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Патент USA US2130407

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‘ Sept. 20, 1938.,
c. H. ANGELL
2,130,407
CONVERSION OF HYDROCARBON OILS
Filed Aug. 5, 1935
me
INVENTOR
TTORNEY
Patented Sept. 20, 1938
2,130,4'?
UNITED stares staar orrice
CONVERSEÜN 0l? HYQDRGCARBOÑ OILS Y
Charles H. Angell, Chicago, Ill., assigner to'Uni
versal Oil Products Company, Chicago, Ill., a
corporation of Delaware
Application August 5, 1935, Serial No. 34,655
5 Claims. (Cl. 196-49)
This invention particularly refers to an im
proved process for the conversion of hydrocarbon
oils accompanied by continuous coking of the
residual liquid conversion products wherein
charging stock for the process, comprising hydro
carbon oil of relatively high-boiling character
istics or an oil containing a substantial proportion
of high-boiling materials, is- subjected to vaporiza
tion by being commingled with hot vaporous prod
ucts from the coking stage of the process and the
resulting non-vaporous high-boiling components
of the charging stock either subjected to coking
together with said residual liquid conversion
products or subjected to relatively mild conver
sion in a reaction chamber of the cracking sys
tem preceding the coking stage by contact therein
with highly heated products from the cracking
coil of the system.
charging stock serves to remove the undersirable
high-boiling materials from the -vaporous prod
ucts, allowing only relatively clean vapors to pass
from the vaporizing chamber to the fractionating
Zone of the system wherein the normal reflux Ul
condensate which is supplied to the heating coil
of the cracking system is recovered. The unde
sirable high-boiling materials removed from the
vaporous products of the coking operation by
contact with the charging stock in the vaporizing
chamber commingle with the high-boiling com
ponents of the charging stock remaining un
vaporized in this zone and, in accordance with the
process of the present invention, these com
mingled relatively high-boiling materials may be
supplied either to the heating coil of the coking
stage or are directed without additional heating
to the same high-pressure reaction chamber of
`
One of the most satisfactory methods which
20 has been developed for the continuous coking oi
relatively heavy oils, such as high-boiling residual
oils resulting from pyrolytic conversion, com
prises passing the oil through a heating coil
wherein it is quickly heated to a high conversion
temperature under non-coking conditions and in
troducing thehighly heated oil into an enlarged
coking zone, preferably operated at substantially
the cracking system to which the highly heated
products from the heating coil of the cracking
stage are supplied.
It will be understood, of course, that the two
alternative methods of operationV with respect
to the disposition of the commingled high-boiling
oils from the vaporizing chamber are not to be
considered equivalent but may be selected, de
pending primarily upon the characteristics of the
commingled oils, to give the best results with re
atmospheric or relatively low superatmospheric
pressure, wherein its reduction to substantially
spect to yield of the desired products, continuity
dry coke is accomplished.
of operation, throughput, etc.
-
In such methods of operation there is a large
amount of available heat in the vaporous prod
ucts evolved during the coking operation due to
the relatively high temperature to which the
heavy oils subjected to coking are heated and, in
accordance with the usual practice, a large pro
portion of this available heat is wasted. Also due
to the high temperature and relatively low pres
sure employed in the coking operation the
vaporous products from the coking Zone normally
contain a considerable amount of high-boiling
subjecting hydrocarbon oil, comprising insuf
ñciently converted intermediate liquid products
of the process, to conversion yconditions of crack
ing temperature and substantial superatmos- 35
pheric pressure in a heating coil and communi
eating reaction chamber, withdrawing both
vaporous and liquid conversion products from the
reaction chamber and introducing the same into
_a reduced pressure vaporizing chamber wherein 40
separation of vapors and residual liquid con
materials, including entrained or dissolved tars
version products is accomplished, withdrawing
and pitch-like material, unsuitable for conversion
in the heating coil of the system to which the
normal reflux condensate is supplied.
non-vaporous residual liquid from the vaporizing
chamber, heating the same to a high conversion
In the present invention a large portion of the
available heat in the vaporous products from the
coking Zone is utilized to effect substantial
vaporization of the hydrocarbon oil charging
stock for the process by directly commingling the
hot vaporous products from the coking zone with
the charging stock in a vaporizing zone succeed
ing the coking chamber. The partial cooling of
the vaporous products from the coking zone thus
55 effected by their contact with the relatively cool
30
In one embodiment, the invention comprises
temperature under non-cracking conditions >in 45
a separate heating coil, introducing the highly
heated residual oil into a coking Zone wherein its
reduction to substantially dry coke is accom
plished introducing vaporous products with
drawn from the coking zone and vaporous prod 50
ucts from the vaporizing chamber into a separate
vaporizing chamber, introducing hydrocarbon oil
charging stock for the process into said separate
vaporizing chamber in contact with the vaporous
products supplied thereto, subjecting the result- 55
2
2,130,407
ing vaporous products from said separate
vaporizing chamber to fractionation, returning
the resulting reñux condensate to the first men
tioned heating coil, subjecting fractionated vapors
of the desired end-boiling point to condensation,
collecting and separating the resulting distillate
products remaining unvaporized in chamber 8 are
and gas, withdrawing from said separate Vaporiz
through line I2 and valve I3 to pump I4 by means
ing chamber high-boiling components of the
of which they are fed through line I5, valve I6
and line 54 to heating coil I'I.
charging stock which remain unvaporized in this
zone, together with high-boiling materials re
moved from the vaporous products supplied
thereto, and introducing the same into the re
action chamber wherein they are subjected to
relatively mild conversion by contact in this zone
' with the highly heated products from the ñrst
mentioned heating coil.
As an alternative to the specific embodiment
of the process above described the high-boiling
oils from said separate vaporizing chamber may
be supplied to the heating coil of the coking stage
of the system, together with the non-vaporous
residual liquid products from the first mentioned
vaporizing chamber, being thereby heated to a
high temperature under non-coking conditions
and subjected to coking in the succeeding coking
zone.
The accompanying diagrammatic drawing il
lustrates one speciñc form of apparatus embody
ing the features of the present invention and in
which the process of the invention may be ac
complished.
cated within a furnace 2 of any suitable form by
means of which the oil supplied to this zone, in
the manner to be later more fully described, is
heated to the desired conversion temperature
preferably at a substantial superatmospheric
pressure and the resulting highly heated products
are directed from the heating coil through line 3
40 and valve 4 into reaction chamber 5.
Reaction chamber 5 is also preferably main
tained at a substantial superatmospheric pres
sure and this zone is preferably well insulated,
although insulation is not shown in the drawing,
in order to prevent the excessive loss of heat by
radiation so that conversion of the heated prod
ucts, and particularly their vaporous components,
may continue in this zone.
withdrawn from the lower portion of this zone
Heating coil Il is located within a furnace I8
and this heating coil and furnace are preferably
of such design, which is now well known, that
the relatively heavy oil supplied thereto, which
is preferably passed through the heating coil at
a relatively high velocity, is quickly heated to a
high conversion temperature without allowing it
to remain in the heating coil and communicating
lines for a suflicient length of time to permit any
excessive formation and deposition of coke in this
zone. The highly heated residual oil is directed
from heating coil Il through line I9 and valve 20
into coking chamber 2| wherein it is reduced to
substantially dry coke by Virtue of its highly heat
ed condition.
The coke produced in chamber 2I may be al
lowed to accumulate in this zone to be removed
therefrom in any suitable well known manner,
not illustrated, after the operation of the cham
ber is completed. Although, for the sake of sim
plicity, only one coking chamber is shown in the 30
drawing twoI or more such zones are preferably
Referring' to the drawing, heating coil I is lo
Ca?
supplied through line II, all or in part, to va
porizing chamber 26 or they may be supplied, all
or in part, by well known means, not illustrated,
to fractionator 34. ,Residual liquid conversion
In the case here il
lustrated both vaporous and liquid conversion
products are withdrawn in commingled state
from the lower portion of chamber 5 and are
employed and may be operated simultaneously or,
preferably, are alternately operated, cleaned and
prepared for further operation in order that the
coking stage, in common with the rest of the sys 35
tem, may be operated continuously. Chamber 2I
is provided with a suitable drain-line 22 controlled
by valve 23 which may also serve as a means of
introducing steam, water or any other suitable
cooling material into the chamber after its opera
tion is completed and after it has been isolated
from. the rest of the system in order to hasten
cooling of the chamber and facilitate the removal
of coke therefrom. Vaporous products evolved in
chamber 2I are withdrawn from the upper por
tion of this zone through line 2liV and valve 25
and are directed through line II to vaporizing
and separating chamber 26.
Hydrocarbon oil charging stock for the proc
ess, which may comprise any desired type of oil „.f
but is preferably either an oil of relatively wide
boiling range, such as crude petroleum, topped
directed through line 6 and valve ‘I into Vaporiz
ing and separating chamber 8. It is, of course,
also within the scope of the present invention to
separately withdraw vaporous and liquid conver
sion products from the reaction chamber in which
case the vaporous products separately withdrawn
line 30 and valve 3| into vaporizing chamber-26
wherein it is intimately contacted with the hot
from this zone at any desired point or plurality of
vaporous products from the coking zone, as Well
points therein may be separately supplied, by well
known means, not illustrated, to vaporizing
as, when desired, from vaporizing chamber 8
and/cr reaction chamber 5, and thereby subjected Gf)
tc'appreciable vaporization. It will be under
chamber 8 at any desired point or plurality of
points in this Zone or they may be directed, all
or in part, to vaporizing chamber 26 or to frac
tionator 34 or, when desired, to coking chamber
2I by well known means, not shown.
Vaporizing chamber 8 is preferably maintained
at a substantially reduced pressure relative to
that employed in reaction chamber 5 by means of
which appreciable further vaporization of the liq
70 uid conversion products supplied to this zone from
the reaction chamber is accomplished. Separa
tion- of vapors and non-vaporous residual liquid is
accomplished in chamber B, the vapors being
withdrawn from the upper portion of this zone
75 through line 9 and valve I0, and they may be
crude, or the like, or an oil of high boiling char
acteristics, is supplied through line 2l and valve
28 to pump» 29 by means of which it is fed through ,
stood, of course, that the charging stock may,
When desired, be preheated to any desired tem
perature below that of the vaporous products
with which it is contacted in chamber 26, prior to
its introduction into this zone although, for the
sake of simplicity, none of the Well known means
for accomplishing this are illustrated in the draw
ing. Cooling of the, hot vaporous products sup
plied to chambers 25 by contact with the charg
ing. stock in this Zone serves to remove therefrom
undesirable high-boiling components including
any tarry or pitch-like material dissolved or en
trained in the vaporous products from the coking
zone. Accurate control of the degree of vapori
2,130,407
Zation to which the charging stock is subjected
in chamber 26 and the characteristics of the high
boiling components of the charging stock and
vaporous products recovered as liquid from cham
ber 26 may be obtained by controlling the quan
tity and temperature of the charging stock sup
plied to the vaporizing chamber and the pres
sure conditions maintained in this zone.
ing stock which are vaporized in chamber 25 and
the components of the vaporous products sup
plied to this zone which remain uncondensed
therein are directed through line 32 and valve 33
to fractionation in fractionator 35i.
The components of the vaporous products sup
plied to fractionator 34 boiling above the end
boiling point of the desired iinal light distillate
product of the process are condensed in this zone
as reflux condensate which is withdrawn from
20 the lower portion of the fractionator through line
35 and Valve 36 to pump 3l by means of which it
is supplied through line 38 and valve 39 to con
Version in heating coil l, in the manner previ
ously described. Fractionated vapors of the de
25 sired end-boiling point are withdrawn, togethei`
with uncondensable gas produced by the process,
from the upper portion of the fractionatcr
through line 4l! and valve Él! and are subjected
to condensation and cooling in condenser G2.
30 The resulting distillate and gas passes through
line 63 and Valve ¿lli to collection and separation
in receiver £5.
Uncondensable gas may be re
leased from the receiver through line 4B and valve
lll. Distillate may be‘withdrawn from receiver
35 t5 through line ¿i8 and valve ¿is to storage or to
any desired further treatment. A regulated por
tion of the distillate collected in receiver ¿l5 may,
when desired, be recirculated by well known
means, not illustrated, to the upper portion of
40 fractionator Sil to serve as a cooling and refluXing
medium for assisting the fractionation of the
vapors and to maintain the desired vapor outlet
temperature from the fractionator.
High-boiling components of the charging stock
45 remaining unvaporized in chamber 2t commingle
in this zone with the high-boiling components of
the vapors removed therefrom by contact with
the charging stock and the commingled mate
rials are removed from the lower portion of
50 chamber Bâ through line 55 and valve 5i to
pump 52 by means of which they are fed through
line 53 and may be directed through valve 5è and
line 55 into heating coil il, to be subjected to
heating in this zone together with the residual
55 liquid conversion products from chamber 8 and
subjected to subsequent reduction to coke in
coking chamber 2l , or, as an alternative method
of operation, all or a regulated portion of the
commingled high-boiling oils from chamber 26
60 may be directed through valve 56 in line 53 into
reaction chamber 5 preferably being sprayed
against the walls of the chamber by means of a
suitable spreader flange or spray arrangement
such as indicated, for example, at 5l. By the
65 latter method of operation the high-boiling oils
from chamber 26 are subjected to relatively mild
conversion in chamber 5 by contact with the
highly heated products from heating coil l, the
resulting vaporous and liquid conversion products
70 commingling with the vaporous and liquid prod
ucts resulting from conversion of the lower boil
ing oils supplied to heating coil i and being sub
jected, in the portions of the cracking system
subsequent to chamber 5, to the same conditions
75 of further treatment previously described.
In a process of the character illustrated and
above described the preferred range of operating
conditions may be approximately as follows:
The heating coil of the cracking stage of the
system to which reilux condensate from the frac
tionator is supplied may utilize an outlet conver
The
relatively low-boiling components of the charg
3
sion temperature ranging, for example, from 850
to 1000° F., preferably with a superatmospheric
pressure measured at the outlet from the heating
coil of from 100 to 800 pounds, or thereabouts, per
square inch. A substantial superatomspheric
pressure, which may be substantially the same or
somewhat lower than the pressure employed in
the heating coil, may be utilized in the succeeding
reaction chamber and the vaporizing chamber to
which the liquid conversion products or both liq
uid and vaporous conversion products from the
reaction chamber are supplied preferably employs
a substantially reduced pressure relative to that
in the reaction chamber which may range, for 20
example, from 150 pounds, or thereabouts, per
square inch down to substantially atmospheric
pressure. The temperature employed at the out
let from the heating coil of the coking stage of
the system may range, for example, from 900 to 25
1050° F. preferably with a superatmospheric pres
sure in this zone of from 20 to 150 pounds, or
thereabouts, per square inch, although lower or
higher pressures may be employed, when desired.
The coking chamber may be operated at any de 30
sired pressure ranging from 150 pounds, or there
abouts, per square inch down to substantially at
mospheric pressure, which pressure, however, is
no greater than that employed in the preceding
heating coil. Th-e vaporizing and separating
chamber succeeding the coking chamber, to which
charging stock for the process is supplied, may
utilize any desired pressure from substantially
atmospheric to 150 pounds, or thereabouts, per
square inch superatmospheric pressure which, 40
however, is no greater than the pressure em
ployed in the coking chamber. The pressures
employed in the fractionating, condensing and
collecting portions of the system may be sub
stantially the same or somewhat lower than the
pressure employed in the last mentioned vapor
izing and separating chamber.
As a specific example of one of the many pos
sible operations of the process as it may be ac
complished in an apparatus of the character il
lustrated and above described, the charging stock,
which comprises an 18° A. P. I. gravity Mid-Con
tinent reduced crude, is supplied to a vaporizing
chamber to which vaporous products from the
coking zone of the system are also supplied and
contacted with the charging stock, vaporous
products from this zone are supplied tp the
fractionator of the system and the resulting re
flux condensate is subjected in a heating coil to
van outlet conversion temperature of approxi 60
mately 950° F. at a superatmospheric pressure of
' about 350 pounds per square inch. Substantially
the same pressure is maintained in the succeed
ing reaction chamber and the resulting vaporous
and liquid conversion products are supplied to a
separate vaporizing chamber maintained at a
superatmospheric pressure of about 50 pounds
per'square inch. Vaporous products from this
zone are supplied to the ñrst mentioned vaporiz
ing chamber while the high-boiling non-vapor 70
ous oils from both vaporizing chambers are sup
plied to a separate heating coil wherein they are
quickly heated to an outlet temperature of ap
proximately 980° F. at a superatmospheric pres
sure of about 30 pounds per square inch and the 75
2,130,407
4
highly heated heavy oils are introduced into al
ternately operated coking chambers maintained
at substantially the same pressure.
The pres
sure employed in the coking chamber is substan
tially equalized in the succeeding vaporizing
chamber and in the fractionating, condensing and
collecting portions of the system. This operation
will produce, per barrel of charging stock, ap
proximately 55 per cent of motor fuel having an
octane number of approximately ’70 by the motor
method and approximately 120 pounds of low
volatile coke of uniform quality and good struc
tural strength, the remainder being chargeable,
principally, to uncondensable gas.
I claim as my invention:
l. In a process for the conversion of hydrocar
bon oils wherein oil recovered from within the
system is subjected to conversion conditions of
cracking temperature and substantial superat
mospheric pressure in a heating coil, the result
ing vaporous and liquid conversion products sep
arated and the latter subjected to appreciable
further vaporization in a reduced pressure va
porizing chamber, the remaining non-vaporous
residual liquid heated to a relatively high tem
perature under non-coking conditions in a sep
arate heating coil and then introduced into a cok
ing chamber wherein its reduction to substantial
ly dry coke is accomplished, the improvement
30 which comprises imparting to said residual liq
uid in the separate coil suilicient heat to effect
its reduction to coke in the coking chamber, with
drawing vaporous products from the ‘coking
chamber and contacting the same in a separate
Vaporizing chamber with relatively cool hydrocar
c. Cl
bon oil charging stock for the process, whereby
the charging stock is subjected to appreciable va
porization andy undesirable high-boiling c_om
ponents are removed from the vaporous products,
subjecting the remaining vapors to fractionation
40
together with vaporous products from the first
mentioned vap'orizing chamber whereby their
insufficiently converted components are con
densed as reflux condensate, supplying reflux
condensate recovered by said fractionation to
the first mentioned heating coil for said conver
sion, subjecting fractionated vapors of the de
sired end-boiling point to condensation, and col
lecting the resulting distillate.
2. In a process for the conversion of hydrocar
bon oils wherein oil recovered from within the
system is subjected to conversion conditions of
cracking temperature and substantial superat
mospheric pressure in a heating coil and com
municating reaction chamber, the resulting va
porous and liquid conversio-n products separated
and the latter subjected to appreciable further
vaporization in a reduced pressure vaporizing
chamber, the remaining non-vaporous residual
liquid heated to a high temperature under non
coking conditions in a separate heating coil and
the highly heated residual oil introduced into a
coking chamber wherein its reduction to sub
stantially dry coke is accomplished, the improve
ment which comprises imparting to said residual
liquid in the separate coil sufficient heat to effect
its reduction to coke in the coking chamber, with
drawing vaporous products from the coking
chamber and >commingling the same, in a sep
arate vaporizing chamber, with relatively cool
hydrocarbon oil charging stock for the process
whereby the charging stock is subjected to ap
preciable vaporization‘and undesirable high-boil
ing components are removed from the vaporous
products, subjecting the remaining vapors to
fractionation together with vaporous products
from the first-mentioned vaporizing chamber
whereby their insufficiently converted compo
nents are condensed as reflux condensate, sup
plying reflux condensate recovered by said frac
tionation to the ñrst mentioned heating coil for
said conversion, subjecting fractionated vapors
of the desired end-boiling point to condensation, 5
collecting the resulting distillate, withdrawing
from the last mentioned vaporizing chamber
high-boiling components of the charging stock
remaining unvaporized in this zone, together
with said high-boiling materials removed from
the vaporous products supplied to this zone, and
supplying the same to said reaction chamber
wherein they are subjected to relatively mild
conversion by contact with the highly heated
products from the first mentioned heating coil. 25
3. A process as claimed in claim l wherein va
porous products from the first mentioned va
porizing chamber are supplied to said separate
vaporizìng chamber.
,
4. A process as claimed in claim 2 wherein Va
porous products from the ñrst mentioned vapor
izing chamber are supplied to said separate va
porizing chamber.
5. In a process for the conversion of hydro
carbon oils wherein oil recovered from within the
system is subjected to conversion conditions of
cracking temperature and substantial super
atmospheric pressure in a heating coil, the re
sulting vaporous and liquid conversion products
separated and the latter subjected to appreci 40
able further vaporization in a reduced pressure
vaporizing chamber, the remaining non-vaporous
residual liquid heated to a relatively high tem
perature under non-coking conditions in a sep
arate heating coil and then introduced' into a 45
coking chamber wherein its reduction to sub
stantially dry coke is accomplished, the improve
ment which comprises imparting to said residual
liquid in the separate coil suiiicient heat to ef
fect its reduction to coke in the coking chamber, 50
withdrawing vaporous products from the coking
chamber and contacting the same in a separate
Vaporizing chamber with relatively cool hydro
carbon oil charging stock for the process, where
by the charging stock is subjected to appre
55
ciable vaporization and undesirable high-boil
ing components are removed from the vaporous
products, supplying liquid products of the con
tacting step from said separate vaporizing cham
ber to said separate coil, fractionating the un 60
condensed vapors from said separate vaporizing
chamber and vaporous products from the first
mentioned chamber and supplying resultant re
flux condensate to the ñrst-mentioned coil, and
finally condensing and collecting the fractionated 65
vapors.
CHARLES H. ANGELL.
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