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Jan. 13, 1942.
2,270,027
l _1_ G_ 'ALTHER
HYbROCARBoN CONVERSION PROCESS
‘Filed Nov. 29, 1939
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>2,270,027
Patented Jan. 13, 1942
" UNITED vSTATES PATENT ori-“ICEv
HYDROCARBON CONVERSION PROCESS
Joseph G. sluier, chicago, n1., assignor to Uni
versal Oil Products Company, Chicago, Ill., a
corporation of Delaware
Application November 29, 1939, Serial No. 306,652
'z claims.
taking place,_the heated hydrocarbons being ing
This application is a continuation-impart of
contact with the exterior of the endothermic re
action zone, in the first pass,vfor the purpose of
supplying heat and, inthe second pass, being in
The present invention relates to an improved
method and means for converting hydrocarbon 5 contact with' the catalytic material for the pur
'pose of effecting conversion. '
i
oilsinto more valuable hydrocarbons. More spe
In one specidc embodiment the invention com
cifically, it i's concerned with a catalytic cracking
lmy co-pending application, Serial Number 301,
554, tiled October 27, 1939. »
'
'
prises passing reflux condensate, formedas here'
process wherein Ithe reactants are employed as
inafter set forth, in contact with- .the exterior
the heat lconvective medium in conducting heat'
from the exothermic catalyst reactivating zone l0 of an exothermic reaction zone to absorb a sub
stantial portion of the heat produced while the
catalyst contained therein ,is undergoing regen
and supplying heat to the endoth'ermic- catalytic
reaction zone.v
eration, subsequently, supplying additional heat
The general procedure in the majority of cata
lytic treatments is to employ an extraneous ma
terial, such' as combustion gases or some other
vto said redux condensate in an external heating
' zone, passing the‘resulting highly heated redux
suitable duid medium, to supply heat to and con
duct heat from the endothermic and exother
mic reaction zones, respectively. The coefiicient
of heat transfer for combustion gases, which is
the more commonly used heat convective me 20
dium, is relatively low as compared to other duid .
media, such as molten salts, ,_which‘ have been
employed. Combustion gases, therefore, are the
leastdesirable as the h‘eat convective medium
from the standpoint of heat transfer, however.,
due to the fact that the corrosion problem when
employing combustion gases rather than molten
salts is less serious. they are more widely used
than other heat convective media. ’
condensate in contact with the exterior'` of an
endothermic reaction zone to supply the neces
sary heatv of conversion to the hydrocarbons in
contact with lthe catalytic material within said
endothermic zone, after which said reflux con
densate is subjected to contact with said cata
lytic material lfor conversion into more .valuable
hydrocarbons, separating the vaporous conver
sion products from the non-vaporous liquid resi
due, recovering the latter, fractionating said _va
porous conversion products, together with charg-4
ing oil, to separate fractionated vapors from the
higher boiling hydrocarbons, recovering the
former and condensing said higher boiling hy
In order tov obviate the disadvantages inher 30 drocarbons as said redux condensate and sub
jecting it to treatment as aforesaid.
'
ent in the systems of the type referred to above.
- The improved method herein provided for
and at the same time obtainV results comparable
simultaneously conducting endothermic, and ex
or better than those previously obtained, my in-'
othermic >reactions in separate zones is not lim
vention provides a novel and useful method and
means for utilizing the materials to be convert 35 ited to the use of any specific form or type of
apparatus, since a great number of speciñc forms
of apparatus may be4 devised which will incor
porate the features of the invention. Neither
is the invention limited to any specific variety vof
zone.
To accomplish the object of my invention, I- 40 catalytic, endcthermic reaction, since its advan
tageous featuresare applicable to a wide variety
may employ two reaction zones containing cata
of speciiìc reactions. However, to avoid coniu
lyst, the catalyst in-one zone being contacted with
sionfthe following description will be directed
vapors undergoing conversion, while the cata
primarily to illustrate the features of the in
iyst> in the other zone is undergoing regeneration
bycontacting therewith' oxygen-containing gases 45 vention as applied tothe catalytic cracking of
hydrocarbon oils and tô. further periodic reactiva
which are used in burning from the catalyst car
tion of the catalytic material employed.
bonaceous substances deposited thereon. In or
In the accompanying drawing, Fig. l illustrates
der to effect the desired heating and cooling in
a simple form of apparatus _embodying'th'e broad
the respective reactors; --I prefer to employ the
hydrocarbons tor be converted, drst in cooling 50 features òf the invention vand in which the im
ed as the duid heat convective medium in con
ducting heat from the exothermic reaction zone
and conveying heat to the endothermic reaction
the exothennic reaction zone, subsequently, when »
necessary, supplying additional heat to said hy
drocarbons in an external heating zone after
which they are introduced to th'e reactor in
proved process provided by th'e invention will be
conducted.
\
\
`
Figs. 2 and 3 are details in section of the two- .
way inlet and outlet valves diagrammatically -in
which the endothermic conversion reaction is 55 dicated in Fig. 1, Fig. 2 showing a valve in one ~
2
2,270,027
position and Fig. 3 showing the passageways
therethrough shifted. _
'
Referring now to the drawing in Fig. 1, reac
tors A and B are shown as comprising a cylin
drical shell I containing a plurality of tubes 2
rolled in between upper and lower headers 3
and 4, respectively. A catalyst bed 5 surrounds
the tubes and is supported by a perforated plate
6. Compartment 1 below lower tube sheet 4 and
compartment 8 above uppertube sheet 3 serves
as the inlet and outlet compartments, respec
tively, for the hydrocarbons employed as th'e
tively inert gases, (such as combustion gases. for
example.) containing controlled amounts o! air
or oxygen.
The reactors are alternately oper
ated with respect to the service for which they
are employed (processing and reactivation), by
means of switching valves VI , V2, V3, and V4.
Any suitable valve arrangement capable of
switching the direction of flow of the stream of
reactants and the stream of reactivating gases
may be employedwlthin the scope of the inven
tion, and. for the sake of simplifying the descrip
tion and illustrating the process without unnec
heating or cooling medium. Compartment 3
formed between the upper tube sheet 3 and the
essary complications, each of the switching valves
is here illustrated as a single two-way valve in
top of the catalyst bed serves as the inlet for
the hydrocarbons to be converted or for the
which the position of the' two passageways there
through may be shifted as illustrated in Figs.
fresh regenerating gases, while compartment I0
formed between lower tube sheet 4 and per
2 and 3.
Assuming that valves VI and V3 are each ad
forated plate 6 serves as the outlet for the con
justed to the position illustrated in Fig. 2,A and
version products or for spent regenerating gases.
Conversion products, formed as hereafter de
scribed, are introduced to separating zone I2 of
fractionator and separator II and, when desired,
commingled either in the separating zone or prior
to its introduction to the separating zone with
charging oil for the process and particularly when
valves V2 and V4 are each adjusted to the posi
tion illustrated in Fig. 3, the hydrocarbon oil in
line 29 ñows through valve VI’ into line 3| and
thence to reactor B. The hydrocarbon oil intro
duced to~ reactor B passes countercurrent to the
iiow of regenerating gases, introduced as here
inafter described, and in indirect heat exchange
relationship therewith in order to absorb the
exothermic heat of reactivation. The oil after
treatment. In separating zone I2 the vaporous
picking up heat in reactor B is conducted through
hydrocarbons are separated from the non-vapor 30 line 32 to valve V2 wherethrough it passes into
said charging oil contains heavy hydrocarbons too
heavy to treat in the ordinary catalytic cracking
ous liquid residue and the latter removed by way
of line I3 and valve I4, cooled and recovered as
a product of the process or subjected to any de
sired further treatment. The vaporous hydrocar
bonsseparated in zone I2 are directed through
line 33 by means of which itis conducted to, heat
ing coil 34. The oil acquires additional heat
in passing through heating coil 34 from furnace
35. After being raised to the desired tempera
ture in heating coil 34, the oil is conducted
separating tray I5 into fractionating zone I6 of
through line 36 to valve VI wherethrough it
fractionator and separator ,II wherein vapors
passes into line 3|’ by means of which it is in
boiling substantially in the range of gasoline are
troduced to reactor A. The heated hydrocarbon
separated from the heavier hydrocarbons and the
oil introduced to reactor A by way of line 3l'
latter condensed as reiiux condensate. Fraction 40 passes therethrough countercurrent to the flow
ated vapors are removed from fractionating zone
of hydrocarbons undergoing conversion in con
I6 by way of line I1 and valve Iß„subjected to
tact with the catalu st mass and in indirect heat
cooling and condensation in any suitable form of
exchange relationship therewith supplying the
condensing equipment, not shown, and thereafter
heat of conversion to said hydrocarbons being
recovered as a product oi the process. Charging
oil for the process is introduced through line `
I9 and valve 20 to pump 2 I. Pump 2l discharges
through line 22 and, as previously mentioned,
when the charging oil contains heavy hydrocar
bons, it'may be introduced to separating zone I2
by directing it through valve 23 or, when desired,
it may be commingled with the conversion prod
ucts formed as hereinafter described, by well
known means not shown, for the purposel of
cooling said conversion products prior to their
introduction .to the separating zone. On the
other hand, when the charging oil contains no
- heavy hydrocarbons but only hydrocarbons suit
able as a cracking stock in the catalytic con
converted.
'
'
The oil after losing some of its heat in reactor
A to the hydrocarbons being converted is con
ducted through line 32' to valve V2 wherethrough
it passes into line 31. When desired, the hydro
t carbon oil while it is being used for conducting
heat from one reactor and transferring that and
additional heat to the second reactor may be
maintained in‘substantially the liquid or mixed
phase by means of a pressure control valve 38 in
line 31. However, the use of pressure control
valve 38 is optional and may be used only when
desired. The hydrocarbon oil in line 31 after
passing through valve 38 is preferably in sub
version treatment, it may be directed through 60 stantially the vapor phase. The resulting va
pors in line 31 are conducted through valve V3
line 24 and valve 25 and commingled with reflux
into
line 39 by means of which they are intro
condensate removed as hereinafter described.
duced to the compartment of reactor A con
Reilux condensate formed in zone I6 is directed
taining the catalytic material.
through line 26 and valve 21 into pump 28 which
The preferred cracking catalysts for use in
discharges through line 29 and valve 30 to the
the present process consist in general of a pre
first reactor of the system and thence to subse
cipitated alumina hydrogel and/or zirconia hy
quent treatment, as will be described later.
drogel composited with silica hydrogel, the gel
In the particular case here illustrated,4 two
composite being washed, dried, formed into par
reactors A and B are employed each containing
ticles, and calcined to produce a catalyst mass.
« a bed of catalytic material capable of promoting
The invention, however, it not limited to these
the' desired cracking reaction when in a fresh or
particular catalysts, for other catalysts, such as,
freshly regenerated state. One reactor is at all
times employed as a cracking zone while the
for example, the hydrosilicates of alumina, acid
catalyst in the other reactor is being reactivated
treated clays, and the like, may be used within
by passing therethrough a stream of hot rela
‘ the broad scope of the invention.
3
2,270,027
tinuously generate fresh combustion gases, forexample, or steam for this purpose, by well known
In the following speciilcation and claims the -
terms silica, alumina, silica-zirconia. and silica
means not illustrated.
alumina-zirconia masses are used in the broad
In the following operation, above described,
when the catalyst is reactor A approaches the
state of reduced activity, at which time it is ad‘
vantageous to employ freshly regenerated cata
lyst for the treatment of the vapors, the supply
of air to the regenerating gas stream is momen
tarily discontinued so that reactor B is purged
of oxygen-containing gases, and while the oxy
sense to designate the synthetic composites re
ferred te above. The preferred catalysts may be
prepared by precipitating silica from a solution
as a hydrogel _within or upon which the alumina
and/or zirconia are deposited also by precipita
tion as hydrogels. The silica hydrcgel may con
veniently be prepared by acidifying an aqueous
solution of sodium silicate by the addition of a
required amount of hydrochloric acid. After
precipitating, the silica gel is preferably washed
until substantially free from alkali metal salts.
gen-containing gases are being purged from re
actor B, valve VI is shifted to the position indi
' cated in Fig. 3.
After a short lag corresponding
to the time required-to drive the cooling oil from
reactor B and the heating oil from reactor A,
The washed silica hydrogel is then suspended in '
a solution of alumina and/or zirconium salts and
an alkaline precipitant, such as ammonium hy
droxide, ammonium carbonate or ammonium sul
valves V2 and VI are switched to positions cor
responding to Figs. 2 and 3, respectively. and
after a short lag, corresponding to the time re
ilde added to the _solution to precipitate alumina
- and/or zirconia hydrogels. AThe final precipi 20 nuired to remove the vapors in contact with the
catalyst in reactor A and the purge gases from
tate, comprising essentially hydrated silica and
hydrated alumina and/or zirconia, is washed to » reactor B, valve V4 is shifted to the position ll
substantially completely remove water solublematerials and dried at about 300° F. to produce a
lustrated in Flg."2. `
_
,
A_ftervalve V4 is shifted, air is again admitted
to the regenerating gases in line 42 whereupon
the catalytic material in reactor A is subjected
v rather crumbly and granular material which may
be ground and pelleted or sized to produce par
to reactivation and the catalytic material in re
fticles of catalyst after which the catalyst par
actor B is utilized to promote conversion of the
ticles are calcined at a temperature in the ap
proximate range of 1000 to 1500*’ F. Various ' vapors supplied thereto. When the position of
other procedures', such as, for example, co-pre-l 30 the valves are shifted, as above described, the
cooling oil passes through valve VI into valve 3|'
cipitation of the hydrated gels may be employed,
by means of which itis introduced to reactor A.
when desired, to produce the preferred catalyst.
T_he cooling oil leaving reactor A' is directed
Temperatures on the order of 800 to l200° F.
through valve l2' to valve V2 wherethrough it
and pressures ranging, for example, from“ sub~
passes into line I3. The heated oil from heating
stantially atmospheric to 200 pounds or more
coil 34 passes through valve Vi into line Il by
per square inch superatmospheric may be em
- means of which itis introduced to reactor B.
ployed when using the preferred catalyst.
The oil after losing some of its heat in reactor B
with the catalyst in reactor A undergo conversion - to the materials being converted is directed
through line 32 to valve V2 wherethrough it
and absorb the heat of conversion in the manner
passes into line l1. The vapors in line 31- are
previously described. The hydrocarbon conver
conducted through valve V3 .inte line 30' and
sion products from reactnr A -are conducted
through line 4I to valve VI wherethrough they . thereafter are contacted with the catalytic ma
terial in reactor B. The conversion products
pass into 'line 4I by means of which they are
The hydrocarbon vapors brought in contact '
'introduced to separating zone l2 for treatment
as previously described.
~ _ With the ilow of hydrocarbon vapors .through
- reactor A. reactivating gases containing 'con
trolled amounts yof oxygen or air are supplied to
thesysteminaheatedstatethroughline “to
valve V3 wherethrough they pass hito line ll'
by means of which they are introduced'to the
compartment of reactor B containing the cata
lytic material. 'I‘he carbonaceous material de
posited on the catalyst during the hydrocarbon
conversion cycle is burned> therefrom upon con
tact with the regenerating
the rate of
burning being regulated by the oxygen content
of the regenerating gases'which is controlled to
prevent the development of _excessive tempera
45 from'reactor B are conducted through line 4I'
« and valve V4 into line 4|, the treatment there
after being substantially as described. Fresh re
generating gases in line l2 are conducted through
valve V3 into line 'Il and thence into reactor A
50
and the spent regenerating gases from reactor A
are conducted through line ll and yvalve V4 into
line
Il.
'
’
-
_
-
Switching of the stream of hydrocarbon vapors
l and reactivating gases is periodically repeated by
reversing the position of the switching valves so ’
.as
that the partially spent catalytic material in one
reactor is continuously being reactivated and the
stream of hydrocarbon vapors is continuously
converted in the other reactor. Preceding the
change of functionq in each reactor, they are
purged with `relatively inert gases and, preferably
tures in the catalyst bed. The heat generated in
` as indicated in the foregoing description, there>
the burning reaction is conducted from the cata
is suiilcient delay between the switching of the
lyst bed in the manner previously described. The
spent regenerating gases leaving reactor B are ` various valves 'to prevent loss of valuable con
conducted through line Il" to valve V4 where- 65
' version products from the reactors being purged
thereof and to prevent the commingling of inert
through theypass into line l! and may be'wasted
gases from the reactors which have been purged ,
or, when deslred„at least a portion may be re
circulated by means of afsuitabielullin?`~ or com- 'I with the stream of conversion products. f
'l'he switching valves may be manually oper
pressor, not shown, to line l! and therein com
Aated but, preferably to simplify operation of the
mingled with .controlled amounts of air or o!y-'
process and to avoid mistakes in the operation of>
gen, thelatter'being supplied inany desired
¿mannen In this manner the' inert components ,_ the valves, all of the valves are preferably oper
ated from a single time cycle controller of any
of the regenerating. gasœ may b_e continuously
well _known form in- accordancevvith a definite
recycled'through the sy‘stem, but it is also within
predetermined schedule... However, except with
the scope ofthe inventicn,-when desired, to con
4
2,270,027
respect to the sequence of operation of the vari
ous valves, this is not a novel part of the present
invention. For the sake of avoiding unneces
sary complications, automatic control valves are
not illustrated.
vthe exterior of said exothermic reaction zone to
absorb heat generated therein, subsequently heat
ing said reactants in an external heating zone to
supply additional heat thereto. Passing the re
5. sulting highly heated reactants in contact with
‘
The results from the process embodying thev
features of the invention herein described that
the exterior of said endothermic reaction zone to
would be expected are comparable to those ob
tained from a process employing extraneous ma
dergoing conversion therein, and thereafter sub
jecting said reactants to contact with the bed of
supply heat of . conversion to the- materials un
terials as the iluid heat convective medium. The 10 catalytic material in said endothermic reaction
thermal eñ‘lciency of the process, however, is
zone as the materials to be converted therein.
greatly improved, due to the fact that a number
4. A process for the conversion of hydrocarbon
of heat exchange steps essential in other forms
of equipment are not required in the invention
oil which 'comprises passing reactants, formed
herein disclosed.
terior of an exothermic reaction zone to absorb
I claim as my invention:
.
l
as hereinafter described, in contact with the ex
heat produced in regenerating catalyst con
1. In a catalytic process comprising endo
thermic and exothermic reactions conducted si
multaneously in separate reaction zones, where
tained therein, subsequently subjecting the heat
ed reactants, while at conversion temperature, to
in the reactants are subjected to contact with a
catalytic material in the endothermic reaction
zone in the presence of which reaction occurs
action zone to supply heat of conversion to the
materials subjected to contact with catalyst con
with a resulting decrease in temperature of said
reactants, and wherein the catalytic material in
the exothermic reaction zone is undergoing re
generation, the improvement which comprises
passing said reactants first in contact with the
exterior of said exothermic reaction zone to ab
contact with the exterior of an endothermic re
tained therein, thereafter subjecting said react
ants to contact with the catalytic material in said
endothermic reaction zone as the materials to be
converted, separating the conversion products
from said endothermic reaction zone into vapor
ous conversion lproducts and non-vaporous liquid
residue, recovering the latter, fractionating said
sorb excess heat generated therein, subsequently
vaporous conversion products in the presence of~
subjecting the heated reactants, while at a tem 30 ‘charging oil to separate fractionated vapors boil
perature at least that of said endothermic reac
ing in the range of gasoline from higher boiling
tion, to contact with the exterior of said endo- , hydrocarbons, recovering the former, condensing
thermic reaction zone to supply heat of reaction
said higher boiling hydrocarbons as redux con
to the materials undergoing reaction therein, and
densate in the fractionating zone and subjecting
thereßfter subjecting said reactants to contact
it to treatment as the reactants, as hereinbefore
with the bed of catalytic material in said endo
set forth.
_
thermic reaction zone.
5. A process for the conversion of hydrocarbon
2. In a process for the conversion of hydro
oil which comprises passing reactants, formed as
carbon oil comprising endothermic and exo
hereinafter described, to contact with the exterior
thermic reactions conducted simultaneously in 40 of an exothermic reaction zone to absorb heat
separate reaction zones, wherein the reactants
produced in regenerating catalyst contained
are subjected to contact with a catalytic mate
therein, subsequently heating said reactants in
rial in the endothermic reaction zone in the pres
ence of which conversion occurs with a resulting
decrease in temperature of said reactants, and
wherein the catalytic material in the exothermic
reaction zone is undergoing regeneration, the im
provement which comprises passing said react
ants first in contact with the exterior of said
exothermic reaction zone toabsorb excess heat
generated therein, subsequently heating said re
actants in an external heating zone to supply
additional heat thereto, passing the resulting
highly heated reactants in contact with the ex
terior of said endothermic reaction zone to sup
ply heat of conversion to the materials under
going conversion therein, and thereafter subject
ing said reactants to contact with the bed of
catalytic material in said endothermic reaction
zone for conversion therein.
' 3. »In a process for the conversion of hydro
carbon oil comprising endothermic and exo
thermic reactions conducted simultaneously in
an external heating zone to supply additional
heat thereto, passing the resulting highly heated
reactants in contact with the exterior of an
endothermic reaction zone to supply heat of con
version to the materials undergoing conversion
therein, thereafter subjecting said reactants to
contact with a bed of catalytic material in said
endothermic reaction zone as the materials to be
converted, separating the conversion products
from said endothermic reaction zone into vapor
ous conversion products and non-vaporous liquid
residue, recovering the latter, fractionating said
vaporous conversion products in the presence of
charging oil to separate fractionated vapors boil
ing in the range of gasoline from the higher boil
ing hydrocarbons, recovering the former, con
densing said higher boiling hydrocarbons as re
flux condensate in the fractionating zone and
subjecting it to treatment as the reactants, as
hereinbefore set forth.
separate reaction zones, wherein the reactants
6. A process which comprises subjecting hydro
are subjected to contact with a catalytic mate
rial in the endothermic reaction zone in the pres
ence of which conversion occurs with a resulting
carbons to catalytic endothermic conversion in a
decrease in temperature of said reactants, and
wherein the catalytic material in the exothermic
reaction zone is undergoing regeneration, said
endothermic and exothermic reaction zones be
ing adapted for alternate utilization of the cata
lytic material contained therein in processing
and regeneration, the improvement which com
prises passing said reactants first in contact with
first zone, simultaneously reactivating a catalyst
by exothermic reaction in a second zone, heating
hydrocarbons to be converted to conversion tem
perature, the heating step including passage of
the last-named hydrocarbons in indirect heat ex
change with‘said second zone to absorb heat gen
erated by the catalyst reactivation therein, pass~
ing the thus heated hydrocarbons in indirect heat
exchange with said first zone to supply heat for
the endothermic conversion, and thereafter in
5
-
-:A24/0,0937
tro'ducing the hydrocarbons to said ñrst zone for
conversion therein.
7. A process which comprises subjecting hydro
,
' erated by the catalyst reactivation therein, fur
ther heating the last-named hydrocarbons to
conversion temperature and then passing the
same in indirect heat exchange with said ?rst
carbons to catalytic endothermic conversionin a
to supply heat tor the endothermic conver
ñrst zone. simultaneously reactivating a catalyst Gn zone
sion, and thereafter introducing the hydrocarbons
by exothermic, reaction in a second zone. passing
to said first zone for conversion therein.
hydrocarbons to be converted in indirect heat ex
’
'
JOSEPH G. ALTHER.
change with said second zone to absorb heat gen
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