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Dern 17, 1946.
T. P._‘.:`«IMF’SON- EVAL
2,412,917
METHOD FOR CATALYTIG CONVERSION
Filed sept. 19, 1942
/7
D
2 Sheets-Sheet@
Dec. l?, 1946.
fr. F'.l SIMPSON Er AL
2,412,917
METHOD FOR CATALYTIC CONVERSION
Filed> Sept; 19, 1942
2 Sheets-Sheet 2
52%
4.3
¿y
4,0 ‘
MM
42
5a
NVENTOR
BY
_
ATTORNEY
2,412,917
Patented Dec. 17, 1946
linurl-:n [STATES PATENT. orrlcs N
,y
METHOD FOR CATALYTIC CONVERSION
ì
Thomas'P. Simpson, `John W. Payne, and John
. A. Crowley, Jr., Woodbury, N. J., assign
Socony-Vacuum Oil Company, Incorporated, a.
' ' corporation of New York
¿
i Application September 19, 1942, Serial No. 458,926
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14 Claims.
f
'I'his invention is directed to
(ci. 19e-_52) n A
methods of con- .
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stream oi.' catalyst for the accomplishment of
conversion, in which the catalytic material is
used only at a high level of eillciency, and in
which the catalytic material is continuously re
ducting reactions in the presence oi.' a contact
mass, such- as, for example, the catalytic conver
sion of hydrocarbons.
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It is known that many operations for the con lCII generated and returned to the conversion step,
both operations being conducted under controlled
version of hydrocarbon materials to other hydro
carbon materials> of differing ~physical and/or
This invention has for a major object the
chemical properties may be carried out catalyt- »
establishment of proper control factors for the
ically. Most of these are carried out by contact
.
ing the hydrocarbon, usually in vapor form and 10 eillcient operation of such a process.
This invention is based. upon the principle ot
at high temperature, with a contact mass com
carrying out -catalytlc reactions by flowing a
posed of particles which themselves have a cata
stream4l oi’ reaction mixture in physical contact
lytic eilect, or which are impregnated with or
conditions.
'
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with a ilowing stream of catalytic material.
act as a support i’or other catalytic material of
In order that this invention may be understood,
a nature appropriate to the result desired. Such 115
reference is made to the drawings attached to
operations may contemplate, for example, the
and made a part of this specification. In these
conversion of hydrocarbons of high boiling point
drawings, Figure 1 shows in diagram form a re
-to those of lower boiling point, or the polymer
ization of light or gaseous hydrocarbons to hy
drocarbons of higher boiling point. Other oper
action and regeneration apparatus suitable for
20 use in this process, Figures 2, 3,4, 5 and 6 are
concerned with internal details of such cham#
bers, and Figure 7 shows in' diagram form a set
up of apparatus suitable for the conversion of
ations of like nature are catalytic dehydrogena
tion, hydrogenation, desulphurizing, partial oxi
dation and similar conversions of _hydrocarbon
hydrocarbon oils.
materials. The method ot operation herein dis
closed is applicable to all such conversions. Of 25 In Figure 1, character 8 denotes a regenera
tion chamber, 9 a purging section, I0 a, reaction
these operations, the vapor phase cracking- of
chamber, II a second purging section, and I2 an
heavy hydrocarbons to gasoline is typical, and
this specification will hereinafter discuss such ‘ elevator for catalyst particles. Regeneration
chamber 8 and _reaction chamber I0 are similar in
4operation as exemplary, without, however, in
tending to be limited thereby or thereto except « construction and internal fittings and consist
(referring now to 8) of an exterior shell 8, which
may be cylindrical or rectangular in cross-sec
tion, with a convergent sealed top I3 and a con
by such limits as may appear in the claims.
Such catalytic processesgenerally make use of
-reactlon chambers containing a fixed body of
' catalyst or contact mass, through which the re
action mixture is passed, and in which, after the
vergent bottomvii, and ?ltted with an interior~
. false bottom I5, which is perforate, the perfora
reaction has slowed down to an uneconomic point,
the contact mass is regenerated in situ. Such
.processes are not continuous, andv only attain
continuity by the provision of numerous reaction
tions therein being too small for the passage of
and on regeneration. Likewise, it is difiicult to
wheel as shown, an intermittently operated valve
set-up or other common' device of this nature'.
Catalyst material introduced through I8 ñlls the
catalyst particles but permitting the passage of
liquid or gas.~ Bottom Il is iìtted ywith pipe I6,
and top I3 with pipe Il. At the -top of I3 is a
chambers which arev alternately placed on stream ~ 40 sealed feeding device I8, which may be a star
maintain constant quantity and _quality of prod
uct withoutnumerous chambers and intricate
scheduling, due to the progressively- decreasing
activity of catalyst.' This same feature, with ap
paratus limitations,` prevents, lto a degree, the
use of catalyst at a uniform high eillciency level. '
Mostv of these difñculties may be avoided bythe use of a method wherein the catalyst or contact
mass is handled continuously as well. This in 50
vention is vspeciiìcally directed to'such a process.
This invention has for its object the provision
of a process of hydrocarbon oil conversion where
in a continuously moving stream of hydrocarbon
oil is contacted with a continuously moving
interior of shell 8, passes down therethrough, 'is
collected by false bottom' I5 and chuterïIB~ and is
removed by a second intermittently‘operating
device, such as star wheel 20.4 This~ arrangement
effects a continuously moving stream of ‘catalytic
material through shell 8. Reaction mixture, in
this case air for an oxidizing regeneration, may
be introduced through pipe I6 and products oi
reaction, in this case flue gas, may be removed
through pipe Il. This effects a continuously
flowing stream of reaction material in physical
contact with the continuously flowing stream of
2,419,917
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catalytic material in shell 8. 'I'he flow shown is
countercurrent. If desired, it may be made con
current by reversing the func\tlonslof I8 and I1.
Shell 8 is also internally iitted with a series of
conduits 2l, equipped with ñns 22,l joined to b1
headers 23 and 24, through which a heat ex
change medium may be passed by-means oi pipes l
4
In certain reactions, no heat transfer elements
are required in the reaction chamber.
Figure 2 shows a cross-section oi case 8 at the
level 2-2 showing how the preferred longitu
dinal passages may be formed by equipping each
heat exchange tube with two diametrically op
posed, longitudinally disposed axial fins. Figures
3 and 4 show other ways of arriving at the
25 and 25. The/liest exchange medium may be
same result. The heat transfer tubes need not
used to control the temperature of reaction by
be arranged parallel to the flow of catalyst, but
extraction of heat from or_addition of heat to .10. may well be transverse thereto, as shown in Fig
ures 5 and 6, wherein transverse tubes 39, carry
the
concurrent,
material countercurrent,
within shell 8, and
or, as
its later
ñow may
shown,¿
be
ing ilns.40, extend between header boxes 4I and
transverse to the direction of ilow of catalytic
A 42 in a shell 43, to exercise the same functions as
material.- Shell I0 is similarly ?tted and simi
corresponding parts in shells 8 and IIJ.
larly operated. Reaction material, in this case 15
It will also be noted in Figures 5 and 6 that
hydrocarbons, is introduced by 21, and removed
the heat exchange elements 39-40 may be spaced
by 28, catalyst movement is controlled by' 28 and
apart -so as to provide within the regeneration
30, and heat exchange medium is circulated by
chamber severalzones intermediate of its ends.
pipes 3| and 32. Confined passage 9, maintained
wherein combustion may take place without sub
relatively full of catalyst by devices 20 and 29, ,is 20 stantial simultaneous removal of heat.
fitted with pipes 33 'and 34, by means of which
The heat exchange medium, if used, may be
steam may be passed through‘the _catalyst for . any iluid suitable for the load and temperature
purging. ` A similar purging passage I I lies below
levels encountered, such as gases, liquids of vari
shell I0, is controlled by devices 30 and 35, and 25 ous kinds, molten metals, or alloys, or fused salts.
iìtted with steam pipes 36 and 31 for purging
Preferably it should be possessed of a low vapor
catalyst after reaction.` From `II- the catalyst
pressure, low viscosity, and high speciñc heat at
drops through 35 into boot\38 of elevator I2 by
operating temperatures and non-corrosive to
which it is elevated and discharged into bin 38a
steel.
above shell 8. Elevator I2 may be of the belt 30
Passages 8 and II, used for purging by passing
and bucket type shown or of any other kind
steam through the catalyst particles, should be so
suitable for the physical properties of the cata
proportioned that a suillcient contact of steam
lytic materials. It will be seen that in apparatus
and catalyst particles occurs to -remove the resid
of the type shown in Figure 1 there is a controlled
ual volatile products of the preceding reaction.
gravity flow of catalyst ‘through shells 8 and ID
'Inrnlng to Figure 7, which shows an operating
into the feed boot 38 of the elevator I2 which re
turns spent catalyst to the inlet of shell I 0, there
setup appropriate for a conversion of hydrocar
bons, such as, for example, a vapor phase crack
. by providing means for carrying out the continu
ing, we find charge oil fed through pipe 44 by
ous catalytic process contemplated herein with '
pump 45 to a vapor preparation unit` 46. Vapor
a high degree of thermal eillciency because the 40 preparation unit 46 vwill consist essentially of a
hot catalyst does not have an opportunity to cool
heater, for which purpose any of the usual forms
to atmospheric temperature during its movement
of heater common in the art, say a pipe still,
through the circuit. Obviously, arrangements
may be used, to heat and vaporize the charge
other than that described above may be employed
and heat it to reaction temperature, and, if the
to eil’ect the movement of catalyst successively
charge- used is not wholly vaporized at the reac
through _a conversion chamber and a regenerat
tion temperature, a vapor separator to remove
ing chamber without permitting it to cool to at
unvaporized liquid'residue. Vapors from 46 move
mospheric temperature. Customary devices for
through pipe 41 into and through reaction cham
the removal of -lines and the addition of makeup
ber 48 (the same as I0, Figure 1), and therein
may be inserted in the catalyst conveyor system.
undergo catalyticA reaction. Reaction products
Special attention should be given to the arrange- d pass through pipe 49 .to product puriñcation
ment of heat exchange tubes within the shells 8
and recovery equipment denoted by 50. 50 may
and I0. These should be so arranged as to pro-- '
be made up of any of the usual fractionation,
mote the passage of catalytic material and reac
separation and disposal devices currently in com
tion material longitudinally through the shell .
mon usel for handling products of cracking re
in such manner that the ñowing material is at
al1 times in heat exchange relationship with the
actions@ If desired, product fractions boiling
above theV desired low-boiling product may be
returned to the system forretreatment, either
heat exchange medium whilein the zone of heat .
exchange elements. It will be seen from Figure
separately or in admixture with fresh charge.
o0
Catalytic material ilowing from 48 is purged in
5I and elevated by 52 to be introduced into 53
ywhich the temperature is independent of con
Jwherein it is regenerated by burning with air
trol other than temperature of reactants and '
supplied by blower and pipe 54, the products of
nature of -the reactions taking piace. »The con
regeneration being disposed' of_ through pipe 55,
duits may be unñnned, but better results are ob~ (55 after which the regenerated catalyst is purged in
tained if the external heat transfer surface of
551and returned to 48. The temperature level
1, regenerator 8,- that a zone above. and a zone
below the heat exchange tubes provide space in
~ the heat exchange tubes is augmented by the
addition of fins thereto.v These fins, primarily
added for heat transfer reasons may be taken ad
vantage of to assist in control of the flow of cata
lyst and reaction fluid and contact therebetween
of the reaction in 48 may be controlled and latent
heat of reaction added thereto by a heat ex
change medium introduced through pipe» 51 and
removed through pipe 58. In the arrangement
tubes, divide the space within the shell into a
shown in Figure rI the same heat exchange me
dium used in 48 may also be used to control the
temperature of regeneration in 53. In the oper
series of longitudinal passages of substantially
.ation described herein, where the regeneration is
constant cross-section throughout their length.
an exothermlc reaction, the function of the heat
by being disposed so that they, together with the
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2,412,917
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catalyst, no detectable> deterioration in quality`
~ exchange :mediumrinthe 'intermediate region of
being found.
chamber 53 is to prevent the temperature of re
generation reaching a point which would cause
_
The control of several features of the operation
is oi considerable importance. In both the re
heat damage to the catalyst and at the -same
generator and reactor, the particle-form solid
catalyst is moved down through the operation
time permitting combustion of the carbonaceous
deposit thereon. . Thus the heat exchange medium
in l! acts to adjust and maintain the .temper
in the form of a solid moving. column while the reactants (oxidizing gas in one case and hydro
' ature of the moving mass in the intermediate
carbons in. the other), are passed countercur
region thereof, between a minimum temperature
below which burning of the carbonaceous deposit 10 rently therethrough. In order to c_ifectively se
in the presence of oxidizing gases at an appre
siable rate cannot occur and almaximum tem
perature above which the catalytic material would _
be damaged by heat. For example, the temper
ature for regeneration of a spent clay type cata
lyst used. in cracking hydrocarbons may range
from around the .cracking temperature (from ~
cure. contact of the reactants with all portions
of the contact mass it is necessary that the re
actants be passed therethrough at such velocity
that the orderly and uniform progress of the
contact mass is not impeded, and that channels
wherein reactants might pass through rapidly
without ~_adequate 'reaction be prevented from
' forming. It has been determined that the prei
about 800° to about 950° F.) to a pealctemper
erable upper limit for reactant velocity is some
ature in the neighborhood of 1050° to-1100° F.
Care should be exercised so that the regenerat 20 what below that at which active physical dis
turbance or "boillng” of the contact mass will
ing temperature does not rise substantially above
occur. Of course, since various reactants may
i200“v F. or serious damage to a catalyst of this
be used. of varying densities and varying vis
type may result.~1'n.the arrangement shown in
cosities at the temperature of reaction, ranging
Figure '1, the heat exchange medium is intro
air to relatively heavy hydrocarbon, the
duced into 53 by pipe 69 and removed by pipe 25 from
actual linear velocities will vary for each re
60; The heat exchange medium is circulated by
actant. Also, for particles of various sizes, the
resistance of a given depth ,of bed isgreater in
uses may be controlled by use of _various combi
some cases, giving rise to another variation in
_ nations of heat exchangers 82 and 83 and by
passes 64, $5 and 86 in a manner obvious to those 30 the actual linear velocity of the reactant.. How
ever, it has been determined that all of these
skilled in the art. In many cases if the reactions
variables
merge in auch a manner that it can be
taking place in chamber I8 have a relatively small
stated that the maximum flow of any reactant,
heat of reaction’ or where maintenance of closely
through any particle form solid catalyst of clay
controlled temperatures is not essential it is un
type, should not be greater than that which will
necessary to circulate the heat transfer medium 35 produce a pressure drop of about 6 inches of
through the chamber. and a satisfactory heat
water per foot of path through the contact
balance and temperatures can be attained by bal
mass, measured between the most nearly adja
ancing the temperatures of the entering re-‘
pump Si andthe temperature for the several _
cent points of inlet and exit.
actants and catalyst,...
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_
As an example of one operation successfully 40
` conducted in such apparatus. according to the
process herein disclosed, coastal gas oil with which
was admixed steam to the extent of about
.
This limiting value of pressure drop will vary
with the apparent density of the contact mass
material in the solid moving column. That is,
Vfor contact mass materials which have a greater'
weight per unit of volume in the state of packing .
they attain in the solid moving column, the
optimum pressure drop will be higher. It will, for
example, range from somewhat less than 6" of
(cold volumes), at a temperature of 800° F. was
water per foot of path for materials having an
contacted with a catalyst of activated clay gran
‘apparent density of 0.6 to somewhatless than
ules at a rate of one volume of oil (cold) to tour
volumes of clay in a chamber through which the 50 11" of water for materials having an apparent
clay passed at such a rate that it remained in _ density of 1.1. Since fuller's earth, "uitrol," acid
treated natural clays. and_most synthetic ma
the reaction zone about 20 minutes... with the fol
’
`-'ioogl
lowing resultsz;...gy4v
„ u
vi»
1». ~
.
_
__ Yield 'ofno" E. PÍ essonne (including iso
A terials now in use and of this general type have
apparent densities ranging from about 0.6 to
55 0.8 a pressure drop of about 6" to 8" of water-per
^ butane and heavier in gas) _vol. per cent-- 67.4
' foot of path is optimum for such catalytic ma»v
Y _ Yield _or _dry gas (lighter-,_ than isobutane)
_, wt. per cent_à
VYield of -corel ______ __
terials of clay type. vHowever, other 'catalytic
4.0
.».-wt. per cent-- 2.5
___.;_voL per cent-.. 35.0
_In this runthe catalyst was passed through the
_ Yield 'of recycle stock.'
materials which are also useful will include ma
terials of higher apparent density, such as cer
tain synthetic associations of alumina and silica,
or may include materials of the clay-type. or of
synthetic origin carrying a suilicient amount of
regeneration chamber (of the same size as the
reaction chamber) at the same rate„and was _ other catalyst, such as certain well known cata
lytic metals carried by clay type carriers. With
burned with a suillcient volume of air to main
65 these, the upper limits of optimum pressure drop
tain above 10% CO: in the exit flue gas.
are indicated.
.
_
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The temperature of the reaction was held by
The limits so far discussed are optimum and
use of the heat exchange medium at 800° F., and
preferred limits, as will be understood from the
in the same manner the temperature of the re
generation was not allowed to rise above 1100° F.
The gasoline _produced was of excellent qual
ity, high in anti-knock rating, and the recycle
stock was clean. light in color, and of about the
same boiling range as the charge. No high boil
following. Obviously. greater economic useful
ness results from greater use of each unito!
reaction space installed. that is from greater
thruput- of reactant_ per cubic foot of installed
contact mass volume. Also, particularly in cra;k-
ing of hydrocarbons, the laydowh of carbonaceous
ing, dirty, liquid cracking tar was produced. The
regenerated catalyst was equal in eñlciency to new 75 >matter'on the contact mass does not increaser
' 2,419,917
proportionately vwith increases in reactant thru
put per unit volume o! contact mass. Reaction
can, of course, be attained above these preferred
, limits, up to rates of reactant thruput which are
actually disruptive of the contact mass; but we
have found that with contact masses of the
general nature of clay that the rate should not
be greater than one giving 7 to 10 inches of
water pressure drop- per foot of path through 1
the contact mass and preferably not greater 10
than one giving about 6 to 8 inches of water
pressure drop per _ foot of path through the
contact
mass.
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sults may be obtained to an operable degree by
burning olf, in each such combustive regeneration ~,
stage without substantial removal of heat, from .
about 0.05 per cent to about '0.60 per cent by
weight of coke, based on contact mass weight.
The controls herein set forth cooperate to per
` mit the establishment of a highly useful cyclic
commercial process. The control set forth for the
conversion reaction -accomplishes high rates of
converted product production per unit of catalyst>
volume employed, while at the same time permit- -
ting relatively low rates of coke deposition. For
this optimum conversion operation, it is .highly
For »the heavier contact mass materials the
desirable to provide a catalytic contact mass of
optimum pressure drop will range upward to
about 11 inches oi' water per foot of path, with
the maximum pressure drop ranging upwardly
to about 13 inches of water per foot of path.
controlled activity. The regeneration control set
forth permits of attaining such controlled re
generation of spent catalysts in proportion .to
. 0f similar interest and importance is the con
_ the amount of coke deposited thereon.
It is to be understood that the specific exam
trol of burning in the regenerator, particularly 20 ples and numerical data herein disclosed are ex
in those portions of the regenerator where burn
planatory of the invention, and that it is not to
ing may take place without simultaneous removal
be limited thereby or thereto except as such lim
of heat. The required temperature limits for
itations are expressed in the claims.
This application is a continuation-impart -of
combustive regeneration are, as a minimum, the
temperature whichv will support combustion, 25 our copending application Serial No. 361,440, filed
namely about '150° F. as a practical minimum and
October 16, 1940, which, in turn, is a continuation
800° F. as a preferred minimum temperature
in-part of our application Serial No. 162,541, filed
level in regeneration. The maximum is that
temperature at which the contact mass will be
damaged or reduced in eiiiciency by heat. As a
matter of practical operation, the operating max
imum will be about 950° F. to about 1100° F., with
September 4, 1937.
We claim:
1.l The method of converting a hydrocarbon oil
Í which comprises passing the oil in vapor phase
and at conversion temperature into contact with
1200°A F. set as an operating maximum which
a substantially compact downwardly moving mass
of particle-form` clay-type, solid catalytic mate
should not be exceeded.
«
In order- to attain the control necessary to 35 rial in which conversion is eiiected, the vapors
being introduced thereto at a flow rate not in
avoid these maximum temperatures and at the
same time assure complete control of carbona
excess 0f sufficient to produce about seven to
ceous deposit, the operation should preferably be
ten inches of water pressure drop per foot of
varied in accordance with .the amount of irn
vapor path through said mass, effecting substan~
purity, usually spoken of as “coke” If the coke 40 .tially complete separation of hydrocarbons from
to be burned oi! is large in amount, say above
said mass, transferring contaminated contact
mass to a regeneration zone and moving it there
about 3 per cent by weight of the contact mass,
~ the exothermic heat generated by its burning is
through as a substantially compact moving mass,
so great relative to the heat capacity of the cata
supplying oxygen containing gas thereto to burn
lyst and combustion' gases that a generally si
' contaminant therefrom and removing heat suf
ñcient to prevent the temperature of regenerat
multaneous burning andremoval of heat is ad
vantageous. If the coke to be removed is below
ing contact mass from rising above .that which
will damage the contact mass` and returning the
about 3 per cent and particularly if it is below 1
regenerated contact mass in heated condition to
per cent by weight of the contact mass, a consid
A
`erably better burn on’ or regeneration may be 50 the conversion zone. .
2. The method of converting a hydrocarbon oil
obtained by permitting periods of burning with
which comprises passing the oil in vapor phase
out substantial simultaneous removal of heat in
order to permit of more cleanly removing dini-_ ’ and at conversion temperature into contact with
a substantially compact, upright column of gravi
cultly ignitable coke. These conditions of rela
tively small coke burnoii! are typical of the regen 55 .tating particle-form, clay-type, solid catalytic ma
eration of contact- mass material spent in crack- ' terial in which conversion is effected, the vapors
being introduced thereto at a iiow rate not in ex
ing, and for this reason, when working with such
a .process it ispreferred to use a regenerator A cess of sufñcient to produce about six =to eight
`inches of water pressure drop per foot of vapor
equipped as shown in Figures-5 and 6 where re
gions of burning without substantial simultane: 00 path through said column, effecting substantially
complete separation of hydrocarbons from said
ous removal of heat are alternated- with heat
' column, transferring contaminated catalytic ma
removal regions. ïHowever, control of maximum
terial to a regeneration zone and moving it there
temperature is necessary in these combustion
regions without heat removal means and this can
through as a substantially compact column of
be provided by so adjusting the intensity of com-l 05 moving particles, supplying oxygen containing
bustion in these regions as to provide a burn-off
gas thereto to burn contaminant therefrom and
positively removing heat sufiiclent to prevent the
which is not suiiicient in intensity to raise the
temperature of regenerating catalytic material
contact mass therein to damaging temperature
from rising above that which will damage the
levels. It has been found that burning off up .to
about 0.6 per cent by weight of coke (based upon 70 catalytic material, and returning the regenerated
contact mass), in each stage of burning without
contact mass in heated condition to the con
version zone.
substantial heat removal will achieve good re
generation and permit adequate protection of the
3. The method of converting a. hydrocarbon
oil which comprises passing the oil in vapor phase
contact mass v material. Dependent upon the
usual variables of combustion control, these re 75 and _at conversion temperature into contact with
anaal?
tinuously passing said material as a substantially
compact column through Aa plurality of zones
a'substantially compact moving mass of gravi
tating particle-form,_ clay-type, solid catalytic
in which combustion occurs without substantial
material in which conversion is effected. the
simultaneous removal of heat, said combustion
« vapors being introduced thereto at a iiow ‘rate
zones alternating with cooling zones in whichv
substantially below~ that- which causes ïphysical
heat is removed by indirect heat exchange with
disturbance of themovingmass, eiîectlng sub- 4
stantially Icompleteiseparation 'of hydrocarbons _
a iluid heat exchange medium, the tempera
ture at all times being maintained between a.'
minimum- temperature at which combustion will
tact mass to_ a regeneration zone and moving
` it therethrough as a substantially compact down 10 take place and a maximum temperature at which
the catalytic material begins to suffer heat dam
wardly moving mass'. supplying omgen contain
age, the amount of burning in each combustion
ing gas thereto to burn contaminant therefrom,
zone being limited to the burning ofi ci from
said'gas being supplied at a flow rate not in
0.05 per- cent to about 0.60 per cént by weight
excess of suilicient to produce about seven to
ten inches of water pressure drop per foot of 15 of carbonaceous material based on catalytic ma
terial weight.
'
gas path through said mass, and removing heat
7. The method of regenerating a particle form
suiilcient to kprevent- the temperature of regen
solid, clay-type, catalytic material contaminated
erating contact mass from rising above that
by a carbonaceous deposit which comprises con
which will damage the .contact mass, and return
ing the regenerated contact mass in heated con 20 tinuously passing said material as a substantially
compact column through a plurality of zones in'dition to the conversion acuer,A :1,
" _' 'A '
which combustion occurs without substantial
4. The method of converting a hydrocarbon oil
simultaneous removal of- heat, said combustion
which comprises passing the oil ln vapor phase
zones alternating with cooling zones in which
and at conversion temperature into contact with
a substantially compact downwardly moving mass 25 heat is removed by indirect heat exchange with
a ñuid heat exchange medium, the temperature
of particle-form solid catalytic materialof clay
at all times being maintained between a minimum
type in which conversion is eilected, the vapors
temperature at which combustion will take place
being introduced thereto at a flow rate substan
from said mass. transferring contaminated con
tially below that >which causes physical disturb
ance of the moving mass. effecting substantially
.complete separation of hydrocarbons from said
' and a wmaximum temperature at which the cat
alytic material begins to suiîer heat damage, the
30 amount
of burning in each combustion zone being
limited to the burning oiî of 0.60 per cent by
weight of carbonaceous material based on cat
mass, «transferring contaminated contact mass
to a regeneration zone and moving it downwardly
therethrough as a substantially compact mov
ins
Supplying engen containing gasÄ
thereto to burn contaminant therefrom, said gas
alytic material weight.
35
being supplied at a ilow rate not in excess of
suiliclent to Aproduce about six to eight inches
of _water pressureI drop per foot of gas path
' through said mass, while removing heat suf
clay type solid adsorbent material contaminated
by a‘carbonaceous deposit which comprises con
tinuously passing said material as a substan
tially compact column through a plurality of.
' zones in which combustion occurs without sub
40
stantial rsimultaneous removal of heat. said com
ficient to prevent the temperature of regenerating ‘
contact mass from rising above' that which will
.damage the contact mass. and returning the
regenerated contact mass in heated condition to
'
8. The method of regenerating a. particle form
busticn zones alternating with cooling zones in
which heat is removed by indirect heat exchange «
» tating particle-form solid catalytic material of
with a fluid heat exchange medium, „the tem
perature at-all times being maintained betweenv
a miniinum temperature at which combustion
will take place and a maximum temperature at
which the adsorbent material begins to suiIer
heat damage, the amount of burning in each
50 combustion zone being limited to the burning
clay type in which conversion is effected, the
per cent by weight of carbonaceous material based '
the
conversion zone.
‘
~
A
5.' 'I'he method of converting a hydrocarbon oil
which comprises passing the oil in vapor phase
and at conversion temperature into contact with
a substantially 'compact moving mass of gravi
oiî of from about 0.05 per cent to about v0.60
vapors being introduced thereto at a flow rate
on adsorbent material weight and the flow rate _
' substantially below that which causes turbulence
of the moving mass, effecting substantially com--`
plete separatlonof hydrocarbons from said mass; 55
'transferrlng':;contaminated' contact mass to a
regeneration'zone and moving it“ therethrough
as a substantially = compact downwardly movingv
of regeneration gases therethrough being not
over sufficient to produce a pressure drop of about i?
seven to ten inches of water'per _footof gasif
path through said material.
9. The method of regenerating a particle form
clay type solid adsorbent material contaminated ï" .
massï‘supplying‘ oxygen containing gas thereto
by a carbonaceous deposit which comprises con.-- '5
f ¿ to burn' contaminant therefrom, said gas being 60 tinuously passing said material as a substantially ~
` supplied 'at a'ilow rate‘substantiallyvbelow that
compact column through a plurality of zones in
which causes turbulence of the moving mass, and
which combustion occurs without substantial
removing heat sumcient to prevent the tempera
simultaneous removal of heat, said combustion
. ture of regenerating contact mass from rising
above that which will damage the contact mass, 65 zones alternating with cooling zones in which `
~ t and returning the regenerated contact mass in
heated Vcondition to- the conversion zone, the
ilow rateol’ vapors ln the conversion section and
heat is removed by indirect heat exchangel with a .
iluid heat exchange medium, the temperature at
all times being maintained between a minimum
temperature at which combustion will take placeKY
_. 'K to an amount giving not in excess of about six 70 and a maximum temperature at which the ad
sorbent material begins to suiîer heat damage,
to eight‘inches ci water pressure drop per foot
the amount of burning in each combustion zone
- of `path-of vapor or gas through said mass.
being limited to the burning oiî of 0.60 per cent
‘6.2’ The _method of regenerating a particle form
` of gas vin the-'regenerator both being limited
.
. '
solid, clay'type, catalytic material contaminated
by weight of carbonaceous material based'pn ad
by a carbonaceous deposit which comprises con
75 sorbent material weight and the flow rate oi re- «
2,412,917
.
generation gases therethrough being not over suf
‘ ilcient to produce a pressure drop of six to eight
inches of water per toot of gas path through said
material.
.
f
12
.
vertedfproducts made per unit volume of catalyst
employed and still at an amount not suilicient
to produce a pressure drop in excess of about
seven toten inches of water per foot of path 0f
vapors through said- material, flowing> the rela- y
_
10. The ¿ method of converting a hydrocarbon
oil which comprises passing the oil in vapor phase
tively low contaminant content contact mass ma- `
and at conversion temperature into contact with ,
, terial therefrom into'aríd through a regeneration a
a substantially compact moving mass of particle-A.'
zone in' which 'said material flows" as a substan- ’
form solid clay-type catalytic material
at al1 times at amoving
temperature
column
high
andenough
is‘maintained
to sup-f "
f which co‘nversion is effected, the vapors being in-„r 10 tiallyeompact
troduced thereto at a flow rate substantially lie-.fi port combustion and below a'temperature high
low that which causes turbulence oi the moving „ enough to eil’ect heat damage to said material,
mass, effecting substantially complete separation, 'burning contaminant from said material in a
of hydrocarbons from said mass, transferring
plurality of regenerative steps in each of which
contaminated contact mass to a regeneration~ „. 15 no more than about 0.05 per cent to 0.60 per cent '
zone, supplying engen containing gas thereto>
by weight of contaminant, based on contact mass
to burn contaminant therefrom, said burning be- p , weight. is removed from said material and in each
ing accomplished by passing said material as a
of which no substantial removal ofvheat is ef
substantially compact column through a plurality"
fected. between said burning zones removing heat t
of zones in which combustion occurs without sub 20 from said material by indirect heat exchange
stantial simultaneous removal of heat, said com- f
with a iiui‘d heat exchange medium, the iiow rate
bustion zones alternating with cooling zones inv
>of regeneration gases being high to effect good
which heat is removedby indirect heat exchange
penetration of said material but not suilicient to
with a fluid heat exchange medium, the tempera
produce a pressure drop in excess of about seven
ture at all times being, maintained between a 25 to ten inches of water per foot lof path of gas
minimum temperature at which combustion will
through said'material and returning the regen
take place and a maximum temperature at which
erated contact mass in heated condition »to the
the catalytic material begins to suiTer heat'dam
reaction zone.
,
`.
age. the amount of burning in each combustion
-
13. A unitary process for conversion of heavy
zone being limited to the burning „oil of from 30 hydrocarbons to lighter hydrocarbons in the pres
about 0.05 per cent to about 0.60 per cent by
ence of a catalytic contact mass oi’ particle form,
weight of carbonaceous material based on cata-V
clay type, solid adsorptive material comprising
lytic material weight, and- returning the regener-_`
the steps of ñowing the contact mass material as
ated catalytic 'material in heated condition into '
a substantially compact moving column through
contact with oil vapor.
'
f
.
35 a reaction‘zone, flowing a stream of hydrocarbons
1l. The method of converting a hydrocarbon
heated to conversion temperatures therethrough
oil which comprises passing the oil in vapor phase
at a high flow rate conducive to relatively low de
and at conversion temperature into contact with
posits of contaminant on catalyst relative to con-.
a substantially compact moving mass of particle
' verted products made per unit volume of catalyst
form solid clay-type catalytic material in which 40 employed and still at an amount not suiñcient
conversion is eii'ected, the yvapors being intro
to produce a pressure drop in excess of about six
duced thereto at a ñow rate substantially below`
to eight inches of water per ioot of path of vapors l.
that which causes turbulence of the moving mass,
. through said material, ilowing the relatively low ‘
eil’ecting substantially complete separation of hy- _ Y contaminant content contact mass material
drocarbons fromV said mass-transferring con 45 therefrom into and through a regeneration zone
taminated contact mass to a regeneration zone,
in which said material ilows as a substantially
compact moving column and is maintained at all
times at a temperature high enough to support
supplying oxygen containing gas thereto to burn
contaminant therefrom, said burning being ac
complished by passing said material as a substan- .
combustion and below a temperature high enough
to effect heat damage to said material, burning
tially compact column throughs plurality~of
zones in which'combustion occurs without sub
contaminant from said material in a plurality of
regenerative steps in each of which no more than
bustion zones alternating with cooling zones in ' _ 0.60 per cent by weight of contaminant, based
which heat is removed by indirect heat exchangey
on contact mass weight, is removed from said
with a iiuid heat exchange medium, the tempera 55 material and in each of which no substantial re
stantial simultaneous removal of heat, said com
ture at all times being maintained between a
minimum temperature at which combustion will
take place and a maximum temperature at which
the catalytic material begins tosuffer lheat dam
age. the amount of burning in each combustionf 60
zone being limited to the burning off of 0‘60 per
cent by weight of carbonaceous material based on
. catalytic material weight and returning the re
generated contact mass in heated condition into
contact with oil vapor.
i
medium, the ñow rate of regeneration gases being
high to eiîect good penetration of said material
but not suilìcient to produce a pressure drop in
excess of about six to eight inches of water per
foot of path of gas through said material and
returning the regenerated contact mass in heated
65 condition to the reaction zone.
12. A unitary process for conversion of heavy ‘
hydrocarbons to lighter hydrocarbons in the pres
ence of a catalytic contact mass of particle form,
clay type. solid adsorptive material comprising
> the steps of ilowing the contact mass material as 70
a substantially compact moving column through
moval of heat is effected, between said burning
zones removingpheat from said material by. indi- rect heat` exchange with a fluid heat exchange ’
,
14.»The method Aof converting a hydrocarbon
oil which comprises passing the oil in vapor.
phase and at conversion temperature into con
tact with a substantially compact moving mass of
downwardly flowing particle-form solid clay~type
catalytic material in which conversion is effected.
a reaction zone, flowing a stream of hydrocarbons
the vapors being introduced thereto at a iiow rate
heated to conversion temperatures therethrough
substantially below that which causes physical
at a high flow rate conducive to relatively low de- „ `
of the moving mass, the iiow rate
posits of contaminant on catalyst relative to con 75 disturbance
being such as to give a pressure drop of not over
2,412,917
14
therethrough as asubstantialiy compact moving
n seven 'to thirteen inches of water per foot of path
of vapor through contact mass for contact mass
materials of` apparent densities in the reactor
ranging from» about 0.6 to about 1.1, the pressure
drop,\within the indicated range being propor
tional to the said apparent density, effecting Vsub
stantially complete separation ofhydrocarbons
from said mass, transferring contaminated con
tact mass ‘to a regeneration zone and moving it
mass, supplying oxygen' containing gas thereto to
burn contaminant therefrom and returning -the
regenerated contact mass in heated condition to
5
the conversion zone.
'
v THOMAS P. SIMPSON.
JOHN W. PAYNE.
‘
JOHN A. CROWLEY, JR.
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