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Патент USA US2408582

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Oct. 1, 1946.
v
D, READ, JR
HYDROCARBON CONVERSION PROCESS
2,408,580
v
Original Filed April 29, 1940
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2,408,580
Patented Oct. 1, 1946
UNiTED STATES PATENT OFFICE
2,408,580
HYDROOARBON CONVERSION PROCESS
VDavis Read, Jr., Riverside, Ill., assignor to Uni
' versal Oil Products Company, Chicago, Ill., a.
corporation of Delaware
Original application April 29„,1940g-Serial' No.
332,136. Divided and this application Septem-ber 27, 1943, Serial No. 503,903 _
'
1
This application is. a division of Serial No.
332,136 filed April 29, 1940, which hasv matured
into Patent No. 2,336,126, dated December 7, 1943.
This invention relates to a process for convert'
ing relatively wide boiling range hydrocarbon oils
into high yields of high antiknockk gasoline and _
more specifically it is concerned with an improve
Y
, ,
2.
Vaporous products, commingling said vaporous
products with said pyrolytic vaporous conversion
products and fractionating the mixture together
with the charging oil to separate. fractionated
vapors boiling in the range of gasoline from the
higher boiling conversion products and charging '
oil, recovering said fractionated vapors, with-r
drawing,V said higher boiling conversion products
ment in the art of' cracking hydrocarbon Oil
and charging oil as light and heavy refluX con
wherein a relatively heavy hydrocarbon Oil is
non-catalytically cracked and relatively light hy 10 densates, supplying said heavy reflux condensate
to the pyrolytic conversion treatment as said rela
drocarbon oil catalytically cracked in the pres
tively heavy oil andv supplying atleast a portion
ence of a catalyst suspended therein. The im
of said light reflux condensate to the catalytic
provement principally involves quenching the
conversion step as said relatively light hydrocar
stream of hydrocarbon oils containing the sus'
„
pended catalyst as it leaves the reaction zone to 15 bon oil.
The accompanying diagrammatic drawing il
arrest the cracking reaction, whereby to reduce
vlustrates in conventional side elevation one spe
to a minimum the formation ofV carbonaceous and
ciñe form of the apparatus which may be em
'
'
ployed to accomplish the Objects of the inven
IA have found that in the catalytic cracking of
hydrocarbon oil in the presence of a catalyst sus 20 tion.
kReferring how to the drawing, heavy reflux
pended therein, the reaction is usually accom
condensate
formed in the manner to be described
plished at high temperatures and if the catalyst
later is supplied to heating coil l. The heavy
. isv allowed to remain in contact with the oil after
reflux condensate in passing through heating coil
the desired reaction is accomplished, vunusually
l is raised to the desired conversion. temperature
25
high amounts of' carbonaceous materials are
which may range, for example, from 850 to 1000°
formed which are deposited with the catalyst in
F., or more, by means of heat supplied from fur
the separating zone.
nace 2. The heavy reflux condensate leaving
In view of the above, my invention provides for
heating
coilv l at an outlet pressure ranging, for
quenching the stream of hydrocarbon oil con
taining the suspended catalyst as it leaves the re 30 example, from 100 to 500 pounds or more vper
square inchv is directed throughline 3 and valve
action zone to reduce the temperature thereofl to
4 into reaction chamber 5. Reaction chamber 5
a temperature below- that at which cracking is
is preferably maintained atv substantially the'
effected, after whichthe mixture` is supplied to a
same pressure. or at a slightly lower pressure than
vaporizing and, separating chamber wherein va
`that employed onthe outlet of' heating coil l and
porous conversion. products are substantially
residual material.
separated from the heavier hydrocarbons and
catalyst.
`
' In one specific embodiment, the invention com
is preferably insulated to reduce radiation losses
therefrom, althoughno insulation is shown in the
drawing.
,
_
l
_
A
,
The. heated reflux condensate in passing
oil to Pyrolytic cracking in a heating coil and 40 through reaction chamber 5 is subjected to `pro
longed pyrolytic conversion at the elevated tem
communicating reaction chamber, separating
peraturev and the resultingv conversion products
non-vaporous liquid residue from> the pyrolytical
are discharged therefrom through line 6 and
ly formed vaporous conversion products, simul
1 into Vaporizing and separating chamber 8.
taneously therewith commingling a slurryv of 45 valve
Vaporizing and separating chamber. 8 is pref
cracking catalyst with a relatively light hydrocar
erably maintained at a reduced pressure relative
bon oil and passing the mixture through a reac»
to that employed in reaction chamber 5 ranging,
tion zone _wherein it isheated to a catalyticA crack.-for example, from substantially atmosphericv to
ing temperature, 'quenching the heated stream
400
pounds> or more per square inch in order to
of hydrocarbon oil and catalyst leavingv the. regg..>
prises' subjecting a relatively heavy hydrocarbon
tion zoney to. arrest the cracking reaction,y sup
plying the quenched stream of. oil and. catalyst to
50 obtain a separation between the vaporous and
liquid. conversionproducts and to effect substan
tial further vaporization of the liquid conversion
aV vaporizingV and` separating chamber wherein
products to forma non-vaporous liquid residue.
said catalyst is reduced to a substantially> dry
Non-vaporous liquid residue separated in cham
powder containing a highl proportion of carbo
55
ber 8 is removed therefrom by way of line 9~ and
naceous materials by separating therefrom the
2,408,580
3
4
valve I0 and may be recovered as a product of
the process or subjected t0 any desired further
is introduced through line 35 and valve 36 to
pump 31, which discharges the charging oil
through line 38 and valve 39 into fractionator I3;
The charging oil and vaporous products sup
treatment. Vaporous conversion products, to
gether with vapors evolved within chamber 8, are
directed through line Il and valve I2 into frac
tionator I3 for treatment in the manner to be
described later.
Simultaneously with the pyrolytic conversion»
treatment of the heavy reflux condensate as above
described, light reñux condensate to which pow
dered catalyst is added in the manner to be de
scribed later, is supplied to heating coil I4. The
slurry of catalyst and oil in passing through heat
plied to fractionator I3_are fractionated therein
to separate-fractionated vapors boiling substan
tially in the range of gasoline from the higher
boiling conversion products and heavier portions
4of the charging oil, the latter being withdrawn
>as light and heavy reflux condensates. Fraction
ated vapors separated in fractionator I3 are di
rected through line 48 and valve 4I to cooling
and condensation in condenser 42. Distillate, to
ing coil I4 is raised to the desired conversion tem
gether with undissolved and uncondensed gases
perature ranging, for example, from 500 to 1200°
from condenser 42, Lis directed through line 43
F., heat being supplied by means of furnace I 5.v » Vand _valve 44.into receiver 45 wherein the distil
Preferably also, heat is supplied to the slurry of
late and gases are collected and separated. Nor
catalyst and oil in heating coil I4 at a rapid rate
mally gaseous products collected and separated
so as to minimize the amount of pyrolytic crack
in receiver 45 are removed therefrom by way of
ing effected and increase the amountl of catalytic 20 line 45 and valve 4l and recovered as a product
cracking.
When desired, a reaction zone other
than a heating coil may be employed, however,
in view of the fact that control of the heating
is more readily obtained in a heating coil than
in other types of reaction vessels the method il
lustrated is the- preferred method.
of the process or subjected to any desired fur
ther treatment. A portion of the distillatecol
lected and separated in receiver 45 maybe re
turned to the upper portion of fractionator I3 to
serve as a reiluxing and cooling medium‘while
the residual portion thereof maybe removed from
The heated mixture of oil and catalyst leav
receiver 45 by way of line 48 and valve 49 and
ing heating coil I4 at a pressure ranging, for
recovered as a product of the process.
example, from substantially atmospheric to 1000
Heavy reflux condensate condensed and sepa
pounds or more per square inch is directed 30 rated within fractionator I3 is removed there
through line I6 and valve Il and, in accordance
from by way of line 50 and is directed through
with the objects of the invention, is commingled
valve 5I to pump 52, which discharges through
with a cooler stream of hydrocarbon oil intro
line 53 and valve 54 into heating coil I, the heavy
duced in the manner to be described later in order
reflux condensate being subjected to treatment
to quench the stream of hot oil to a tempera
as previously described.
.
ture ranging, for example, from 400 to 800° F.,
Light reflux condensate separated in fraction
and the resulting mixture ofconversion products,
ator I3 is directed through line 55 and valve 5S
cooling oil, and catalyst is supplied to vaporizing
to pump 57. Pump 51 discharges through line
and separating chamber I8. Chamber I8 is pref
58 and a portion is directed through line 59 and
erably operated at a reduced pressure relative 40 valve .62 into line I5 to serve as a quenching oil
to that employed on the outlet of heating coil
as previously described. Still anothcr'portion
I4 ranging, for'example, from substantially at
thereof may be removed from the system by wayv
mospheric to 400 pounds or more per square inch
of line 63 and valve 54 for use in preparing the
whereby to separate vaporous conversion prod
catalyst slurry in the manner to be described
ucts and catalyst.
45 later. The residual portion of the light reflux
Chamber I8 is operated as a catalyst separat
condensate in line 58 is directedthrough valve
ing chamber wherein the catalyst is reduced to
65 and is commingled with a slurry of cracking
a substantially dry powder containing a high
catalyst preparedin the same manner to be de
proportion of carbonaceous materials formed by
scribed later and the mixture supplied to heating
reducing the liquid residue to a substantially dry 50 coil I4 for treatment as previously described.4
coke. It would be desirable to employ more than
The catalyst slurry comprising, for example,A
one chamber in order that one or more of the
a mixture of powdered cracking catalyst and light
chambers may be cleaned while another or others
reflux condensate or any relatively light hydro
are employed inthe conversion treatment. In
this type of operation, the catalyst is removed as
a substantially dry powder containing a high
proportion of carbonaceous material and may be
supplied to a catalyst regenerating system not
shown in the drawing to prepare the catalyst
for reuse.
The vaporous conversion products separated in
chamber I8 are removed therefrom by way of line
33 and directed through valve 34 into .line I I,
commingling therein with the vapors removed
carbon oil of characteristics similar to those of
the light reflux condensate is supplied tol the
system by way of line 66 and is directed through
valve 61 to pump 68 which discharges through
line 69 and Valve 'I0 into line 58, commingling
therein with the light reflux condensate as previ
ously described.
,
Catalysts which have been found .to be effec
tive in the catalytic cracking of hydrocarbon oils
may comprise, for example, powder or granules
from chamber 8, which mixture is supplied to 65 of silica or other siliceous andrefractory ma
terials composited with compounds selected from
fractionator I3. Fractionator I3 and the con
the group consisting of alumina, zirconia, va
densing and receiving equipment in communica
nadia„and thoria. In addition, the hydrosili
tion therewith are preferably operated at a su
cates of alumina, acid treated clays, or the like,
peratmospheric pressure of the same order as
that employed in chambers, 8 Yand I8. Simul 70 have also> been found to be effective in the crack
ing treatment of hydrocarbon vapors. .
’ '
taneously with the introduction of the vaporous
Although the catalysts above recited are gen-products to fractionator I3, charging oil which
erally considered to be the preferred catalysts,
may comprise, for example, a relatively wide boil
their use is not to be construed as a limiting
ing range hydrocarbon oil such as crude oilv or
reduced crude oil or any desired fraction thereof, 75 feature, for various other catalysts wellknown to
2,408,580
5
those in the art may be employed within the
broad scope of the invention.
I claim as my invention:
t
1. A process for the production oi motor fuel
which comprises subjecting a relatively heavy hy
drocarbon oil to pyrolytic cracking in a heat
ing coil and communicating reaction chamber,
separatingr non-vaporous liquid residue from the
pyrolytically formed vaporous conversion prod
ucts, simultaneously therewith kcorrm'iingling a
slurry of cracking catalyst with a` relatively light
hydrocarbon oil and passing the mixture through
a reaction zone wherein it is heated to a catalytic
heated to a conversion temperature, quenching
the stream of hot oil and catalyst leaving said
reaction zone to arrest the cracking reaction by
commingling therewith a colder stream of hydro
carbon oil, supplying the resulting mixture of
cooling oil, catalyst, and catalytic conversion
products to a vaporizing and separating chamber
wherein said catalyst is reduced to a substantially
dry powder containing a, high proportion of car
bonaceous materials by substantially completely
distilling therefrom vaporous products substan
tially free of entrained catalyst, commingling
said vaporous products with said pyrolytic va
porous conversion products and fractionating the
cracking temperature, commingling a relatively
mixture together with the charging oil to separate
15
cool oil with the heated stream of hydrocarbon
fractionated vapors boiling in the range of gaso
oil and catalyst leaving the reaction Zone to ar
line from the higher boiling conversion products
rest the cracking reaction, supplying the quenched ,
and charging oil, recovering said fractionated
stream of oil and catalyst to a vaporizing and
vapors, withdrawing said higher boiling conver
separating chamber wherein said catalyst is re
sion products and charging oil as light vand heavy
duced to a substantially dry powder containing 20 reflux condensates, supplying said heavy reflux
a high proportion of carbonaceous materials by
condensate to the pyrolytic conversion treatment
substantially completely vaporizing the hydrccare
as said relatively heavy oil, supplying a portion
bon introduced to said chamber and separating
of said light reilux condensate to the catalytic
therefrom vaporous products substantially free of
conversion step as'said relatively light hydrocar
entrained catalyst, commingling the last-named 25 bon oil, and supplying another portion of the
vaporous products with said pyrolytic vaporous
light reiiux condensate to the aforesaid quenching
conversion products and fractionating the mix
step as said colder stream of oil.
ture together with the charging oil to separate
3. A hydrocarbon oil conversion process which
fractionated vapors boiling in the range of gaso
30 comprises fractionating the charging oil in con
line from the higher boiling conversion products
tact with cracked vapors to form a relatively
and charging oil, recovering said fractionated va
heavy fraction and a lighter fraction, thermally
pors, withdrawing said higher boiling conversion
cracking theheavy fraction and separating re»
products and charging oil as light and yheavy re
sultant cracked vapors from residual products,
ñux condensates, supplying said heavy reflux con 35 commingling a cracking catalyst with a portion of
densate to the pyrolytic conversion -treatment as
said lighter fraction and subjecting the resultant
said relatively heavy oil and supplying a portion
mixture to catalytic cracking conditions while
of said light reflux condensate to the »catalytic
passing through a conversion Zone, quenching
conversion step as said relatively light hydrocar
the effluent of said conversion zone by commin
bon oil, and utilizing another portion of said light 40 gling therewith another portion of said lighter
fraction, separating the commingled materials
reflux condensate as said relatively cool oil.
2. A process for the production of motor fuel,
into vapors and catalyst-containing residue, sup
which comprises subjecting a relatively heavy oil
plying thus separated vaporous products of the
to pyrolytic cracking, separating the resulting
catalytic cracking and vaporous products of the
conversion products into pyrolytic vaporous con 45 thermal cracking to the aforesaid fractionating
version products and non-vaporous liquid residue,
step for fractionation therein together with the
simultaneously therewith commingling a rela
charging oil, and iinally condensing the fraction
tively light hydrocarbon oil with powdered crack
ated vapors.
ing catalyst to form a slurry, supplying the re
DAVIS READ, JR.
sulting slurry to a reaction zone wherein it is 50
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