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Патент USA US2411592

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Nov. 26, 1946.
Filed Oct. 31, 1942
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Nov. 26,_ 1946.
2,411,592 '
Filed Oct. 31, .1942
2 Sheets-Sheet 2
Patented Nov. 26, 1946
* 2,411,592 _
Edward D. Reeves, Cranford, N. J.,_assigno'r to
Standard Oil Development Company, a corpor
ration of Delaware
Application October 31, 1942, Serial No. 464,085
‘ 7 Claims.
(01. 260—-680)
therefrom, regenerating the catalyst in a sepa
rate regeneration zone, and returning the re
generated catalyst to the reaction zone for fur
The present invention relates to improvements
, in a process of and apparatus suitable for carry
ing out reactions involving solids and gases and,
ther use in the process. A great deal of research
more particularly, it relates to an apparatus in
which a gas and a solid in powder form may be 5 has been directed toward improving the latter
type of process which has come to be known as
contacted under reaction conditions where said
the ?uid catalyst type of operation.
reaction causes deposition of contaminants on
My present process relates to improvements in
the catalyst, the apparatus being adapted to pro
apparatus suitable for carrying out the ?uid cat
place in one portion of the apparatus while the 10 alyst type of operation, and in its essence it in
volves an elongated vertical chamber of vre
regeneration of fouled catalyst takes place in
stricted cross sectional area, disposed and divided
another portion of said apparatus and is further
into two contiguous compartments, in the upper
provided with means for returning regenerated
of which the conversion reaction takes place,
catalyst to the reaction zone so that the operation
,vide means for causing the main reaction to take
15 while in the lower compartment the catalyst is
' may be performed continuously.
In a great many chemical reactions, the pres
ence of a solid catalyst in contact with reactants
regenerated and returned to the upper compart
ment. Certain necessary apparatus and com
ponent parts are aililiated with the compartments
in vapor or vapor-liquid phase greatly improves
just mentioned in order to provide maximum eili- '
the operation, particularly from the standpoint
of quality of the product. For example,‘ in gas 20 ‘ciency, all of which will more fully appear herein
after from the ensuing claims which are to be
oil cracking, the presence of a catalyst such as
read in connection with the accompanying draw
an acid treated clay of the bentonite or mont
morillonite type in the gas oil vapors undergoing
The main object of my present invention is to
cracking greatly improves the octane number of
‘ the gasoline produced by cracking.
In certain 25 ‘provide a compact and e?icient apparatus in
other reactions'such as the dehydrogenation of
ole?ns to form diole?ns, the presence of a suitable
catalyst such as that disclosed in the application
of Kenneth K. Kearby, Serial No. 430,873, ?ied
February 14, 1942, now U. S. Patent 2,395,875, 30
dated March 5, 1946, makes possible the produc
tion of certain desired ole?ns and diole?nsin
good yields.
In the early stages of solid catalytic treatment
which catalytic reactions involving powdered
catalyst may be carried out continuously with a
minimum amount of equipment and utilities.
A more speci?c object of my invention is to af
ford facilities for the proper regeneration of cat
alyst fouled during contact with the reactant va
por in a regeneration zone which is contiguously
disposed below the reaction zone and permits the
flow of fouled catalyst by gravity from the con
of hydrocarbons 'for one purpose or another, the 35 version'zone into the regeneration zone.
I- attain these objects by means illustrated in
catalyst was disposed in the form of a stationary
the accompanying drawings in which
bed in a reactor and the hydrocarbon oil was
Fig. I is a vertical diagrammatic showing, part
vaporized and forced through the bed of catalyst
ly in section of my improved reactor and its im
at reaction temperatures, whereupon the desired
conversion took place. However, in this type of 40 mediate accessory apparatus; Fig. 11 is a modi
?cation of Fig. I, in which I show a standpipe to
operation deposits were formed on the catalyst
cause circulation of catalyst.
which eventually necessitated discontinuing the
Similar reference characters refer to similar
productive phase of the operation and treating
parts throughout the views.
the catalyst with a substance adapted to remove
the contaminants and restore the catalyst activ 45 Referring in detail to Fig. I, I represents a
conversion chamber and .2 a regeneration cham
ity, because when the catalyst had acquired a
ber integral therewith and together forming a
maximum amount of the contaminating sub
vertical cylindrical pipe or shaft separated, how
stance deposited as a result of the reaction, its
activity was impaired.‘ Later in the development‘ ' ever, into the two chambers or compartments by
of these catalytic processes of the type indicated, I 50 a grid plate 3 disposed as shown about the mid
vertical point of the said cylindrical shaft. Dis
it was found that they could be operated con
posed at the upper end of the vertical shaft and
tinuously by suspending a powdered catalyst in
integral therewith is a disengaging chamber 4 of
‘. the vapors, forcing the suspension through a re
greater internal diameter than the conversion
action zone, withdrawing the reaction products
from the reaction zone, separating the catalyst 55 chamber immediately below. There is also dis
posed in an upper portion of disengaging cham
ber 4 a suitable ‘dust separator such as a Cottrell
precipitator l0 shown diagrammatically. At the '
bottom end of regeneration‘zone 2, I provide a
out oi’ powdered catalyst occurs to the extent
that when the vapors reach the Cottrell precipi
tator [0 they contain only about 0.0025 pound of
catalyst per cubic foot of vapor or less. The va
suitable feeding mechanism for the ?owing pow 5 pors still containing, however, a small amount
dered material in the bottom of the chamber.
of catalyst pass through the Cottrell precipita
In the illustration, 1 have shown'a screw con
veyor IS. The screw conveyor discharges pow
tor and are withdrawn through line 50. The re
action product in line 80 may be processed by
distillation and solvent treatment to recover the
butadiene and to recycle unreacted ole?ns in
equipment not shown. The puri?cation and re
covery of butadiene does not form an integral
part of this invention and it may be accomplished
in apparatus not shown.
The catalyst which descends through the grid
plate 3 into regeneration compartment 2 is
dered material into a suitable mixing device such
as an ordinary injector where it is intermixed
with steam discharged into said injector through
a pipe 2| where it forms a suspension of the pow
‘der in the steam, and this suspension is then
carried by a pipe 25 into the upper part of con
version chamber I. The reactant is discharged
into the lower portion of the conversion com
partment through a pipe 21, and a diluent if used
may be discharged into reaction compartment
through line 28. The inlet pipe 21 and line 28
treated by steam entering through lines 40 and '
4|, and in the case or butene dehydrogenation
employing the catalyst mentioned above, the
may be made mutually intercommunicating by 20 tarry and cokey contaminants undergo water-gas
a valve 30. I have also provided means for in
troducing steam or some other stripping gas into
the bottom of the regeneration chamber 2 as
through lines 40 and 4|. If desired, air may be
reaction to form C0 and CO2, thus consuming
the contaminants on the catalyst and purifying
the same. These gaseous products of regenera
tion, together with steam, pass upwardly into the
introduced into the bottom 01' the regeneration 25 conversion zone, but in the case of butene de
chamber through lines 40 or ll.
hydrogenation they in nowise interfere with the
Having generally described the essential ele
reaction and, moreover, when they are with
ments of my improved apparatus, I shall now set
drawn with the reaction products through line
forth an example illustrating the method in which
50 they may be readily separated from the reac
30 tion products, for example, by caustic soda or
poses of illustration that reactant material intro
sodium carbonate, or a combination of these, or
duced into the reactor through line 21 is a C4
otherwise removed in known‘manner. It is not
it may be employed. It can be assumed for pur
hydrocarbon fraction containing butylenewhich
satisfactory, according to best practice, to regen
I desire to be dehydrogenated to butadiene'. The
erate the catalyst in regeneration chamber 2 with
feed stock entering through line 21 is at a tem 35 air because of the introduction of nitrogen which
perature of MOO-1200" F. and by using a proper
is a di?icult substance to remove. However, it it
catalyst such as that disclosed in the Kearby ap
is desired to supply oxygen to aid in the regen
plication previously mentioned, 1. e., a catalyst
eration in chamber 2, same is preferably supplied
containing about 79 parts by weight of'mag
in relatively pure form or intermixed with a
nesium oxide, about 20 parts by weight of F6203, 40 minimum amount of nitrogen.
about 5 parts by weight of C110, and about 1%
In Fig. 11, I have shown a modi?cation in which
parts by weight of K20 present in the conversion
catalyst may be withdrawn by gravity through
chamber in the form of a powder having a parti
a standpipe 29, mixed with steam in an injector
cle size of from 200-400 mesh to form within
_22 to form a suspension disposed in the bottom
the said chamber a dense phase suspension hav 45 of the standpipe 29, the steam entering through
ing a weight of about 10—20 lbs. per cu. ft., the
pipe 2|, and the suspension then discharged into
butenes present in the feed stock, particularly
the bottom of regenerator 2. The rate of ?ow of
the butene-2, undergo dehydrogenation to form
catalyst in standpipe 29 is controlled by a slide
butadiene. The reactant. is added by dilution
valve 23 or any other suitable means. Supple
with steam and consequently the entering gas
mental steam may be discharged through the
preferably contains 4-20 volumes of steam per
bottom of regenerator through line '32. The hy
volume of hydrocarbon, and this mixture of
drocarbon feed stock may be introduced as in the
steam and catalyst forms the suspension having
previous modi?cation through line 21, together
the density indicated previously under best op
with steam added through line ,28. Gas such
erating conditions. The linear velocity oi! the
as steam is discharged through pipes 3| into pipe
gases in the'converslon chamber is such that the
29 to ?uidize the catalyst therein. The manner
catalyst tends to gravitate slowly downward
of operating the modi?cation shown inFig. II
through the foraminous member 3 into the re
generation chamber 2, while the‘ gaseous. reactant
product proceeds upwardly into ‘disengaging
chamber 4. It the linear velocities of the gas
within the chamber I are from 1/2-3 ft. per sec
ond, catalyst will settle out by gravity as indi
cated but, nevertheless, it will be in a highly
is otherwise the same as that shown in the 'modi
?cation of Fig. I.
In butene dehydrogenation there is or course
an absorption of heat due‘ to the nature of the
reaction. In order to compensate for the heat
of reaction, preheated steam at a temperature
of approximately 1300° F. is employed, or the
?uidized state, that is to say, it will not be com 65 catalyst may be heated by heat exchange while
pacted but rather it will be in an ebullient state
passing through line 29 in communication with
of motion resembling somewhat a boiling liquid,
a heating device 2, diagrammatically shown.
and although the general direction of the cata
(See Fig. I)._ When oxygen is introduced into
lyst will be downwardly there will be a multi
the regeneration chamber, the heat lost in con
plicity of cross currents and upwardly directed 70 1/ version chamber 1 may be compensated for by
currents having a dense phase level in about the
means of the heat generated in the regeneration
region of L. Above L, however, due to the ex
chamber. 2 at least in a large degree, and there- panded cross-sectional ‘area 0! disengaging
fore the hot regenerated catalyst is withdrawn
chamber 4, the velocity of the up?owing vapors
from regeneration chamber 2 and without op
will be greatly reduced so that further settling 75 portunity substantially to cool, it is returned to K
pose more than one heat exchanger or other
heating means for heating the regenerated cat
alyst to higher temperatures. This has the ad
vantage that the feed stock entering through line
21 need not be heated to as high a temperature
the conversion chamber, thus transferring heat
from the regeneration chamber to the conversion .
While I have described my invention in detail
with reference to butene dehydrogenation, it is to
as would be necessary where the catalyst is not ,
be understood that the process and apparatus are
equally applicable to the cracking of a gas oil, to
externally heated in the manner indicated. A
further modi?cation of my invention falls within
the reforming of naphthaa-to the polymeriza
the scope of cooling a portion of the regenerated
tion of ole?ns and to numerous other hydrocar
bon reactions ‘wherein hydrocarbon vapors are 10 catalyst‘ and discharging it into the region of the
conversion chamber just above L or in the dis
treated with a catalyst in powdered form under
engaging chamber 4 where it serves to quench
conditions such that the conversion results in
the reaction products to temperatures below that
the deposition of combustible material on the cat
at which decomposition may occur. Thus the
I consider one of the main advantages of my 16 catalyst may be cooled to a temperature of say
300-500° F. and discharged in quantityinto the
invention to be that in the case of butene de
reaction products from which the catalyst ab
hydrogenation which is carried out at tempera
stracts heat and insures against losses by decom
tures around 1200"’ F., that preheating above
position or the butadiene, if that isthe product
this temperature before discharge into the re
action zone is avoided since heat is available in 20 being manufactured.
I am aware that prior to my invention ?uid
the conversion zone from the reaction taking
catalyst processes were known and used by others,
place ‘in the regeneration chamber. When a
and I do not claim such operation of any appa~
butene is preheated above 1200° F. there is danger
ratus therefor broadly.
of thermal degradation with consequent loss in
What I claim is:
yields. In the normal operation, due to the endo 25
1. The combination in a ?uid catalyst appa
thermic nature of the reaction, the feed stock is
usually heated above reaction temperatures to . ratus comprising a conversion chamber and a re
generation chamber contiguously and*~vertically
compensate for the heat lost during the endo
disposed, a foraminous member interposed be
thermic reaction of dehydrogenation. As indi
cated, this dangerous heating above reaction tem-' 30 tween said chambers, a disengaging chamber dis
posed immediately above said conversion cham
peratures is obviated in my process. Another ad
ber, the disengaging chamber being of, an inter
vantage of my invention is that because it is un
nal diameter greater than the said’ conversion
necessary to preheat above reaction tempera
chamber, feeding means for withdrawing pow
tures, it is not necessary to use expensive alloys
which must be used'when very high temperatures 35 dered material from the bottom'of the regenera
tion chamber, and conduit means adapted to'con
are employed. In the dehydrogenation of butene,
vey powdered material in the form of a suspen
according to my process, for the reasons given, the
sion to the conversion chamber, all substantially _
feed stock entering at 21 will not be heated above
as set forth.
reaction temperatures. or course, among the
2. In combination, a vertical elongated zone of
advantages of my improved apparatus is the 40
restricted cross-sectional area, a foraminous
maintenance of continuity of operation in a, single
member disposed in the said‘ elongated zone
unit or reactor, whereas in the ?xed bed type or
forming two chambers within said zone, a dis
operation it will obviously be necessary to use a.
engaging chamber superimposed on the upper
plurality of reactors to maintain overall con
tinuity of operation since in that type of opera 45 end of said elongated zone, said disengaging
chamber being of greater cross-sectional area
tion it is necessary to discontinue the reaction to
regenerate the catalyst. This plurality of re
than the ?rst-named zone, a standpipe in com
actors greatly complicates and increases the nec
munication with the uppermost of ‘said chambers,
adapted to withdraw powdered material by grav
essary equipment, requiring among other things
complicated manifolding systems and automatic
valves, both of which are apt at any time to get
out of working order.
ity therefrom, a gas-solid mixing means disposed
at the lower end of said standpipe, conduit means
‘ extending into said mixing means adapted to
convey a gas into said last-named means where;
Another advantage ‘of my processis that in a
?xed bed type of operation a large part of the
by solid material therein may be dispersed in said
cost of catalyst preparation lies in forming the 55 gas, and conduit means connecting the said mix
catalyst into pills. In my operation, the catalyst
ing means with the bottom of the lowermost said
chambers , whereby a suspension may be dis
is simply a powder and does not have to be pilled.
A further advantage of my invention is that in _ charged, into said bottom of said lowermost
?xed bed units the contact time between gas and
3. The combination of a ?uid catalyst appa
catalyst in'the reaction zone must be very short, 60
ratus comprising a vertical, elongated, substan
, say of the order of 0.3 second, in order to prevent
tially cylindrical shell type vessel, a foraminous
degradation of the butadiene formed. This
member interposed at substantially the mid
short contact time requires high temperatures in
vertical point of said vessel, the foraminous
order to get the desired conversion, and of course
it is the high temperature which causes the degra 65 member forming a demarcation between an up
per conversion chamber and a lower regeneration
dation of the product. In my apparatus I may
chamber, a disengaging chamber superimposed
operate at considerably lower temperatures and
on said conversion chamber, the said disengag
may therefore extend the contact time to '10 sec
ing chamber being of greater cross-sectional area
onds, which means that I may operate at around
1000° F. as compared with the 1200° F. tempera 70 than said cylindrical vessel, means for causing
ture commonly employed in the ?xed bed type of
outside circulation of powdered material contin- ,
uously between said conversion and regeneration
Numerous modi?cations of my invention may
chambers, means for supplying a reactant to a
be made without departing from the spirit there
point at the lower end of the conversion cham
of. For example, in line 25 (Fig. I), I may dis 76 ber, conduit means for supplying regeneration
gas to the lowermost point at the bottom of said
regeneration chamber, and means disposed at the '
upper portion of said disengaging chamber for
withdrawing gaseous material.
4. The apparatus set forth in claim 3,-in which
ber a ?uidized powdered catalyst material, caus
ing the powdered material to gravitate through
the means for circulating powdered material be
the gas in the conversion chamber to permit said
a foraminous member into a regeneration cham
ber contiguously disposed immediately below said
conversion chamber by regulating the velocity of
tween the said chambers comprises a solid feed
ing means disposed at the lower end of said re
gravitation, contacting the catalyst in the re
generation chamber with steam whereby con-'
generation chamber adapted to withdraw pow
taminants thereon are consumed and catalyst is
dered material therefrom, an injection means l0 revivi?ed, withdrawing revivitied catalyst from
adapted to form a suspension of said powdered
the bottom'of said regeneration zone, and recy
material and a gasiform material, and conduit
means adapted to convey the suspension formed
in the injection means to the conversion cham
cling it substantially uncooled to a point near the
top of said conversion zone.
5. 'Ihe apparatus set forth in claim 3, in which
the means for causing circulation of powdered
material between the conversion chamber and
the regeneration chamber comprises a standplpe
preheated oleflns into a vertically disposed con
version chamber of restricted cross-sectional
area, simultaneously discharging into said cham
7. In the catalytic dehydrogenation of olefins,
the improvement which comprises discharging
' ber a ?uidized powdered catalyst material, caus
whose upper end is in communication with the 20 mg the/powdered material to gravitate through
upper portion of the conversion chamber and
a foraminous member into a regeneration cham
whose lower end is in communication with an in
ber contiguously disposed immediately below- said
Jection means, means for injecting a gaseous me
conversion chamber by regulating the velocity of
dium into said injection means to form ‘a sus
the gas in the conversion chamber to permit said
pension, and conduit means -for conducting the 25 gravitation, contacting the catalyst in the re
suspension formed ‘in the injection means into
generation chamber, with steam whereby contam
the lower portion of the regeneration chamber;
inants thereon are consumed and catalyst is re
6. In the catalytic dehydrogenation of butenes,
the improvement which comprises discharging
preheated butenes into a vertically disposed con
version chamber of restricted cross-sectional
area, simultaneously discharging into said cham
vivi?ed, withdrawing revivi?ed catalyst from the
bottom of said regeneration zone, and recycling
30 it substantially uncooled to a point near the top
of said conversion zone.
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