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Патент USA US2132639

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„ "Oct.' 11', 1938.
J. c. MORRELL. f
2,132,639v '
TREATMENT OF HYDROCARBON OI`LS
Filed Aug. -l0, 1936v
272@
A
n
l F38
PgatentednOct. lll, 1938
» x 24325639’
y ‘ UNITED STATES PATENT oFFI'CEÍ* 7
" . ' 2,132,639
' y
TREATMENT oF ¿nynnocaanou oms
Jacque C. Morrell,` Chicago; Ill., assigner to Uni-.1"
l versal Oil Products'Cornpany, Chicago, lll., a >
corporation oi’ Delawa
Í (Applicacxdnaumc’lo, 193s,E semi No, 95,166` o
s
This is a -continuation*-in-part of myco-pend~
ing application> Serial #524,430, filed March 23,
1931.
;
»
‘
'
(ci: 13s-4s)
prior to their discharge from the lower portion'
,f Theinvention relates to animproved kprocess
5 for thecracking of hydrocarbon oils ofrelatively
thereof. The secondary charging stock is heated
to a substantially higher cracking- temperature K
high-boiling characteristics to produce substanor,~ln part, to‘each'ot these zones.
‘Y’
`
'
.
r`When highly heated products from the, sec~
ondary charging stock heating coil are supplied
15
10»
the process.
The process employs two charging stockì‘jmé
of which comprises hydrocarbon oil oi'high-boil
ing characteristics or, of relativelyv wide,
crease the temperature *andrete of cracking'in 15
` »the reaction chamben- In this method otoper'a- `
tion,
ber :without encountering theexcessive formation
anddeposition of `coke in the heating coil(y 'I'he
vaporous. components yare _ thereby subjected, ' in
the reaction chamber, ‘
the relative quantities of the two. ~
The process," is ‘preferably conducted, in a
>the 1owervporuon ofthe
_,
,
,
L5 the coking chamber. Separate heating coils are
employed for independently heating the primary '
and secondary charging _stocks each to the' de
sired temperature'. preferably at a, V.substantial
~ substantial forma-lé`
tionand deposition of coke inthis me and the
communicating lines,` while the „q
vtity sup
` pass downwardly through this `zone andare sub- .t .plied to the coking chamber is' suiiicient tore
;` Jected to appreciable
duce .the residual products in this zone to coke
continued cracking therein, . of
the desired low volatility.
-
2,182,639
2
line 8 and valve l preferably into the upper por
Vaporous products are directed from the cok
tion of reaction chamber I0.
ing zone to a fractionator wherein their com
Chamber I'II is also preferably maintained at
a substantial superatmospheric pressure and, al
ponents boiling above the range of the desired
gasoline product of the process are condensed
as reflux condensate. The vaporous products re
10
though not indícateà inthev drawing, this zone ,
is preferably insulated to conserve heat.
heated products supplied to chamber I0 pass
downwardly through substantially the entire
and of good antiknock value, are subjected to
condensation and the resulting distillate re
length of this zone and, in the particular case
here illustrated, both vaporous and liquid prod 10
ucts are withdrawn in commingled state Vfrom
covered.
y
‘
The reflux condensate formed by said frac
tionation is, of course, the result of cracking the'
' two virgin charging stocks and I have found that
this reflux condensate- contains a substantial
amount, at least, of oils which, although of
15 higher boiling characteristics than the secondary
the lower portion of the reaction chamber and
are directed through line II and valve I2 into
chamber I3.
It is also within the scope of the invention, 15
although not illustrated in the drawing, to
separately remove vaporous and liquid conversion
products from the lower portion of chamber I0
charging stock, may be further cracked to vbet
ter advantage under the relatively severe crack
ing- conditions employed in the secondary charg
ing stock heating coil than under the ymilder
20 cracking conditions employed for the higher
and to introduce both of these materials into
chamber vI3 at the same or at separate points 20'
’ in this zone
boiling primary virgin charging stock. There»
fore, in the present process, such components of
ing, together with the secondary charging stock,
25 are segregated in the fractionatingstep from its
.higher boiling components .and supplied for addi
tional cracking to the secondary charging stock
heating coil.
so
~
or, when desired, to supply a regu
lated portion or all of the vaporous products
separately withdrawn from chamber IIs directly
4to fractionator I8 instead of to chamber I3.
the reflux condensate as are suitable for crack
y
The
sulting from such fractionation, preferably com
prising gasoline of the desired end boiling point
However, in accordance with the preferred 25
method of operation, the total vaporous and
liquid conversion products from chamber II! are
supplied to chamber I3 either as a single stream
or as separate'streams.
30
In chamber I3 the heavy residual liquid com
.
I have further found that „the relatively high
boiling fractions yof’ the .reflux condensate, com
ponents separate from the‘vaporous components
prising' its components remaining after the
separation therefrom of the fractions supplied
reduced to substantially dry coke, the coking
operation being vaccomplished either with or
without the assistance of other highly heated
conversion products supplied to this zone, as will
to the rseco'ndarycharging stock- heating coil, are
ordinarily suitable for- further cracking under
A"mi the
conditions employed for the primary charg
ing stock, even though they are of higher boil
ing characteristics or contain a substantial
quantity -of‘materi'als of higher boiling charac
than the primary charging stock. Such
'V40 teristics
materials are, therefore, in the present process,
returned to the primary charging stock heating
coil for further cracking.
¿
of the materials supplied to this zone and are
be later described, and in either case being as
sisted by the reduced pressure employed in cham
ber I3 relative to that utilized in chamber I0.
It is, of course, also wit-hin the scope of the .40
invention, when desired, to employ- two or more'
coking' chambers, although only one is illustrated
in the drawing, and when a plurality of coking
`
It will be ‘apparent from the foregoing descrip
tion of the operation, that it provides a~unifiedI
process for the selective simultaneous cracking
.45l
' of both light and heavy oils and the Areforming
of gasoline to produce high yields of gasoline of
good antiknock value and minor yields of gas
50
and good quality coke.
'
I am fully aware that various steps and fea
chambers is employed they preferably are a1
ternately operated, cleaned and prepared for fur 45
ther operation in ¿'order‘that the coking stage, in
common with the _rest of the system, may be
operated continuously. Coke produced is allowed
to accumulatein the coking chamber or chambers
in operation and may be removed therefrom in 50
any well known manner, not illustrated, after
the coking zone is substantially filled or after its
tures of the process such as the reforming of
gasoline, the use of a high-pressure reaction
operationv has been completed for any other
chamber and reduced pressure vaporizing cham
reason.
ber connected in series and the production of
55
product of the process are
- coke as_the residual
not in themselves new in the art but the improved
process of this invention depends upon the co
operative relation of the various steps and fea
tures of the process which cooperate in a new
60 and advantageous manner to >produce the de
sired final results.
The accompanying diagrammatic drawing
illustrates one specific form of apparatus in
which the process of the invention may be con
ducted.
`Referring to the drawing. primary charging
stock of the n_ature previously indicated issup
plied through line I and valve 2 to pump 3 by
means of which it is fed through line 4 and valve
70 5 to heating coil 6. The oil is heated in this zone
to the desired cracking temperature, preferably
at a superatrnos’pheric pressure, by means of
heat supplied from furnace 1. The heated prod
ucts are discharged from heating coil 5 through
75
=
.
f Chamber I3 is provided with a drain-line Il 55
and valve I5 and this line may ralso serve, when
desired, as a means of introducing steam, water
or other suitable cooling material into the cham
ber, after its operation has been completed and
preferably after it has been isolated from the 60
rest of the system, ln order to hasten cooling and
facilitate removal of the coke therefrom.
'
Vaporous products are withdrawn from the
upper portion of the coking chamber and directed
through line I6 and valve I1into fractionator 65
I8, wherein their components boiling above the
range of the desired final light distillate product
of the process are condensed as reflux condensate.
Fractionated vapors of the desired end-boiling
point, consisting preferably of good antiknock
gasoline and gaseous‘produ'cts of the process, are
directed from the upper portion of the fraction
ator through line I9 and valve 20 to cooling and
condensation in condenser 2l. The resulting dis
tillate and- uncondensed gases are directed
2,182,689
through line 22 and‘valve 23 to collection and
3
ing stock, ordinarily require theuse of` more se
separation inreceiver 24. Dlstillate may be `with
drawn from the-` receiver through line 2T and-valve vere'cracking condltionslto >produce the .maxif
28 to storage or to ‘any desired further’ treatment. _ mum yields of good quality gasoline than `a virgin
Uncon 'iensed gases ‘may be released from receiver oilof similar‘boiling characteristics. k_The low
24 through line 25 yand valve 26o. When desired, boiling fractions of the reflux‘condensate sup
regulated quantities of the distillate collected in plied to heating coil 484preferably are substan
receiver 24 maybe recirculated by Well known tially'devoid of‘ materials 'boilingL within the
means, not illustrated in` the drawing, kto the range ofthe distillate recoveredffrom receiver
24 `and. are ypreferably of higher. boiling charac-v
upper‘portion of fractionator I8 to serve 'asare
teristics ‘than’ the"secondary charging stock or
sisting fractionation -ofthe’vaporsfand to main-v _contain ra, substantial quantity of materialsmboil
tain the desired vaporjoutlet temperature there ing above the range `of the 'secondary .chargingv
fluxing and cooling \ edium in'k this zone for >as->
from.
c
I
o
,.
.
v
,
10
stock. Y The components of the mixture of `pre-'`
.
Simultaneous with the operation above 'de-_' y.viously cracked and virgin _oils thus suilbliedto
' scribed, secondary- charging stock of the errar;v »
nearing coil' «i` are, therefore,I “suitable for treatf
15
acter previously mentioned' is supplied through' L. ment under the samelcracking cQnditions to proj
duce
high
yields
of
gasoline
of
good
antiknock
line 4I' and valve`42 to pump 43 by means of which"
_'
.
A
_’
it isfed through'line 44, Vvalve 45 and line 33> value.
The higháboiling fractions ofthe reflux con
to` heating coil 40.
‘
n
‘
'o ¿
The oil passing through heating coil 40 is main# densate supplied to heating coil '6 preferablyl are 20
tained at the desired cracking temperature and substantially devoid of` any components Aboiling
preferablyV at a substantial vsuperatm«.)spheric below the range of the primary charging stock
pressure lfor a predetermined time,v the tempera» supplied> to heatingV coil B or within the range`
ture, pressure and time Yconditions employed in
this zone being regulated to materially` improve
of the low-boiling reiiuxwcondensate> fractions
supplied to heating coil 40 and contain yany`coin-.
ponents ofthe reflux Icondensate', of higherboiling
characteristics than'the' primary charging stock.^
It‘will, of course, bey understood that Withthe
vert the higher boiling oils supplied to -this. 4zone "
into substantial yields of'good quality gasoline._ ` fractionating methods and apparatus necessitated
Heated‘products arey discharged from heating by economic considerations therer will ordinarily
the antiknock value of the poor quality gasoline or
gasoline fractions supplied thereto and tocon
be some overlapping of the various fractions sep-h
coil 4U through line
i
41 and may be directed, all '
or in part, into coking‘chamber I3, -entering either " arated ‘in fractionator I8 but preferably, in the
the upper portion of this zone through valve 48 present processthe components of the low~boi1ing
fractions of the 'reflux condensate, which boil'r
inline 41 or entering the lowerportion of thiskr within
the range of the gasoline product collecting
vzone through linef49 and valve `SII or being dif
rected, in part, into both the upper and lower in receiver 24, do `noty exceed approximately 5 to 6'
percent andthe "components 'of the high-boiling.. portions of the coking chamber.
‘
`
of they reflux‘condensate which boil'
All>` or a regulated’portio'n of the highly heated y»fractions
products from heating coil 48 may, when desired, within _the _range of the lower boiling fractions .
be directed' from 'line 4‘I` through line 5I and supplied to heating coil V4I) are also kept' ata mini- o.
mum consistent wi„hr o economic fractionating
valve 52', preferably into the upper portion of re»
,action `chamber I0 and in the preferred method of methods` and means. A
The preferred operatingconditions which ’mayA
operation a regulated portion of the heated prod
‘ucts from coil 40 ' is thus supplied `_to ‘reaction be employed to produce the desired results in an
apparatus such as illustratedand above described
chamber'lû, `while the remaining portion is in
troducedinto the coking,chamber."=`
A `The reflux
.
are approximately asf follows: The 4temperature y
‘
employed at the outlet from- the nrst mentioned
condensate formed in fractionator . heating
coil is preferablyA of `the Order of À800 Yto f
`I8 is` preferably separated, as here> illustrated, .
50 into selected relatively low-j-boiling fractions best
. suited for further cracking' in heating coil 48
and the’higher boiling fractions which may be
cracked to better advantage in heating coil 6.
'I'he 4high-boiling fractions of the reflux con
densateare directed fromi the lower portion of
fractionator I8 through line 29 and valve 30 to
pump 3 I, by means of which they are fed through
line 32 and valve 33 into l‘ine 4 and thence to
heating coil 6.
The relatively low-boiling fractions of the `re
flux condensate,which preferably constitute a
major portion of the total reflux formed in the
fractionating step, are withdrawn from one or a
plurality of suitable’intermediate points in the
i5 fractionator and directed through line 34 and
valve 35 to pump'36 wherefrom they are fed
950° F. and the pressure employed at this I point in .
the'system may range: for example, fromMlOO to
500 pounds, or
o
thereabouts, per sq. in.l , Thetcmn ‘.50
perature employed at the outlet from the second «
mentioned heating coil may range, for example,
from 950 to 1050° F., preferably with a superat
mospheric pressure at this point in the system of
from 200 to 1000 pounds, or thereabouts, per-sq.
in. and, as previously mentioned, the temperature
and cracking conditions employed in the second
mentioned heating coil `are more severe than those
utilizedin the ñrst mentioned heating coil. The
pressure employed in the reaction chamber pref 60
erably is substantially the same as thatemployed'>
in the'vcommunicating heating coil utilizing the
lowest pressure, which is usually the first men-I
tioned heating coil, and the average temperature
through line 31 and valve 38 into line _38 and
thence to heating coil 40, together with the sec
in the reaction chamber preferably is substan-v , -
ondary charging stock. `
ployed at the outlet from the firstmentioned heat»
It will be noted, in connection with the draw
«ing and the above description thereof, that the
`reflux condensate formed in fractionator I8 con
tains no oil which has not been previously sub
jected tocracking. Such oils, and particularly
5 those resulting from the cracking of virgin charg
tially thesame or somewhat higher than that em- j
ing coil. The coking chamber is preferably oper
ated at a substantially reduced pressure relative
to that employed in the reaction chamber and 70,
may range, for example, from 150 pounds, or
thereabouts, per sq..in. down to substantially at,- t
mospheric pressure. The fracti0nating„condensing and collecting portions of the System prefer
2,132,689
4
ably employ superatmospheric pressures substan
tially the same or somewhat lower than that em
chamber and introducing the same into a reduced
pressure vaporizing zone wherein .vapors are sep
ployed in the cokingrzone.
arated fromresidue, subjecting vaporous prod
`
i
"As a specific example of the operation of the
Ul process of the invention as it may be lconducted in
an apparatus such as illustrated and above de
il)
chamber, withdrawing said products from the
ucts from the vaporizingzone to fractionation,
whereby their components boiling above the range
of the desired gasoline product of the process are
scribed, the primary charging stock comprises a condensed as reflux condensate, subjecting vapors
mid-continent gas oil of about 36° A. P. I. gravity, remaining unconden‘sed by said fractionation to
havingan end-boiling point of approximately r120" -cooling and condensation, recovering as the re
F. and this material is subjected, together with
the components of the reflux condensate boiling
taneously subjecting a secondary virgin charging
, above appœximately 600° F., to a cracking tem
oil, of lower boiling characteristics than the first
mentioned charging oil and containing atleast a
substantial quantity of vcomponents of poor anti
perature of ‘approximately’ 930° F. at a superat
mospheric pressure of ‘approximately 400 pounds
per sq. in., as measured atthe outlet from the
knock value boiling within the range of gasoline,
to a higher cracking temperature than the first
mentioned charging oil and to substantial super
heating coil to which these materials are supplied.
The
secondary
charging
stock
comprises . a
straight-run gasoline from paraiîinic crude and is
at'mospherìc pressure in a separate heating coil,
whereby to materially improve the antiknock 20
value of its gasoline components, commingling
highly heated products discharged from said sep-v
arate heating coil with the heated products from
the first mentioned heating coil and `causing the
commingled materials to pass through substan-v 25
tially the entire length of the reaction chamber,
subjectedin a separate heating coil, together with
20 the fractions of the reflux condensate boiling be,
tween approximately 400 to 620° F., to an outlet
conversion temperature of approximately 1000°
F.` at a superatmospheric pressure, measured at
the outlet from the heating coil, of approximately
650 pounds per sq. in. _Approximately 60 per
cent of the total products from the last mentioned
heating coil are supplied to the reaction chamber
and the remaining 40 percent, or thereabouts, are
introduced into the coking chamber, which latter
30 zone is operated at a superatmospheric pressure
of approximately 50 pounds per sq. in. Substan->
tially the same pressure is employed in the frac
whereby to increase the temperature and rate of
cracking of the total products from the first men
tioned heating coil in therreaction chamber,- sup
plying to said separate heating coil components of v30
said reflux condensate which are of higher boiling -
characteristics than Asaid secondary charging oil
and are substantially devoid of components boil
ing within the range of said gasoline product,
whereby to subject the same to further cracking
tionating, »condensing and collecting portionsof
the system. This operation will yield, per barrel
of total charging stock, approximately 75 percent
of 400° F. end-point gasoline‘having an antiknock
with said secondary charging oil.
2. A process such as defined in claim' 1 wherein
valueïof approximately 70, by the motor method,
and approximately 17 pounds of low volatile coke,
the remainder being chargeable, principally, to
40
uncondensable
gas.
p
I claim as my invention:
'
'
1
a portion of said reflux condensate is returned to
the ñrst mentioned heating coil for further crack
.
ing.
3. A process such as ydefined in claim 1 wherein
,
. l
10
sulting distillate a good quality gasoline, simul
,
1. A process for the pyrolytic conversion of hy
drocarbonvoils which comprises heating a virgin
charging oil heavier than ‘gasoline to cracking
temperature at substantial superatmospheric
pressure in a heating coil, introducing the result
ant heated products into an enlarged reaction
chamber also maintained at substantial 'superat
mospheric pressure, causing both vaporous and
liquid components of saidheated products to pass
50 through substantially the entire length of _said
a regulated portion of said highly heated products
discharged from said separate heating coil is in
troduced into the vaporizing zone.
f
l
4. A process such as defined in claim 1 wherein 45
a portion of said reflux condensate is-returned to
the first mentioned heating coil for further crack
ing and wherein a regulated portion of said highly
heated products discharged from said separate
heating coil is introduced into the vaporizing zone.
.JACQUE C. MQRRELL.
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