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Патент USA US2403486

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July 9, 1946.
J. M. BARRON
2,403,486
COMBINATION CATALYTIC AND THERMAL CONÑ‘ÍERSIONA
Filed Dec. 19, 1944
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2,403,486
Patented July 9, 1946
UNITED STATES PATENT OFFICE
2,403,486>
COMBINATION CATALYTIC AND THERMALv
CONVERSION
`loseph Mason Barron, Port Arthur, Tex., assignor
to The Texas Company,¿NeW York, N. Y., a cor
poration of Delaware
Application December 19, 1944, Serial No. 568,886
6 Claims. (Cl. 196-f49l
l
This invention relates to the combination cata
lytic and thermal conversion of hydrocarbons and
contemplates particularly a method of processing
high boiling or residual petroleum stocks to ulti
mate yields of coke and high antiknock gasoline`
or motor fuel.
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such as crude oil or topped crude containing a
large content of gas oil is introduced by a pump
I0 to heating coil II whereinrit is heated to a
cracking temperature. The heated eiliuent is di
rected through a transfer line I2 to the upper
portion of a reaction chamber I3. Highly heated
vapors and gases enter the lower portion of the
reaction'chamber through a line I4. The reac-ï
In accordance with the invention, petroleum
stocks such as crude oils and topped crudes are
contacted with highly heated light stocks of the
tion Vchamber is maintained at a high cracking
tained under superatmospheric pressure and at
a cracking temperature. The contacting of these
a superatmospheric pressure such as v20G-60d
p. s. i. The downilowing liquid is subjectedto
nature of gasoline or naphtha as well as normally 10 temperature of theorder of 900° F. by reason of
the heated entering ñuids and maintained under
gaseous hydrocarbons in a reaction zone main
countercurrent contacting with the- upwardly>
obtain thermal conversion of the intermingled 15 rising vapors at the high temperature, in a zone
free from bañles or other obstructions, to not only
constituents and also to obtain maximum vapori
produce cracking but also to cause `maXimum
zation so that the separated vapors will contain
vaporization. Liquid is prevented from accumu
not only the gasoline components but'also the
lating by rapid withdrawal from the chamber
bulk of the gas oil constituents. The thermal
cracking to which the constituents are subjected 20 through a line I5 and it is, in fact, best to'oper
ate the reaction chamber “dry," that is, without
in the reaction chamber functions particularly to
any liquid level therein.
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crack paraiiìns and concentrate naphthenes and
The separated vapors pass from the separating
aromatics to produce good material for a succeed
and cracking chamber I3 through a vapor line I6
ing catalytic cracking step. Products vaporizedk
in this combination cracking and separating step 25 to a catalytic cracking zone I1 wherein the vapors
dissimilar stocks is conducted in s_uch a way as to
constitute the charging materialfor a succeeding
catalytic cracking step. The residual product from
the thermal cracking and separating step is sub
jected to coking and vapors evolved in the coking ,
are subjected to catalytic conversion in contact
with a solid comminuted or pulverulent catalyst.V
The contacting of the vapors and gases with the
catalyst may beaccomplished in various ways„`
30 such as passing the vapors through a stationary
bed of catalyst, passing the vapors over a con
ing fractions from higher boiling fractions. . The
operation are fractionated to separate lower boil
lower boilingvfractions, after being subjected to
tinuously moving mass of granular catalyst, or
thermal conversion or reforming, are directed to
the thermal cracking and separating Zone for.
in the stream of gases and vapors for conversion
promoting the vaporizing and cracking of the re
sidual charging stock. Higher` boiling fractions
from the coking operation are passed through a
heating zone and subjected to thermal cracking.
Higher boiling fractions obtained in fractionating l
the catalytically cracked products are likewise
passed through a heating zone and subjected to
thermal cracking. The thermally cracked prod
ucts from these two heating zones are combined
and the mixture is subjected to catalytic crack
ing, Normally gaseous hydrocarbonsrecovered
from the combination process arersubjectedl to
thermal conversion and then directed to Vthe
by suspending finely divided or powdered catalyst;v
under iluid catalyst conditions. The preferred
catalysts are the silica-alumina catalysts, such as`
in the form of activated clays or as synthetic pre
cipitated composites vof silica and alumina.
When using the catalyst in the form of iixed beds
a plurality of catalyst cases are employed which
may alternate on processing and regenerating in
a well-known manner, and when using catalyst
suspended in the vapor stream or under ñuid
catalyst cracking conditions, the catalyst may be f
continuously withdrawn for regeneration. Thev
vapors and ïgases are contacted with the catalyst
at temperatures such as 800-1000° F, under mod- -
thermal cracking and separating Zone or com
erate superatmospheric pressures, preferably not`
invention, reference is had to the accompanying
drawing which is a flow diagram illustrating Aa
while at the vsame time recombination reactions
with the gaseous hydrocarbons and catalytic re
exceeding about 100 p.V s. i_` to affect the catalytic
bined with the vapori'zed eñluent therefrom, which
passes to the catalytic cracking stepV mentioned. 50. cracking of higher boiling hydrocarbons into
lower boiling products of gasoline boiling range,
For` the purpose of completely disclosing the`
particular embodiment of the invention;
.
Referring now to the drawing, charging stock `ist.
formingof gasoline constituents takes place.
The products ofthe catalytic conversion pass"
2,403,486
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through a transfer line I8 to a fractionator I9.
mary section 20 and a secondary section 2I sepa
rated by a condensate tray 22 and the transfer
line I8 is branched so that the catalytically
cracked products may be delivered to either the
line 45 to a heating coil 46 wherein the oil is
subjected to conditions of thermal cracking. In
the cracking coils 42 and 46 the oil is subjected
to temperatures such as 900-10G0° F. with coil
outlet pressures of from 400-'700 p. s. i. to produce
extensive thermal conversion. The particular
primary or secondary fractionating zones. The
fractionator is provided with suitable cooling and
conditions obtained in the cracking coils 42 and
46v may be varied in accordance with the char
The fractionator is preferably formed with a pri
refluxing means so as to take off as vapors a prod
acter of the stocks directed to these coils, but in
uct of desired end point, as for example, 400° F. 10 general the catalytic gas oil being cracked in coil
end point for ordinary motor fuel or 375° F; end
46 will stand a soaking volume factor of from
point for aviation motor fuel. The overhead va
5-'7 (basis '750 p. s. i.) at about 950° F. heater
outlet temperature, and the gas oil from the cok
ing operation being cracked in coil 42 will stand
pors are condensed in a cooler 23 and the distil
late is collected in a distillatedr'uni or gasïsepa
rato;1 24.
`
Referring now to the disposition of the residue
withdrawn from the reaction chamber I3 through
line I5, this residue is directed through a pres
sure reducing valve 25 to a coking drum 26. By
15 a soaking volume factor of 8-10 with a coil out
let temperature of about 1000° F. In the crack
ing coils 42 and 46 extensive thermal conversion
takes place which involves particularly the crack
ing of oleñns and paraihns, with the result that
reason of the manner of contacting the heavy 20 the effluent from these cracking coils is 4of re
stock with the light stream of gases and vapors
duced parafñnicity and contains high concen
ink the reaction chamber it is possible to main
trations of oleñns, naphthenes and aromatics.
tain the liquid residue being vwithdrawn at a
The thermal cracking not only produces gaso
suflicient temperature and sufliciently free from
line but also yields higher boiling components of
gas oil constituents that this residue may be 25 increased susceptibility to catalytic cracking.
flashed to coke in the coking drum solely by its
The effluent from the thermal cracking coils
contained heat. While any deficiency in heat
42 and 46 is combined in a transfer line 41 which
may be overcome by including a portion of the
vapors with the residue withdrawn from the re
mixture is subjected to catalytic cracking in con
action chamber, it `is preferable to maintain the
’ tact with cracking catalysts, such as any of those
quantity of vapor thus withdrawn at a minimum
and to rely on the temperature of the liquid resi
due to accomplish vautogenous- coking. By with
drawing the residue at temperatures around
S20-930° F. conversion to a marketable coke may
be accomplished by flashing solely by the con
tained heat of the residue. In practice, a plu
rality of c-oking drums are employed so as not to
leads to a catalytic cracking zone 48 wherein the
previously mentioned, in accordance with any of
the several methods which have been outlined forv
the _catalytic cracking Zone I1. The mixed stocks
subjected to catalytic cracking undergo various
reactions including conversion into lower boiling
hydrocarbons accompanied with exchange reac
tions and cyclization functioning to form con
stituents in the gasoline boiling range of high
antiknock quality. And the oleñn content of the
interrupt the continuity of the complete process.
The coking drum is maintained at loW pressure 40S gasoline constituents, formed by the preceding
such as 50 p. s. i. down to approximately atmos
thermal cracking, is reduced.
pheric pressure.
`
The catalytically cracked products are directed
The vapors evolved in the coking‘drum pass
through a line 49 to the fractionator I9 or more
through a vapor line 21 to a fractionator 28 which
i particularly to the fractionating section 26 there
is preferably formed with a primary section 29 ~ of. The effluent from the catalytic cracking zone
and a secondary section 30, separated by a con
48 will generally contain some higher boiling con
densate tray 3l, with the vapor line entering the
stituents of a somewhat more refractory nature
primary' fractionating zone 29. In the latter frac
than those _contained in the eflluent from the cata
tionating vzone the vapors are subjected to a pri
lytic cracking ’zon'e I1 and consequently it is or
50'
mary dephlegmation at relatively high tempera
dinarily desirable to direct the products from the
tures' approximating 800° F. throughout the zone
cracking zone 48 to the primary separating sec
to separate out the synthetic tar. This tarry
tion 20 while delivering the products from crack
product may be withdrawn as a fuel oil product
ing Zone I1 to the secondary fractionating section
through line 32 or directed by a pump 33 to the
2|. A quantity of residue may thus be separated
coke drum 26 for conversion to coke. The gasv 55 in the dephleämator 29 which may be withdrawn
oil condensate is collected on the tray 3l; the
through a line 50. This residue may be removed
naphtha vapors'pa'ss'to a cooling coil 34 for con
from the system as a product of the process or
densation and the naphtha distillate is collected
it vmay be sent to the fractionating Zone 29 for
in a receiving drum or gas separator 35, having
re'fractionation therein.
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a Vgas line 36 which may extend to a low pressure en
The ultimate gasoline product resulting from
gas` recovery system (not shown).
n
the combination of the several thermal and cata
The coke still naphtha is lwithdrawnfrom the
receiver 35 -and directed by pump 31 through
lytic conversion processes described herein is col
lected in the receiving drum 24, This distillate
may be withdrawn from the receiving drum and
line38 to a heating coil 39 wherein it is subjected
to/thermal reforming at temperatures such as 65 directedAv by ,pump 5I through line 52 to a sta
900-1050° F. under pressure such as 400-600 p. s. i.
The vaporous products of conversion Yare directed
bilizer 53. Uhcondensed vconstituents are re
moved from the receiver 24 through a line 54.
through the transfer line I4 to the lower portion
On account of the relatively low pressure exist
of >the reaction chamber I3.
ing in the receiver 24 the gases will contain con
Condensate from tray 3| is directed by a pump 70 siderable quantities of hydrocarbons adapted for
40 through line 4I to a heating coil 42 wherein
inclusion in the gasoline product. To recover
the condensate is subjected to conditions of ther
these constituents the gases flowing in line 54`
mal cracking. The catalytic gas oil collected on
may be diverted to a 'pump or compressor 55 by
the tray 22 of fractionator I9 isl withdrawn
which the gas may be placed under several hun- '
through a line 43 and ydirected by pump' 44 through 75 dred poundsvv pressure and directed through a
espansa
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petroleum and‘containing both residual and gas
0001er 5.6 te. a. drip v,drum- 51; .from lwhich . con
densate (may be withdrawn through _a line 58 and
sent to the ,stabilizer 53. rIfhe latter- is provided
o'il¿_ components thereof, the process " that com
prises introducing said charging> stock to a reac
with suitable` cooling, refiuxing vand reboiling
means *_ (not shown) for rectifying the gasoline
tion chamber, passing naphtha through a heating
zone ‘wherein it is heated to a cracking tempera
distillate, the final stabilized product being with
drawn through _a line 59. Uncondensedconstitu
ents Spass through cooler 50 to a distillatedrum
6|V from which uncondensed gases are removed
ture and. subjected to reforming, introducing the
heatedA naphtha into said reaction chamber’to>
subject the residual stock to> cracking and vapori
zation, passing _separated vapors from the reac
tionchamber to a'catalytic cracking zone where
throughaline62._
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The distillate. collecting in> drum 6| under pres
sures of .ZOO-400 p. s. i. consists largely or essen-_
tially of 'C3 and C4 hydrocarbons.v '_I‘hese nor
Inally gaseous constituents Yare. _directed by a
pump A63 through a line 64, thence through a
in the vapors are subjected to >catalytic crack
ing, fractionating the y resultant catalytically
cracked products in a fractionating zone to sepa
rate higher boiling from lower boiling products,
15
branchline 65 to heating coilA 66 or through a
branch line 6l tol heating coil 68, or a portion of
thezgases may be directed to each of these heat
ing coils. The gases are subjected inthese heat
ing coils to high conversion temperatures of the
20
order of 1000°`F.-1100° F. under 400-800 p. s. i. to
' eifect'the cracking of parañîns as well as the
passing the higher boiling products to a heating
zone wherein they are subjected to cracking tem
perature with su?licient time of reaction to ef
fect extensive thermal cracking including the,
cracking of oleñns and paran-ins, withdrawing re,-~
sidual products from the reaction chamber'and
subjecting them to coking, fractionating the
vapors from the coking operation to obtain Aa
lower boiling fraction comprising gasoline con
polymerization of oleñnic constituents. The ef
fluent> from gas conversion> coil 6B is delivered
stituents and a higher boiling fraction, directing
through a transfer line 69>to the lower portion 25 said lower boiling fraction to the aforesaid heat
of the reaction- chamber I3, `together with’the
in_g'zone- for reforming therein, directing _said
eiliuent from the naphtha reforming coil 39. The
higher boiling fraction to a heating zone where
in it is heated to a cracking temperature and sub
eil‘luent from the gas conversion coil 68 is deliv
jected to extensive thermal cracking including
ered through a transfer line 10 to the vapor -line
IS. The stream from the coil 68 may.- thus serve 30
to increase the temperature of the vapors flow
ing fromV the reaction chamber to the catalytic
cracking Zone lvl and Aalso to vary the space ve
locity or time of contact of the Vhydrocarbons with
the catalyst.
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the cracking of olefìns and paraffins, combining
the resultant heated products of reduced paraf
?inicity from said thermal cracking operations
and subjecting the mixture vto catalytic cracking
and >passingthe resultant catalytically cracked
35 product to said fractionating zone.
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v3v. In the combination thermal and catalytic
Although apreferred embodiment of the> in
vention has been described herein, it will be un
derstood that various changes and modiñcations
may be made therein, while s_ecuring to agreater
or less extent some or all of the benefits of the
cracking of hydrocarbon oils for the unitary proc
essing of a charging stock obtained from crude
petroleum and containing both residual and-gas
oil components thereof, the process that com
invention, without departing from the spirit and
prises passing lower boiling fractions ‘through a
scope thereof.
heating zone wherein they are heated to a crack-_
vIclaim:
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ingte'mperature, directing the resultant heated
products to the lower portion of a vertically vdis
cracking of hydrocarbon oils for the unitary 45 posed reaction chamber maintained under super
atrnospheric pressure and wherein separation of
processing- `of av charging stock obtained from
vapors fromwliquid residue takes place, intro
crude petroleum and containing both residual
dncing saidycharging stock to the upper portion
and gasoilV components thereof, the processr that
of the vertically disposed reaction chamber, sub
comprises introducing said charging stock to a
reaction chamber, passing lower boiling hydro 50 jecting the down-flowing liquid and upwardly
rising vapors to countercurrent contacting with
carbons through a heating zone wherein they are
in the reaction chamber at cracking temperature,
heated to a cracking temperature, directing the
passing separated vapors from the reaction
resultant heated products to said reaction cham
chamber to a catalytic cracking zone wherein
ber to subject the residual stock to cracking and
suchofractions are subjected to catalytic crack-_
vapori-zation therein,_ passing. separated vapors
ing, withdrawing residual products from the re
from the reaction chamber to a catalytic cracking
action chamber and subjecting them to coking,
zone wherein such fractions are subjected to cata
fractionating vapors evolved from the coking
lytic cracking, withdrawing residual products
operation to separate light fractions from higher
from the reaction chamber and subjecting them
to coking, fractionating vapors evolved from the 60 boiling fractions, directing said light fractions
coking operation to separate lighter fractions
to the aforesaid heating zone for conversion, sub
from higher boiling fractions, directing said
jecting said higher boiling fractions to cracking
'1. In the combination thermal and catalytic
lighter fractions to the aforesaid heating zone
temperature with suñîcient time of reaction to ef
for conversion, subjecting said higher boiling
fect extensive thermal conversion including the
fractions to cracking temperature with su?licient 65 cracking of oleñns and parañins, subjecting the
time of reaction to effect extensive thermal con
resultant thermally cracked products of reduced
version including the cracking of oleñns and
parainnicity to catalytic cracking and fraction
paraii‘ins, subjecting the resultant thermally
ating the products produced in the catalytic
cracked products of reduced paraiiînicity to cata
cracking operations to recover the catalytically
lytic cracking and fractionating the products 70 cracked gasoline.
produced in the catalytic cracking operations to
4. In the combination thermal and catalytic
recover the catalytically cracked gasoline.
cracking of hydrocarbon oils for the unitary
2. In the combination thermal and catalytic
processing of a charging stock obtained from
cracking of hydrocarbon oils for the unitary proc
crude petroleum and containing both residual
essing of a charging stock obtained from crude 75 and gas oil components thereof, the process that
2,403,486
7
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compr1ses passing naphtha through a heating
passing the separated vapors to a catalytic crack
Zone wherein it is heated toY a cracking tempera
ing zone wherein the vapors are subjected to
catalytic cracking, fractionating the resultant
ture and subjected to conversion, introducing the
catalytically cracked products in a fractionating
zone to obtain'fractions comprising a normally
heated ynaphtha into the lower portion'of a ver
tica-lly disposed reaction chamber maintained un
der superatmospheric pressure and wherein sep
gaseous fraction, a gasoline fraction and a higher
boiling fraction, heating the normally gaseous
fraction to subject it to thermal conversion and
aration of vapors from liquid residue takes place,
heating -said charging stock to cracking temper
directing the resultant conversion products into
ature and directing the heated oil tothe‘upper
portion Íof the vertically disposed reaction cham 10 the lower portion of said vertically disposed re
actionchamber, heating the higher boiling irac
ber, subjecting the downño‘w liquid and upwardly
tion to a cracking temperature to subject it to
rising vapors to countercurrent contacting with’
thermal cracking, withdrawing residual products
in the reaction chamber at cracking temperature,
from the reaction chamber and subjecting them
passing the separated vapors to a catalytic
cracking zone wherein the vapors are subjected
to coking, fractionating the vapors from the cok
ing operation to obtain a lower boiling fraction
containing gasoline constituents and a higher
boiling fraction, directin‘g said lower boiling frac
to catalytic cracking, fractionating the-resultant
catalyti'cally cracked products in a fractionating
zone to separate higher boiling from lower boil
ing products, subjecting the higher boiling prod
ucts to cracking temperature with suiîicient time
of reaction to'e?fect extensive thermal cracking
including the cracking of ole?ìns and parafñns,
withdrawing residual products from the reaction
chamber and subjecting them to coking, irac
tion to the aforesaid heating zone for reforming
therein, directing said higher boiling fraction to
a heatingA zone wherein it is heated to a crack
ing temperature and subjected to thermal
cracking, combining the resultant heated prod
ucts from said thermal cracking operations and
subjecting the mixture to catalytic cracking and
passing the resultant catalytically cracked prod
tionating the vapors from the coking operation
to obtain a lower boiling fraction containing gas
oline-,constituents and a higher boiling fraction,
directing said lower boiling fraction to the afore»
said heating zone for reforming therein, direct
ucts to said iractionating zone.
6. In the combination thermal and catalytic
cracking of hydrocarbon oils the process that
comprises introducing a heated' residual 'stock to
a reaction chamber, passing lower boiling hydro
ing said higher boiling fraction to a heating zone -
wherein it is heated to a cracking temperature
and subjected to cracking temperature with suf
ñcient time of reaction to effect extensive ther
mal conversion including the cracking of ole
carbons through a heating zone whereinl they are
heated to a cracking temperature, directing the
resultant heated products to said reaction cham
ñns andparaiiins, combining the resultant heat 35 ber to subject the residual stock to cracking and
vaporization therein, passing lighter fractions
ed products of reduced parafñnicity from said
evolved from the reaction chamber to a catalytic
thermal cracking operations and subjecting the
cracking 'zone wherein such fractions are sub
mixture to catalytic cracking and passing the
jected to catalytic cracking, withdrawing resid
resultant catalytically cracked products to saidr
fractionating zone.
40 ual products from the reaction chamber and
subjecting them to coking, fractionating vapors
evolved from the coking operationV to separate
lighter fractions from higher boiling fractions,
5.7Inv the combination thermal and catalytic
cracking of hydrocarbon oils the process that
comprises passing naphtha through a heating
directing said light ‘fractions -to the aforesaid
zone wherein it is heated to a cracking tempera
ture and lsubjected to conversion, introducing the
l heating zone for conversion, subjectingfsaid high
heatedA naphtha into the lower portion of a ver
tically disposed reaction chamber maintained'un
der superatmospheric pressure and wherein sep
aration> of vapors from- liquid residue takes place,
heating a residual stock to cracking tempera 50
er boiling fractions to thermal cracking, subject
ing the resultant thermally’cracked products to
catalytic cracking and fractionating the products
produced in the catalytic cracking operations to
recover the catalytically cracked gasoline and a
ture and directing the heated cily to the upper
normally- gaseous fraction, heating the normally
portion of the vertically disposed reaction cham
ber, subjecting the downiiow liquid and upwardly
rising vapors to countercurrent contacting with
in the> reaction chamber at cracking temperature,
gaseous fraction to-subj'e'ct it to thermal conver
sion and directing the resultant conversion prod
uct’s to saidreaction chamber.
JOSEPH IMASON BARRO'N.
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