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Dee. 17, 1946. "
J. R. RosE
Filed June 26, V1945l
I à BY@wir
Patented Dec. 17, 1946 y
\ `
James R. Rose, Arlington, Va., assignor,A by direct f `
v » and mesne assignments, to Potomac Hydrocar
, bon Process Corporation, p ashington, DLC., a
corporationof Delaware
Application .lune 26, 1945, Serial No. .601,675 \ .
,4 claims.
(c1. ‘19t-52) "
" This invention relates to the manufacture of
fractory` material, such as`> “Berl saddlesf’l or
liquid hydrocarbons suitable for motor fuel, and
more particularly to the manufacture of high
octane gasolene.
“Raschig rings.” - A steam coil 32 is located at the
lower portion of the tower and a water circulating
' The general purpose 4and object of the invention-
valved pipe 34 communicates at one end with‘the
is to enable a large proportion of the hydrocarbon
base employed in the practice of my invention to
be converted into gasolene of ‘the character re
«ferred to; also to enable this conversion to be ac
complished economically and rapidly. I accom
plish these objects in and through the use of the
apparatus or system illustrated in the drawing,
wherein the figure ‘is a ñow diagram illustrating
my preferred apparatus or system and showing
the relations of the various parts of such appara'
tus or system to one another.
Describing the apparatus or system shown in`
the aforesaid drawing, I0 denotes a pump having
an `inlet II for liquid hydrocarbon and an outlet`
I2 communicating by a pipe I3 and through a
valve I4 with a cooler I5, the lower portion of
which in turn is connected by a pipe I6 with a col-4
lector Il provided with a valved outlet pipe I8 ex
tending from the upper portion thereof. „l
A valved pipe I9 communicates at one end with
the lower portion of the collector and at its oppo
site end with the first cracking element20 in the
bottom row of several vertically spaced rows of
such elements, the said elements being shown as
of the usual tubular form and the tubes in differ
ent rows being connected in series and the final
tube in each row being connected with the first
receiving tube in the row next thereabove. Four
such rows are shown, the same being arranged
within a cracking stove, and the ñnal tube in the
uppermost row communicates by means of a pipe
2`| with a catalyte container tube 22' which is
shown as, extending horizontally of the stove and
as located adjacent to the top and preferably
about midway between the sides of the stove.
The container tube 22 communicates through
a pipe 23 with the lower portion of a large ver~
tically arranged catalyte container tube 24 lo
coil 33 Within the upper portion of the tower.` A
lower portion ofthe tower and atits other end
with a tank 35 in which the finished product is
‘A valved pipe 36 extends from the top of the
tower -to the top of a compressor 3l; and a valved
pipe 38 extends from said compressor to the cool
er I5, conveniently through a portion «of `the
pipe I3.
In operating the apparatus or system just de
scribed, a liquid hydrocarbon base element, such
as crude oil "and/or low octane gasolene, is in-L
trocluced into the pump I0, where it is subjected
to a pressure of from 700 lbs. to 1000 lbs. per
square inch, the pressure varying in accordance
with the nature of the particular liquid hydro-`
carbon used, but not being below 700 lbs. per
square inch. From the pump, the liquid is de
livered through the valved pipe I 3 into the cooler
i5 and thence into the liquid collector I1.
From the collector Il, the liquid flows, under
the pressure `imparted thereto by the pump,
through the cracking tubes 20 in succession and
thence into one end of the catalyte container tube
22 which preferably contains a catalyte composed
‘ of a mixture of carnotite and barium ñuoride,
preferably in the proportions of 16 parts by
weight of carnotite to from l to 12 parts by weight
of barium fluoride (as set forth in my Patent
2,126,284). The gaseous product resulting from
the foregoing cracking operation passes from the
opposite end of the tube 22 into the bottom of the
vertical catalyte container tube 24. ‘ The catalyte
which I `use in this container tube is preferably
that described and claimed in my Patent 2,173,376,`
issued September 19, 1939, and consisting of the
following ingredients mingled in substantially the
following range of proportions:
Parts by weight`
cated within the stack 25. A pipe 26 communi
cates at one end with the upper portion of this 45 Natural phosphate rock _____________ __ 10 to 50F'loridan clay ______ __ _______________ _ V10v to 50
catalyte container tube `and at its other end with
Zinc phosphate ___-____ ______________ _ 5 to ‘30
Va cooler 28, `the pipe being provided with an ex
Barium khalide (preferably chloride)___ .5 to 30
pansion Avalve 2l intermediate of the container
'Fire `bond _________________________ __ 10 to 40
tube 24 and the said cooler 28. From the cooler
Carnotite 25% to 100% by weight of the total
28, a pipe 28a extends to the top of a collector 29;
weight of all other ingredients.
a valved pipe 30 communicates at itslower end
with the lower portion of the collector 29 and at
The container tube 24, it will be noted, is ar-`
its upper portion with a stabilizing tower 3 I, preff
erably substantially midway `of the height of the
latter.` This toweris packed with suitable re
ranged within the lower portion of the stack
which receives the products of combustion> from
` the'crackingistove whereby -the said container
jected to a temperature of from 700° to 1200° F.,
the temperature being dependent upon the nature
Vfrom the cracking operationpassesithe expansion
of the liquid hydrocarbon which issupplied to
the said; tubes):
square inch and that the mixture of the hydro
carbons from these two sources is subjected tov
this pressure until thè gaseous productresulting
tube, as well as the tubes 20 and 22, are sub
valve 21.
It will be noted further that the arrangement,
From the top of the tube 24, -the gaseous prod-_
of the cracking and catalyte tubes within the
cracking stove and the arrangement of the‘cata
' uct resulting from the passage of the hydrocar
bon through the cracker tubes and the catalyte
container tubes is delivered to a pipe 2S, provided ‘
lyte container tube 24 in the stack enablesa most Y ì
with an expansion valve 21 where by the pres
efficient utilization vof the heating agent 'for the
`purpose *of cracking the hydrocarbon vmixture
sure on the gaseous product'is‘ quickly 'reduced to ,
150 lbs. per square inch, thereby setting .up an
' supplied thereto.
intense cooling action, with resultant liquefac
tion, the liquefaction being facilitated by the
' »Having thus described my invention, whatI
claim is:
cooler 28.
livered through a pipe 28a to the collection cham
speciñed comprising pressure-creating means,
ber 29; and from the collection chamber the '
means for supplying a hydrocarbon base fluid to
. 1. An apparatus or system for the lpurpose
said pressure-creating means, a cooler, a conduit
liquid is delivered through the pipe 30 into the
for delivering the fluid from the pressure-creat
stabilizing tower, midway of the height of the
latter, where it is diffused over the refractory 20 ing Ameans tothe cooler, Ia >cracking stove, -{c_tplu
rality ,ofV communicating cracking elements-_ar-v
rangedone above another in said stove »and a
material, being subjected to the heat of the steam
coil3‘2'in the'íbottom of the tower, which serves
catalyte container oí greater diameter thanthe
to boil off the lighter gases and leave behind the
heavier polymers, which .are largely within the
cracking elements and located above the `crack
ing elements in the said stove andy-communicate
ing with. the uppermost of. said elementsa con.
gasolene range of hydrocarbons.
¿The gases in the upper portion of thev tower
duitior delivering ñuid from the cooler toithe
are subjected to the action of the coil 33 which
lowermost oflthe said cracking' elements, »a
serves `to condense the heavier of the> gases which
burnerin saidstove below the said` elementsÍfor.
reach this point, the condensate-thus formed
consisting ofthe heavier polymers which are 30 heating the saidelements .andthe catalyte con*
tainer, a vertical stackextending above the stove
largely within the gasolene range of hydrocar-and connected to the .stoveat a >point-adjacent
bons and which are collected in the bottom of
to the upper portion of the latter, means for de-»
the. tower, whence Vall such..polymers are deliv
livering, thereinto the products> of .combustion
ered to the tank .35.' VThe lighter gases, which
consist of a mixture. of >hydrocarbons of the CH4, 35 from the burner in said stove which. have con
tacted the said elements and thesaidßcatalyte
C21-Ie, Cal-Is and 04H10 series, are conducted by
container,l ay vertically extending -catalytev con-V
the pipe 30 to the compressor 31 where they are
tainer inthe said stackcommunicatingat apoint
subjectedto the same pressure as that imparted
adjacent to its bottornwith the` `iirst mentioned
to the hydrocarbon'liquid by the. pump I0. The
components that are condensable into liquid at 40 catalyte container and arranged to be exposed.
substantially throughout its entirelength to the
this pressure are removed from the mixtureA while
rising products of co-mbustion in said stack, a
theuncondensable components may be delivered
delivery pipe communicating with the upper por.r-> `
as “dry gas” iroma collector’ l ‘l through the pipe
tion of the vertical catalyte container, an eXpan
sion valvein said pipe, a cooler with which theV
delivery end of said pipe communicates,v a _col-'
lector, a pipe connecting the secondcooler .andi
the collector, a stabilizing tower, a Vpipe ,com
Ymunicating at one end with thesaidfcollector
i8 `and may then be used as lfuel for a burner
A which serves to heat the tubes in the crack
ing stove and the tube‘24`in the stack 25. `The
operation of the system or apparatus withthe
base, hydrocarbon constituted by the mixture of
the normally. liquid hydrocarbon with that ob
tainedby compressing the gaseous product from 50 andat its upper `end with said stabilizing tower
substantially midway of the height ofthe'tower,
the stabilizer tower will proceed from this point
„a heating device in the lowerportion-of said sta
in the manner described hereinbefore in con
bilizing tower, a condensingV device in the upper
nection with the liquid hydrocarbon from» the
pump I0.
Asthe Vflow, of cracked material in a gaseous
portion Vof said stabilizing tower, a' pipe coml
55 municating with the tower below theheating
device, and a tank withl which the deliveryend,
form is always toward a zone of less pressure, I
of said pipe communicates.
have taken advantage of this fact to cause the
mixture of liquid hydrocarbon delivered by the
pump Iâ with that resulting from the condensa
tion of gases supplied to'and delivered from the
compressor 31 to move constantly upwardly from
the time Vthe mixture' enters the ñrst` row of
cracking .tubes until it reaches the expansion
chamber 28.. Furthermore, the crude oil is in
troduced to the hottest cracking element or hori- '
' _2. In the apparatus'or system as set-forth. in
claim 1, a compresso-r, means for delivering non»v
condensed gases from the stabilizing tower, tothe
said compressor, and means for/delivering the
Huid from the said compressor into the conduit
which deliversfluid into the 'lowermost ofthe.
cracking elements. "
_3. _The process'of manufacturing liquid hydro,-4
carbon suitable for motor fuel which comprises..
subjecting a. hydrocarbon base fluid to a pressure
of from 700 tolODO pounds per square inch; coolf»vv
cracking tubes and toward the outlet. ‘ Due to
ing the fluid and conducting the same under such
this kmode of introducing and circulating the hy-.`
drocarbons through' the cracking and catalyte 70 pressure in' a constantly Vupward direction'
through a vertically arranged series of cracking4
tubes, the formation of; heavy bottoms is pre
elements and a catalyte container; >subjecting»
vented to a large degree. It should -be noted that
the liquid hydrocarbon delivered by the pump lilA
thesaid cracking elements and the c_at'alyteV con-`
tainerto a heating .medium contacting'iirst they
andfthat delivered from the compressor 31' are
zontal rows of> cracking tubes, following which
the streamñows upwardly rthrough the cooler
under apressure of from 700 to 1000 lbs.l per
“ lowerm'ost ofthe cracking elements "and there
after contacting the cracking elements there
above and the catalyte container whereby the
said elements are subjected to an initial tem
tainer; and subjecting the liquid thus obtained to
agstabilizing action thereby to evolve, from such
Iiàuîd, hydrocarbon gases and heavy liquid hy
perature, in the lowermost of said cracking ele
drocarbon polymers.
ments, of from '700° to 1200o F.; delivering the Cl „4. In the process set forth in claim 3J delivering
gaseous 'product from the said catalyte container
the hydrocarbon gases not condensed by the sta
to a second catalyte container located above the
bilizing action into the hydrocarbon base ñuid
ñrst catalyte container and heated by the heat
under a pressure of from 700 to 1000 pounds per
ing medium which has ñrst contacted the crack
square inch and together with said base ñuid into
ing elements and the ñrst catalyte container; 10 the vertically arranged series of cracking ele
liquefying, by sudden reduction of pressure and
ments. .
by cooling, the gaseous product produced within
and delivered from the second catalyte con
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