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Патент USA US2115606

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April 26, 1938.
J, Q_ ALTHER
2,115,606
PROCESS FOR HYDROCARBON OIL CONVERSION
Original Filed vApril 17, 1929
45 4445
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2,115,606
Patented Apr.`~ 2b, 1938
` UNITED STATES PATENT OFFICE
2,115,606
PROCESS FOR HYDROCARBON GIL
CONVERSION
Joseph G. Aimer. chicago, nl., assigner to Uni
versal Oil Products Company, Chicago, Ill., a
corporation of Delaware
Original application April 17, 1929, Serial No.
355,704. Divided and this application June 27,
1936, Serial No. 87,689
14 Claims.
This is a division of my co-pending application
Serial No. 355,704, iiled April 17, 1929, now Pat
ent No. 2,091,261.
This invention relates to improvements in proc
ess for hydrocarbon oil conversion, and refers
more particularly to improvements designed for
the efficient cracking of hydrocarbon oils to con
vert and produce therefrom products having
higher commercial value.
10
The utility of the invention as well as many -o'b
`iects and advantages thereof will be brought out
in the following description.
The principal object of the invention is to sub
ject hydrocarbon oil to such conditions of tem
perature and pressure as to produce maximum
yields of lighter gravity products suitable for use
as motor fuel with a minimum coke and gas loss.
tion,`I have shown the accompanying drawing,
which is a diagrammatic view, but not to scale,
of an apparatus suitable for carrying out the in
vention.
Referring to the drawing and to the operation
of the invention, the oil to be treated is directed
through line »I and branch 2, having valve 3> into
a heating coil 4, located in a furnace 5.
In heating coil 4 the oil is heated to a tempera
ture within the cracking range under a suitable 10
pressure. The amount of oil passed through the
coil per unit time, and the size of the apparatus
are so correlated that under the temperatures and
pressures used the degree of cracking obtained in
the heating coil is preferably short of that de
gree of reaction at which formation oi’ coke and
sludge-like matter occurs, or exceeds a predeter
Another object is to provide for lowering the mined desired degree.
,
«
reflux ratio by making it possible to convert a
Chamber I0 may take any desired form and size
20 greater proportion of `the higher boiling point in relation to the capacity of the apparatus. It
hydrocarbons per pass through the unit. This may be unheated and insulated against loss of 20
is of particular importance in effecting the ca ~heat by radiation and may be maintained at a
pacity and thermal eiliciency of the process.
temperature not substantially higher than the
Another purpose of the invention resides in the temperature of the oil introduced thereto from
25 employment of means to increase the decomposi
heating coil 4 through line ‘6 and valve 1.
tion of both the vapors and liquid from the pres
On the other hand, particularly for the -heavier sure expansion drum under controlled conditions charging stocks and depending upon the limita
, designed to accomplish the best results. This tions imposed upon the amount of coke and sludge
feature not only has an effect in increasing the to be formed or contained in the products, it
30 yields of lighter hydrocarbons obtained from the may be desirable to maintain the materials in
operation but also in improving their quality, chamber l0 at; a' temperature lower than that
especially for use as a motor fuel, in that they reached at the discharge of heating coil 4 to de
will consist more largely of higher antiknock crease the rate at which the reaction proceeds
compounds.
35
„
Briefly, the process of
the present invention is
as follows:
The> charging stock plus reñux will be pumped
through a conventional furnace having a large
heating surface from which the heated oil may
be transferred to a drum.
be substantially that oi' the coil outlet or lower,
but in the preferable operation this pressure
should be as high as possible inorder to increase
This drum may be ‘ the capacity of the unit and raise the thermal 40
unheated but lagged against excessive radiation
losses. Expansion takes place in the drum from
which vapors may be withdrawn separately, pass
ing preferably through a vapor heating coil to
45 provide further conversion and into a zone of
lower pressure into which residual oil from the
expansion drum may be directed.
'
,
From this point on the usual operation takes
place, i. e., all the vapors from the ¿flashing still
50 are directed to a dephlegmator where the suf
ficiently converted fractions are separated from
the heavier ends (reflux) by the incoming cold
raw oil or other cooling medium, said reflux be
ing returned to the cracking coil for retreatment.
55
in chamber I0. To this end the oil may be cooled in a, manner hereinafter described.
let
The pressures on the expansion chamber may
In order to more clearly understand the inven
efliciency of the process.
‘
The vapors pass out of chamber I0 through
line I9 and, as a feature of the invention, ll2 may
subject all or part'of the vapors removed from
chamber l0 to ladditional heating at elevated tem-fl 45
peratures to effect a controlled degree of sci-called
vapor-phase cracking whereby I am enabled to
produce lighter valuable distillates >having the
characteristics of motor fuels or gasoline, possess
ing high anti-knock properties due to the'pres 50
„ence of controlled proportions of, aromatic and
unsaturated hydrocarbons formed by said vapor
cracking.
`
g
'
.
For this purpose a vapor coil 22 may be posi
tioned in furnace 5 and located therein in such 55
2
2,115,606
a manner that the combustion gases pass over
coil 22 before passing over coil 4. In this manner
and because the combustion gases passing over
coil 22 are at a higher temperature than when
they pass over coil 4, a greater degree of radiant
heat may be utilized in coil 22 than in coil 4.
Coil 22 may be connected to vapor line I9 through
branches 23 and 24, respectively, controlled by
valves 25 and 26. By proper regulation of valves
10 26, 25, and 26, any desired amount of vapors
separated in chamber I6 may be passed through
the vapor heating coil 22. 'I'he vaporous prod
ucts from line I9, including the heated products
supplied thereto from coil 22 pass through line
15 |66 into chamber 54 at any desired point in this
zone by regulation of valves 51, preferably en
tering the lower portion of this zone and com
mingling therein with the liquid products sup-`
plied, as will be later described, from chamber I6
20 to chamber 54, whereby to supply additional
heat to said liquid products and assist their fur
ther vaporization.
The heavier liquid products are withdrawn
from chamber I6, preferably from the bottom
thereof, through line 5I having valve 52 and are
directed to flash chamber 54 to be subjected
therein to ñash distillation to any desired de
gree. Chamber 54 is provided with a bottom
draw-off 6I, having valve 62, whereby liquid or
30 semi-solid products may be removed therefrom.
Solid matters formed in the operation of the
process and deposited in chamber 54 may be re
moved therefrom through top and bottom man
holes in the usual manner.
35
Raw oil to be treated in the process may be
drawn from suitable storage tanks (not shown)
be desirable to cool the vapors immediately- after
they are subjected to vapor-phase cracking in
coil 22. Suitable lines and valves (not shown)
may vbe provided whereby material passing
through line 41 may be diverted and injected in
to line 24'through which the vapors leave coil
22. Line 90 controlled by valve 96’ is also pro
vided for introducing regulated quantities of the
materials passing through line 41 into line I9 and
provision is also made for diverting regulated 10
quantities of oil from line I through line 61 and
valve 61’ into line 6.
_
A portion of the non-condensable gas from
receiver 11 may be returned to vapor line I9
leaving reaction chamber I6 by means of valve 15
92 in line 93. This gas will pass through coil 22
together with the vapors from the reaction
chamber or be by-passed through valve 26, de
pending upon the operation desired. In any
event the uncondensed gas and vapors may be in 20
troduced into chamber 54 at any desired point in
this zone and, in the event the liquid level in
chamber 54 is above the point of introduction,
the hot gas and vapors will act as a partial pres
sure agent to facilitate vaporization in this zone. 25
By controlling the point of entry by means of
valves 51, the vapors may enter flash chamber
54 either above or below the liquid level main
tained therein. If full advantage of partial pres
sure eifect of these vapors is to be taken, they 30
should enter at the lowest point in chamber 54
in order to increase vaporization and facilitate
reduction of the percentage of unvaporized oil.
The valves and pumps shown permit the opera
tor to maintain suitable pressures on the various 35
parts of the apparatus. The flash chamber 54
and its connected parts such as dephlegmator 69,
through line 46 and pump 44. From'line 43 and
by suitable control of the valves shown, all or a
condenser 16 and receiver 11 are preferably main
portion of the raw oil to be treated in the process
tained at a pressure substantially lower than the -
may be diverted through line 45. having valve
46, then to line 41 which connects with the main
feed line I, whereby all or a portion of the charg
ing stock may be fed directly to the heating tubes.
Vapors separated by flash distillation in cham-'
66 having valve 61 to fractionating column 69,
pressure maintained in chamber I6. Any suitable 40
pressure may be maintained in vapor cracking
'coil 22 in relation to the pressure maintained in
chamber I6. Heating coil 4 in chamber I6 may
be maintained at substantially the same pres
sure or the pressure maintained in chamber I6 45
may be lower than that maintained in the heating
wherein they are subjected to controlled con
coil although still substantially above atmospher
densation by introducing into dephlegmator 69
suitable cooling medium through line 16 having
ic pressure.
ber 54 may be removed therefrom through line
valve 1I; or raw oil to be charged to the process
may be diverted from line 46 through line 12,
having valve 13 and introduced to column 69.
Vapors uncondensed in column 69 may be re
moved therefrom through upper draw-oil! line
14, having valve 15, and passed to condenser 16,
thence to receiver 11, having usual gas release
valve 16 and distillate release valve 19. The frac
tions of the vapors condensed in column 69 may
`
As an illustration of the temperatures which
may be maintained 'in an operation carried out in 50
accordance with the invention, the oil may be
heated in heating coil 4 to a temperature of, say
920° F.' to 960° F., said oil entering chamber I6
at a temperature near but relatively lower than
said temperature. In chamber I6 the oil may be 55
maintained at a temperature of, _say 850 to 900°
F. The vapors leaving chamber I6 and recycled
gases from receiver 11 may be heated in vapor
’ be discharged from the bottom thereof throughv ,coil 22 to a temperature of approximately 975 to
line -66, in which may be interposed pump 6I,v 1100° F. In this illustration a pressure of ap 60
from which they are directed through line 64,
Ahaving valve 65, lconnected with feed line 41,
whereby said fractions may be returned directly
to heating coil 4.
.
It may be desirable to control the degree of
reaction respectively taking place in heating coil
4,' chamber I6 andvapor coil 22, by controlling
the temperature, characteristics and quality of
materials passing respectively through these
70 zones. For instance, it may be desirable to intro
duce into the oil transferred from heating coil 4
to chamber I6, liquid products or condensates
from other parts of the process. _It may also be
desirable to do the same thing for the vapors
withdrawn from chamber I6. In addition it may
proximately 450 pounds may be maintained on
heating coil 4.and chamber I6. The pressure
may be reduced on flash chamber 54 down to ap
proximately 25 pounds. The vapors leaving 65
chamber I6 may be passed through vapor coil 22
under a pressure ofl approximately 100 pounds,
more or less.
It is to be understood that the preferred meth
od of operation is of the low level type, where
70
in a minimum quantity of residual oil ismain
tained in the chamber I6. That is, residual oil
is withdrawn from chamber I6 before it has had
sumcient time to form more than 5 per cent of
sludge or coke-like constituents.
75
3
2,115,606
I claim as my invention:
1. In-a process wherein hydrocarbon oil charg
ing stock is heated to a temperature sufficient to
effect substantial vaporization thereof, its result
ing vaporous and liquid components separated
and the vapors supplied to a separate cracking
zone wherein they are subjected to temperature
_and pressure conditions regulated to effect the
production therefrom of high yields of good anti
10 knock gasoline, the improvement which com
prises commingling relatively hot- conversion
products from said cracking zone with said liquid
components, whereby to effect appreciable further
vaporization of the latter, removing'the remain
15 ing unvaporized residue from the system, sub
jecting the vaporous products including those re
sulting from further vaporization of said liquid
components to fractionation for the formation
of reflux condensate, subjecting fractionated va
20 pors of the desired end-boiling point to condensa
tion, separating the resulting distillate and un
condensed gases, recovering the distillate, and
returning a portion of the uncondensed gases to
said cracking zone and therein heating the same
25 to an ofl cracking temperature together with said
vaporous components supplied thereto.
,
2. In a process wherein hydrocarbon oil charg
ing stock is heated to a temperature sufficient
to effect substantial vaporization thereof, its re
30 sulting vaporous and liquid components separat
ed and the vapors supplied to a separate cracking,
zone wherein they are subjected to temperature
and pressure conditions regulated to effect the
Y production therefrom of high yields of good anti
as knock gasoline, the improvement which com
prises commingling the relatively hot conversion
products from said cracking zone with said liq
uid components, whereby to effect appreciable
i further vaporization of’ the latter, removing the
40 remaining unvaporized residue from- the sys
> tem, subjecting the vaporous products, including
` those resulting from the further vaporization of
said liquid components, to fractionation for the
formation of reflux condensate, returning reflux
condensate'formed by said fractionation to fur
ther treatment within the system, subjecting frac
tionated vapors of the desired end-boiling point
to condensation, separating the resulting distil
late and uncondensed gases, recovering the dis
50 tillate and returning a portion of the uncon
densed gases to said cracking zone and therein
heating the same to an oil cracking temperature
_ together with said vaporous components supplied
thereto.
3. In a process wherein hydrocarbon oil charg
ing stock is heated to a temperature sufficient to
effect substantial vaporization thereof, its result
ing vaporous and liquid components separated
and the vapors supplied to a separate cracking
zone wherein they are subjected» to temperature
and pressure conditions regulated to efl'ect the
production therefrom of high yields of good anti
knock gasoline, the improvement which corn
prises commfngling relatively hot conversion
(i5 products from said cracking zone with said liq
uid components, whereby to effect appreciable
further _vaporization of the latter, removing the
remaining unvaporized residue from the system,
subjecting the vaporous products. including those
70 resulting from the further vaporization of said
liquid components, to fractionation for the for
mation of reflux condensate, comminglfng reflux
condensate formed by said fractionation with the
`charging stock undergoing treatment in the first
mentioned heating stage of the system, subject
ing fractionated vapors of the desired end-boiling
point to condensation, separating the resulting
distillate and uncondensed gases, recovering the
distillate and returning a portion of the uncon
densed gases to said cracking zone and therein
heating the same to an oil cracking temperature
together with said vaporous components supplied
thereto.
l
,
e
4. In a process wherein hydrocarbon oil charg
ing stock is heated to a temperature sufficient to 10
effect substantial vaporization thereof, its re
sulting vaporous and liquid components sepa
rated and the vapors supplied -to a separate
cracking zone wherein they are subjected to tem
perature and pressure conditions regulated to 16
effect the production therefrom of high yields of
good antiknock gasoline, the improvement which
comprises commingling relatively hot conversion
products from said cracking zone with said liq
uid components, whereby to effect appreciable 20
further vaporization of the latter, removing the
remaining unvaporized residue from the system,
subjecting the vaporous products, including those
resulting from the further vaporization of said
liquid components, to fractionation for the for 25
mation of reflux condensate, subjecting fraction
ated vapors oi’ the desired end-boiling point to
condensation, separating the resulting distillate
and uncondensed gases, recovering the distillate,
reheating a portion of the uncondensed gases to 30
a high oil-cracking temperature and commin
gling the same directly and without substantial
cooling thereof with said liquid components from
the first-named heating stage.
'
5. In a process wherein hydrocarbon oil charg
ing stock is heated to a temperature sufficient to
effect substantial vaporization thereof, its result
ing vaporousand liquid components separated
and the vapors supplied to a separate cracking
zone wherein they are subjected to temperature 40
and pressure conditions regulated to effect the
production therefrom of high yields of good anti
knock gasoline, the improvement which com
prises commingling relatively het conversion
products from said cracking zone with said liq 45
uid components whereby to effect appreciable
further vaporization of the latter, removing the
remaining unvaporized residue from the system,
subjecting the vaporous products, including those
resulting from the further vaporization of said 50
liquid components, to fractionation for the for
mation of reflux condensate, eommingling reflux
condensate formed by said fractionation with
« the charging stock undergoing treatment in the
first mentioned heating stage of the system. sub
jecting fractionated vapors of the desired end
boiling point to condensation, separating the re
sulting distillate and uncondensed gases, recover
ing the distillate, reheating a portion of the un
condensed gases to a high oil-cracking tempera
ture and commingling the same directly and
without substantial cooling thereof with said
liquid components from the first-named heating
stage.
„
6. In a process wherein hydrocarbon oil charg
ing stock is subjected to cracking temperature at
65
substantial superatmospherfc pressure, the' re
sulting vaporous and liquid conversion products
separated and the vapors subjected to appreciable“
additional conversion at increased temperature 70
in a separate cracking zone, the improvement
which comprises commingling the additionally
cracked vapors, while still ’at a higher tempera
ture than said liquid products, with the latter
in a separate zone, whereby appreciable fur 75
4
2,115,6oc
ther vaporization of the liquid products` and
appreciable cooling of the additionally cracked
vapors is accomplished, subjecting the vaporous
products from said separate zone to fractiona
tion for the formation of reflux condensate, re
turning reilux condensate formed by said frac
tionation to the first mentioned cracking step,
subjecting fractionated vapors of the desired
end-boiling point to condensation, separating the
10 resulting distillate and uncondensed gases, re
covering the distillate and returning a portion
of the uncondensed gases to the second mentioned
cracking step and heating the- same therein to
said increased temperature together with the
15
first-mentioned vapors.
A
7. In a process wherein hydrocarbon oil charg
ing stock is subjected to cracking temperature
at substantial superatmospheric pressure, the
resulting vaporous and liquid conversion prod
20 ucts separated and the vapors subjected to ap
preciable additional conversion at increased tem
perature in a separate cracking zone, the im
provement which comprises commingling the
moved, the vapors subjected to vapor-phase
cracking conditions in a separate heating coil
and supplied therefrom to a separate chamber
wherein they are afforded additional conversion
time, the improvement which comprises con
tacting relatively hot vapors resulting from said
vapor-phase cracking with liquid conversion
products withdrawn from said separating cham
ber, whereby to effect appreciable further vapor
ization of the latter, recovering the remaining
unvaporized residue, subjecting the vaporous
products, including those evolved from the liquid
products by said further vaporization, to frac
tionation, supplying reflux condensate formed
by said fractionation to the first mentioned 15
cracking
operation,
subjecting
fractionated
vapors of the desired end-boiling point to con
densation, recovering and separating the result
ing distillate and uncondensed gases, reheating a
portion of the latter to a relatively high tem
perature and introducing the reheated gases di
rectly and Without substantial cooling thereof
into said second mentioned chamber.
additionally cracked vapors, while still at a
10. The improvement as defined in claim 9
higher temperature than said liquid products,
further characterized in that said portion of 25
the uncondensed gases is reheated in said sepa
with the latter in a separate vaporizing zone,
whereby appreciable further vaporization of the
liquid products and appreciable cooling of the
additionally cracked `vapors is accomplished,
30 subjecting the vaporous products from said sepa
rate vaporizing zonek 'to fractionation for the
formation of reflux condensate, returning reflux
condensate formed by said fractionation to the
first mentioned cracking step, subjecting frac
tionated vapors oi' the desired end-boiling point
to condensation, separating the resulting dis
tillate and uncondensed gases, recovering the
distillate, reheating a portion of the uncondensed
gases to a high oil-cracking temperature and in
troducing `the same directly and without sub
stantial cooling thereof into said separate vapor
izing zone.
rate coil in admixture with the first-named va
pors.
»
11. A conversion process which comprises pass
ing hydrocarbon oil through a heating coil and y30
heating the same therein sufliciently to vaporize a
substantial portion thereof, separting resultant
vapors from unvaporized oil in an enlarged zone,
removing the unvaporized oil and introducing
the same into a second enlarged zone, removing 35
vapors from the first-named enlarged zone and
heating the same to vapor phase cracking tem
perature in a second heating coil, subsequently
introducing the vapor phase cracked vapors into
contact with the unvaporized oil in said second
enlarged zone, removing admixed vapors and
gases from the second enlarged zone and sub
8. In a process wherein hydrocarbon oil charg- ' jecting the same to condensation to separate
ing stock is subjected to cracking temperature at vapors from gases, heating a portion of the
separated uncondensed gases to a high oil 45
substantial superatmospheric pressure, the re
ducing the same directly and without substantial
cooling thereof into contact with the unvaporized
oil in said second enlarged zone.
tionally cracked vapors, while still at a higher
characterized in that said portion of the gases f
temperature than said liquid products, with the
latter in a separate zone, whereby appreciable
is heated in said second coil in admixture with
the vapors being heated therein to vapor phase
further vaporization of the liquid products and
appreciable cooling of the additionally cracked
vapors is accomplishedl subjecting the vaporous
products from said separate ione to fractionation
for the formation of reflux condensate, returning
.reflux condensate formed by said fractionation
to the ßrst mentioned cracking step, subjecting
fractionated vapors of the desired end-boiling
point to condensation, separating the resulting
distillate and uncondensed gases, recovering the
distillate and returning a portion> of the un
condensed gases to further treatment in the
same cracking step to which said vaporous
products are supplied and heating the same
therein, to said increased temperature together
70
cracking temperature and subsequently intro
sulting vaporous and liquid conversion products
separated and the vapors subjected to appre
ciable additional conversion at increased temper
ature in a separate cracking zone, the improve
ment which comprises commingling the addi
with the first-mentioned vapors.
‘
9. In a cracking process wherein hydrocarbon
oil charging stock is subjected to cracking condi
tions in a heating coil. the resulting heated
products introduced into a separating chamber
wherein their -vaporous and liquid components
75 separate and from which they are separately re
12. The process as defined in claim 1l further 50
cracking temperature.
13. In a hydrocarbon oil conversion process 55
wherein there is formed a mixture of vapors and
gases which is fractionated and then subjected
to final condensation and the incondensible gases
separated from the final condensate, the method
which comprises heating hydrocarbon oil to dis 60
tillation temperature in a, heating coil and sepa
rating the same into vapors and unvaporized oíl
in a separating chamber, introducing the un
vaporized oil into a second chamber maintained
under lower pressure than the first-named cham 65
ber, simultaneously heating vapors from the first
named chamber and a portion of said incon
densible gases to a high oil-cracking tempera
ture, introducing the thus heated vapors and
gases into contact with the unvaporized oil in 70
said second chamber, and supplying admixed
vapors and gases from the second chamber to
said fractionating step.
`
v
.
14. In a hydrocarbon oil conversion process
wherein there is formed a mixture of vapors and 75
aumcoe
5
gases which is fractionated and then subjected to ing vapors from the first-named chamber and a
iìnal condensation and the incondensible gases portion of said incondensible gases to a high
separated from the ñnal condensate, the method oil-cracking temperature, introducing the"`thus
- which comprises heating hydrocarbon oil to dis heated vapors and gases into the lower portion
g. tillation tempera-ture in a heating‘coil and sepa .of the second chamber` to ñow in countercurrent 5
rating the same into vapors and unvaporized oil contact with said unvaporized oil, and supplying
in a. separating chamber, introducing the unva admixed vapors and gases from the second
porized oil into the upper portion of a second chamber to said fractionating step.
chamber maintained under lower pressure than
10
JOSEPH G. ALTHER.
the first-named chamber, lsimultaneously heat
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