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

Supreme Court brief1931

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CLEF K = vor

Vol. Vill

"TRANSCRIPT OF RECORD

PATENT sarap holt

— y 3 <a

& upreme Court of the United States =

OCTOBER TERM, 1930 ;

\ \ No. 378. |

é STANDARD OIL COMPA (INDIANA), STAND!

OIL COMPANY (NEW JERSEY), STANDARD DE

_ VELOPMENT COMPANY, ET AL, APPELLANTS,

eo: C4 Stoo

- ‘THE UNITED STATES OF AMERICA ,

“APPEAL FROM THE DISTRICT COURT OF THE UNITED STATES

\ FOR THE NORTHERN DISTRICT OF ILLINOIS

oe (35, 300)

SUPREME COURT. OF THE UNITED § STATES |

3 OCTOBER TERM, 1930

min

| STANDARD 0 OIL: COMPANY (INDIANA), STANDARD

~ OIL COMPANY (NEW JERSEY), STANDARD DE-

VELOPMENT COMPANY,.ET AL, APPELLANTS, *

Tee vs. me TA oe

“THE ¢ UNITED STATES ze AMERICA.

+ APPEAL FROM THE. DISTRICT COURT OF THE UNITED STATES

; FOR a NORTHERN DISTRICT OF isp

pre Se

- INDEX ci

Petitioner's exhibits : Ea nate Saw Original “Print

- 177—Letters patent No. 1,119,496........... vejl74 4475

_*/178—Letters patent No. 1,119,700.......... “1177 ‘ 4480

. 179—Letters patent No, 1,129,084.......... ‘1180 3= 4485

180—Letters ‘patent No. 1,175,909........ .. 1185 4494.

181—Letters patent No. 1,187,380.......... 1190 4508 ©

: 182—Letters patent No. 1,221,790.....:.... 1194 4511 .

188—Letters patent No. 1,242,795.......... 1208 4542

184—Letters patent No. 1,242,796....:..... 1218 4551 ~

185—Letters patent No. 1,320,354....... ++. 1219 _ 4563

186—Letters patent No. 1,320;726.....:.... 1287 4594

187—Letters patent No. 1,320,727.......... 1246 © 4611

188—Letters patent No. 1,827,263.......... 1258 . 4635

189—Letters patent No. 1,302,584.......... 1270 “4660.

_ 190—Letters patent ‘No. 1,396,909........:. 1274 4668 °.

191—Letters patent No. 1,410,797........,. 1282 4682

« 192—Letters patent No. 1,416,232.......... 1287 ©=— 4691

+... : 198—Letters patent No. 1, Spode setne 06 ©

yore & DreTweier (Ino.), PRINTERS, WASHINGTON, D. C., Ocrones 6, 1930~

194—Letters patent No. 1 433,519.

195—Letters patent No. 1,448,254

196—Letters: patent No. 2:461,017: ....5..:.

197—Letters patent No.. 5

108—Letters patent. No. °

199—Letters paterit No. ;

227—Letters. ‘patent. No. 1,226,990

228—Letters patent No. 1,241,979

229—British patent No. 10,218....:........ 3

230—British patent No. 23,446

231—British patent No. 3413

232—Excerpt from a treatise on petroleum

. and paraffin..

247—Excerpt trem treatise on pressure dis;

tillation by Dr. Krey

' 248—Excerpt from article on German: ‘petro- -

” 249-—Eixcerpt from treatise on: decomposi-

tfon of solid | and liquid’ hydrocarbons by°

_ pressure and heat, by Josef Jacunski..

250—Excerpt from treatise on decomposi-

tion of heavy mineral oils by heating, ‘by

400—Letters patent ‘No, 1,553,861........,.

401—Note- SD WORRIES. oo sic ews cc ecv cece

407—Letters . —_— No. iene

-' £08—Letters patent No. 1,230,065 :

409—Letters patent No. 1,582,929........ eer

tA --410—Drawing ‘of Burton high pressure still.

411—Note re exhibit...

418—Lxeerpt from _treatise on détermina-

of unsaturated hydrocarbons in gaso-

e, by B. W. Dean and H. H. Hill. eens

471—Bxeerpt from outlines of industrial

472—Bxeorpt trom -tréatise on petroleum —

industry, by David T. Day....<.........

_ petroleum industry, by Raymond F. Bacon

1414

1346 \: 4914

1440 }.4921

1441. 4922:

1518. 5008

15155010

a ot. * ee PERE

. oes se : v .

-= + _* Defendants’ exhibits: , gs a Ee Te Se GS

’ No. 511—Letters patent No. 1,239,000..:....... 1518 . 5013 .

512—Letters patent No. 1,239,100.......... - 1530 45643

| 513—Letters patent No. 1,487,045...:.....: 1585 5053 _

. @01—Excerpt from circular No. 98 of the aes

: Bureau of Standatds..........2....+++: 1539 5059

602-—Rxcerpt, from analysis, by-C. Kugler. 1542 . 5062 -

‘ 603—Drawing ..... se eeresaueescesneceees 1544 5065

Re _ Petitfoner’s exhibits: - : Bre seae

oe No. 604—Excerpt from. outlines ‘of industrial Sea es

chemistry, by Frank H. Thorp......:... 1546 | 5066 _

605—Letter. from Standard Dev. Co. to =

Commissioner of Patents; December 14, _- ~~

ee rere ope Ceiavadescebees sss:

Defendants’ exhibits : ; oe

= No. 606—Structural formula......../..--es+++ 1552 5072

5 = . 610—Sketch of high pressure apparatus for ;

ae 7 ellie ei ES Sa eaneeaan bes sae 1555. «5074

\ Sree eit tweet trout trestles on dtetisiaiion a

: seetelin ent, erorens, WS Sydney Youns: 1556-5075

es 612—Drawings' .<...2i+++20e+ee00+s Sebece 1560 5079 ~~

613—Letters patent No.~-1,366,956........... 1565 «5083

614—Statement re shale oils.......... seen 1568 $5087

’

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Ffol.1174] | Perrrtoner’s Exuterr 177.

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METHOD OF DISTILLING PETROLEUM.

APPLICATION FILED APR. 20, 1614. -

4,119,496. it«s~*«*~«~*~S*Cé te, 2,

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4476 Foren pre eee Sage

‘{fol. 1175) w- United: States Patent Office so

ee ‘Mager M. Clark, of Alton, Tlinois

(Method of Distilling Petroieum .

1,119, 496. Speciation of Letters. Patent. . “Patented Dee.

_ + 1914 : ak

"Application ied April 20, 1914. Serial No. '939, 243

To all whom it may concern :

Be it known that’ 1, Edgar. M. Clark, a ditieen. of ‘On :

United States, residing at Alton, in thé county of Madison

‘and State of Illinois, have invented a new arid useful Im.

provement in Methods of Distilling Petroleum, of which.

the following is a specification:

My invention relates to an improvement in distilling pe-.

- troleum, particularly for obtaining therefrom prunes e

point. hydrocarbons.

Where in distilling petroleum, according. to. common

tan the liquid material is contained in a reservoir-

ike still, to the bottom of which the heat is «applied, the

danger i is ever present. of an opening fo in‘ the boiler-

bottom, due to-flaw in the metal, the bottomburning out, or

other cause. When this occurs, the entire contents of ‘the

. still discharge |into the fire, prodneing: a more or less dis- S :

.astrous conflagration. This result is more likely to en-. |

= sue where the distillation:is carried on at a temper ature

sufficiently high to.crack the petroleum-contents of. the

still, whereby free carbon is developed | and accumulates

on the still-bottom, on which it lies in red-hot cama

- and tends to burn it out.

- The primary object of my. in¥enition is to. provide: a

. method of distilling petroleum, whereby discharge of the

contents of. the still, Ahrough an accidental. opening occur-

ring therein from.any cause, shall not produce serious con-

sequences but shall-avoid damage of any kind ‘other than

the loss of a. small part-of the charge and pemnporery dis- -

’ abling of the still.

The accompanying aucaine illustrates diagrammatically, |

"as suitable for the practice of my’ improved method, an

quipment of apparatus involving* a so-called pressure-

or,

till, in 7 the distillation is carried on under = tem- _ a

perature’ ‘(of 650° to 850°. F.). and a pressure of 3 to 7 at- —

~ Tnospheres Eredaees by thé vapors aacharee from the

still.

At‘1 is shown an hia ‘asi or reservoir su nerad 3 mm

, - elevated position and having a rounded bottom, f m above

¢ which leads a pipe 2 containing a ‘force-pump 3, of any

‘suitable construction. This pipe leads from the discharge- . ..

‘ side of the pump to one end of a pipe-coil 4 in a furnace .

5, which is preferably coal-burning. The opposite\end of

the coil communicates through a pipe 6 with the reservoir

_ 1 at its upper. end, from which leads a discharge-pipe 7 © _

to the upper end of a water-cooled condenser-coil 8, the

_ discharge-end of which, containing a valve 9, leads'to a

- receiving-drum 10 for the distillate. A pipe 1 rises from

| the lowermost branch of the coil 8 through the condenser-

aes above which the pipe con a valve 12. -

ag apparatus is particularly designed for the

een natactare of- gasolene by distilling under pressure’ the

cenia of petroleum-distillation, such as fuel-oil, to pro: |

duce it. It is:to be understood, however, that my invention

is applicable generally. to the distillation’-of petroleum = ~

+ while it has peculiar advantages in connection with. the

_ pressure-distillation process referred to.. In the apparatus —

\2 illustrated, the liquid material to be distilled is charged’

into the reservoir, which may ‘contain several thousand

gallons. With the pump in action and the furnace going, |

the valves 9 and 12 beine closed, the: contents: of the res-

ervoir -are circulated, passing from the reservoir by way

of the pipe’ 2 through the pump, which. forces the liquid

: ae relatively-fine stream through the ¢oil 4, whence it.re- -

- ~ turns in heated condition through the pipe 6 to the reser-

_. voir. By continuing this circulation, the heated liquid re-

.. turning fromthe coil 4 to the reservoir heats the contents

. of the latter and the resultant. vapors -pass off through the

upwardly-inclining pipe 7 and condenser. These vapors

- build up a pressure on the contents of the reservoir of

from about 3:to 7 atmospheres and-raise their tempera-

ture ‘to about 650° F. and as. the. run proceeds, to about’

,. 850° F. Gases accumulating in the condenser are allowed *

‘to escape from time. to time,,on opening the valve 12, for ~

. relieving the gas-pressure, which is liable t6 accuinulate in -

_-, the coil and obstruct. the action of the apparatus. From —

_. time to time. the valve'9 i is opened for Sas the dis-. .

: . > j 5 :

e : . ‘ : . : 4 ‘x ‘

-tillate into the drum 10. This distillate is cred gpcene ie

ioe superior quality and it may be subjected to Oe set ae

‘’ " ment, well-known in the art, for refining it. ,

By thus subjecting to the action of heat-the material ‘on ue

der treatment in a relatively fine stream, while free: ‘earbaen ©

__ is formed in the liquid passing through the coil 4,it courses

under the’ high pressure at which the liquid is circulated

_ [fol. 1176] so rapidly through the same as to pre ent ac

* eumulation therein of the carbon, which it carries. back -

into the reservoir in the bottom of which it may accumu- _

late without injurious effect, since there is.no fire under. ~

the reservoir. Should, however, a leak accidentally occur ~

in the coil, so little of the liquid will discharge into-the fire —

| the furnace that no damage will ensue: My improved:

_ method, therefore, not only greatly. decreases’ the danger.

of accident, but if the latter occurs the resultant damage

_is comparatively immaterial. Moreover, it enables from ~

_ 8.to 7 runs to be made of the still without. requiring the ap-

paratus to be stripped and cleaned, whereas where the

__ boiler 1 is fired but one run can be made without. stopping

_ and cleaning the carbon depoffit out of..it.

_ While.a pump is shown for circulating the liquid ma- ..

terial; any other way of producing the necessary rapid

circulation i is intended to be within my invention. -

_ - What I claim as new and desire to secure by Letters

Patent is: :

1. The method of ¢ disti | petroleum, Which consiats in

circulating it forcibly andfrapidly in a. relatively-small ~

stream under confinement fd subjection to a.cracking tem-..

> perature from and back ta bulk-supply of the liquid ma- |

- “terial, taking off. and condensing the resultant vapors and .

Pe maintaining a pressure of said vapors on said supply.

0 ie Method of distilling liquid residue of petroleum-

Bes eR geee which consists in circulating said liquid forcibly.

and rapidly in a relatively-small steam and under confine-

~ ment and subjection to heat from and back to a bulk-supply __

. of the residue, taking off and condensing the resultant va-.

pors and maintaining said liquid at a temperature of from

about 650° F. to about 850° F. under .a pressure thereon

of said vapors of about 3 to 7. atmospheres. | |

_. .8.The method of. distilling liquid residue of italia: me

~somians which consists i in eee said liquid — a

ee te | 4479.

and rapidly in a relatively-small stream under confinement ==

— gnd subjection to heat from and back to a bulk-supply of .

_- the residue, taking off and condensing the resultant vapors —

- and'maintaining said liquid at-a temperature of from about ~—

650° F. to about 850° F. under-a pressure thereon of said. _

* vapors of about 3 to-7 atmospheres exerted throughout —

. their course to-and during condensation. eS Rae ceed

Be Pe a ee vee \ io) eer ML Clark,

. Tn presence of Nellie B. Dearborn, Daisy C. Thorsen.

: ee -Correetion in Letters Patent No. 1/119,496 a

_» It is hereby certified that Letters Patent No. .1;119,496, ©

_. granted December 1, 1914, upon the application of Edgar

* M. Clark, of Alton, Illinois, for an improvement in “* Meth-

- ods of Distilling ,Petroleum,”’ was. erroneously issued to

_ the inventor, said Clark, whereas said Letters Patent should

_ ® have issued to Standard Oil Company, of Whiting, Indiana,

- a corporation of Indiana, as assignee of the entire interest.

_ "in Said invention, as shown by: the records of assignments © ©

in this office; and that the said Letters Patent should. be —

_. yead with this correction therein that the same may con-

“. form to the record of the case in the Patent Office. —

” Signed and sealed this 15th day of December, A. D., 1914. .

‘J.T. Newton, Acting Commissiorier.of Patents. - (Seal.)

ame ES % |

[fol 2177} Peririoner’s Exurerr 178

R. E, HUMPSREYS. -

METHOD OF DISTILLING HYDROCARBONS,

‘ “APPLICATION FILED JUBE 96, 1914

4,480,700, °°" Patented Des. 1, 1914

WH PAWN

a |

a) oot

{fol. 1178]: . United States Patent Office

Robert. E. cai pans: of. Whiting, Indiana, Assignor ew:

Standard Oil Company, of =e Er a Corpora- .

tion of Indiana |

Method of Distilling Hydrocarbons

1119, 700. Specification of Letters Patent. Patented Dee. Pe

fe ee

- Application fied June 26, 1914. Serial No. a7 412

Bx all whom it may concern: ,

Be it known that I, Robert E. Humphreys,- a citizen of

the United States, residing- at_Whiting, in ‘the county of .— -

Lake and State of Indiana, have invented a rieéw and useful —

improvement in the Method of Distilling Hydrocarbons, of

“which the following is a specification. 3 |

My invention consists in a novel method for the distilla-

tion of hydrocarbons, its object being primarily so to treat

hydrocarbons of relatively high boiling-point (such, for

example, as the product known in the trade as fuel-oil, a

para-fixt oil, the boiling oint of which is upward of 500°

F.), as to produce therefrom hydrocarbons of muck lower

boiling-point, such as the commercial product known as :

gasolere which is a para-fin oil of much lower boiling point.

In the practice of my process, in its preferred form, I

employ as measures of commercial expediency, all the de-

vices, and processes which have been found useful for that

-purpose.. Among these processes and devices may be men- - 7

_tioned the process of the Burton Patent No. 1,049, 667, dated

January 7, 1913, and the process of my application, Serial

No. 813,220,’ filed J january 20, 1914.. However desirable

these features are in practice, they form no part of my

present invention and are, therefore, not here illustrated,

but are enumerated.in order that those skilled in the art

- will understand that the highest possibly efficiency requires 3

‘that the present invention be ‘supplemented by what is now

. the most approved practice in the same general field.

‘My process is preferably carried out in an apparatus,

; “such as that herein mere hae in which—. ces

ecciaas

PR ‘

Figure 1.1 is a side soctiouni elevation, and Fig. 23 is, a top

plan of the ee a suitable for carrying out the pr

Referring t the drawings, 3 is a still which may be ‘*f |

ordinary form. Extending: obliquely upward, from the still

_ is a conduit.c Cpa of two pipes, 4, side by side, each con-

‘trolled by.

valve 5. The pipes 4 communicate with a

header 6 which. opens into a condenser 7. The condensed .

products enter a receiving drum 8, and the uncondensed

gases pass out eercags a: relief pipe. 9 controlled iy the «,

valve 10. |

. The valve in the ‘relief. -pipe is so manipulated as to main-

: ‘tain in the system a pressure of upward of 4 atmospheres;

-go that the distillation takes place at the temperature re-

quired by the high pressure thus produced. When’ the raw -

material-is the commercial product known as fuel oil,, the

‘temperature’ will be upward of 650°: F. and the distillate

entering the receiving drum 8 will be crude gasolene.

The essence of the present invention is the use of the in-

clined conduit, consisting of the pipes 4, and in practical

~—operation‘the u

is’ commonly termed in practice, is most important. - Its :

operation i is as follows: The complicated chemical processes _

going on in the still produce products of varying gravities,

and consequently. of varying molecular weights and boiling-

points. The fractions vary from non-condensable. gases

through the light napthas down to fractions which are but -

slightly lighter than the raw material. The operation of

the inclined conduit, or run-back, is td condense the heavier -

_ fractions of the distillate and automatically to return them eae,

- to-the still 3 for further treatment therein. In other words,.

this inclined conduit has the practical effect of subjecting © ;

the heavier fractions repeatedly tq the action of the pres- ©

sure and temperature in the still, until the desired molecu-

' lar re-arrangement has occurred, while permitting those

fractioris which have already been ‘sufficiently acted upén to

- pass over and be condensed.. It is manifest, therefore, that

the size and dimetisions of the inclined conduit, or run-back,

is.of considerable importance, ard I may suggest, by way

eee example that I have found thut in the use of a still 8 ft.

_ in diameter and 20 ft. in length an inclined conduit, or run- —

_. back, consisting of two pipes each 12 inches in diameter and

— 40 ft. tong es a distillate of the proper gravity 4 a

o- 4

-t ;

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' .

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- x ¢

crude gasolene... The use of. two pipes is a vantageous be-

eause, when the end of the run approaches and the flow of. ,

that-condensation.can be maintained of: the proper amount.

the vapors is slow, one half the conduit can be closed, so

While-as. heretofore stated, I prefer to Pe the vapors

. under pressure throughout their course and while under- .

going both the initial and final condensation, das by: control-'

ling the relief pipe 9, it is manifest that the pressure control

. of the final condensation, i. e., the condensation of the light -

(fol. 1179] vapors which pass from the run-back is not es- -

' sential to the invention. Such fractional condensation: as ‘

_oecurs in the run back itself, however, should evidently be

under pressure for the carrying out of my process, as -

otherwise there:would be considerable difficulty in return-

ing the condensed fractions to the still for, further treat-

_ment therein.

T realize that ¢ considerable variation: is ‘losaible. in the

_ details of the process hereiri shown, and I do not.intend to .

limit myself thereto, except as pointed out in the following

claims, in-which-it-is my intention-to claim all the novelty ©

_itherent'in the process as broadly as is ee by ™ ,

state of the art. :

_ What I claim as new and desire to secure ed Letters Pai.

ent i is:

1, The mathiod of treating liquid spikion of the asain

series of petroleum distillation having a boiling point of

upward of 500° F. to produoe therefrom hycrogsroge oils

i, of the same series but of- be which-con=

‘sists in distilling the high boiling point hydiveatbons under

a pressure of upward of four atmospheres, cooling all the.

vapors passing from the still while under such pressure to

condense. the heavier fractions thereof, and simultaneously.

returning the condensed heavier fractions ‘to the still to

undergo therein further treatment, and leading off and con-

densing the light vapors. ;

2. ‘The method of treating’ liquid residue of the paraffin |

- — of petroleum distillation having a boiling point of .

- wpward of 500°:F. to produce therefrom hydrocarbon. oils

_/ of the same-series but of lower boiling points, which con-

sists in distilling the high boiling point hydrocarbons under

a api of upward of four atmospheres, vice: all the

re 3

‘

4484

vapors passing from the still to condense the heavier frac-

tions thereof and simultaneously returning the condensed ©

heavier fractions to the still to undergo therein further

treatment.and leading off and condensing the light vapors, '

maintaining such distillation pressure of upward of four

. atmospheres on said vapors throughout their course to and

while undergoing condensation.

_ In testimony whereof I Bes hereunto set my hand this ©

atth day of June, me

Robert E. Humphreys.

_ In the presence of two subosttbhiie witnesses ; A.C: :

Fischer, F. A. Florell. -

- [fol 1180} iia a |

| PETITIONER'S EXHIBIT ‘179 5

: ,) E.. M, OLARK. og )

' ART OF PETROLEOM DISTILLATION:

APPLICATION TILED APR. 20,1916. - Js

- Patented Feb. 16, 1915.

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‘ (fol. 1182] : United States Patent Office }

'. Edgar M. Clark, of Alton, Illinois, ‘Assignor to Standard

Oil Company, of Whiting, Indiana, and aera samt

a Corporation of. Indiana ;

Art of Petroleum Distillation

% % 129, 034. ‘Specification of Letters Patent. Patented Feb.

4 16, 1915

epplieation: filed April 20, 1914. ‘Serial No. 833, 244

To all whom it may concern :

_ Be it known. that I, Edgar M. Clark; a citizen of the

- United States, residing at Alton, in the county of Madison |

and State of Tllinois, have invented: a new and useful Im-

. provement in the Art of Petroleum. spi of which

the following is a specification. |

In the art of distilling residue of petroleum distillation,

such as gas oil or fuél-oil, af atmospheric pressure, vapor-

«* jgation begins. at a temperature of about 250° F., and all

will distil over at a temperature upwards of 650° F. In

distilling this residue under a pressure upward of three

atmospheres, producing a range of temperature , of: about

- 650° F. to 850° F., actording to the inventiogs of Letters’

Patent No. 1,049 667, granted January 7, 1913, to W. M..

Burton, a: material quantity of. fixed gas (amounting: to

‘ rs 2 per cent. of the stock charged into the still) is pro-

uced,

_ In the: ‘practical application of the konees of: the. afore-

said, patent, a battery of stills (usually ten or more) is.

used: Each still is provided with its own condenser and

with further separate equipment involving a drum: for re-

_ ceiving the ‘products of the condenser and separating the

water and | gas from the condensed distillate, and a meter

for measuring this distillate in its course to storage. : Both

the gas and distillate discharge lines are’ ‘equipped with

valves for controlling the rate of. dischar ‘When’ a still’:

in the battery is freshly charged and fired, “the valves in

these discharge lines are closed. As. the firing of the still

: is: continued and: the aaa of its Sparen ee to

. ‘ e ‘

‘ x ,

4488 . ; .

‘

4 abort 250°, F., water and petroleum vapors distil ‘over

through the condenser into the receiving drum. ‘As the dis-

‘tillation proceeds’ small quantities of: uncondensed vapor or

gas collect in the apparatus, and after.a material quantity

‘of low grade distillate (upward of about 8 per cent. of the

stock charged) has been ‘produced, sufficient gas has col-

lected in the apparatus to create a pressure: of vapors

through the condenser. Continued firing of .the’still raises -

further the temperature of the contents producing increas-

. ing formation of gas and building up of pressure in the

apparatus. When the desired temperature (about 650° F.)

and pressure (say about 70 to’75;lbs.) have been attained,

‘the gas ins the apparatus is ‘allowed to escape slowly

through a valve in its discharge line from the top of. the

. receiving drum. Vapors will then begin.to come over

through the condenser, and high-grade liquefied distillates

-will”be produced and be discharged from the receiving

drum thrqugh the meter into sterage. Since this distilla-

tion process is necessarily slow, the formation of gas: in

very gradual. Production of the high-grade distillate is

dependent on constant pressure on the apparatus. A slight

drop in pressure causes the vapors to come over more

freely and produces low-grade distillate, and, conversely, .

even a slight increase in pressure entirely stops the flow of

vapors with resultant danger to the apparatus.

It is the. primary purpose of the present invention to —

provide for so controlling-the discharge of gas and liquefied .

distillate that a minimum amount of the latter of low grade

_and-e-maximum amount thereof of high grade shall be pro-

. It is a further purpose) to safeguard the apparatus by’

duced. .

preventing any extraordinary. excess of pressure therein,

and also‘to so apply a gas-pressure of about 70. to 75 Ibs.

from stills in the battery that are running to the contents -

of a still when freshly charged as to prevent distillation of

‘such contents before the desired temperature has been at-

Tn the accompanying drawings, Figure 1 illustrates dia-

grammatically, by a plan viéw, a battery of stills and the -

equipment that belongs with them for practising the inven-

_ tion in a preferred manner, and Fig. 2 is a view in sec-

_ tional elevation, the section being taken on line 2, Fig. gg

‘,- 4 ee

ee eee o-

°,

}

‘

7 for co

Four stills 1, denoted - respectively A, B, © and D, are

-. indicated by dotted representation and will suffice for the

- purposes of the explanation hereinafter given. These stills ,

are shown under a shed 2, between walls 3, and’ they com-

~ muni¢ate with a stack 4; common: to all, for carrying off

products of poco ray from the furnaces under the stills,

one of these furnaces being represented at J" in Fig. 2. A

vapor pipe 5 leads from the top of each still to the upper —

end of the water-cooled coil of a separate. condenser 6, and

from the bottom of each coil leads, through the inner wall.’

3" of a housing, of which the side walls 3° are shown, a pipe

goalie the products of the condenser, composed

(fol. 1183] of liquefied distillates and the light, gaseous |

oducts of distillation which have not yielded to the action

- the condenser, into a separate drum 8 at the top of the.

atter. Frém ‘the bottom of .¢ach drum leads a pipe 9 con-

taining 4 meter 10 for measuring the liquefied distillate and

having two valved branches 10* and 10” which discharge, — .

respectively, into header-pipes 11 and 12 closed at one end. -

and containing similar shut-off valves 13 and 13’ respec- .

tively. These header-pipes discharge to storage-tanks (not -

shown), Each drum’ discharges -gas from its upper end |

through a pipe 14 having two valved branches 14* and’14” |

'« leading, respectively, into header-pipes 16 and 17, which are

. closed at one end and contain similar shut-off valves 18 and

18” respectively, these’ pipes which also lead to storage-

.tanks (not shown), being connected by: a pipe 19 containing

a pressure relief. valve 20 of any ordinary or suitable type..

At 21 is shown, leading from the bottom of each drum to

a gutter 22, a valved pipe for drawing off the watery prod- |

uct of condensation. of .the wepees soneentad in the early’

part of the run. t

For the purpose of’ exptnition’ let it be assumed that

(hree of the stills 1, namely those denoted as A, B and C,

are running at the cracking temperature of upward of 650°

_F. and under a pressure of about 70 to.75 tbs, of the gases

on‘the contents of the stills. The valves in branches. 14.

‘ connected with these three stills are open and the gases are

‘ discharging into the header-pipe 17 and are being held back.

by the partly closed valve 18 in the latter and the relief

Valve 20, to produce the required pressure of 70 to 75 Ibs.

~ in the pereeesns | and een the apparatus of: the —

~ 4490

running stills. ‘The valves in the pipes 21 belonging to

these ‘three stills are closed, since all watery vapor from

| them has been distilled off before they reached the crack---

| ing temperature. The vaives in branches 10° are open and ©

high-grade liquefied distillate is being discharged from the

‘bottoms of .the three respective condensers, through: the

meters into the header-pipe 12 and through its partly open.

‘valve 13 to storage. The rate of this discharge is reg:

ulated by the valvé 13 in the header-pipe 12 to niaintain the.’

required pressure throughout the apparatus and discharge

the distillate as it is produced. . The'three stills thus run-

ling are all subject to the same pressure by reason of the

_ valves in‘branches 14” leading to the header-pipe 17 and the

\ valve in branches 10° leading to the header-pipe 12 beifg

open. These stills being cdnnected by the header-pipes/17 .°

and 12, give a sufficient volume of gas-and liquid distiflate -

to make the rate of their discharge easily .controllab 3

the valves 18’ and’ 13’. Let it also be assumed that the\

fourth still, denoted as D, has just been freshly charged and

fired. The valve in pipe ‘91 and the valves in branches 10°, .

“@ 10° and 14, belonging to that still, are’closed, and the cor-.

' §- responding valve in branch 14* is opened. The still D is <3

thus closed to the 70 té 75 Ibs. pressure maintained in the -.

header-pipes 12 and 17, and is open only-to the héader-pipe.

16, which conducts the gases to. storage, or to the furnaces.

Phe" ‘firing ofthis still is continued with\ resultant rise of .

temperature of its contents. At about 212° F. the watery

portions of these contents are driven over through the re-

spéctive condenser 6 into the drum communicating there- |

with. From time to time the valve in the respective pipe |

. 21 is opened to. discharge the water into the gutter 22.

. When the water has all.been driven off, which is indicated:

_. by the temperature of the contents of the still D, the eil

portion thereof will. begin to distil over at about 950° Bes

-To. stop this distillation and the resultant production oft" Pe

| low-grad @ distillate, the valve i in the branch 14* belonging. -

to-the stiN Dis closed-and that, in the corresponding branch — «

_ 14° is gradually apened. This allows the'gas fromthe three

other stills, that are running under a pressure of.70 to 75

Ibs." in- fhe header-pipe 17, to exert. its. pressure back yy

| ‘the branch 14°, belonging to still D, and the in- 5

es nee the a of that still to stop fe

se the flow of v vapors from the latter: In this way the pressure

‘upon the contents of the freshly-charged still is raised. to’

*. that upon the stills-A, B and C. The firing of still Dis -

‘continued until the temperature of its contents is. raised to

upward of 650° F., when that still will begin-to' drive over.

its gases through the condenser, and drum and branch 14’,

belonging to it, into the header-pipe 17, and the production

of high-grade liquefied distillate will begin. The valve in.

branch 10° is now opened and the high-grade distillate-pro-

duced discharges into the header-pipe 12 in connection with

that produced from the other running stills. The four stills

are Now running in conjunction, all subject to the same con-

trol and the same Pressure-influences. The sudden sonar

and i, valves. Lat. it further be presumed that a still,

say that denoted A, has.completed its:run and‘is ready to

be drawn off, cleaned and freshly charged. Its furnace-fire

-. is drawn, and the valves in branches 10° and 14° are closed.

thereby shutting it off from the 70,¢o 75 lbs, pressure inthe —

: header-pipes 17 and 12 and from the influence of the stills

_ B,C and D. The valve in the respective branch 14* is

£ slowly opened to perift the gas to pass through the header-.._

~ [fol. 1184] pipe 16 to storage or to the furnaces; and the -

- _valve-in branch’ 10* is also opened, to ‘permit low ‘grade or

_* inferior liquefied distillate produced after closing off’ the

- header-pipe 17, to pass through the header-pipe 11 ‘to stor-

- As soon as the gas that was held under 70 to 75 lbs.

pressure in the equipment belonging to still A has. been dis-_

ae charged, the. tar-or residual contents of the still are drawn

-_ off, ‘and it is made ready to clean and ‘receive a fresh .

charge. As will be understood. each still in a pater? is :

_ handled in this way'after completing its run.

I realize that considerable variation is ‘possible in the

_ | details ‘of construction. thus specifically shown and de-

-~ seribed, and-I do not intend by illustrating a. single, spe-

of “cific, or preferred embodiment -of my invention to be lim-

ited thereto; my invention being, in the following claims, |

to daim protection upon all the novelty there may be in my

invention as broadly as the state of the art will permit. _

_. ‘What I- claim as new and desire to. secure by egies

_ Patent i Is: : oe

Y Rh oee

1. A. petroleum-distilling plant comprising, in combina- .

tion, a battery of stills, condensers into which the vapors

’ from the stills discharge, and a valved header connected

with the condensers to receive therefrom the uncendensed

‘gaseous portions of said vapors. and confihe them under

: pressure, and means whereby. such pressure produced in a -

late stage of. distillation may be used to exert pressure on

the material under distillation i in ‘an. early stage of distilla-.

- tion. ;

2. ‘A’ petroloum-distilling plant comprising) in combina-

tion, a battery of stills, condensers. into which the vapors

from the stills discharge; a header connected with the con-

densers to receive therefrom the condensed distillate, and a °

valved header connected with the. condensers to receive

therefrom the uncondensed, gaseous portions of said vapors -

and confine them under pressure, and-means whereby such °

pressure produced in a late stage of distillation may be

@ used to exert pressure. on: the material under distillation i in

an early stage of distillation. \ :

3. A petroleum-distilling dank comprising, in sommbina-

tion,'a battery of stills, condensers into which the vapors

from the stills discharge, drums communicating’ with the

lowér discharge-ends of the condensers, and a valved °

- header connected with the upper parts of the drums to re-

ceive therefrom the uncondensed gaseous portions of said

vapors and confine them under pressure, and -means

whereby such pressure produced i in a late stage of distilla-

tion may be used to exert pressure on the material under

distillation - in an early stage of distillation. es

4, A petroleum-distilling plant comprising, in ‘combina- een

_tion,'a battery of stills, condensers into. which the vapors

from the stills discharge, drums communicating: with. the

lower discharge-ends of the condensers and provided: with

drain-pipes, a header connected with the.drums to receive - : |

therefrom the condensed distillate, and a valved header .

connected with the condensers to receive therefrom the un-

condensed gaseous: portions of said vapors and confine

them under pressure, and means whereby such pressure

produced in a late stage of distillation may be used to exert

- pressure on the material under distillation i in an | early stage

of ee. ii ~

~ °

: - *

headers, for the purpose set forth.

4493

5A petroleum-distilling dink comprising, in octiistiig :

tion, a battery of stiJls, condensers into which the vapors

from the stills discharge, drums communicating with: the

lower discharge-ends. of the condensers, a pair of headers, |

meter-containing pipes leading from the lower-ends of the .

drums and each having valved branches leading. respec-

tively to said headers, a pair of valved headers, and pipes

leading from the upper parts of the drums and each having

valved branches leading . respectively to said | valved

6. A petroleum-distilling plant comprising, in combi ;

tion, a battery. of stills, condensers into which the vapors"

from the stills discharge, drums communicating with the

lower discharge- ends ‘of. the condensers, ‘a pair of valved

_. headers, pipes leading from the upper parts of-the drums Line

and each having valved branches connected * ‘respectively

— with said headers, and a pressure-relief valve’ in 1 pipe- ..

iain —— said headers. .

3 | Edgar M. ‘Clark.

In presence ¢ of Ottilie C. Avion Nellie B. Dearborn ‘

4494

[fo]. 1185]

wad PETITIONER'S. EXHIBIT 196

W, A. HALL.

process FOR THE CONVERSION OF HEAVY HYDROCARBONS INTO LIGHTER HYDROCARBONS,

APPLICATION FILED JULY 24, 1914

1,175,909. Cg ae : Patent! Mar. tas

BRANANAS

‘4

.7 ;

;

AA \ \

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[fol 1186) United States ‘Patent Office

- William A., Hall, of New York, N. Y.

Process for the Converaton of Heavy Hydreseebann into

Lighter Hydrpesrbons

ah 116, 909. Specifications of Letters Patent. Patented

Mar. 14, 1916 Maiobe

Application. filed July 24, 1914. Serial No. ‘802, 965

_ To all whofq it may concern: — 3 Ve |

Be it known that I, ‘William Augustus Hall, a citizen t—

the United States Republic, and resident of New -York,

___N-¥,, United States of America, have invented a certain

“new and useful Improvement in Processes for the Conver-

sion of Heavy. Hydrocarbons Into Lighter Hydrocarbons,

_ of which the following is a specification: ;

_ This invention relates to improvements in the’ hydro-

*genation of heavy hydrocarbons ‘with the object of con- -

'.. verting them into hydrocarbons: of ‘lower specific gravity ie

and boiling .point such as can be used successfully in ~

internal combustion. engines of thie’ automobile type. :

Inthe practice of dther processes/of hydrogenation -

known to me the hydrogenation of the oil has been effected.

by affixing tothe hydrocarbon m lecule additional ge:

' drogen derived from some extraneous source, which may ©

. be free gaseous. hydrogen, or producer gas, or’ nascent

- hydrogen from the decomposition of water, the affixation: |

‘being usually accomplished by the well known catalytic ac-

tion of nickel or other metal which will act in'a similar _

“manner, a process of this general character | being claimed |

- in my copending application 769,610, filed May 24, 1913.

_ These: processes have been found very expensive -as free

eS hydrogen i is a costly material, and the N, CO and CO, con-

tent of producer or water gas has presented difficulties. ~

* .The improved prpcess consists in subjecting the vola- —

_tilized heavy hydrocarbon, in the. absence-of steam or any

extraneous source of hydrogen, either in the form of water, .

steam or addéd. hydrogen, to the action of heat.and pres- —

_- .gure in the presence of a catalyst capable of effecting the —

me fixation of toe to. beanie allowing the ists vies

oes

ucts to expand and thereby deposit carbon, and cooling the

-residual products té produce by condensation a liquid .

hydrocarbon containing less carbon than _the- ‘said heavy

hydrocarbon, and especially adapted for use in high speed’

- internal combustion engines. 3

It has also been proposed to jiass a mixture of oil and

ater or steam through tubes containing metallic nickel ©

rods in a retort maintained at a dull red heat. My inven-

tion is. distinguished from such a process ini that I -pass the

vaporized oil through tubes containing rods of nickel or-

- other hydrogenating catalyst, but with the addition thereto |

of: no hydrogen, and no water or steam. :

If the hydrocarbon oil is heated under a moderate pres: .

‘ gure, say a pressure of about 5 atmospheres, to a tempera-

ture of upward of 600° _C., in the presence of the catalyst,

and in the absence of steam or any extraneous source of -

_ hydrogen, either in the form of water, steam or added hy-

drogen gas, an efficient conversion of the oil takes place,

‘the oil. being partially. decomposed and gases set free, such

. gases being in turn decomposed by the heated catalyst with

liberation of hydrogen which in a nascent state is to a con-

siderable: extent affixed to the condensable portion of the

- decomposed hydrocarbon oil. 4

eee catalysts:I employ are pe such as ; the metals, a

_or oxids of the metals, nickel, cobalt, silver, palladium, -

_ chromium. or manganese, which substances are hereinafter

. referred to under the term “catalytic body of the nickel

type.” )

ore Apparatus ‘suitable for the performance of the process

is shown diagrammatically in the accompanying drawing.

As. shown, the apparatus includes a preheater A for

- raising the temperature of, the oil and to some extent vola-

- tilizing the same before it enters the tubular converter B, —

Bo that the gas may be: produced at as early a stage in the

‘process as possible. ~ :

The converter shown is constituted by a serpentine. in-

clined metallic tube so arranged that the circulation is

through the top section, then down and through the next,

and so on to the bottom, the exposure being at first to the __

— lowest temperature, which is at the top, and gradually in-

_ ¢reasing toward the. bottom. In the tubular elements of

_ the converter is — the ental material which rests

in contact with the heated walls of the tube. From the con-

verter B the products are passed into an expansion chan?

ber C where their temperature is somewhat reduced. The

said expansion chamber C may be provided with a metallic

gauze screen D, preferably of conical shape, which will col-.

lect and extract any loose carbon that may be set free (it

being found that ‘such carbon is most readily deposited

- [fol. 1187], at the point where the expansion occurs and to’

the greategt extent if the pressure be suddenly reduced ~

front that 1 the converter (about 5 atmospheres ) down to .

atmospheric pressure). This loose carbon is of course a

product of the decomposition and its extraction from the -

heavy oil to # large extent accounts for the reduction of ©

the specific gravity. |

It is to be noted that the: pressure | of the vapors drops

materially, in passing from the converter B to the gham-

ber C. This drop in pressure appears to aid materially

in the deposition of free carbon in large quantities in the.

receptacle C,. By causing the earbon to deposit in the re-.

ceptacle C, instead of in the. elements of the converter B,

there is no danger of the converter Beene. clogged by

- means of this loose carbon.

It will be noted that the gases, and v Vapors produde by .

the decomposition of. the oii, will be caused to flow tather —

_ rapidly through the retort, and since the cross ‘section of

‘the space in the retort is rather small, owing to the fact.

that the metal rod therein takes up quite a large part of:

_ the space therein, the current of gases and vapors flowing

through the retort will carry along all the free carbon, or -

soot-like material, consequently not much of tliis will de-

posit within the retort. After the pressure falls, and the

gases enter the larger’chamber C, most all the free carbon .

will deposit in the expansion chamber C, and on the gauze

member D. Tarry, matters will likewise be separated in

the chamber C. From the said expansion chamber C the

products are passed through a cooling condenser E and

into a receiving tank F' from which can be extracted any

.. fixed gases that have not- combined with the condensable

portions. The condensate is found to be an entirely dif-

- . ferent product from the oil started ‘with—it' has a much

| lower specific gravity and — . and when redis-

| e878.

4498

f i atta

tilled arid fractionated yields a large portion of volatile —

spirit eminently adapted for use in automobiles. For in- hi

stance if the raw material used be “‘ ‘gas oil” (that tae

- trol./ The cont of this process ‘also contains a pro-

portion of unsaturated hydrocarbons. The quantity of

aes hydrocarbons may vary more or less, but the —

uantity is always rather small, as compared with the

@ products of sonie of the other processes with which I am

familiar. Of course it is not necessary to redistil the con- —

_densate, as the fractionation can be effected by a dephleg-

mator situated between the converter and the condenser.

Having described - ‘my invention, I declare that what I .

dais and desire to secure , by Letters. Patent of the —

’ States is:

1. The herein described method of ‘Muvartion. shitieils

heavy liquid hydrocarbons into lighter and more volatile —

hydrocarbons; which comprise- the step of vaporizing said

‘relatively heavy hydrocarbons, and causing a current of the

‘ vapors to flow, in the absence of extraneous: hydrogen, and. :

inthe absence of free oxygen, in contact with a catalyst =~

-eapable of effecting the fixation of hydrogen to hydrocar- ~

‘bons, said catalyst»being maintained at a temperature not

low 600° C., and said vapors being maifttained —

materially above atmospheric, thereafter

‘in the ‘pressure. is materially lower, ‘and the

ases. is materially: lower, than in the vessel

- containing the catalyst, whereby the bulk. of the free car-

_sbon separates, and is deposited i in said expansion vessel, 2

and thereafter cooling the residual products, to produce

_ by condensation, a liquid hydrocarbon containing less car-

_; bon than said relatively heavy hydrocarbon and especially

_ adapted for: use in high speed internal combustion engines,

2. The herein described method of converting relatively i

great hydrocarbons into lighter and Jnore volatile hydro-

-earbons suitable for use in internal“combustion engines, . -

cose _—— soepeee aimed said dpe _— a

hydrocarbons alone, causing thie” vapors thereby produced,

in the absence of extraneous hydrogen, and in the absence

* of free oxygen, to flow rapidly through a confined space

under a pressure of several atrhospheres, at a temperature -

sufficiently high to crack at least a portion of said hydro-

carbon, in contaet with ‘a catalytic body, allowing the va-

pors so produced to expand into a separate expansion ves-

sel, wherein the pressure is materially lower, than in the

receptacle containing the catalytic ‘body, and wherein the

‘yate of flow of the vapors is lower than in the receptacle

. eontaining the catalytic body, whereby free carbon will be .

: - deposited in said expansion vessel, and thereafter coo]-.

_ ing the vapors to condense liquid hydrocarboris. -

‘3, The herein described method of converting HN a

heavy liquid hydrocarbons into lighter and. more volatile

hydrocarbons adapted for use in high speed internal com- .

bustion engines, consisting in vaporizing. ‘the relatively

heavy hydrocarbons, and subjecting the vapors under pres-

gure, in the absence of extraneous hydrogen, and in the ab-

- gence of free oxygen, to the action of a éatalyst capable

_ of effecting the fixation of hydrogen, fo hydrocarbons ata .

temperature sufficiently high to cause the.separation of free —

’ earbon, allowing the products to expand into a separate :

ee [fol. 1188] expansion vessel, wherein a pressure is Main-~

. tamed, considerably lower: than the pressure in the recepta-

cle containing the catalyst, whereby’ the non-volatile mate-:

. Yials-are: separated’ in said expansion vessel, and : there-

after cooling the. residual products,: to produce by con-

‘densation, a liquid containing less carbon. than the rela-

tively heavy hydrocarbons employed. :

+ 4. In the treatment of hydrocarbons, of relatively high

_ boiling points, for the production of hydrocarbons of lower

_. ‘boiling points, the step of passing a current of vaporized

- hydrocarboris, at a cracking, temperature, and in the ab-

sence of extraneous hydrogen, i in contact with a hydrogenat-._

ing catalyst, under a pressure of several atmospheres. -

5. The step of. .passing. a cent of hydrocarbon vapors

under a pressure materially above atmospheric, i in contact

. with a nickel catalyst, at a temperature sufficiently high

to liberate free — in the anes a extraneous sabewegt

fia

5 oe. uN

“Fae oes) Bee ae .

4500 —

_ 6, In the production of motor fuel from heavier hydro-

carbons, the step ‘of passing hydrocarbon vapors alone into

contact with a catalytic, at a temperature above 600° C., .

under pressure materially above atmospheric. 7

7.’The herein described method of converting pelnsivals 7

heavy liquid hydrocarbons into lighter and more volatile

hydrocarbons, which comprises the step of vaporizing said ©

relatively heavy hydrocarbons, . and. causing a current of .

the vapors. to flow, in the absence of extraneous hydrogen, .

and in the absence of free oxygen, in contact with a cata-

lyst capable of effecting the fixation of hydrogen to hydro-

carbons, said catalyst being maintained at a temperature

above about 600° C., and said vapors being ‘maintained

under pressure. materially above atmospheric, thereafter * ©

allowing the products to expand into a separate expansion.

vessel, wherein the pressure is materially lower, and the ©

‘speed of the gases: is materially lower, than in the vessel

containing the catalyst, passing the gases and‘vapors while :

at said lower pressure, through a device capable of remov-.

ing free carbon, and thereafter cooling the residual prod-

ucts, to’ produce by .condgpsation, a liquid hydrocarbon

containing less carbon than said relatively heavy hydro-

-earbon and especially adapted for use in re os in-

tefnal combustion engifes. : ae

: 8, The. herein described method of con werting relatively

; heavy. hydrocarbons into lighter and more volatile hydro- aj

carbons, suitable for use in. internal combustion engines, -

which process. comprises vaporizing said relatively heavy

‘hydrocarbons,alone, causing the vapors thereby produced,

without the Addition of: other gases or vapors, to flow

rapidly through a confined space under superatmospheric

pressure, and at a temperature sufficiently high to cause -

the liberation of freé carbon, while’in contact with a cat-

alytic body, allowing the vapors so produced to expand

into a separate expansion vessel, wherein the pressure is \

materially lower than in the receptacle containing the cata-

lytie body, and wherein the rate of flow of the vapors is

— than in the receptacle containing the catalyti¢ body,

media, the gases and vapors through a sephrating

ud He

. . 4

a SL

9, In the production’ of motor fuel, the step of suddenly

lowering the pressure of a flowing mixture containing gases

and vapors and containing suspended particles of free car-

ben carried by said mixture, while causing said gases and

pors to enter an expansion vessel, wherein the speed of

| _ flow of. the gases | and vapors is materially decreas, 1.

10. A process of converting heavy hydrocarbon oils into

hydrocarbons of lower boiling points which comprises pass-

ing the ‘vapors of the hydrocarbons to be treated, under -

‘pressure materially above atmospheric and in the absence

of steam; over a substance capable of producing a cata- “_

'. lytic action, while maintaining ,said sucht sn a a tem-.

perature approximating red heat. -

"11. A process of converting ‘heavy ‘patrolonm ale into -

‘hydrocarbons of lower boiling points which comprises weve aa

ing the vapors of the hydrocarbons to be treated,

| superatmospheric pressure snd in the absence of 8

‘over a hydrogenating catalyst while.m ~~ said cata-

_ oils of which at least portions have boi

rially higher than. those of ordinary |

4 12, A process of converting heavy sie aati « oils into. |

_ hydrocarbon oils having lower boiling ‘points, which coni-

. ‘prises passing the vapors of said heavy hydrocarbon oils,

under a pressure materially above atmospheric, and in the

. lyst ata temperature iain red heat.

absence of steam, ‘over a catalyst, while’ maintaining said.

oe eatalyst at a temperature approximating a red heat.

hydrocarbon ,

g points mate-

solene, the ‘herein

described: improvement which compri ses passing such oil,’ ~

in the form‘of a flowi#g-current,-in the substantial ab-

sence of extraneous water, through a coil maintained at a: ,

13. In the manufacture of motor. fuel fron

_ temperature not materially below 500° C., ‘while ‘at a

pressure sufficiently low to allow vaporization, but acc

rially above atmospheric, and thereafter rapidly, lowering z

/. * the pressure of the’ flowing mixture containing gases and

vapors ‘and containing suspended particlés of free carbon _.

-. carried by said mixture, and causing said gases and vapors

to-enter an expansion vessel, wherein the speed of flow |

of the gases and vary} is materially deorensed, EP ec ot

. Baa

14, A process of. converting aes hydrocarbon lie into

8 1189] hydrocarbons of lowering boiling points which

“eomprises passing the vapors of the hydrocarbons: to be

: treated, under a pressure of several atmospheres, in the

absence of steam, over a metallic substance capable of

producing a catalytic action, while maintaining said .sub- _

stance ata temperature capable | of cracking the heavy oils.

15. A process of converting lamp oils or other hydro-

carbons into hydréearbons of lower boiling points, which»

comprises passing the vapors of the hydrocarbons to be- - :

treated, under a pressure of several atmospheres, over a _

-“eatalytic metal maintained at a temperature at which said _

catalytic metal Possesses catalytic activity. . ae ,

16. A process. of converting heavy . hydrocarbons into

hydrocarbons of lower boiling points which comprises pass-

‘ing the vapors of said hydrocarbons, under superatmos-

pheric pressure and in the absence of steam-or added hy-

drogen’ over a substance capable of producing a catalytic

action, while maintained ata temperature capable of erack-

ing oils...

hte Pe process of converting heavy hydrocarbons ine

hydrocarbons of lower boiling points, which comprises

passing the vapors-of said heavy hydrocarbons in the ab-

sence of steam or other extrafieous hydrogen, under super. eS

_- atmospheric pressure, over a ‘catalytic body ofthe nickel” ~

Py type, ’? at a temperature approximating a red heat, - -allow-

ing the products. of the reaction to expand.to a lower pres- —

| ‘sure, and removing the solid materials from the vaporous a

products. : °

.18. In the manufacture of mikes fuel. aa nyikesear ban

oils of which at least portions having boiling points ma-

terially higher than those of ordinary gasolene, the step of |

passing such an oil in the form of a flowing current, in the

substantial absence of: extraneous. water, through-a coil

. maintained at a temperature not materially below 500° C.,

while at a pressure sufficiently low to allow vaporiagsion, a

bat materially above atmospheric..

In testimony whereof I have signed my namé to this

specification i in nas _sisreeanee of two subscribing: witnesses.

itl Alfred 8. Barbey, 0. J. Worth.

William A. Hall. =f

[fol. 1190] Pirrrionen ’s Exuusrr No. 181 é

4 3 | ¢. s. PALMEk. |

PROCESS OF TREATING PETROLEUM RESIDUES. -

ication: fueto wae. 2, 1907

"1,187,880. Pe ee Patented June 13,1916,

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[fol 1191] United States Patent Office

_ Charles s. Palmer, of Upper, Montelair, New Je ersey

: Process of Treating Petroleum Residues

“187300. nm segs of Letters Patent. Patented as

|. | June 13, 1916. ieee

Application filed March 2, 1907. Ser ial, No. 260, 975

. To all whom it may concern:

Be it known that I, Charles S. Salen, a citizen of the

United States, and resident of Upper Montclair, in the

county of Essex and State-of New J ersey, have invented

certain new and useful Improvements in Processes of |

_ Treating Petroleum Residues, of which the following is’

@ specification.

My invention. relates partioalariy to improvements in

making volatile hydrocarbon compounds from petroleum

residues, such' as ‘‘Florence,’’ ‘‘Boulder,’’ ‘“‘Wyoming,’™

“California’’ and ‘‘Louisiana’”’ residues or pitches which

_ are substantially non-volatile below 300° centigrade:

_ The usual process of “‘eracking”’ or decomposing petro-

- Jeum residues consists in subjecting the same to a high

degree of heat whereby they are partially decomposed and

disintegrated into, volatile compounds. Thése are simul-

taneously distilled with the result that more or less residual

eoke or carbonaceous residue is produced. This carbon or

‘earbonaceous residue resulted from the decomposition of |

the compounds treated, into free carbon, at the relatively”

high temperature and relatively low pressure employed.

- In practically ali cases. where. pressure was employed the

temperature was in excess of 350° C., whereas the pres-

~ gure was at or below two atmospheres. gt an

3 The important features of my process: consist:

(1.) In the complete separation of the so-called Neal a

ing” from the step of distilling, the former being carried

out at high pressure, usually in excess of four atmospheres, —

_ while the latter is conducted ey at or a helow atmos-

' pheric pressure. —

Perea

(2: :) In conducting the ‘toracking”’ i in as comatzucted ae

aa = of ee enormous | Pressures, i

while sesbios sufficient: heat: theréo to liquefy, to: vola-

tilize, to create a predetermined pressure, i: e. autogenous

pressure, to furnish latent heat of volatilization, and to.

- furnish the requisite endothermic heat of formation.

(3.) In, utilizing the pressure element to ‘direct and con-— :

trol the reaction quite contrary to usual expectations, the —

greater the pressure the gréater will be the decomposition,

recomposition and polymerization into volatile products, « .

which are formed in spite of the pressure and work with

and intensify the pressure. -The: pressure is ‘controlled in

each castbyjthe equilibrium established and. varies accord-

ing to’ the materials treated, the resulting products, and the .

- factors of heat and time of action but ordinarily the pres- .-

gure when if reaches 130 pounds i is sufficient to effect the

“nécessary conversion.

- (4.) The time of action. This aang cade from the

time required for the preliminary melting and heating i in

the reservoir, occupies but a very few minutes.

Tht carrying out the said process in accordance with my

invention, the residues, ‘substantially «non-volatile, below —

—- . 800°-C., such as ‘‘Florence,’’ ‘*Boulder,”’’ “Wyoming,”

“California”? and “Louisiana” pitches or residues, are

- first introduced into a steam jacketed reservoir’ wherein the

' game are melted, and thence are introduced: into a high

pressure digester wherein they are subjected to the ‘requi-

. site conditions of temperature, and pressure necessary for

carrying out the process, the means for producing the

__ Tequisite temperatures and pressures &. Being indicated —

in the drawings accompanying this specification and form-

. ing a part thereof.

In the drawings, Figure 1 is an elevation chiefly i in-sec-. |

tion of an apparatus adapted for this purpose. Fig. 2

represents a curve illustrating the process in operation. -

_ Referring to the drawings the reference numeral 1, desig-

~ nates a tank or reservoir provided with a cover, 2, a ‘steam

jacket 3, a ‘drainage pipe 4, and a steam inlet pipe 5. An

_ outlet pipe 6, proyided with a valve 7, is connected by a -

pipe 8; provided with a valve 9, with a digester 10. The -

digester, which is constructed preferably of half-inch steel,

. « 48 provided with a cap or closure 11, securely packed in. the

usual manner, a manhole 12, and. pipe extensions’ 13, i

@ and 21 respectively. A jacket 15 preferably as shown being. - ~

-- provided with steam coils 16, completely sur esaid -

digester, openings being provided it both the digester and —

the said jacket. for the insertion of a pressure-gage 17 and

a thermometer 18. The pipe-extensions 14 and 21 project..

“through the jacket 15 and are provided with a check valve

19 and a stop-cock. 20 respectively.. These extensions are

connected with piping 22 and 23 to a still 24, of well known

“eonstruction, provided ‘with the usual steam-coils 25, inlet

. and vapor outlet 27, and thermometer 28. Wea oe

~The residues treated in the above described apparatus,

as actually practised, consisted in so far as could be deter-

mined from the specific gravity and melting points, of mix-

_ [fol. 1192] tures of hydrocarbons of the paraffin: series .

- OsHyae of the range CoH, to CsHss. Said residues are —

empirically known as residues or‘ pitches from, as for ~~

example ‘‘Florence,’’ ‘‘Wyoming,4’ ‘‘California’”’ and.

“Louisiana” pitches, which. were ‘the ones actually tested

and operated on by this process.. nay Arn 3

_ During the treatment in the digester, 10, ‘which usually’ 2

did not exceed a few minutes, the pressures gradually in-

_ ereased with the temperature, according to the curve shown

in Fig. 2, until a pressure of 130 pounds was reached, when

there was apparently a sudden conversion of the materials

"present into more volatile compaunds which caused a rapid

_ increase in the pressures as shown without the indication .

of any great increase in temperature. Since the heat was. -

being uniformly applied thereto, it is apparent that at this =

pressure there wag.a large absorption’ of heat, which pre-

. vented any noticeable indication of an\increase in tempera- . -

ture. Such absorption of heat being evidently due to the —

formation of new compounds which as the results slow are

- to a certain extent, at least, cyclic in character. -" = 5

_- In order that the pressure may be accurately controlled

during the operation, I provide the check valve 19, which a

may be adjusted for any degree of pressure desired, when

- upon an increase of the pressure above that to which the

valve is set, the vapors from the digester will pass over:

Oe 8 ae eee eR

The steam heating coils are utilized in the apparatus for __

- ¢arrying out my invention in preference to other common

_ heating means, because of the accuracy with which the tem- —

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| perature ot can ne adjusted, particularly if specheniols steam

> is marion therein ‘as is preferably the case. _

‘The volatile products obtained from the above’ treatment, -

as actually carried out, were drawn off through the pipe = —%

23 and collected in a still and subjected to distillation sepax §

rately from the. undecomposed residues remaining” in said

e digester, at atmospheric pressure and upon fractional dis-

tillation gave results substantially“as follows: Up to 100° es

_ C;, about 5% distillate; between 100° C. and 150° C., about

| 10% to 20% distillate; between 150° OC. and 200° C., about

10% to 20% distillate; between 200° C. and 250° C. about

20% to 30% distillate ; between 250° Cc. and 800°C, about

10% distillate. |

‘While the first fraction doubtless contained some volatile

paraffin C.H...., the higher distillates: were mixtures. of |

some paraffins, some benzenes C.H,, &c. and considerable

naphthenes or ‘‘cyclic’’ or ‘‘closed ring’’ paraffins, such

- for example-as- polymethylenes, 28, CoH, 2 and their ‘homo- es

logues. = + Ta wee

: The materials which had been previously non-volatile—_.

"below 300° C., after treatment uniformly yielded from 65%

__. or treatment, and were again treated there was no a

- to 75% of volatile. matters at temperatures varying from

100°. C..to 300° C.. Moreover, when the residues of one

treatment ‘were mixed with the residues of another b teh

le resi-

due remaining from the last fraction of one trea

teven..

if subsequently treated alone, would often be d mposed on

in a manner substantially similar to that: of untreated resi-_

dues when heated alone since each treatment’ would have —

its quota of undecomposed residue according to the equi- . .

librium established. * Accordingly, each regidiuie when re-

treated would decompose exactly as though it had not been _

previously treated, as decomposiiion. takes place at the :

appropriate equilibrium and Tong before all the residue. i is:

- transformed. - . en

In Fig. 2 the curve - ean illukteaten: the process when. a4

fe operating up to 300° C. and the pressures ranging from 30.

pounds up to 160 pounds, and in fact experiments show, .

that when operating even up to 400 pounds, the decomipo-—-

sition, | recomposition | and. polymerization, other a

_ being equal, is directly dependent upon the increase. of

_ ‘pressure, and that: the radical — a —:

new ‘stimpénat having new siobacoilate arrangements, does’ —

not begin muc): below five or six atmospheres independent :

of the temperature. On the other hand, the said experi-

‘ments indicate that at pressures ranging from 20 to 30 .

atmospheres the formation of new compounds. takes place

with great rapidity. In all eases the volatile products of

decomposition - increase with more pressure at -tempera-

tures from 200° 300° C. This indicates it is not’ merely —

the high temperature, but rather. moderate temperature -

and high pressure that govern the decomposition and de- .

termine the result.

‘As a specific example: When operating. with heavy, .

waxy, tarry or pitchy’ materials, such as: ‘‘Florence,’’ |

**Boulder,’’ ‘‘Wyoming,’’ ‘‘California’’ and ‘‘Louisiana’’.

age at temperatures ranging from 200° to 325° C. and

u pressures of from 60 to-90 pounds, but. a rela-

ively small percentage approximating from’ 25% to 35% .

of volatile products: were obtained. With temperatures

from 200° up to 325° C. and pressures ranging from 100 ©

to 150 pounds to the square inch, a large percentage °

of the originally non-volatile material treated was trans- -

_ formed into volatile’ compounds, the percéntage rang- _

. ing from 50% ‘to 75% of the original. At pressures

ranging from. 150 pounds' up to 300 and 400 pounds per

‘square inch, and at temperatures of from 200° to 325°

C., from 75% to 90% of the materials were converted

into volatile products.” These products were in all cases _

subjected to distillation, - at, or below atmospheric pres-

[fol. 1193] stire, separately from the digesting operation.

Thus if one starts. with a mixture consisting, for example,

B. of paraffin of the C.Hm,, series itis obvious that if it is .

- attempted to split up the said mixture into lighter mdle-

cules of the same series that there will be enough hydrogen ©

_ to satisfy but a part of the possible’ new molecules that — i

_ may be formed. The result will be the formation of com- |

pounds as CH, or even CrHn-- “2y CrHin-- -4 “CaHas- <6, &.

Now these unsaturated, so to speak, possible compounds, Be ae

. Might include the true unsaturated derivatives of the ethy-

lene and cetylene series, although normally this is rarely © ee

the case, or of the benzene; toluene, naplithalene, anthra- = -

cene; ete., groups which occasionally happens to be the case,

§ oro the ore series, the re as di-, tri-,-

tetra-, penta-, iene ihlksheain &e., and their derivatives

. as is often and usually the case. ©

' Yhrotghout the claims the term ‘hydro-aromatio” “as.

-used, includes the cyclic and hydrobenzenes, including naph-

thenes and the poly-methylenes, the hydrobenzenes tefe

to being such compounds as C.H.H:, C.H.H, and C.H.H..

_~ The positive addition of catalytic materials, as /originally

described in this application, to the materials peated, is

- + not claimed, as such, inthis application, but is specifically —

reserved for a co-pending divisional application: —

_. It is evident as herein described that the requisite pres- 2

sure for effecting the transformation by decomposition,|

recomposition and polytnerization of the residues treated

into the desired volatile hydrocarbon compounds is created:

by and is directly dependent upon the temperature which is’

employed in the operation. Moreover, in view of the fact |

that the digester is sealed immediately after the introduc- |

tion of the residues to be treated, it is evident that this

pressure is created wholly without ‘the introduction, and in

the absence, of a foreign compressed gaseous medium. |

)

: Having thus described my invention, what I claim is:

1, The process of ‘treating. petroleum -residues of the

paraffin series to increase the yield of volatile compounds

above that normally obtainablé therefrom, which consists

in digesting the same in a confined space under a pressure

.. inexcess of four atmospheres and not exceeding 400 pounds

per square inch, said pressure being principally -auto-

time sufficiently long to induce transformation of the major

.portion of said materials treated into more, volatile prod-

‘. ficient carbonization occurs to substantially interfere with

. such transformation, and said digesting being conducted

_. With the treated materials being continually subjected to

_ the pressure throughout the said digesting period of the

evolved volatilized pemeiane eadtigted by added aqueous

apne.

2. The process of treating . part aes reuidues. of. the

_parattin series to increase the yield of volatile compounds .

3 above that normally obtainable therefrom, which consists. -

in ens the same in a confined space under a pressure

ous, and at a temperature in excess of 200° C., fora

ucts, said temperature being. below that point at which suf-

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ee 1 a eee

‘in excess of eight atmospheres. and not exceeding 400

pounds per square inch, said pressure being principally

autogenous, and at a temperature in excess of 200° C., for .

a time sufficiently long to induce transformation of the

_ major portion\of said materials treated inté more volatile

_ products, said temperature being below that point at which

| sufficient: carbonization occurs to- substantially interfere

with such transformation, and said digesting being con-..

ducted with the treated materials being continually sub-

jected to the pressure throughout the said digesting period __

ff the evolved volatilized compounds undiluted by added

sare vapors. | " ae?

3. The process of treating. petroleum residues of ©

the paraffin series to increase the yield of volatile com- —

- pounds above that normally obtainable therefrom, which

consists in digesting the same in a confinéd space under a

pressure in excess of four atmospheres. and not exceeding

400 pounds per square inch, said measuré being: principally

- autogenous, and at a temperature in excess of 200° C. for -

a time sufficiently long to induce transformation of the

major portion of said materials treated into more volatile |

products, said temperature being below that point at which

- gufficient carbonization occurs to substantially interfere

with such transformation, and said digesting being con-’

ducted with the treated materials being continually sub-

jected to the pessure throughout the said digesting period =~

of the evolved volatilized compounds undiluted. by added _

aqueous vapors and thén relieving said pressure and sepa-.

rating the evolved wvolatilized compounds from the non- . -

-volatilized compounds. . 6s Ni ee

’ Signed at New York, in the-county of New York and.

State of New York, this twenty-sixth day of February,

ALD. 1907. © te \ ae

Dk ie pea Gharles 8. Palmer. \.

"Witnesses : W. H. Swenarton, Jas. H. Griffin,

4 ~ NS

(tl. 1194), pee ee

ae PETITIONER'S EXHIBIT. VER eae

‘H. P, CHAMBERLAIN,

OBTAINING provucis FROM PETROLEUM BY DECOMPOSITION oF courentar HYDROCARBONS

me Shia et THEREOF.

1 221,790. Lalani sais ocr. 20, 1913. : Patented nee 3.1917 |

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pie eal Cea

, Seana |

[fol. 1195] _ United States Patent Office >

Horace P. Chamberiain, of Buffalo; New York, Assignor to

‘Standard Oil Company of Hew York, of New sats N. Yo

a Corporation of New York -

- ‘Ontisining, Products from Petroleum by Decomposition of Pa

. Component Hydrocarbons Thereof , ;

th 790. — of Letters Patent. Patented Apr. ;

: 3, 1917 : :

| Application filed October 20, 1913. ‘Serial No. 796 B10

To all whom it may concern:

. Be it known that I, Horace P. Chamberlain, a citizen of

the United States, residing at Buffalo, in the county of

Erie and: State of New York, have invented certain’ new

‘and useful. Improvements in Obtaining Products from Pe-_.

_ troleam by Decomposition of Component - Hydrocarbons —

Thereof, of which the following is a specification. s

This invention relates more particularly to obtaining

naphtha, burning oil (kerosene), an asphaltic material and

another hereinafter mentioned product from petroleum -

which is of a character to yield paraffin wax; but each of

the improvements composing the invention is intended to . §

be secured for all the uses to which it can be applied with %

_ or without modification. | |

Heretofore.in my experience petroleain (of the char- .

acter mentioned) dras most*commonly' been subjected im the

- verude form in which it is produced at the wells, after sepa-

ration therefrom. of water and earthy matter by settling,

to distillation under atmospheric pressure at gradually in- |

creasing temperatures in one or more stills: (with. interme- __

- diate transfer of the residual oil when more than one still- ~

js used, with cooling or cooling and storage of the so trans-

ferred oil when necessary Or desired and with .condensa- _

tien of the Ny ut in a series of condensers ‘at different

| rosaries wes uring part at least. ‘of the distillation) ; such

distillation has been continued until only a dry coke re

mains as undistilled residue; and distillates have been ob-

tained principally, if not exclusively, in,the several forms —

; (0), of eceaee se. in: one or more grades, (b) watel

meer

* . tillat

ve. 2 PS ent \

..qwhite burning oil (kerosene) disti te, (c) mixed distil-.

late which consists in part of hydrocarbons ‘with boiling -

points normal for naphtha, in part of higher ‘boiling hy- .

drocarbons with viscosities normal for burning.oil (kero- |

sene), and in part of hydrocarbons with viscositieS too’great

. fot normal constituents of burning oil (kerosene) and not

"great enough to be normal in other than light grades of

- jubricating oils, (d) heavy: paraffin distillate, :

paraffin slop, and (f) crude still wax, also bag

slop, as wax tailings or as gum. From’ thy

') heavy

pwn as wax

4 om’ the’ heavy paraffin

_* glop and the erude still wax, an additional amount of

ont Raha e distillate has been obtained by further dis-

ion of them.. The points at which the different cuts ©

_ (divisions or collections in different receivers) have been

made have differed somewhat in different establishments .

_- and also at different times in the same establishments, ow-

ing to different views of thé manufacturers as to the best —

methods of working, and so on, or to different ‘market con- -

ditions. The normal boiling points of burning oil (kero- —

sene) hydrocarbons have been recognized as between 302°

F. and 572° F., or 518° F. (Allen, Commercial ‘Organic |

' Analysis, vol. 2, London, 1886, pages. 397 and 398); as so:

defined, boiling points normal for naphtha would extend —

up to 302° F.; but for some years naphtha has included less

volatile hydrocarbons; and for the purposes of the pregent

_ ‘specification volatility normal for naphtha should be taken

- to include boiling points up to 338°-F. For the same-pur- |

. poses viscosities normal for burning oil (kerosene) hydro-

-earbons may be taken to extend up to seventy seconds at

100°. F. by an Engler viscosimettr, on which water would —

exhibit a viscosity of fifty-three seconds at the same tem-

~~ perature; and the intermiediate viscostties mentioned may

be taken as from seventy to one hundred and seventy sec-

_ onds by. the same Engler instrument ; which is also referred -

‘to whenever viscosity figures are given hereinafter, _

. With a view to increasing the ‘yields of naphtha and —

burning oil (kerosene) hydrocarbons, it was long ago pro-

posed to distil under superatmospheric pressure oils which

are composed of, or. contain higher boiling hydrocarbons, 4

as crude petroleum, for example, or undistilled residues -

-° of.erude petroleum after removal therefrom of crude naph-

_ tha and water white burning oil (kerosene) distillate (with ~

ades of

or without. obtaining more or

_ tillation of crude petroleym, and its.-undistilled residues

under sufficient pressure fould be carried on with safety .

in stills of practical size only to a ggmparatively slight ex-°

- tent on account of overheatingsthe still bottoms. More re- —

cently it has been proposed to distil under superatmos- .

pheric pressure distillate oils composed of hydrocarbons

‘with the intermediate viscosities mentioned, which for want

-[fol: 1196] of more profitable employment have commonly

been disposed ‘of as gas-oil-or fuel oil. They have been

obtained in part as distillate’ in-reducing (partially. dis- ° :

tilling) heavy paraffin distillate, from which. paraffin wax

- has previously been separated by chilling and pressing,

and also’as residues (bottoms) in distilling the water white

distillate and the mixed distillate already mentioned, re-

spectively. So far as I am aware. their component hydro-

_earbons ‘have been (all or practivally all of them) below .

+ and usually well: below one hundred and seventy. seconds

in viscosity at 100° -F. What practical use has been made .

of these proposals I am not sufficiently informed to’ state.

. I hae discovered that the entire heavy paraffin distil-—

late obtained in the distillation of crude petroleum as afore-

- said, treated, with-sulfuric acid and alkali, and retaining

’ its content of paraffin wax, can. be distilled under suitable

‘superatmospheric pressure with the production of what

may be called-high pressure distillate yielding (by appro-.

priate refining) a notable proportion of finished n a -

with boiling points up to 338° F. (more than ave ob-

tained from high pressure distillate produced by distillat-~

ing said_gas' oils or fuel.oils under like~conditions), and

also a large proportion of refined burning oil’ (kerosene)

of better quality than oil distilling over between the same’ _

limits of temperature, 338° F’. to 518° F., which I-have ob-" —

_.thined from the high pressure distillate produced by dis-

tilling said gas oils or fuel oils under like conditions. --—

- (he burning oil. (kerosene) from ‘heavy paraffin distil-

late has been lighter in gravity and lower in viscosity than

- that from said gas oils or fuel oils-and has also proved it-

self superior to the latter in burning tests;.not exhibit-. ~~

ing the sanie tendency-as the latter to smoke, to producé a

hard crust on the wick or to throw out mushroom-shaped _,

r less of the mixed distillate’

herein above mentioned).- Such. proposals seem ‘to have

little; if any, practical value; because, for one reason, dis- |

4515

formations of carbon on the wick. This improved quality -

of burning oil (kerosene) is of special importance on ac-

3 - count of the scarcity of high. quality oil which could be used /

to mix with inferior oil in order to increase the yield of

a desired standard.

The treatment of the heavy paraffin distillate with sul-”

-furie acid and alkali and the presence therein of paraffin

- wax aid, each of them, in securing the results stated; but

"> it is believed that advantage over the prior state of the art

5 ‘ean be obtained without the aid of either of said features. oa

* Heavy paraffin distillate in each of four forms, that is to

"gay, either pressed or unpressed and either treated or un-

. treated with sulfurie acid: and alkali, can be ‘distilled un- :

- der pressure in accordance with the invention, although

not for all of said forms with the same advantage. ‘

_* Such heavy paraffin distillate in each of said forms con-

tains liquid hydrocarbons with viscosities normal to heavy

‘ ' and. medium grades of lubricating oils and also hydro-

‘carbons with the intermediate viscosities mentioned in such

relative proportions that in the distillation under pressure

- the decomposition of the-hydrocarbons of each of said kinds ~

is modified. by the presence of the two other kinds. -For

exerting such modifying effect the hydrocarbons of any of

said kinds should not be less than about ten-per cent. by

volume of ‘the’ sum total-of the three kinds; and in the

_ distillate mentioned the kind present in least proportion i is

in excess of such ten per cent. Said distillate is also co

far free from still wax and like heavy matters_of sticky

character and from elements. yielding the same or coke

that charges of the said distillate of practical size can be:

distilled under a superatmospheric pressure of: seventy

five pounds tothe square inch to the extent of fifty. per

x. tent. or more by volume without heating the-still bottom -

to redness. I have‘also discovered that certain advantages

_ over the prior state’of the art can be obtained by distilling

as aforesaid oils related. to heavy ese: distillate as here-

inafter explained.

_ In yielding naphtha and burning oil: ‘(harosesia’ the ‘i

composed hydrocarbons may yield also a residual -product

of an asphaltic character which is useful and I believe new i

__. and-which is included inthe invention as a new article of

Ae manufacture or composition of matter.

* we.

ape :

IT have also discovered I believe a new process of dis-

_ tilling hydrocarbon ‘oils under superatmospheric pressure;

which I have applied to heavy paraffin distillate in each of ue

' the forms mentioned; but which I believe can be applied - '

advantageously (as compared with the prior state of the

- art) te other forms of petroleum (including crude oil and

undistilled residues i in case it should be found expedient to

- distil-the same under superatmospheric pressure, as well

. as the herein above mentioned gas oils or fuel oils and other

distilled or:partly distilled products), and also to hydro-

carbon oils from other sources than petoleum

I have also devised a distilling apparatus which is useful.

for performing said process and which I believe to be new

and consequently mgere as forming pant of the present in-

vention.

The accompanying drawings represent by way of example

an apparatus within the invention, Figure 1 being a longi-

tudinal vertical section, partly in elevation, of the still and ~

accessories, without the condenser, Fig. 2 a view in cross

section, partly. in elevation, showing still and condenser,

and Fig. 3 a detail view in séction on an enlarged scale of:

an expansion valve appropriate to. be employed as a va-

por throttling device in said apparatus. -- ~. “4

‘{fol. 1197] The still-a-is advantageously of. box-like form °

and of a large enough capacity to be of practical value in

industrial use, say a horizontally disposed cylinder eight

feet in diameter and eighteen to thirty feet in length, or -

of other appropriate dimensions. It is supported above ~

a fireplace b for heating and has its upper portion exposed* *.

to the atmosphere with little or no protection. against cool--

ing. It is best provided with a dome c also exposed to the

atmosphere. The heating means may be of any appro-.~

priate description. .A burner d is shown by way. of ex- |

ample, the same having a gas supply pipe e connected -

therewith and provided with a controlling valve f. Any _

desired number of bhirners can be used; also one or more

fires burning solid ¢r liquid fuel can be used i im connection |

.with supplementary gas burners; or other heating arrange- |

‘ments can be adopted. The still, when its bottom beeomes_

heated to incipient redness (the ordinary. indication of —

danger toa still bottom from overheating should distilla-

tion be contmued) Ought-then' to be able to withstand an.

‘guternal —— in such. + eacat oF eighty pounds age

pieg ar Be

4517

square | tachi’ above atmospheric pressure as to) afford ae

proper margin of safety.

. The intermediate section of the still (see Fig. 2) is 19

x 27 best protected both from the atmosphere and - ‘from the’

_ fire gases, the cubic contents of the so protected portion be- .

ing not less than about half the capacity of the still. As

shown, about a third of the exterior surface of the still is

exposed to the atmosphere, | approximately another third

is exposed to the fire gases, and the remaining portion, ap- :

proximately one-sixth on each side, is inclosed by and in. -

contact with the walls of the still ‘setting and'is so pro-

tected thereby both from the’ ener and from the

fire gases.

The vapor pipe g leads drsiala acai ctoa condauet of

any known or suitable form; shown as a coil h immersed

in a fank j. Water of a temperature to condense naphtha

_and heavier vapors is. supplied to. tank j by water. inlet —

_. pipe k and withdrawn therefrom in a warmer state by water

outlet pipe l. At m within tank 7 is a gas separating box

with a gas escape pipe » leading from its top and a distil-

late outlet. pipe p leading from the bottom to a receiver (not

shown). At-q is a gas main for carrying away the gas to.

be burned. - Additional fuel would; of. course, be needed for

heating the still ain case gas from the same-should be ©

burned under it.

The vapor pipe g is pecvidied with an ‘iconalion valve r

intermediate the dome c of still a and the condenser. As the

best conduct. of the pressure distillation requires a close

regulation of the volume of escaping vapors, the valve port

s (Fig. 3) is best of small size as compared with the bore ©

of vapor pipe g; which bore ‘should not be less than about -

three inches in diameter: in order to’avoid difficulty from

choking. As shown, the. valve is closed by a screw ¢ and

-has a stuffing box u for its stem. Stuffing boxes are also

. shown at w and z for the pipe connections. . : :

- Phe valye shown is a form known on the market as of

needle type and employed (for one. purpose at least)! as

*. an expansion valve in ice machines using liquefied ammo--

“nia as the, refrigérating agent. ,A valve of more pro-

nounced needle form (more acute taper and further pro-

" jection into the port) might have advantages; but the form

shown has been found useful. A valve of other than needle

type is net necessarily excluded. Heretofore in plans for :

4518 | ae

distilling petroleum and other hydrocarbons oils under su.

pératmospheric pressure it has been proposed to employ

_a relief valve which rises automativally when the pressure

‘reaches a certain degree and closes when the pressure falls

below the same degree. The use of such automatic valve

is- not necessarily excluded; but its use. is attended with

- no advantage, in my opinion; while, on the other hand, it

- adds complication to the apparatus and is liable to cause

‘danger or inconvenience by sticking. If used, it would be

advantageous to provide means for manually regulating

the extent of the valve’s opening and for forcing it posi-

- tively to.and from its seat, should occasion arise.

The still is shown provided. with a pressure gage y for —

- exhibiting the pressure ‘inside the still, a safety valve zfor .

relieving said pressure should it. accidentally becomé ex-

3 cessive, a pyrometer 2 for exhibiting the temperature of |

' the oil in distillation, a second pyrometer 3 for exhibiting

the temperature of the vapars.in the vapor space at the

front of the still, a third pyrometer 4 for exhibiting the

temperature of the vapors as they leave the dome c and pass

over to: ‘bescondensed as distillate, a valved oil supply pipe

5, a valved discharge pipe 6 for the residual product, a.

‘steam pipe 7 for introducing steam at the.close of each run

in order to expel hydrocarbon vapors and to cool the still

. ‘off more rapidly, and a manhole 8 for cleaning. out the still

at the end of each run. Each pyrometer is inclosed:- in a

_ protecting sheath or pipe 9 closed at the inner end. ,Elec- —

trie pyrometers with wires 10 are indicated. —. :

For obtaining the oil to be supplied to still a crude pe- -

troleum may. well be distilled to dryness under atmospheric »

' pressure in one or more externally heated stills (not shown)

with gradual rise of temperature’ and with fractional con-

‘densation of the vapors in the latter part.at least of the

- Tun, customary apparatus. being used for the purpose.

[fol. 1198] After the collection of the water white burning

oil (kerosene) distillate and of.such amourit of the mixed

distillate coming over subsequently as may be desired, the

distillate which is subsequently | received in such disfilla-

' tion may well be collected in the receiver 3 ‘heavy par-

affin distillate as long as it is sufficiently free from still wax

tobe readily pressed for paraffin wax. Assuming that the a

_ erude oil operated upon is from the Kansas oil fields and

has itealt z ecsiers gravity of 0. 863, such collection may se

well include all the distillate which at the condense

Fy > Jet is between 0.855 and 0.904.in specific gravity at 60°.

Distillate which is.received afterward in’said -distillatior

of the crude oil may well be itself distilled to dryness, and

the so obtained distillate, so long as it. is free from still

eo be added to the heavy paraffin distillate of the crude ©

_ oil rin. .

~ The thus. obtained material ‘would ‘Best be treated ‘with

sulfuric acid and alkali in the manner customary for treat-

ing heavy parafin distillate therewith preparatory to chill- .

ing and pressing, to wit, -by agitation with them in suc-

cession and by separation of the resulting sludge after -

‘each agitation. So treated, and with its content of paraffin

wax intact, it would constitute heavy paraffin distillate in:

the form in which it is considered best to: employ the same

for decomposition in the still a.

It would ‘consist: principally of hydroearbons, whigh (if

separate) would be liquid at 60° F.; but it would also con-

tain over four per cent. by volume of paraffin wax (in so-

lution). Its liquid portion would-comprise hydrocarbons

with viscosities normal to medium grades of lubricants (to

wit, from one hundred and seventy seconds to two hundred

and ninety seven seconds) and also hydrocarbons with vis- _

cosities normal to heavy grades of lubricants (to wit, from

two hundred and ninety seven seconds upward) as well as

hydrocarbons whose viscosities lie between those normal —

to burning oil-(kerosene) and those normal to medium lubri- -

eants (to wit, between seventy seconds and one hundred and |

seventy seconds). Each of these species of’ liquid hydro- :

_ carbons would be present in above 10 per cent. by volume.

' A sample from a particular lot of treated and unpressed

heavy paraffin distillate which had as a whole a specific

gravity of 0.881 at 60° F. and whose distillation under .

pressure gave results hereinafter set forth was chilled and -

sed for paraffin wax and ‘yielded the latter at the rate

“of sixteen and a half pounds to each 42-gallon barrel: of the

_ unpressed distillate (equivalent to six per cent. by volume). ”

The so-pressed sample was then reduced with super--

_ heated steam introduced into the oil and with fractional con- —

densation of vapors in a series of condensers at different.

temperatures in the manner customary .in obtaining lubri-

— oils itight and median a as diatiates and

Oe |

4520 |

heavy grades as residues) from pressed paraffin aan

and in such reduction yielded (1) distillate with viscosities —

/ at the condenser outlet up to seventy. seconds equal to one

per cent. by volume of the unpressed distillate, (2) distil-

late with viscosities at the condenser outlet between seventy

‘seconds and one hundred and seventy seconds equal to fifty. a

- six 44/100 per cent. thereof, and (3) distillate with viscosi- :

ties at the condenser outlet between*one hundred and. sev- —.

enty seconds and two hundred and ninety seven seconds

- equal to thirteen 89/100 per cent. thereof, leaving (4) resid-

nal oil equal to twenty 38/100 per cent. thereof. There

was thus an estimated loss of two 90/190 per cent, by vol-

ume in the assay. |

The treated and. unpressed heavy paraffin distillate is

introduced through pipe 5 into the still a until the latter is

‘ say six-tenths full: The contents of the still are then grad-

ually raised in temperature, with valve r open, until the ©

-air has been expelled from the:still and oil appears as con-

densate at the condenser outlet. Next the valve ris closed 4°

and the pressure: in the still.a is allowed to accumulate

until the gage y shows say 75 pounds per square inch above

- atmospheric pressure. Thereupon the valve r is cautiously -

- opened; and the heating is carefully regulated to maintain

said pressure of 75 pounds without greatly exceeding it. -

The extent. to which the valve r is opened is an important

matter. It may well be opened to such extent that distil-'

late is received from the condenser.& at the rate of about

two per cent. by volume of the original charge‘per hour of

running. It may be opene¢ to a lesser extent, as much less

as may be desired; since the only objection to the resultant

_ slower, ranning would. be the increased expense due to the

longer time to make the run. It may be opened to.a greater

_ extent; but with too large an opening excessive firing would

be necessary to maintain. a proper pressure in the still a;

and, in consequence of such firing, the hydrocarbons pass-

ing over might average too high in specific gravity for

profitable working...A general increase of'as much as twen-

_ ty four one thousands (0.024) in the specific gravity of the

high pressure distillate (as compared with that obtained

. in a distillation of oil from the same lot: at the said two

~ per cent. _ per hour rate) would probably indicate a fatal

. troslenest in the _— of nig preeare distillate. Such ae

e235

; ‘eomparison should be made ebaeel wastiphts to be collected -

at corresponding periods of the runs,.to wit, when the dis-

tillate received in each run shall be the same percentage

‘ef the original charge. F

[fol..1199] The valvé r can be adjusted inion a ‘run, if

considered necessary or expedient, but in normal running

the valve opening may be constantly established, so as to

~ allow a continuous escape of the vapors through it; and

. mately uniform escape of vapors: with. an “approximately

' gniform pressure in the still. :

As distillation proceeds, .the oil-in distillation heouine: a

gradually hotter. Its temperatures will be higher than -

~ those of the oil in a parallel run under atmospheric pres- -

gure; but they may be (and in distilling heavy.paraffin dis-

‘ _ found to be) below those at which the vapor tension of the

-. undecomposed oil is estimated to equal the still pressure on

. the basis of considering the rise in vapor tension of the.

- -wndecomposed oil for a given number of degrees F. above

. its boiling point to be equal (or sufficiently near equal) to .

the rise in vapor tension of benzene (coal tar naphtha,

- O,H.) for. an Real number of. degrees F’. above its boiling :

. point and the temperatures of the oil in distillation in a —

parallel run under atmospheric pressures to represent (with .

- ‘gufficient accuracy) the boiling points of the undecomposed —

il... Hereinafter a.table is given which. shows the tempera- .

-, tures of the oil in parallel runs on heavy paraffin distillate

_ under atmospheric pressure and under seventy five pounds

superatmospheric respectively; and it will be observed by

* reference thereto that at corresponding periods ‘of the runs.

~ - the difference is less than 131° F.; which. is the difference

-. in temperature between benzene at its boiling point (where .

its vapor tension equals. the pressure of the atmosphere)

and at the point. where its vapor tension:is seventy five

pounds to the square inch above atmospheric pressure. See

_ .. ‘The evolved vapors are cooled in the exposed upper part.

_ of still @ and in dome c fo considerable extent (say between

. about 150° F. and about.350° F. below the contemporaneous —

temperatures of the oil in distillation) before they pass

|; over to be condensed as distillate. ‘Such cooling results in

Ae partial condensation of said: vapors and the formation

it need not be altered in size, thus allowing an approxi-' :

, fillates under a pressure of seventy five pounds have been —

4822 /

- of condensate which returns to the oil in distillation. Itis —

conceived that some hydrocarbon components. of the oil in.

still a will vaporize without decomposition, owing to the .

_ presence in the still a of the vapors of lighter (more vola-

- tile) hydrocarbons formed by decomposition, notwithstand- —

ing the fact that the temperature of the oil in distillation is _

below the estimated boiling point of the latter under the ©

‘pressure in the still a.

The following table gives, figures. which were. obtained 4 -in

- runs performed at the rates indicated in the table with a _-

small still (a horizontal cylinder 20 inches in. diameter by

42 inches long with.a dome four inches in diameter and six

inches high) on batches from the same lot of oil, one under

atmospheric pressure arid the other under a super-atmos-

pheric pressure as near 75 pounds to the square inch as: —

practicable without falling below. the same... The total

« hours’ and minutés of performing the respective runs, in

- connection with the total percentages received therein, show- /

‘average: yields of distillate | equal to. about seven and a half 2

per cent’ by volume of the original. charge per hour in one hi

run and about eight per cent. per hour in the other; but in

_ industrial operations a lesser. rate’ is considered better as

hereinabove indicated.

The specific gravities i in the table are those of the sseeardl

fractions of distillate of 5% each by weight; and the times

in minutes are thosecin which. said fractions were severally .

: received. : .

iis pressure. \ _ 5 pounds gage pressure,

: . . \ \ -

ceca ee EN Cie We g oe

yrecthios Qu” 8 Bs a \ 38 sg E - :

mom oe Bk Ug . Nght, S244

aes | 1 7 tu i are

.1.:.... 663 588 8236 40 .766\ 512 .7669 48

A Breen - 679 582 8473 43 756 620 .7673 43

g...... 691 624 8529 45 766 525 .7682 46

Avct.. TOL. 635 8536 «+38, 769 530 .7762 35.

NS 710 635 8581 40 775 . 529\..7770 - 37.

- B..J0 TE 658. 8540 «43 «778 «530. 41.

Ho i he 922 656 8571 41: 777 536. _ 88

| 8...... 734 676 .8560. 40 782 540 421

\9....... 740 680 .8555 44 793 545 46

\100.... 741. 635. 8473 43 804 550 ° .7945 \ 37°

it... 752 655 8519 (40 811 554 . .7967 es |

ae | Ree 760, 688 .8514 38 815 546 .8053 36

(A3..... 765 691 8524 39 834° 550 : 8170 40\

I ts. bean to mney those skilled 3 in the art to practios ‘the.

. ‘invention.

| ee 770 =696 .. 8534 45 / 842 546 ~.8299 90

Total distillate 70% ; time . h 39 m. ; ; total distillate 70% 5

time9h. 36m...

Percentages in table by: Salant: not volume; total distil-

late 72% by volume in run under atmospheric pressure, and

| 718.2% by volume in run under 75: pounds gage pressure. .

In giving these and other figures in detail, it will be un- .

“derstood. that they are by way of example. only, in order .

fol. 1200] It is oonsidered. best in distilling under pres- a

~ gure that the evolved vapors should not be heated above the

wa _-tontempotaneous. temperatures of- the oil in distillation.

_As shown, therefore, only the bottom.third or thereabout of

. the exterior surface of the still is exposed to the fire gases;

~ go that the walls-of the vapor space, even when this space .

is enlarged by progress of the distillation, will not.be ex-

: posed thereto. The cooling of the vapors is effected as

shown by the exposure of the still top and dome to the cool- _

ing influence of the: atmosphere. The work dle igi

4524

the vapors in expanding as they pass the valve r in distilla-

tion under high pressure, with said valve within a short

distance from dome c, also exerts a cooling effect on the

vapors in said dome c. The condensate as formed drops

(or else runs down the sides ‘of the still): into the oil in dis-

tillation. A partial condenser exteriorly located and con-

nected with the still by a vapor pipe and a run. back for.

returning condensate could be used instead of or in addi.

tion to cooling in the vapor space: (instading dome Since

. when a dome is used).

. By having the middle section of the still inclosed by and

in contact with the walls of the stilt: ‘setting, +the-vapors are . ¥

protected not only against overheating, . as just mentioned, -

but.also against the undie cooling which might result from

enlargement of the vapor space during the run, were said .

middle-section exposed to the atmosphere.

The distillation would best be continued as long as it is

_ safe to do so, in view of the superatmospheric pressure in __

the still. The limit: of safety would probably be about

reached when the appearance of the still bottom indicates Se :

ineipient redness, .

The run being thereupon dovinhidaited, ‘the asphaltic: ma-

"- terial in the still a is withdrawn through pipe6andacooler — .

(not shown) into an appropriate receiver (not shown) } the -

_ still is subsequently cooled (after introduction of free.

steam through pipe 7. to expel the vapors, the manhole 8

operied as the steam first enters) ; the still is cleaned; -

d it is then ready to receive a new charge of the treated

unpressed heavy paraffin distillate.

. The high pressure distillate from condenser coil hi may -

well be collected in a single receiver (none shown) and be eS

then fractionated into naphtha, burning oil (kerosene) and

a heavier oil useful as. gas or fuel oil. Said heavier oil,

also any residue obtained in rerunning the’ burning oil ie

(keresene) portion of the high pressure distillate, could be . -

added in whole or in'part to a new charge of the heavy par-

affin distillate, if so preferred. Other. oils could also be

'. added, if so desired such as résidues (bottoms) from Tre- _

' ‘punning the water white distillate and the mixed distillate.

- (of the crude oil run.’ Instead of a single condenser h as

shown, a series of condensers maintained at we tem- - a

i peratures — be — to the er war

| a0) oi

. .The asphaltic residual material withdrawn from the still

ga at the close of the high pressure run in which the figures.

of the table were obtained had as a whole a specific gravity

of 1.0772, and was.as a whole ninety eight 65/100 per cent..

soluble in carbon-bisulfid and eighty two 95/100 per cent. \e

soluble in naphtha obtained frem Kansas crude oil and con-

sisting of hydrocarbons : with specific gravities ranging

from 0.7526 to 0.7692.

- If so desired, the pressure distillation can be arrested —

. before the material in the still attains the specific gravity

mentioned. Also, if,so desired, further distillation can be

carried on under atmospheric or other reduced ‘pressure, —

with or without introduction of free ‘superheated steam or |

_ other aeriform fluid (including atmospheric air, — =

be desired to modify the composition by oxidation).

obtained fromthe high pressure still the asphaltic ner

' will ordinarily be soft and sticky even at zero F., on account. _

of the conduct of the distillation only while it can be carried

on with safety ; but by. reduction (partial evaporation)

under atmospheric presgure at appropriately high temper-

. ature and with introduction of superheated steam: inte-the

.. melted material, it can be brought to such condition that _

\. when cool a lump of the samé can be molded and drawn out -

_ into threads. Distillate obtained from such reduction can

~. be.added to heavy paraffin distillate to. be distilled under °

the high pressure mentioned ; it ¢ould be used as gas oil or —

fuel oil; or it could be otherwise disposed of, as preferred. as

a solution of the asphaltic material as: obtained ; from. -

=. the high pressure. still in the naphtha mentioned (in. such

_. proportions as to give the desired fluidity for application)

constitutes an excellént varnish or protective coating. ‘The

- material can be.so dissolved and used after reduction (par-.

tial evaporation) and oxidation (either or both). It: can |

be: used also (alone or in connection with asphaltum and.”

with or without reduction: and oxidation, either_or both, as ©

-. May be,.necessary or expedient) ‘for paving and. roofing

_. purposes and for other purposes i which asphaltam, has Z

__ been applied. - ;

While it is considered best. to vt the pressure “gtill:

_ . with an oil whi¢gh represents an entire range of hydrocar- *.

~ bons from and |ineluding some with. the intermediate. vis-

neities men ionie¢ t te end onee® nese nications from

SoA

* 4526 | |

~ heavy paraffin slop, dander" less of sai Se iipdtcchctens aa 7

. be-collected separately, if so prefe ‘and only the re-

mainder of them charged i wh 7

- [fel. 1201] It is also permissible within the limits-of-the— ee

invention as expressed in one or more claims be thake arti-

ficial mixtures of hydrocarbons with the inte rifediate vis-

cosities and those with viscosities a: al to lubricating oils —

of (either or both) medium. and -heavy grades, the words

‘‘artificial mixtures’’ being used in‘oppgsition to a natural -

‘mixture of said kinds of hydrocarbons such as exist, for

example, in heavy paraffin distillate obtained as aforesaid.

_ Also oil composed of or containing hydrocarbons with the _

_ intermediate viscosities‘ mentioned can bé ‘enriched with

paraffin wax or an appropriate substitute artificially, or pie

' eollecting a distillate containing paraffin wax. , .

Net further within the limits of the invention, oil contain-

. ing liquid hydrocarbons with viscosities normal\ to medium

and heavy lubricating oils (either or both) and ail contain-

ing hydrocarbons with the -intermediate viscosities men-

tioned | be distilled separately under pressure and. the

resulting products can then be mixed. In this -way burning ~

oil (kerdsene) from distilling oil of the latter kind under

“pressure can. be impraved by the better quality of that from

: distilling oil of the former kind. I have obtained larger

_._ yields, however, both of naphtha. and of burning ‘oil; (ker-

-osene) from distilling mixtures of (1). hydrocarbons -with.

. viscosities normal to heavy lubricating oils arid:(2) liydro-

‘earbons with the intermediate viseosities-mentionéd than ~

from distilling like volumes of said two kinds of liquid

hydrocarbons separately ; ; and,I believe that the same prin--

. ciple would hold true in respect to mixtures containing

3 “hydrocarbons with viscosities normal to medium lubricat-

_ ing oils. It is also my belief’ that better results are attain-

able*by distilling oil in which two or more of said three

_ kinds of liquid hydrocarbons are naturally present than by -

-separating such hydrocarbons and then forming a mixture |

‘artificially of them in their original proportions. he

In making heavy paraffin distillate a certain amount of ;

_ decomposition is considered necessary in order to form

_ erystallizable paraffin wax. .It is provoked by introducing

little or no inert. orm finid (like superheated steam)

“ into = still and = ecoling: the evelved a ———

. x : wt PEAS r : . - > : ae?

Sj form-a co condensate which i is returned to the oil in distil.

lation. The cracking customary in making heavy paraffin

e distillate is considered advantageous where sych distillate

is to be subjected to pressure distillation, for one reason be-

| : - eause it removes from the distillate certain coke forming

elements ; and, if preferred, it can be carried furth«r in pre- —

paring distillate for subsequent pressure distillation than

is customary in preparing heavy paraffin distillate. On the

other hand, it néed not necessarily be carriéd to this extent

or to any avoidable extent within the limits of the invention

as essed in some at least of the claims. Aeriform

" fluid,/such as superheated steam, could, for example, be

introduced into crude petroleum in preparing a distillate ~

to be itself distilled i superatmospheric pressure.

: ‘In the pressure distillation it is considered best, as men-

_ ~ ‘tioned herein above, to\use about 75 pounds to the square

- inch above atmospheric pressure. Above this pressure the

yields of naphtha and burning oil have not been found by

me to increase (rather ‘the reverse) ¥ while, of course, the

danger increases with the \pressure. Below 75 ‘pounds

pressure I have found the yields to fall off gradually with

‘the diminution of pressure; sy that under 30 pounds the

yield of naphtha has’ been about three-fifths and under 20

pounds less than half of the yield under 75 ra while

. the. yield of burning oil (kérosené) under has

- been about four-fifths and under 20 pounds less thas three-

- fourths of the yield under 75 pounds. In order that, in a _

run under 30 pounds, the temperatuags of the oil in distilla-

~* tion may not be as high as those at which the vapor tension

of the undecomposed oil is estimated to-equal the still pres-

sure, said temperatures should not be so much as about 73°

F. above the temperatures attained at corresponding pe-

. Tiods in a parallel run under’ ‘atmospheric pressure. In

runs under a pressure other than 30 pounds and 75 pounds, -.

the temperatures of the oil. in distillation should be within

a corresponding maximum above the so attained temper-

atures in order that they may be less than those at which.

the vapor tension of the undecomposed il is estimated to

- equal the still pressure. ‘The vapor tensions of benzene |

-(C.H.) are known for a wide range of temperatures. Such

. tension amounts to 30 pounds superatmospheric at about

. 73° F, above the boiling point, to wit, at abont 250° F., the

‘boiling: ‘point = being.about 177° F. |

we ies

The ciatiction of the invention, or of. L appliaabie por- a

tions thereof, to petroleum not of a characer to yield par-

affin wax and to hydrocarbon oils.other than petroleum will s :

be sufficiently evident from the preceding - description,

. There may well be petroleum which does not yield parafin =

wax, but which does yield distillate. composed of liquid ae

hydrocarbons divisible by their respective viscosities into: ~

the three kinds mentionéd; and there msy well be petro- -.

leum. which does not: yield distillate having hydrocarbons

. .80 divisible; but all crude petroleum can - be. distilled to

dryness under a suitably low pressure and ‘with or without. —

designedly provoked cracking in order to obtain’ distillate

[fol. 1202] to be decomposed by distillation under high

boiling hydrocarbons yielded by such petroleum down to

buat excluding last-runnings that would be objectionable by - _

* reason of the presence therein of still wax or like heavy

matters of sticky character, but not necessarily excluding ae

. desirable hydrocarbons recoverable ,by the rerunning of

slops. —

~ Instead of relieving the vapors (to wit, at valve r) from

the high pressure under which they are evolved i in a still:-a

prior to their condensation (to wit, in condenser h), they

ean be held under said pressure (to wit, by appropriate

provisions, not shown, such as valves, for example, in pipes

* essarily discarding all the new, useful and original features

of the present invention. “Hither way the contents of the

~\ still would ‘be confined in order ‘to develop. therein the _

superatmospheric pressure. mentioned. -

Working on the continuous. system (in which a more or

less continuous stream of oil is supplied to.a high pressure

still and a like stream of residuum withdrawn therefrom

. during the progress of the distillation) is not necessarily

excluded from the scope-of the present invention; although -

it is considered more advantageous to work by 'the batch -

system, as herein above described (in which a charge of oy |

is supplied to still a and then run off to the desired extent,

the still being. merenpen emptied preparatory to receiving

a new charge).

- The mention of wiithoades «modifications i is not intended to

— others not mcptioned | in which the substance of 9h

ee ene x

. =

or more of the siskaliiatian veritten claims may Be eatheaied.”

: In reciting in claims following that the oil is ‘‘free from.

- still wax and like heavy matters of: sticky character and

‘from elements yielding the-same or coke,”” a. practical .

rather than a theoretically perfect freedom is to be under-

- stood. It suffices, for example, for the oil operated upon to :

be distillable in an externally heated: still of the dimensions

-hereinbefore mentioned for still @ fohagead six-tenths full)

- under a super-atmospheric pressure of ‘seventy five pounds _

. to the square inch at the’ aforesaid rate of two per cent..per.

hour to the extent of fifty per cent. or more by volume of its —

component hydrocarbons which have viscosities. above

seventy seconds at 100° F. without, heating the aul bottom

to redness.

I claim as. my invention or. discovery:

1. The process of obtaining tvthonatbo products by de-

composition “of hydrocarbons, which process consists in

operating upon an oil that contains hydrocarbons with vis-

cosities intermediate seventy seconds and one hundred and’

seventy seconds at 100° F.’and also liquid hydrocarbons

- with higher viscosities in the relative proportions of not

less than ten per cent. by volume of hydrocarbons of either

kind to not exceeding ninety per cent. of hydrocarbons of

the other kind and that is free from still wax and like heavy

matters of sticky character and from elements yielding the”

same or coke by distilling such oil at decomposing temper-—

atures under.a superatmospheric pressure of not less than

thirty, pounds per square inch, substantially as described.

.2. The‘ process of. obtaining hydrocarbon. products. by

. . decomposition of hydrocarbons, which process‘ consists in

. operating upon an oil that contains paraffin wax and also

' liquid hydrocarbons with viscosities @vo great for normal

constituents of burning oil (kerosene) in the relative pro-

' portions of not less than. four nor more than ninety per cent

_ of paraffin wax to not more than-ninety-six per cent. nor

_ less than ten per cent. of said liquid hydrocarbons and that

is free from still wax and like heavy matters of sticky char-

. acter and from elements yielding the same or coke by soe

. tilling ‘such oil at eter sao fomperstanes under a su

284-378.

- 4530

‘atmospheric. nveestre of aot less than thirty pounds per ee

square inch, substantially as described. -

3. The process of obtaining hydrocarbon products by de-

composition of hydrocarbons, which process consists in. sub-

jecting to distillation at decomposing temperatures under a

superatmospheric pressure of not less than thirty pounds

per square inch the heavy .paraffin distillate which is col-

lectable-in an appropriate distillation of crude petroleum

of a character to yield paraffin wax, which is free from

~still wax and like heavy matters of sticky character and.

from elements yielding the same or coke, and which consists

of hydrocarbons with vistosities ranging from. below: one

hundred and seventy seconds at.100° F., to above two hun-

dred and ninety-seven seconds at 100° F., upward of ten per

cent. by volume of said hydrocarbons having viscosities

intermediate seventy seconds ‘and one hundred and seventy

seconds at 100° F., substantially as described.

| 4, The process of obtaining hydrocarbon products by

- decomposition of hydrocarbons, which’ process consists in

distilling crude petroleum approximately to the point . ce

which the distillate would no longer be free from still

or like heavy matters of sticky character, collecting distil.

- late up to this point from a-point so early in the run that |

‘ hydrocarbons with viscosities intermediate seventy seconds

and one hundred and seventy seconds at 100° F. represent

Biogen of ten per cent. by volume of the so collected distil-

Jate, and subjecting the so, collected distillate to distillation

~ at decomposing temperatures under a superatmospheric ~

~ [fol.1203], pressure. of not’ less than thirty. pounds ~

- square inch, substantially as. described. +

5. The process of obtaining hydrosarboa “products by

decomposition of hydrocarbons, which process consists in |

distilling crude petroleum approximately at least to dry- aw

~~ ness, collecting distillate in such complete distillation in

distinct portions, one of them containing the runnings to

approximately the point at which the ‘so cdllected distillate

would be no longer free from still wax and like heavy mat-

. ters of sticky character from a point so-early in the run.

that’ hydrocarbons with viscosities intermediate seventy -

seconds ands one hundred a seventy seconds at 100° P-:

couroesat upward of ten per cent. by volume of the 80 col oe

ected distillate, and the other of them comprising the sub- -

~ sequent runnings, distilling these subsequent runnings

A approximately. at least to dryness with collection by itself .

of distillate free from still wax and like heavy matters of -

sticky character, mixing this latter distillate with said first —

portion of distillate from the crude oil run, and subjecting -

the mixed distillates ‘to. distillation at decomposing tem- _

‘peratures under a superatmospheric pressure of not less _.

than thirty fijuinss per grass inch, parte as de-

scribed.. . .

6. The process of abiaising sisenschonk: produets “ de- —

composition of ' hydrocarbons, which process consists in ob-

taining oil that consists of a natural mixture of hydrocar-

bons with viscosities intermediate seventy seconds and one.

ee and seventy seconds at 100° F. and hydrocarbons

with ‘higher viscosities including those above two hundred _

and ninety seven seconds at 100° F. in the relative propor- -

- tions of not less than ten per cent. by volume of. hydrocar- 7

_ bons. of either kind to not exceeding ninety per cént. of

hydrocarbons of the other kind and that is free from still :

“wax and like heavy matters of sticky character and from

elements yielding the same or coke, and distilling’ such oil

- at decomposing temperatures under a superatmospheric

pressure of not. less than thirty = per 2 ind inch,

substantially as described.

7. The process of obtaining hydrocarbon ~--—— by

“decomposition of hydrocarbons, which process consists in -

_ distilling. at decomposing temperatures. under a super-

‘atmospheric pressure of not. less than thirty pounds to the

square inch, hydrocarbons that have viscosities interme- J

diate seventy seconds and one hundred and seventy seconds

matters of sticky character and from elements yielding the.

same or coke and in also distilling at. decomposing tempera-

tures under said superatmospheric pressure liquid hydro-

seconds at 100° F. and that are similarly free from said

mhatters and elements, and uniting hydrocarbons given off

' a8 vapors in such distillation from said two kinds of parent _

pene: in the relative: — of not less a

the other ‘kind,

exceeding ninety per cent. of product fro

‘substantially as described.

8. The process of obtaining hydrocarbon. products by ds:

composition of hydrocarbons, which process consists in dis-

tilling at decomposing temperatures under a superatmos- -

_ pheric pressure of not less than thirty peunds to the square

_jnchy paraffin wax in a form that is free from still wax and

’ like heavy matters of a sticky character and from elements

yielding the same or coke and in also distilling at decom:

posing temperatures under said superatmospheric pressure

liquid hydrocarbons that have. Yiseosities too great for _

_ burning oil (kerosene) and that are free from still wax and. -

' like heavy matters of a sticky character and from elements °

_ yielding the same or coke, and uniting hydrocarbons given —

off as vapors in such distillation from said paraffin wax and ~

said liquid hydrocarbons in the relative proportions of not .

_ les’ than four nor more than ninety per cent. by volume of —

product from said paraffin wax to not‘ more t doin ninety-

. Six per cent. nor less than ten per cent. of product from

_ said liquid hydrocarbons, substantially as described.

| ten per cent. by woken of geoduct tisen as kind to not

oe 2. an asphaltic material for: varnish making and other

' uses, the same being as a whole more than ninety per cent.

by volume soluble. in bisulfid of carbon &nd more. than-sev-.

enty five per cent. soluble in petroleum naphtha, and con- -

_ sisting over fifty per cent. of hydrocarbons that are heavier

than water and are of.a coherent and ductile character and

that ‘are residues of -the decomposition of hydrocarbons ~~~

with viscosities intermediate seventy seconds and.one hun- -

dred and seventy seconds at 100° F. and.also of liquid

- hydrocarbons with higher viscosities in the relative propor- —

tions of not less than ten per cent. by volume of product . —

from hydrocarbons of either. kind to not exceeding ninety .

percent. of product from hydrocarbons’ o the other kind,

substantially as described. - -

10. An asphaltic material for varnish making and ‘other

* ses, the same being as a whole more than-ninety per cent.

- by volume soluble in bisulfid of ¢arbon and more than sev-

enty five per cent. soluble in petroleum naphtha, and con- -—

4 ping over fifty per cent. of = that are heavier 5

than water and are of a coherent and ductile character .

"and that are residues of the decomposition of paraffin’ ‘wax

and also of liquid hydrocarbons with viscosities too great

for normal constituents of burning oil (kerosene) in the —

[fol. 1204] relative proportions of not less than four nor —§.

_-; +more than ninety per cent. of product from paraffin wax to .

-. not more than ninety six nor less than ten per cent. of

product from said haw Lnieitericete substantially. as

"described. ‘

11. The process of distilling eksolbni or wliiek vai:

carbon oil under superatmospheric pressure for obtaining ?

products. by decomposition, which proces§ consists in (1)

heating said petroleum or other oil in an appropriate form

to temperatures sufficient to effect decomposition of the oil

under a superatmospheric pressure of not less that thirty

‘pounds per square inch, when the still. contents are suitably

confined, (2) candueting the evolved vapors to condensing .

- means through an opening that is constantly established in ~

- normal running and is of appropriate size to keep the spe- /

- gifie gravities of distillate leaving said condensing mean

_ within twenty four éne thousandths of those obtained i

corresponding periods in a test run in which such passing —

_ vapors have formed condensate at the rate of two per cent. -

oO. volumé of an original charge per hour, and (3) ontrel

_ ing said heating and confining the liquid contents of the still

in such manner as to maintain the oil is distillation at a de-

composing temperature and under a pressure of evolved

vapors which is above a minimum within the preasurp: .men-

_ tioned, substantially as described. |

cites “The process of distilling petrolenm < or other nydnis

_° earbon. oil under superatmospheric pressure. for obtaining :

products by decomposition, which process consists in (1) a

-heating said petroleum or other oil in an appropriate form |

to temperatures sufficient to effect decomposition of. the oil -

under a superatmospheric pressure of not less than thirty *

pounds per square inch, when the still contents are- suitably

confined, (2) conducting the‘evolved vapors to condensing

_ -means through an opening that ‘is constantly established

“in. normal running and.‘is not alterable automatically by‘ S

"variations of pressure either to be automatically closed and

— -Teestablished by euch variations or: ‘ be otherwise varied

‘2,

- 2 ° - eas

ee ¥ 2 Eee ot

- .. . en e® \ ,* . e cs :

y ms / s-*9 28 nee

. . *

= - ; -. ‘ 3

= iiikationtin shikoatiy: ana is of appropriate size to keep the

- ‘specific -gravities of distillate “leaving said condensing: -

- means within twenty four one thousandths of those ob- ~~

tained i in corresponding periods i in atest run in which.such °°

passing vapors have formed condensate at the rate of two

per cent. by volume of an original charge per hour, and (3)

controlling said heating and confining the liquid contents of

_ the still in such manner-as- to maintain the oil in distilla-

tion at a decomposing temperature and under a pressure of

. evolved vapors which is above a minimum within the pres-- :

_ sure mentioned, substantially as described.

| 13. The process of distilling petroleum or. other iar. .

carbon. oil under a superatmospheric pressure for obtaining

products by decomposition, which . ‘process consists in. (1)

heating said petroleum or ather oil in an appropriate form

to temperatures sufficient to efféct decomposition of the oil

_ -under a superatmospheric pressure of not less: than thirty

’ pounds per square inch, when the still contents aré suit- .

ably confined; (2) conducting the evolved vapors to condens-

Ing means through an opening that is constantly estab-.

lished in normal running. and can be closed and reestab-

- lished and also varied in size manually by an attengant and

that is of appropriate size to keep the specific gravities

_of distillate leaving s

- four one cher

periods in a‘ test run’ in which such passing vapors have’ —

id condensing means within twenty - : ;

of those obtained in corresponding

formed condensate at the rate of.two per cent. by volime of | --

an original charge per hour, and (3) controlling said heating

and confining the liquid contents of the still. in such manner oe

as to maintain the oil in distillation at a decomposing tem-

‘perature and under a pressure of evolved vapors which is -

above a ‘minimum within | the pressure mentioned, substan- .

. tially as oe

gel 4. The process: of distilling petroleum 0 or ‘other yrs:

‘earbon oil: under superatmospheric pressure for obtaining

- products by decomposition, which process consists in, (1)

heating said petroleum or other oil in an appropriate form.

under a superatmospheric pressure of not less than’ thirty

pounds per-square inch, sufficiently to induce decomposition _

_ of component. hydrocarbons, (2) efféctings said. decomposi-

tion 2t/ ‘gradually metenatng temperatures. that are e below

s x

the wasutive sea: at. which the iodine’ vapor” :

. of the ‘undecomposed oil i is estimated to equal the sti

atmospheric effecting said decomposition at temperat

mot so much as seventy: three degrees F. above thos

/ tained in a hagin ed cians under atmospheric”

pressure is sae effecting said lemme at tem- I

peratures within a corresponding maximum above the so”

_ attained temperatures, (3) cooling the evolved vapors to

| _ between one hundred and fifty and three hundred and fifty -

to ya pe oil in dillation, and re; condensing the residue of

said vapors as distillate, substantially as described. .

et 15..The process of distilling. petroleum or’ other hydro-

| a. [fol. 1205] carbon oil under -superatmospheric pressure for

‘ obtaining products by decomposition, which Process con-

sists in (1) heating said petroleum or. other oil in an appro- .

\ priate form. under a superatmospheric pressure of-not less.

than thirty pounds per square inch, sufficiently to induce

_. ‘decomposition of component hydrocarbons, (2) effecting

. said decomposition at gradually increasing temperatures

that are below the respective points at which the ordinary

_-vapor tension of the undeéomposed oil is estimated to equal

the still pressure, to wit, ‘when the still: pressure is thirty -

pounds superatmospheric effecting said decomposition at

- temperatures not so much as seventy three degrees F.

above: those .attained in a ‘parallel distillation under

atmospheric. pressure, when the still pressure is seventy

_ five pounds superatmospheric effecting said decomposition

_ degrees F. above the so attained t emperatures, and when

another ‘still pressure is employed effecting said decom-

_ position at temperatures within a corresponding maximum

above the so attained temperaturés, (3) cooling*the evolved.

| Vapors to: below 590° F. and not so low as to prevent the

| passage over of hydroéarbons, with boiling points inter-.

ee.

condensate to the oil: in distillation, and (5) cordensing thé, :

residue of said vapors as. distillate, eobskantiatiy as de-.

: scribed.

16. The process of istilling petroleum or" othe Reaee: a

‘ earbon oil under superatmospheric pressure for obtaining

products by decomposition, which process consists in (1). |

heating said petroleum or other oil in an appropriate form

under a superatmospheric pressure of not less than thirty

pounds and not so much as one hundred pounds per square |

inch sufficiently to- induce. decomposition of. component |

hydrocarbons, (2) effecting ‘said decomposition -at grad-—

ually increasing temperatures that are below the: respec--.

tivé points at which the ordinary vapor tension’ of the

undecomposed oil is estimated to equal the still pressure,

_ to wit, when the still pressure is thirty pounds: «superatmos-

| - pheric. effecting said decomposition at temperatures not so

- much as seventy three degrees F. abov those attained ina |

‘parallel distillation under atmospherie pressure, when the ;

still pressure is: seventy five pounds su uperatmospheric’ ef-

fecting said decomposition at temper™btures not so much as |

one hundred and thirty one degrees F. above the so at-.

tained temperatures, and when another still pressure is

employed effeeting said. decomposition at temperatures

within a corresponding maximum above -the so attained

: temperatures, (3) eqoling the so evolved vapors to between

one hundred and fifty and three hwpadred and fifty degrees |

F. below the contemporaneous te eratures of the oil in

distillation, (4) returning so fornifd: condensate to the oil

in distillation, and (5) ‘condensi the. residue of “said

Vapors, as distillate, substantially as described. a TS

17 The process of distilling petroleum or other hydro-*

carbon oil under superatmospheric pressure for: obtaining”

products by decomposition, which process consists in (1)

Restnie said petroleum | or other oil i in an appropriate form

most a superatmospheric pressure of not less‘than thirty .

ds and not so much as one hundred pounds per square

inch, sufficiently to induce decomposition of component —

increasing. temperatures that are below ‘the respective:

points at which the ordinary vapor tension of the undecom- ~~

posed oil is estimated “at equal the still prenanre, to wit, .

“ah

PO el Nl

hie 5

when the still pressure’ is 4 thirty ee siubblliendictals te

- effecting said decomposition at temperatures. not so much

- as seventy three degrees F. above those attained in a par-

allel distillation under atmospheric pressure, when the still. -

pressure is seventy: five pounds-superatmospheric effecting

said decomposition at temperatures not so-much as one _

hundred and thirty one degrees F. above the so attained —

. temperatures, and when. another still pressure is employed

~ effecting said. decomposition at temperatures. within a cor-

responding maximum above the so attained ig spares ras

(3) cooling the so evolved vapors to below 550° F. and not.

. «80 low as to prevent the passage over of hydrocarbons with

- boiling points intermediate 338° F. and 518° F., (4) return- — ;

-. ing so formed condensate to the oil, in distillation, and (5)

coniensing the residue of ‘said’ vapors as distillate, sub- He

_- stantially as described.”

18} The process of distilling petrolevin. 9 or other hydro-

carbon oil under superatmospheric pressure for obtaining

products” by degomposition, which process consists in (1)

- heating to decomposing temperatures a batch of said petro- eae

leum or other oil in an appropriate: form under-a super-

: atmospheric. pressure of not less than thirty pounds per.

square inch, 2) so cooling the evolved.vapors in the space

above the oil in distillation by exposure 6f the still-top'to .

: _ \the atmosphere as to effect a partial condensation ‘of the

ee vapors in said space, (3) protecting said vapors against

excessive cooling due to enlargement of said space by dim-

-inution in volume of the oil in distillation as well as against

supéfheating above the contemporaneous temperatures of: -

. said oil, (4) returning condensate formed by said cooling to

the oil in distillation, and (5) conducting residual. vapors

away for condensation as 5 distillate, REE ADHANY as de- es

~ seribed.

hs ‘The process of distilling susie or ‘other hividies i

[fol. 1206] carbon oil under superatmospheric pressure for .

obtaining products by, decomposition, which process con-

- sists in (1) heating to decomposing temperatures a batch

of said petroleum or other oil in an appropriate form under

a superatmospheric pressure of not less than thirty pounds :

per square inch, -( 2). so cooling the evolved vapors in the

“Space: above the. oil in distillation by exposure ‘of the still

> 4538".

| __top to the atmosphere as to effect a partial condensation of —

the vapors in said space, (3) protecting said vapors against «—

.- excessive cooling due to enlargement of said space by‘dim- _.

inution in volume of the oil in distillation as well as against

superheating above’ the contemporaneous temperatures ‘of:

_ said oil, (4) returning condensate formed by said cooling

to the oil in distillation, and (5) conducting residrfal vapors -

away through a throttling device for condensation under

reduced pressure as distillate, substantially as described.

20. The process of distilling petroleum: or other hydro-

- carbon oil under superatmospheric pressure for. obtaining ;

products by decomposition, which process consists ‘in. (1).

‘Poatine said petroleum or other oil in an appropriate form

.' under a ‘superatmospheric pressure of not less: than. thirty

~ pounds per square inch sufficiently to. induce decomposi-

tion. of component hydrocarbons, . (2) effecting, said de-

composition at gradually increasing temperatures under

. an at least approximately uniform pressure, (3) preserv- - “

“ing the evolved vapors. from heating above the contempo-

raneous temperatures of the oil in distillation, (4) allow-

ing the vapors to escape continuously through a throttling

device at a sufficiently small rate to produce: distillate -

whose specific gravity. will.not be moré than twenty four ee

‘one-thdisandths (0,024), if any, greater than’ that of’ the -

obtained in’a parallel distillation

distillate which would b

performed at. a two pe cent per hour rate; ,and:(5) con-

_densing the so escaping ‘V pors as piers ‘substantially Ls

as described. i

21. ‘The process. of disti ling Pires poe oy ee hydro-. |

- carbon oil under superatmpspheric pressure for obtaining

products by decompositigh, which. process consists in (1)

lieating said petroleunf or other oil in an appropriate from

under a ‘superatmospheric pressure of not less than thirty

pounds per square inch sufficiently to induce decomposi-.

tion of component hydrocarbons, (2). effecting said. de-

composition at gradually increasing temperatures under a ..

an_at least approximately uniform pressure, (3) cooling. —

_ the evolved vapors under superatmospheric pressure to:

below 550° >and not so low as to prevent the passage

-over of hydrocarbons with boiling points intermediate 338° -

F to “ae Ee (4). ieee the: 80 formed condensate to .

Stor ase

‘ .

~>-under a superatmospheric pressure of not less than thirty ~_

4539

| ? the oil in distillation, ( 5) allowing the uncondensed vapors

to escape continuously through a throttling device at a

- sufficiently small rate to. produce ‘distillate whose specific _

- gravity will not be more than. twenty four one-thousandths |

(0.024), if-any, greater than that of the distillate which

would be obtained in a parallel distillation performed at a

_ two per-cent. per hour rate, and (6) condensing: the so es-

, ecaping vapors as: distillate, substantially as desertbed.

992. The process of ‘distilling petroleum or ‘other. hydro- —

carbdn oil under superatmospheric pressure for obtaining

products by decomposition, which process ‘consists in (1) _

heating said petroleum or other. oil in an appropriate form

pounds pér square inch ‘sufficiently to-induce-decomposi- —

tion of component -hydrocarbons, .(2) effecting said'de- .

. composition at gradually increasing temperatures under an

at least approximately uniform pressure, (3) preserving

the evolved vapors from heating above the contemporane-

ous temperatures of the oil in distillation, (4) cooling the -

evolved vapors under superatmospheric pressure to below —

550° F. and not so low as to prevent the passage over of

hydrocarbons with boiling points intermediate 338° F. to

518° ¥., (5) returning the so formed condensate to the oil

in distillation, (6) allowing the uncondensed vapors to es-

- eape continuously through a throttling’-device at a suffi-

ciently. small rate to produce distillate whose specific

gravity will not be more than twenty four one-thousandths ——

_ (0.024), if-any, greater than that of the distillate which

‘would be obtained in a -parallel distillation performed at |

a two per cent. per hour rate, and (7) condensing the so.

escaping vapors as distillate, substantially as described.

23, Apparatus for distilling petroleum or other hydro-

carbon oil under superatmospheric pressure for obtaining

_ products by decomposition; which apparatus comprises (1)

a horizontal cylinder still having its upper part exposed to —

_ the atmosphere for cooling and its lower part to fire gases

for heating, and an intermediate portion, equal. in cubic

‘convents. to not less than half the capacity of the still, that

. 18 protected both from the atmosphere and from the fire

gases, said still being of practical size, strong enough to —

resist all internal superatmospheric pressure of more than

, 4540"

thirty pounds to the square inch; adapted for hate run-

ning in which the volume of oil in ‘the still diminishes\dur-

ing the run, a and so constructed interiorly. that condensate

formed’ in thé vaper space is returned to the oil in dis-

‘ tillation, (2)/an outside condensér provided. with a distil-

‘late draw off, (3) a vapor. pipe leading from said stil} to

said outside condenser, and (4) means ‘for maintaining a

[fol. 1207] superatmospheric pressure in excess of thirfy

pounds per square inch in said still during septa sub: °

stantially as described,

24. Apparatus for. distilling nebroleany:: or other Keine: ey

carbon oil under. superatmospheric pressure for obtaining

products by decomposition, which apparatus comprises (1)

a horizontal cylinder still having its upper part exposed to

.. the atmosphere for cooling and its lower part to. fire gases

for heating, and an intermediate portion, equal in cubic

contents to not less. than half the capacity of the still, that

is protected both from the atmosphere and from the fire

_ gases, said still being of practical size, strong enough to

resist an interna ore than,

3 thirty pounds to the square inch, adapted. for batch: run-

; ning in which the volume of oil in the still diminishes dur- .

ing the run, and so constructed interiorly that condensate _

formed in the vapor space is returned to the oil in distilla-

-tion, (2) an ‘outside condenser provided with a distillate

raw off, (3) a vapor pipe leading. from said still to said

outside condenser, and (4) a vapor throttling device located

Sobciehedtone said still and said ottside condenser and ‘-

adapted:to hold the vapors in said still under: supefat-° _

-.mospherie pressure in excess of thirty pounds per square ° i /

a inch, while allowing said vapors to escape through said | .

throttling device to said outside condenser, see,

_ as described.

25. The process of. sbteining soiieentben. rboduets by

decomposition of hydrocarbons which process consists in

distilling crude petroleum to beyond the point: at which the

stream at the condenser outlet exhibits a viscosity of one

hundred and seventy seconds at 100° F., collecting in this

‘ distillation a cut of distillate, free from ‘still wax and like a

_ heavy matters of sticky character, which cut begins so far. —

-. below and ends so far above the point just mentioned that —~ .

| oe

_ neither the liydrocarbons therein with viscosities inter- c

mediate seventy seconds and one hundred and seventy sec-. .

onds at 100° F. nor the more viscous hydrocarbone con-

stitute less than.10 per cent. by volume bof all the com-

‘ potent hydrocarbons thereof with viscositids above seventy

- geconds at 100° F., and subjécting so. obtained and so con- ..

‘stituted distillate to distillation at decomposing tempéra-

tures, under a superatmospheric pressure of not less than

thirty pounds. per square inchy substantially ‘as described.

ae testimony wheréof I affix my. signatu: re. in “presence.

of two witnesses.

aap -Morace-P. Chamberlain,-

. Witnesses: G: W. Armstrong BE. A. Cotten.

4542 | ? if ee

[folk 1208] Perrrioner’s,Exureir 183 -

W. A. HALL.

PROCESS For THE PRODUCTION OF MOTOR SPIRIT FROM HEAVY HYDROCARBONS, ¥

APPLICATION FILED MAR, 12, 1914.

1,242,705.” 1" "Patented Oot. 9, 1917

~ ffol. 1209] United ‘States Patent Office .

‘William Augustus Hall, 6f New York, My

Process for the Production of’ Motor: ‘Spirit from Heavy

‘ Hydrocarbons °

1,242,795. _ Specification of Letters Patent. Patented Oct.

an \ ome tS ae |

Applidation filed March 12, 1914. Serial No. 824, 194

__.Po'all whom if may concern: Le .

Be it known that I, “William Augustus Hall, a citizen OF ca

}. -the’ United States of America, and residing at New York

” City; New-York, United States of America, quanta: cee

“a certain new and useful Improvement in Processes for the

Production of: Motor-Spirit from ‘Heavy Hydrocarbons, of

which the following is a, specification.

This invention relates to an improved process for the

‘ production of a liquid motor: fuel’ suitable for use. in the.

* usual carburetors of i ternal combustion engines, from

heavier and less volatile hydrocarbons.

The said improved process contemplates the channel

affixation of a hydrocarbon gas to vaporized, normally.

liquid, chemically unsaturated hydrocarbon, the said gas

and liquid having the properties hereinafter egpevtl there :

being produced a fourfold effect :

. First, a greatly increased volume of fuel pciduaal over

‘the volume obtained by any of the processes depending en- °

tirely upon cracking, with-which I am familiar;

Second, a materially lower boiling. point than that of

said unsaturated hydrocarbon, or of ordinary gasolene ob- |

Third, ‘a lower. epecific. gravity than that of said un-

saturated hydrocarbon, or of. ordinary gasolene obtained

* by cracking heavier oils, and

*. Fourth, greatly increased. fractions volatile at compara-

- tively low temperatures, as compared with said. unsatu-_

“rated hydrocarbon, or with ordinary gasolene. | ;

ae I process forming the subject matter of my present

application is not a ‘process of hydrogenation, in the ordi-

. .

oo .

\ . -

. .

—

_nary7 meaning of that: tral, for very little free hydrogen: «=> |]

“is present (either from the. cracking or from any other °

‘souree) and, as far'as I have beén ablé to ascertain, nove"

‘is utilized in any pari of the process, and no ‘nickel or

other metallic catalyst i is present in any part of the appa- °

ratus. \

My present process is, on the contrary, a process of -pro-

ducing gases containing considerable amounts of con-

‘densable hydrocarbons, such as propane, butane,. pentane, -

‘and hexane and the subsequent affixation of these gases to

the vapors of an. ‘unsaturated sists ies herein referred

’ to'as ‘‘liquid. base.’’ |

In order to produce satisfactory results in accordarice

with the present process, it is necessary that the “liquid

‘base’? and the gases should both be of the proper char-

acter. The ‘‘liquid base’’ should best contain considefable

quantities of unsaturated hydrocarbons, in order to make —

‘the chemical affixation of the gases take place readily. Un-

der certain conditions, however, it appears that some of

the gases are chemically affixed to saturated, as well as td.

unsaturated bodies. The gas must. contain considerable ~

amount of hydrocarbons containing at ecid pio three.

- carbon atoms and can not consist entirely, or even prin-

cipally. of hydrogen and methane, if good results are to be

secured. It is preferable that the gases. also contain some

unsaturated hydrocarbons.

_ The preferable ‘‘liquid base’? .is that volatile liquid of

which the vapors exist (mixed with gases) in ‘the vaporous _

product produced by cracking a ‘relatively heavy hydrocar-

bon. oil under a. pressure of (e\ g.) about 70 pounds per

‘4 “square inch and at about 600° or 650° OC. This tempera-

ture-is méasured by.a pyrometer placed between the verti- ,

eal pipe coils in the furnace-A. ereafter I cool ‘the gases"

: and vapors to a temperature of about 200° C., with or with-

-' out more or less lowering of pressure. Such’ a ‘liquid

_» “pase’’ can be produced i in other ways} and it is particularly .

‘characterized in that it consists essentially of normally -

_ liquid hydrocarbons, whose vapors, if cooled under ‘a pres-

- sure of about 70 pounds per squaré inch, with a wet gas —

(having the composition above referred to), will nite

.. chemically with constituents of said gas, to produce a motor —

: _ fuel.. The said vaporized ‘‘liquid base’’ and gas must be -

4545

| present togethér at a temperature materially above atmos-

_ pheric, for example 100 to 200° C., and under pressure, .

to produce this union. '

_ ‘The motor fuel does not anpeat to consist of the ‘Viquid

-base’’ with the gases dissolved therein, since the product

-* can be. distilled without the loss of more than small amounts

of the gaseous : ‘portions which have been affixed to. the

: “liquid base.’’ If the product were solely a solution of

_ the gases in the ‘‘liquid base’’, the gases would be lost if

- the product were distilled. Of this ‘‘hquid base’’, the more

volatile portions, especially, usually contain large amounts

‘(say 30 to 50%) of hydrocarbons of the’ ethlene series, un-

- saturated hydrocarbons.

- This ‘‘liquid, base’’, in the preferred ode: of execution

-_ [fol. 1210] of ‘the process, is ‘made by cracking a cheap hy- |

' drocarbon, for instance, a distillate such as gas oil. A’suit-

able gas oil is one having a specific gravity, of from about —

about 80 to about.180° C. -

A construction of appatatus suitable for the performance

oe A of the improved process is illustrated diagrammatically i in

the figure of the accompanying drawing. :

Referring to the drawing, A denotes a converter in

whiak the gas oil is subjected to a temperature of. about

650° C., under a ‘pressure of ‘about 70 pountis per square

inch, whereby the oil is cracked and a considerable portion

gasified. From the converter A the mixture of. oil vapor

/ .and gas is passed through siitable coolers B, B’ (cooled

by a suitable fluid introduced: through pipes P) whereby

the temperature of ‘the mixture is lowered to about 200° C.

C, C’ denote separators in which the major part of ‘all frac-

tions non-volatile at about 200° C: is removed, in the liquid

state, from the remaining gases and vapors. The vapors

of liquid, which aré volatile at a temperature of approxi-

~ mately 200° C., together with any mist of condensed liquid

particles which may be carried along, together with the

gases present, may then be conducted directly through a

cooler or. condenser -D, under approximately the pressure. -

of the converter, and ‘the condensate-collected in the re-

ee E. or.may bé still further compressed by means

of a mechaniéal compressor indicated conventionally at

-F. The liquid, the rene of which sasid with: the gas to

it 285—378- |

be > ‘ ‘

f , Chi ate lel Yr,

nae ; \

‘

» , * ‘

"the compressor is that herein relérved. to as the- ‘liquid

‘base’,

Stich a liguid } is itself not a satisfactory fuel for motor:

.cars., It is this liquid which unites with the gases, during

the compression and. subsequent. cooling, to produce the

motor fuel. ~ od

In some respects this ‘‘liquid base’’ is similar. to the

well known cracked hydyocarbon spirits at present pro- ‘

diced by cracking oils of higher boiling’ paints than ordi-

nary gasolene, such as crude oil or solar oil which | have

little or no value as‘a motor car fuel unless redistilled and

. cut at a low temperature, e.g. about 150° C., at which [point

“the yield is ‘very small.

In a converter, I produce the vapors of such a ‘‘liquid

' base”’, but in the final condensation I obtain a product hav-

_ ing a low boiling point, and a large fractign volatile at low

temperatures, the\product being different from the ‘‘liquid

base’’, on'account of the affixation of gases thereto.

‘The ‘liquid base” may, for example. be made by héat-

ing to.a temperature of above 500° C., an oil known as

‘‘Crown Diamond paraffin oil’’, a low grade burning oil

“of about .815 specific gravity. The “liquid base’’ so pro-

duced is a product having a gravity of about .769 (at 15°.

C.), and which has the <acabeetn eee table:

Wivet Gaee 633 Fai oi iowe de hic oi BIe-O, se

Total may “0s eS kl} EI Oa enMaiD | 1

as FOR PR ee uk RAMEE Fee es 2% -

baci OR tiga: SCOR GON Pid OEE CTE SETY Oe)

$66 90:20:43.5, 065 5 MNS de grow C4 5 AN boi sits Coby sity 14%

¢ $4 i) ROARS SOR Shs GRE eae a ae 50%

“ Aa i ORE ei, ic tae eo Mal wan 577°

Such a ‘Hiquid base’? or half produet i is found to be an’

excellent medium, to which to affix the wet gas. The prod- _

uct produced by compressing the vapors of this ‘‘liquid

-base’’, with the gases present was a product with a gravity

“of .755 (at 15° C, ) with the i Miptilintton table: —

rg distillate up to 60°8C. Vea, Rast aegiieapy ae

RS ht5%., aaa 84 ee oa ge

Gt fy AP oa ah OR | Se PO seg SEER ed EGA 15 %

< SEN ot es Se RN meas s Ry hh oie bine ae eae

wef ‘6 colt. lic AR ai aD RS aE a Pei 48.5%

60 %

“ “ 6 86-960... 8, UE ASRS es 2

)

‘more calorific value. . .

BAT

The invention is, of course, not limited to this specific ar

example, which is given merely for the purpose of showing

‘the différence between the ‘‘liquid.base’’ and the ‘‘motor | ~

fuel.’’. On account) of the chemical affixation produced, I

’ am to cut the spirit at a high temperature, say 200° Cor :-

“even high, (as compared with 150, in the case of ‘‘cracked

gasolene’’), thereby obtaining a much greater yield and |

If, desired I may so conduct the operation in the con-

verter as to produce the desired qualities and quantities’

of gas and ‘‘liquid base,’’ which with.some oils such as

gas oil ted heavy distillates above the lubricant fractions

ean be obtained! by the cracking of said oils at, about 650°

(. under 70 to 80 pounds pressure, while maintaining the

proper spéed pf flow. In this way there is produced a large

- amount of ‘gas, which if sepa ated; would remain as a per-

’ r

manent gas at ordinary atmospheric conditions, but a large

portion of which gas will combine chemically. with the.

spirit portion of the ‘‘liquid base’ after the tarry and -

heavy. residues have been removed, provided the gases and .

. the “liquid base’’ (while the latter is-in a state of vapor):

be subjected to sufficient pressure, while at a temperature _

Certain oils do not, readily respond to the cracking pro-

cess and from such oils a sufficient amount. of the desired

‘liquid base’’ cannot’ be obtained to supply the medium

produce with ease large quantities of the gas desired. In

or the\largest portion of it from one oil, and the ‘‘liquid

[fol,1211] base’’ from another oil, and to combine thenr

in the manner herein set forth. . ‘. ae

IT am aware that heavy -hydrocarbon liquids have been -

chatged with hydrocarbon gases, as is done in the produc- _

tion of the so-called.‘‘natural gas amg or ‘‘casing-'

head gasolene,’’ but such processes, ag far as I am aware,

' such ar it may be found desirable to produce, the gas

- are based in most cases on the principle of solution and

‘ accomplished by high pressure and refrigeration, it. being

‘known that most gases are far more soluble in cold solvents

than in hot; I believe, however, that it has not heretofore

been proposed to affix snch gases chemically to a “‘liquid -

base’’ while the latter was at a high temperature and in .

_ a state of vapor, the ‘‘liquid base’’ being a/spirit obtained

e eA. |

4548 ©

1: by eviialiase and containing a large proportion of ethylene

| - hydrocarbons which ‘‘liquid base’? is arene for the chem-

- jeal affixation of hydrocarbon gases.

It is to be noted that in carrying out the process of the.

hapabenk application, I preferably do not add water, hydro-

-. gen or. gases. containing hydrogen, or carbon. monozid to

_ the oil or oil vapors. Also I do. not treat the gases and

- vapors with.any. catalytic material. _

While I have stated.that the pressure in the coils B: B..

_C, and C’ may be much lower than in the converter A, ‘this

feature: is not claimed herein, but in my copending appli-

cation No..829,634, filed os 4, 1914. 3

_ Tclaim: .

1. A’ process of making a mo fuel which compriges

producing a mixture of vapors and gases, said vapors

taining a considerable percentage of compounds of / the

ethylene series, by cracking hydrocarbon oil under a pres-

‘sure materially above atmospheric and at a temperatura

‘not lower than. about 500° C. , Separating out those a

and above, leaving a mixture of gases-and vapors at a tem. er

perature of over 100° C., and thereafter cooling said mix. -

ture including the gases and remaining vapors while wn-. ie

der a pressure aiaaziae above atmospheric, ¢ to condense

- out a motor fuel. |

9: A process of. wie’ a motor fuel which comprises s

heating portions of different hydrocarbon oils, to tempera- .

tures. in excess. of 600° C., under a pressure materially —

above atmospheric, cooling the gases and vapors thereby

. produced, down to at least about 200° C. but down to.100°.. —

C., to condense products having high boiling points, and .

“i removing at least the major part of the condensate from

.._ the remaining gases and vapors, subjecting the remaining ~~.

- gases and vapors thereby: produced while still in a heated. .

- condition, to pressure materially above atmospheric, and

‘finally further cooling the gases and vapors while under a

pressure materially. above oe to condense out

ve the motor fuel. ,

24 process 2 producing a moter fuel, which comprises

_ eracking a hydrocarbon oil under pressure , materially above

_ atmospheric, at a temperature sufficiently high to convert

8 _— of the oil inte laces mene; 1 and to oe Taper oP

~~ containing: considerable | percentages of nnsatarsted - hy-

- drocarbons ; cooling the vapors.and gases sufficiently to

‘eause the portions having boiling’ points of about 200° .C.,

*. to condense out; and thereafter subjecting -the resulting

‘ gases.and vapors at a temperature of, 100 to-200°.C., to a

pressure of not less than about 70 pounds per square ‘inch, |

to proms a chemical affixation of the gases and TAREE

-4, A process of: making a motor fuel, which comprises

| tae a mineral oil under a‘ pressure of several, atmos-’

pheres, at a temperature of above 500° C., cooling the gases

and vapors, while still-under a pressure. ‘of several atmos-

. arate out materials having high boiling points, thereby pro-

ducing a_mixture containing the gases and containing the

vapors of those portions. which remain in vapor form at |

_ the ‘temperature employed in said step, subjecting said

mixture to a pressure above that used in the said.cooling -

step, atid ‘thereafter cooling said mixture while under a

pressure at least as great as that employed in the. —

here ing. operation, to condense out the er fuel.

5. A process of making a motor fuel from nydionaibebin :

of. higher boiling. points, ‘which comprises cracking ‘said

~ hydrocarbons by :pagging the’ same'‘through a chamber at. -

a temperature of about 600° .C., under a pressure of sev- os

eral atmospheres, separating. from the gases and vapors

thereby produced, 4 part at least of the ¢onstituents thereof |

which have boiling points above 200° C., thereby -produc-

ing a mixture of gases and. non-condensed vapors at a tem-

perature of 100 to 200° C,, subjecting said mixture to a

pressure. materially" above atmospheric, and thereafter

~ cooling said mixture under a pressure not less than used

jn the first “step, to condense out the mot

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