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Патент USA US2405097

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July 30, 1946.
F. c. NEUHART
~
2,405,097
PROCESS FOR NONDESTRUCTIVE- HYDROCA_RBON CONVERSION
Filed G612. 5, 1942
HYDROCARBON & H CL.
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RECYCLE OF HCI
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SLUUGE DISPOSAL
FNVENTOR
FRED C4 NEUHART
53
Patented July 30, 1946
2,405,097
UNITED STATES PATENT OFFICE
2,405,097
PROCESS FOR NONDESTRUCTIVE
HYDROOARBON CONVERSION
Frederick C. Neuhart, Shidler, Okla., assigncr to
Phillips Petroleum Company, a corporation of
Delaware
Application October 5, 1942, Serial No. 460,854
1 Claim.
(Cl. 260—683.5)
1
2
This invention relates to non-destructive hy
drocarbon conversion processes utilizing sludge
ence in this application to sludges refers pri
marily to sludges formed by contact of the hy
forming metal halide catalysts of the Friedel
Crafts type. More, particularly it relates to the
drocarbon reactants with aluminum chloride,
actions catalyzed by aluminum chloride, alumi~
and/or suspended therein.
rather than to suspensions or slurries of alumi
utilization of metal halide-hydrocarbon sludges C21 num chloride prepared for direct use as a primary
formed in non-destructive hydrocarbon con—
catalyst, although the sludges may have appre
versions such as isomerization and alkylation re
ciable quantities of aluminum chloride dissolved
num bromide, and the like.
The utilization of such sludge to avoid wast
Of great commercial interest at the present 10 ing its catalytic activity would be of appreciable
time are the isomerization and alkylation of low
economic advantage and would also simplify
boiling hydrocarbons, particularly members of
problems of sludge disposal. My invention pro
the para?in series such as the butanes and pen
tanes. \In these reactions a simple chemical.
change is effected under relatively mild condi
tions.
In the case of isomerization a change in
vides for such utilization in an effective manner
as will be hereinafter described.
formation and the rate of depletion of its cata
carbon skeleton without change in number of
lytic activity is provided. The sludge formed by
carbon atoms occurs, and in the case of alkyla
tion the direct union of two molecules, such as
an isopara?in and an ole?n, occurs to produce
the process of this invention is relatively free
from asphaltic or tarry materials, and has ap
preciable catalytic activity which maybe ex
a higher molecular Weight saturated hydrocar
bon. These reactions are known to be catalyzed
to a greater or lesser extent by the so-called
Friedel-Crafts
type
metal
halide
ploited at mild conditions of temperature similar
to those used in the reaction zone proper.
Aluminum chloride sludge has been found to
be highly corrosive to most ordinary metals and
catalysts,
among the better known of which may be men
tioned aluminum chloride, aluminum bromide,
boron ?uoride, zinc chloride, ferric chloride,
antimony tri?uoride, and other polyvalent metal
Furthermore
15 an automatic balance between the rate of sludge
25 other materials of construction when in motion.
Thus it would be relatively undesirable to use
such sludge by circulation at relatively high
rates of ?ow, bubbling gaseous reactants through
halides. Aluminum chloride has to date re
it, or subjecting the sludge in other Ways to
ceived the greatest commercial acceptance due to 30 violent agitation. One preferred aspect of my
its activity, relatively low cost, and availability.
invention is the utilization of the catalytic ac
Accordingly, because of its importance, and for
tivity of sludges in such a manner as to avoid
the sake of convenience, I shall describe my in
erosion and/or corrosion problems from motion
vention with particular reference to the isomeri
of the sludge.
zation of normal butane to isobutane as catalyzed 35
It is an object of this invention to provide for
by aluminum chloride. Application of the in
improved non-destructive hydrocarbon reactions
vention to other similar hydrocarbon conversions,
wherein a Friedel-Crafts type metal halide is
using aluminum chloride or other Friedel-C‘rafts
used
as catalyst under relatively mild conditions.
type metal halide catalysts which form sludges
under the conditions of operation, will be ap 40 Another object is to provide for the utilization
of metal halide sludge formed during such re
parent to those skilled in the art in view of the
actions. A further object is to provide for carry
disclosure to follow.
ing out such hydrocarbon conversions as isomeri
In an isomerization process utilizing anhy~
zation, alkylation and the like with aluminum
drous aluminum chloride as a catalyst, the
halide and similar catalysts continuously. Yet
aluminum chloride may be charged to the proc
another object is to utilize the catalytic activity
ess either as a solid, or as a slurry formed by
dissolving and/or suspending a considerable
of aluminum chloride-hydrocarbon sludges.
amount of aluminum. chloride in hydrocarbons or
Still another object is to provide for establish
other suitable liquids. In either case, a liquid
ment of a balance between the rate of sludge
sludge is formed after a short period of opera 50 production and the rate of deactivation thereof
tion, and the sludge, which at the outset is active
in such processes. A still further object is to
as a catalyst, gradually becomes deactivated with
prevent severe erosion and corrosion of equip
use. Such sludges may comprise complexes of
ment used in the process. Another object is to
aluminum chloride with hydrocarbons, as well as
provide‘ suitable apparatus for such processes.
dissolved aluminum chloride. In general, refer
55
Many other objects and advantages of the in
2,405,097
3
vention will become apparent as the disclosure
proceeds.
In general, in carrying out the invention,
sludge formed during conversion of the low-boil
ing hydrocarbons over solid aluminum chloride
and similar catalysts, is contacted with incoming
reactants prior to their contact with the catalyst.
This is done in such a manner that the catalytic
activity of the sludge serves to effect an appre
ciable proportion of the desired conversion, and
the sludge becomes more or less completely de
activated. This is preferably accomplished by
dividing the catalyst chamber into an upper and
a lower section, ?lling the upper section with
4
which the invention may be applied. Tempera~
tures in the sludge contacting zone will generally
be about the same as those in the catalyst zone
with a small temperature gradient sometimes be
ing found due to heat of reaction. Hydrocarbons
may be passed through the apparatus in gaseous
or liquid form with the former often being pre—
ferred. Catalyst activators such as hydrogen
halides and the like are often used.
The accompanying drawing shows diagrammatically one form of apparatus for carrying out
the isomerization of normal butane to isobutane,
portions of the outer walls of the chambers being
cut away to expose the contents thereof to view.
The drawing and description will also serve to
solid granular anhydrous aluminum chloride 15 exemplify my invention. Numerous other modi
either alone or supported on inert carrier mate
?cations may be used, for carrying out isomeri‘
rials, and ?lling the lower section with stone
zation or alkylation reactions and the like by
rings or other suitable inert packing. The hy
following the teaching of this disclosure, and
drocarbons to be converted are passed continu
no particular limitations are therefore implied.
ously upwardly from the bottom of the chamber
In the drawing, dry gaseous normal butane,
through the packing and the solid aluminum
either pure or containing minor amounts of iso~
chloride respectively. The sludge produced from
butane and/or lighter gases, such as propane,
the solid aluminum chloride as the conversion
along with activating amounts of anhydrous hy
proceeds, drains downwardly onto the packing to
drogen chloride or other activating agent, is in—
give a highly extended surface of active sludge. 25 troduced to the system and into the bottom of
An automatic sludge balance is established by
catalyst chamber l through conduit 3. The hy
this arrangement because the greater the per
drogen chloride in most cases will comprise from
centage of the conversion borne by it, the smaller
3 to 15 mol per cent of the feed and may be
the volume of the sludge produced from the solid
introduced into the reaction chamber in other
aluminum chloride; and as its activity becomes 30 ways if desired. It is sometimes quite advanta
depleted, more and more of the conversion is
geous to introduce the hydrogen chloride sepa
borne by the solid aluminum chloride which in
rately into chamber l somewhat above the level
turn automatically produces more sludge to re
of the inlet of line 3, at or below the level of
place that deactivated. Although not so satis
11 by means not shown. In this way the
factory, the solid catalyst may be disposed in one r plate
concentration of hydrogen chloride at the bot
chamber and the packed section provided in a
tom of chamber l, and in the sludge withdrawn
separate chamber, with the sludge being contin~
uously or intermittently transferred from the
therefrom, is reduced to a minimum with an
attendant reduction of corrosion. Hydrogen
chloride incorporated in the sludge from the
4-0
any suitable means.
upper part of chamber I is suflicient for promot
Another advantage of the arrangement de
ing any catalytic reaction occurring in the lower
scribed above is that the motion of the sludge
part thereof, but is almost completely stripped
at the walls of the containing vessels is reduced
from the sludge by the gaseous butane by the
to a minimum, the flow rate of sludge through
time the sludge reaches the bottom of the cham
the apparatus is slow, and consequently the
ber. Chamber i is operated at a pressure of 100
erosion and/or corrosion is reduced su?iciently
to 150 pounds per square inch gauge and a tem
to permit the use of steel and other ordinary ma
perature of about 200° F. The feed introduced
terials of construction.
7
through conduit 3 is heated to the approximate
catalyst ?lled chamber to the packed chamber by
The contact time of the hydrocarbon reac~
reaction temperature by means not shown. If
tants with sludge will vary with the type of con 50 necessary the butane is dehydrated before enter
version involved. This contact time is generally
ing the system. The flow rate will. generally be
chosen so that the sludge removed from the
between about 0.1 to 2.0 liquid volumes of hydro
bottom of the packed contacting zone is sub
carbon feed per volume of catalyst chamber per
stantially deactivated. The automatic balance
hour.
between sludge formation and depletion referred
Granular solid anhydrous aluminum chloride
to above, operates in any case and it is merely
of about 20 mesh or larger is packed into the
a matter of experiment to choose a contact time
top of chamber I, being separated from the bot
which gives optimum utilization of catalyst activ
tom part of this chamber by means of a screen
ity for a particular type of conversion. When
it or other means which will permit the reacting
the preferred type of catalyst chamber contain
ing a packed section below the catalyst proper is
used, sludge may sometimes be removed from the
60 hydrocarbons to pass upward through the full
length of the tower and the sludge to ?ow down
ward over the packing. Screen 4 may be dis
bottom thereof and passed to one or more other
pensed with and the solid aluminum chloride
packed chambers for contact with at least part
allowed to rest on the upper surface of the pack
of the incoming reactants in order to deplete 65 ing. The packing which ?lls the bottom section
completely any catalytic activity remaining in
of chamber I may be ceramic-ware rings or other
the sludge. In effect such subsequent chamber
contact material not readily attacked by alumi
or chambers function as extensions of the ?rst
num
chloride.
packed section. Sludge expelled from the sys
As the isomerization reaction proceeds, a liquid
tem may be sent to sludge disposal or to a process
aluminum chloride sludge is formed which con
for the recovery of metal halide as desired.
tains
considerable aluminum chloride that is still
Temperature and pressure conditions used in
catalytically active insofar as the isomerization
my process are mild so that no extensive decon1~
reaction is concerned. The sludge produced runs
position occurs, being ordinarily the conventional
down from the solid aluminum chloride and dis
conditions for the various types of conversions to
2,405,097
tributes itself upon the packing in such a manner
as to give a highly extended surface of catalyti
6
pressured into the top of chamber 2 through con
duits 1 and 9. Chamber 2 is similar to the lower
part of chamber l, containing packing adapted
to be converted upward from the bottom through
to insure intimate contact between sludge and
chamber I, they ?rst come into contact with the CI hydrocarbons.
All or part of the butane and hy
least active aluminum chloride sludge and as
drogen chloride feed to the system may be passed
they progress upward they come in contact with
through chamber 2 in contact with the sludge
sludge which is more and more active until ?nally
before entering chamber 5. Conduits 5d and l l
the solid aluminum chloride is reached. A sub
stantial part of the hydrocarbon conversion will 10 are provided for this purpose. 'Valves 5:, l3, l4,
and I5 are provided in conduits 8, 9, l9, and H
have taken place before reaching the solid alu
for
shutting off chamber 2 entirely or for control
minum chloride. The remaining hydrocarbon
ling the ?ow of hydrocarbons and sludge there
conversion will be brought about by the solid
through as required. Isomerization of part of the
aluminum chloride, and simultaneously alumi
butane
is accomplished in chamber 2 and the
num chloride sludge will be produced which ?ows
remaining catalytic activity of the sludge is thus
down onto the packing in the bottom of chamber
exploited. The spent or deactivated sludge from
I to replace the sludge that has been spent or
chamber 2' is collected in receiver l5 and may pass
deactivated.
therefrom through line 11 to subsequent use,
The amount of sludge formed will depend upon
sludge disposal, aluminum chloride recovery
the percentage of conversion load the solid alu~
processes, etc.
minum chloride has to bear. For example, if
As has been indicated previously, it is preferred
there is very little sludge, or what sludge there is
that the charge stock be dried .before being passed
in the bottom part of chamber l is largely spent
to the system. However, it has been found that
or deactivated, very little hydrocarbon conversion
most
commercial dehydration processes leave
will take place in this part of the chamber. Con
minor
amounts of water in the effluent hydrocar
sequently the solid aluminum chloride will have
bon material, ordinarily of no great consequence
to bring about a larger percentage of the conbut enough to have an adverse effect upon alu
version which in turn results in the formation of
minum
chloride. My process has the additional
sludge in relatively large quantities which ac
advantage that the charge is thoroughly dehy
cumulates in the bottom of the chamber. As
drated by the sludge before the hydrocarbon ma
additional butane is brought into the tower for
terial reaches the aluminum chloride. Other
conversion, the sludge produced will bear a sub
impurities in the charge are also removed by the
stantial part of the conversion load and the
cally active sludge. By passing the hydrocarbons
solid aluminum chloride a smaller part
fore. Therefore, a smaller amount of
produced. Thus an automatic balance
tained between the rate of formation
than be
sludge is
is main
of fresh
sludge.
There are other ways in which this process may
“ be practiced other than those indicated by the
drawing without departing from the spirit of the
invention. For example, any number of cham
bers such as chamber l or chamber .2 or both,
the rate of deactivation of the sludge.
The e?luent from chamber l which leaves the 40 may be employed. Either parallel or counter
current flow of the hydrocarbon with respect to
top thereof through conduit 5 comprises uncon
the
sludge flow, or combinations of both, may
verted normal butane, isobutane produced in the
be used, although the countercurrent how of
process, traces of 5-carbon-atom and heavier hy
sludge and hydrocarbons in chamber l as shown
catalytically active aluminum. chloride sludge and
drocarbons,
hydrogen
chloride,
and
minor
amounts of other gases lighter than isobutanc ,
which may have been introduced into the feed
and/or
chamberproduced
1. Hydrogen
by side reactions
propane are
occurring
frequent—
the drawing is preferred. The relative direc
tions of flow in chamber 2 may be varied with
more latitude. Chambers or towers may be op
erated in series or parallel or combinations of
both. Other systems of sludge collection or dis
ly used in the process to minimize undesired side
posal
from the chambers may be employed.
reactions and maintain catalyst life. The amount
of propane used may be as high as in per cent so While the use of packed towers is preferable for
the reasons hereinabove set forth, other means
or more, while smaller volumes of hydrogen are
for
contacting sludge with reactants may be used.
usually used, if at all. It will be noted that the
This invention is applicable to non-destructive
total volume of reactants and products passes
hydrocarbon conversion processes using alumi
through ?rst the sludge and then the primary
catalyst without any intermediate or concomit i; 5 num chloride or other Friedel-Crafts type metal
halide as the conversion catalyst, provided a liq
ant separation of products. The further treat
uid sludge still catalytically active results. It is
ment of the e?iuents in conduit 5 is shown on the
drawing diagrammatically by unit l8; it will be
understood that these e?luents may be subjected
to any of the separating or other steps known
to the art. These usually include the recovery
of isobutane as a product of the process through
conduit l9, and separation of hydrogen chloride,
at least part of the propane, and unconverted
normal butane, which are recycled via conduit
20 to catalyst chamber I. Various other expedi
ents which are known to the art will, of course,
be utilized as particular circumstances indicate.
The sludge expelled from the bottom of cham- ‘
her I is collected in receiver 6 from which it may
be removed and discarded or sent to other dis
posal or utilization by conduits 1 and 8. If it is
impractical to deactivate the sludge completely
in chamber I, all or part of it may be pumped or
particularly applicable to hydrocarbon conver
sions such as isomerization and alkylation, espe
cially when low-boiling hydrocarbons such as
pentane and lighter are involved.
I claim:
A process for the isomerization of normal bu
tens to isobutane which comprises passing an an
hydrous gaseous mixture comprising a major
proportion of normal butane admixed with minor
proportions of hydrogen chloride through at least
one packed chamber containing a packing ma
terial adapted to eifect intimate gas-liquid con
tact, passing a partially deactivated aluminum
chloride sludge from a source hereinafter de~
scribed into said chamber for contact with said
gaseous mixture at conditions of temperature,
pressure. and contact time to effect a preliminary
conversion of normal butane and to utilize cata
2,405,097
7
partial deactivation of said sludge and to e?ect
gaseous mixture into the bottom of a catalyst
in said upper section a further production of iso
butane and the formation of said sludge, remov
lytic activity of said sludge, passing resulting
chamber for upward flow therethrough, said cat
alyst chamber being provided in an upper sec
tion thereof with a solid anhydrous aluminum
chloride catalyst and in a lower section thereof
with a packing material over which aluminum
ing partially deactivated sludge from the bottom
of said catalyst chamber for passage into said
packed chamber as hereinabove described, pass
ing gases from the top of said catalyst chamber
to separating means, separating isobutane prod
chloride sludge formed from said catalyst be
uct, and recycling hydrogen chloride and uncon
comes distributed, at conditions of temperature, 10 verted normal butane to further isomerization.
pressure, and contact time to effect in said lower
FRED. C. NEUHART.
section a partial production of isobutane and a
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