-bromated hydrocarbons had been left over. The quanti-

ties of bromin used for combining with the olefins were:

For fraction 996.0600 45-75°. 75-100° 100-125° 125-150" 150-175°

Quantity used ...... ' 118 208 300 ‘221 ° - 10

Bromine consumed. . 64.8 120. 6 i) ie 45.6

hi, ng in% to 29° 30 32 35.5 84

Or | apes _-“hexylene hexylene “heptylene nonylene octylene

a so) 35 87 38 39

ps atnn sas seeps heptylene octylene nonylene decylene

| bes it can be seen that the method ‘of determining the

ole

s by the aid of bromine gave about the same results _

as with the use of sulphuric. acid (upon the average 37%).

It is furthermore shown that, in agreement with the results —

- obtained by the dissociation of heavy oils, the quantity of

. the elefins grows relatively as the boiling point of the oils

_. increases. ‘

: The ernde bromide separated in a manner as hereinbe- .

ratus at from 10-12 mm. ; but even by repeated rectification

only fractions of wide range could be obtained. ;

The specogr. and composition of these fractions are sum- "

marily shown i in the Siow ing, ese Patel:

- [fol. 755]

+42-50° ~~ 50-80° ~~ 60-70". 70-80°° 80-88°

Spec, eS: 5) reese: Loa e 1.5821 ria 1.5563 ‘ 1.5249 ; 1.51

eevee GF. 66 65.22 . 63.96 62.71 61.64

f sg ee eee ee ee oe ee 30.07 | eeeene 82.28 eeeeee

H. ene aeeseene . ee 5.02 eevee ks ae ee

95-105° 112-125° 125-132°

Spec. gr (150) . eveeee . 1, 4685 1.4263 1 4120

OE uiivitcsevisvaesscess 59.36 57:07 °=—s«88. 20

i. Sees e ser roseons . . ‘84.84 RE ME eae See PY ee hea et **

H eee eeweeeeeeeeeee peers 5.57 ae een 2 8 ee? Or wae ae se et

Fraction: 195 /132° showed slready m marked dnbicitlon

of en ere :

Caleulated composition of dibromids of:

Amylene ae Heptylene Octylene - Nosiytons.

69. 62.00 58.83 55.94 -

: ane 5.8 Om |

es will eg noted that Pats 50/60° corresponds quite

exactly to the -hexylene’ _bromid, and fraction. ‘70/80° to

heptylene bromide. The other fractions seem. to be jmix- .

tures of higher and lower homologous olefin bromide. —

The proof for naphthenes by determining. the refractive -

index of light customarily applied to other oils failed. to

furnish reliable results-in this case; hence, we were com-_

pelled to ascertain the presence of naphthenes according to

the method suggested by Kraemer and Housler, namely,

-. from the composition of fractions of definite boiling points, -

‘ from which by prior cold treafment with bromine and by -

. distiling off the more volatile non-attackable hydrocarbons —

with aqueous vapor, the oelfins, then’ with sulfuric acid and

nitrosulfuric acid and the balance of nitro-products: result-

ing therefrom with tin and muriatic acid, then the aromatic

: hydrocarbons, were removed. The oils after washing with.

solda solution and drying with calcium chlorid were then

| fractionated, and were then determined as follows:

10-80 98-99" . 123-104°

6805 0.6985 0.7170

“84.15 84.44 84.56 % .

» 16.10 15.65: > 15.58 -

" 149.5-150.5° "180-162 ct

The 5 sughtoaie showed tase Gut = 85.71, H = 14.29%,

while the paraffins had this composition : |

[fol. 756] Hexane (69°) . — (98°) Octane (125°) Nonane(150°) *

oe: ‘the first place increasing sitiahd and decreasing

__- hydrogen with growing boiling point and the elemeritary

| composition. coming close to ~ — with SorTeepane “s

oe O08, hae

- ing boiling Sointa; go to aoe that the: above Erections, as

found previously consist substantially: of paraffin hydro-

carbons; still, since the carbon content is throughout sdme-

what higher, and the hydrogen content lower (while if the

ordinary run of the’ analyses the opposite would be true),

_. the tends to indicate the presence of naphthenes.'In order | :

to isolate these in a condition, considerably greater

‘qua tities of distillates \obt: ?

- @88 trom fatty substances, would be required than had'been

ained by the high-pressure proc-. .

»at/our disposal because of the difficulties attendant apon : .

their production. :

'. But the presence of benzol hydrocarbons could be adele

demonstrated in the pressure distillation of fish-oil; benzol

in ‘the fraction 76/83° by nitration (the smell of nitro-

benzol being clearly noticeable), then reduction into anilin

and the use of the chlorid of lime test and by. the conversion

of aniline to benzytidenanilid (melting point determined at

44°) and into acetanilid (fusion point 113°); toluene in the —.

fraction 106/114° by nitration as 2-4 dinitrotoluene (melt--

ing point'70°) ; m-xylene &s trinitrometaxylene (fusion. pt.

178°) in fraction, 130/138°, while the presence of mesity-

lene.and psendocumene seenis to be indicated only by the —

. formation—thongh this is a characteristic and significant. .

_ fact—of a mixture product of ‘the two trinitro-derivatives

(fusion pene 170°) hs the nitration of the fraction amy /- a

169°.

Together with the xesults previously Hublished. it ean ‘be

said that in the prod ts of pressure-distillation of fis _

the presence of hydrocarbons of the paraffin series. (liq

and solid), of the ethylene series, and the benzol series hae oe

» been proved reliably, while the presence of naphthenes may

be taken to be highly probable; and since in. our experi-

ments purée, glycerids and other fats and oils generally ,

showed the same behavior-as fish-oil, the reaction may be —

considered to hold generally for all’ fatty substances. The _

formation of cyclic hydrocarbons, especially of the benzol

_ series, from fatty substances at such comparatively low _ a

me temperatures may not be without he, interest.

_ Raslarahe hee Laboratory. - :

80m 1

e (fol. 757] . Taawenattow OF Purrriowsn’ Ss ‘Exanré No. 101 |

| Berichte der. Deutschen. Chemischen Gesselschatt

Vol. 26, Pages 1449. 145k

Detection of Pavaiin and Lubricating Oil in the Pressure

_ Distillates of Fish-Oils -

By 0. Engler and L. Sitiger

«(Communication from the’ Chemical Laboratory ot

| . Jahn. )

tion with the theory of petroleum formation from rei

: of animal fats, that in the pressure distillates of natural -

Karlsruhe Te ical: University) .

(Reseived on Juy 5; read’ before the meeting by i,

The noint has baie raised i in various quarters in co nec- -

[fol. 758} glyceride and higher fatty acids investigated in:

_ the loeal laboratory neither. paraffin nor lubricating oils

have been found. As a matter of fact, in a.test made at the

+ very beginning we were unable to discover ‘paraffin in the

- pressure distillates of fish-oil. To the determination by

analysis of lubricating oil in the higher fractions we did not

ascribe any great importance, wé therefore did not use

much care in its isolation. Now, the emphasis that has

again in more recent times been laid upon these gaps in-* :

duced us to resume our investigations along these_pavticu-.

lar lines, especially since an ample amount was still avail- ae ,

-. able of the fish-oil distillate which we had obtained by the i

kind cooperation of Dr. Krey, of Webau. -

. Much to our surprise a crystalline separation was no- |

_’ tieed in the different portions of high-boiling-point residues

_* : of fish-oil pressure-distillates kept in some small and larger

\. ontainers which had ‘never been observed before, and

\. which evidently was produced only then’because previous

to that time the weather had been extremely cold, the dis-

‘ N J tillated\ having . been subjected to this cold for some. pro-

enged period of time in unheated store rooms. It was

oe sy to demonstrate that these crystalline separations, as.

matter of fact; consitsed of pa and not pean: a

‘hon. a Rienosintod solid erearice or fatt acids.

pa ]

}

This led us to. resume : the’ direct analysis of our. ‘ernde

pressure ‘distillates; however, while the Zaloziecki method

is usually very: reliable (see Dingler’s polytechnisches Jour-

-nal, 267, p.. 274), we failed to obtain from the distillates

. “other than amorphous masses flowing even at ordinary »

|. . temperature. Also the examination of the fraction boiling

. . over 300° gave no better results. .

_ However, when the portions of high boiling point of the

fish-oil distillate,’ after removal of all traces of non-dis-. —

sociated fat ’ subst.nces by the aid of soda lye, had been ~

exposed for weeks in sucvession to the cold of the winter

- or to artificial chilling, on remelting the solidified masses,

it was readily possible to find solid crystalline paraffin,

which drawn. off by suction at loy+emperature, by repeated

‘dissolution in. ligroin re-precipitation ‘with 75% alcohol,

and treatment in ligroin solution with animal charcoal, was

obtained in the shale of white crystalline masses having a. 3

melting point ranging between 49 and 51°. Analysis -

-sshowed the following results (specimen I directly, and .

specimen II after renewed purification. by a. car-

boni¢ acid through the refused paraffin) :

(fol. 759] 45 BAe f

) ~/ 2.» 3088.70 ° 87.70.

i6S4, 4810... -

In view of these findings, the proof. that cP taps is formed:

in the distillation of fatty substances in the presence of high |

pressures may ‘be taken to have been furnished.

Now, in order to demonstrate also the.presence of lubri- :

eating oils, a few kilos of the crude pressure distillate were >

shakeii' with soda lye, next with water and sulphuric acid, —

and, finally with water, then distilled, the different fractions _

being again washed with solda lye (concentrated), water,

sulfuric acid, then water, solda lye, and water, and again

| subjécted to distillation; the heavy oils were then trans- —

parent, light-brown in color, while they exhibited marked _

orescence after washing with soda lye. The heavy oils

their chemical purification should be advantageously .

2 lated with ligroin as otherwise the action of the sulfuric

_ /acid would be unduly strong. me

In comparing the viscosity of the ensuing oils with water, &

" Decause of the émall seen invelved, a small glass vis-

mn + was

ia | or

o “goatenater with an ‘extrusion hole of 1 mm. width was used,

- from which the water was found to run out, at 20°, 13 sec- -

_ over. between 290 and 300°, when heated from from 50-60°,

- exhibited a spécific viscosity of 1.6 while for sifigle fgac: vee

same temperature, which goes to show. that: the ——: of

‘lubricatjfg oil is proved. beyond doubt.

‘uffortunate point is that the constitution of th

yr and

Pores With

the lubricating oils obtained: by eae means ae Kraemer’.

and Spilker (see. this paper, 24 p. 2785), and whether their —

formation is associated possibly haa the glyceride or Reh

compounds formed therefrom. . ~ ey

As regards the identity in properties of the. ‘pressure dis- |

tillates of -fish-oil with natural petroleum, we believe we —

must call attention to fumernol-sulfon and tumenol-sulfonic —

acids proved to exist separated recently by: E. Dieckhoof

‘ (see Dingler’s Polyt. Journal, 274, p. 41) in the products

obtained by the action. of funing sulfuric, acid upon pres-; _

sure-distillates of fisk-oil, which, in their properties and in

their composition, perfectly agree with the tuminol bodies |

i separated by ‘A. - Speed. from sabbath pefroleuine. :

a F ees:

¥xe5 . ; _¢. f Ps et pee \e P Mi Fees Mies

(fol. 760] Ticacibion or Perrin’ Tisnagt Mo, OS

Berichte der Deutschen Chemischen Gesellschaft |

Vol. 38, Pages 2965-2270 eae

bs: ‘The Dissociation of Viscous Substances Lubricating Oils sby

. ; _ Pregsure Distillation

wee By G. Kramer and’ A. Spiker ee

. (Heceived Jaly 11)

In the study published. by us last year seaicatlia ee

" nature of petroleum, the possibility has been discussed by -

us to — nh the aerate process. sgsioe

-—

————___—

the study of the ensuing dissociation products, the nature

of lubricating oils and paraffin oils ‘of high boiling point.:

and we have come to the conviction that. this method is prac-

ticable for certain substances related to the said oils. How-.

ever, we.did not succeed in throwing light on the constitu-

tibn. of the said mineral-oil hydrqgarbons in this manner,

"and in realizing what we are really aiming at; indeed; we

“could only prove in a negative sense that the theory (also °-

held by ‘us) namely, that these oils’ could oily be due in °

_ part to the addition of aromatic to unsaturated hydrocar-

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