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Патент USA US2405364

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Aug. 6,1946.
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- H. R. MARKLEY-
‘
2,405,364
HYDRQOARBON ‘CONVERSION PROCESS AND ‘APPARATUS
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Filed on; 5; 1942*
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INVENTOR.
.
HOWARDIRHINEHART MARKLEY‘
BY
ATTORNEY.
Patented Aug. 6, 1946
2,4053%
UNITED STATES PATENT OFFICE
2,405,364
HXDROCARBON CONVERSION raoosss
AND APPARATUS
I
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Howard B. Markley, Oklahoma City, Okla, as
signor to Phillips Petroleum Company, a corpo
ration of Delaware
Application October 5, 1942,, Serial No. 460.855
5 Claims.
1
(Cl. 260—683.5)
This invention relates to hydrocarbon conver- sions and more particularly to a method of ob- -
taming satisfactory operation of such conversions
tions involve considerable hazard to personnel, the
deposits thus removed are completely lost or are
contaminated by contact with air and arevnot re
wherein material is deposited from a ?ow stream
turnable to the catalystvchambers, and the clean
at an undesired point in the process ?ow. Still 5 ing operations subject the equipment to additional
more particularly it relates to a method of re
corrosion and wear.
moving solid metal halide catalyst deposits from
The principal object of the present invention
a point in the process ?ow at which they are un
desirable and redepositing the catalyst so re
is to provide a method overcoming all of the dis
, advantages just enumerated. Another object is to
moved at another and desired point in the system.
Even more speci?cally ‘it relates to an improve
ment in the isomerization of normal butane to
provide a highly improved method for removing
obstructions in equipmnet used for carryingout
conversions of the type described above. Another
isobutane by means of aluminum chloride as the
object is to accomplish removal of the catalyst
catalyst and wherein aluminum chloride is
deposits and return of the catalyst to the catalyst
present in volatilized form in the vaporous iso 15 chamber without disassembly of any equipment
merization e?luent and is deposited in subsequent
or exposure to air or moisture. Another object
portions of the apparatus, by which improvement
is to simultaneously preheat the feed stream and
these deposits are removed in a highly improved
remove the catalyst obstructions. dissolve and/or
manner and returned to the catalyst chamber.
suspend the catalyst so removed. in the feed and
The invention also relates to improved apparatus 20 return it thus to the. catalytic converter. Another
for carrying out the process aforesaid.
object is to provide a process of the foregoing
Thus, in known processes of isomerizing nor
type wherein normal butane is isomerized to iso
mal butane to isobutane by means of aluminum
butane
by means of aluminum chloride or bromide
chloride and in the presence of hydrogen chloride
and the vaporous reaction e?luentis condensed in
and wherein the eilluent is in the vapor phase, the
process being conducted‘ in the vapor phase," water-cooled condensers whereby» the vaporous
aluminum chloride or bromide deposits in and ob
volatilized aluminum chloride carries over with
structs-the condensers.
the vaporous e?‘luent from the catalyst chambers.
A further object of the invention is to partially
It is carried through separatory equipment, and
‘ upon cooling forms a solid deposit in water cooled
condensers and in lines between the catalyst‘
chambers and the condensers.
or completely dislodge or remove material car
30 ried
in the e?luent from a catalyst chamber and
This deposited
aluminum chloride causes reduction of flow, in
creased pressure drop, and at some points com
plete stoppage in the lines and condensers. It
also reduces the heat transfer in condensers and‘ '
the like.
Previous practice has been to provide parallel
deposited in a cooler or condenser or lines and
separatory equipment between the catalyst cham
ber and the cooler or condenser in order to relieve
a stoppage or- restriction of the flow caused by the
deposit. It is a further object to accomplish this
dislodgement or removal of the pressure or
velocity of a stream in the process ?ow used as a
?ushing stream. As will hereinafter appear, this
condensers and piping, and, as soon as clogging
or stoppage occurs in one condenser or line asso 40 ?ushing stream may or may not be entirely
mechanical in its action, it may or may not con
ciated therewith, to remove that condenser sec
tribute to, or be aided by vaporization, sublima
. tion from service and to put the other into serv
tion or dissolution of the deposited solid, and it
ice. The clogged or stopped equipment was then
may or may not be aided by the application ‘of
disassembled, as by removing the condenser heads
'
and cleaning the tubes thereof to remove the de 45 heat.
posits. This cleaning has heretofore been done ‘
Still another object is to carry the obstructing
either mechanically, as by passing suitable clean
material removed in accordance with the fore—
ing equipment through the tubes, or by a water‘
going objects with the ?ushing stream back to
Wash.
the catalyst chamber or to some other desirable
A great many disadvantages attend the prior so point in the process where it can be used again or
practice just outlined. Among them are the fol
discharged from the system.
lowing. Labor requirements are excessive, shut
Yet another object is to providev improved ap
downs are excessively frequent, interior corrosion
paratus for effecting the foregoing objects,
results from the introduction of air and atmos
Numerous other objects will hereinafter ap
pheric moisture and water, the cleaning Opera 55
pear.
V
2,405,364
4
3
The accompanying drawing portrays diagram
matically one arrangement of equipment which
has been found particularly suitable for carrying
out the process of the present invention as ap
manner and without opening up any equipment,
waste of solvent or waste of heat.
‘
Referring now to the accompanying drawing,
reference numeral l denotes the incoming normal
butane feed line. Pump 2 passes the feed through
feed heater 3 and thence via line 4 to catalyst
chamber 5. The preheated feed may pass from
mally solid ‘ readily volatilizable metal halide
line 4 via line 6, valve 1 and line 8 directly to
catalyst of the Friedel-Crafts type which appears
converter 5, although as will presently appear,
in the vaporous reaction effluent and gives trouble
by deposition in solid form in portions of the 10 after operation is established or if clogging is
encountered, it will pass at least partially through
processing equipment after the catalyst chamber.
one of parallel condensers 9 or Ill wherein it
In accordance with the present invention, the
effects a cleansing action and is additionally
foregoing objectives are attained by segregating
heated.
the clogged or restricted portion of the equip
Catalyst chamber 5 is provided with the metal
ment following the catalytic converter from the 15
halide catalyst, usually aluminum chloride. The
path of the conversion e?luent flow, directing said
reaction eilluent in vaporous form leaves via line
e?luent through an alternative or duplicate por
H and then passes through that one of con
tion of equipment, directing a portion or all 'of
densers 9 or NJ which is not being cleansed by
the hydrocarbon feed in liquid phase, vapor phase
ormixed phase through the clogged or restricted 20 incoming feed, and leaves the system via line l2
equipment preferably in a direction opposite to v for further processing after being cooled suffi
ciently to condense out the volatilized catalyst
that in which the e?luent flow took ‘place, thereby
together if desired with a portion or all of the
cleaning -out the restriction or stoppage, and
thence passing the hydrocarbon feed together . hydrocarbon content.
The regular ?ow may be from line 4 via lines
with the dislodged, vaporized or dissolved de 25
6 and 8 to converter 5, the e?luent passing through
posited material into the catalytic converter.
line I l and thence through one or both of valves
In a preferred embodiment, provision is made
13 and I4, condensers 9 and Ill and valves l5>and
for heating the hydrocarbon feed stream em
I6, respectively, to line [2 which conveys it to
ployed as the cleaning liquid prior to and during
its passage through the restricted or stopped 30 another part of the plant. Cooling water to con
densers 9 and I0 goes in via valves l1 and I8 and
section of equipment. Where this equipment is
leaves via valves l9 and 20 respectively. With
a water-cooled condenser cooled by water when
such ?ow, valves 2|, 22, 23, 24, 25, 26, 27 and 28
vaporous reaction effluent is passing therethrough,
would be closed.
i
this heating may conveniently be done by passing
steam through the water side of the condenser 35 . In the event an obstruction or restriction of
during the cleansing operation.
?ow occurs in the tubes of condenser 9 for exam
As brought out impliedly in the foregoing, it
ple, valves l3 and iii are closed, diverting all of
‘is preferred to provide duplicate equipment so
the chamber eiiiuent through condenser l0.
that one is being cleansed while the other is being
Valves l1 and i9 are closed stopping the water
used for e?luent ?ow. Thus where a water 40 circulation in condenser 9. Valves 23 and 25 are
cooled condenser is provided for condensing or
opened admitting steam to the water side of con
cooling the reaction eiiluent it is preferred to have
denser 9. Valves 22 and 21 are opened and valve
at least two so that onemay be cleaned by the
1 closed so that the feed stream is diverted
?ow of the conversion chamber feed while the .
through condenser 9 before entering the catalyst
other is condensing or cooling the chamber ef 45 , chamber. This flow is maintained until pressure
?uent. In this way, by switching the flow at
readings indicate that the restriction in con
predetermined intervals and‘ preferably before
denser 9 has been adequately relieved. 'I'he
deposition has occurred to an extent approach
valves may thenbe returned to their original
ing complete stoppage, the apparatus and process
positions and condenser 9 thereby returned to
may be operated continuously for extremely long 50 condensing service.
plied to the catalytic conversion of hydrocarbons
by means of aluminum: chloride or related nor
intervals without shutdowns.
'
' The invention is especially applicable to those
If an obstruction should occur in condenser ll),
opening and closing the proper valves in the
proper manner which will be obvious will divert
hydrocarbon conversions wherein a readily vol
atilizable normally solid material is employed as
the feed stream through condenser 9 so as to
the catalyst and wherein the-reaction eilluent'is 65 relieve its restriction.
'
a vapor. In such cases, the catalyst is vaporized
It will be obvious that the operation of the
and is present in the effluent in the vapor form
valves to effect the desired ilow may be done
> to a substantial degree with the result that upon
either manually or automatically. A convenient
cooling, as in the conduits and especially in con
method is to install automatic control means of
densers through which-said e?luent is directed, 60 such nature that alternate ?ow between parallel
deposition in solid form with restriction or even
equipment is controlled in response to the in
stoppage‘ of flow takes place.
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crease in resistance to flow or pressure drop
An example of a conversion where the inven
caused by the deposition of the catalyst, whereby
tion has found especial application is the isomer
the moment restriction of a predetermined extent
ization of normal butane to isobutane with alu 65 is built up, the e?luent flow and the feed flow are
minum chloride or bromide or related metal
halide as the catalyst and in the presence of
hydrogen halide as a promoter, wherein the reac
tion is conducted in the vapor phase and the
e?iuent is in vapor phase. also. In such a conver
sion restriction or stoppage of following equip
ment, including lines and especially water-cooled
condensers, is commonplace. This invention
switched or alternated.
I
An especially valuable way of carrying out con
version of the type described herein is, through
70 out operation, to alternate the ef?uent flow (and
the feed ?ow correspondingly) between two con
densers. By operating in this manner stoppage
or serious restriction is completely avoided. It is
' preferred to do the switching before the deposited
completely eliminates such restriction or stop
page in a simple, convenient and economical 76 catalyst seriously interferes with ?uid ?ow or
2,405,364.
5
‘In this way ‘absolutely :trouble
"free operation vpractically inde?nitely is assured.
‘It will be 'obvious that parallel lines and'par
7 heat transfer.
allel units of all equipment which may be in
stalled between the ‘catalyst chamber and the
condensers may be advantageously provided’iin
‘the same way as duplicate alternately employed
e?luent condensers are described above ‘and that
in ‘such .case ‘the same procedure described ‘for
the "parallel condensers is used to :?ush either
line or unit of equipment so ‘interposed while .the
other is in service on the chamber .e?luent.
remove the deposits in ‘the condensers 9; and "I0,
it will be understood that it ‘may be inJIiquid ‘or
liquid-vapor phase. It will also be ‘understood
that the feed may be cold as'it enters condensers
9 and I0 and converted to the vapor‘phase or to
mixed phase .as it passses'therethrough. It is
further to be noted that the conversion step in
5 may be conducted in vapor phase or in vapor
liguid phase.
I C-laim:
,
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V
:1. 1A;pr.ocess .for the vapor-phase isomerization
'
of, normal :butane which comprises ;,passing a va
porous feed comprising normal butane and an
following:
.
hydrous hydrogen {chloride through an elongated
lJL-ess .labor 1-is required and .in case of auto-. "15 reaction zone containing ,a body of anhydrous
- matic switching :practically no labor is involved.
aluminum chloride : catalyst under, conditions ef
2. "The system is :subject to ‘fewer shutdowns
fecting substantial :formation, of isobutane "and
Among the advantages of "the invention are the
entailed by cleaning operations. Where periodic
concomitant sublimation _of~m-inor amounts of
switching is practiced'be'fore a serious restriction ' aluminum ‘chloride from' saidcatalyst into the
or obstruction is built up, practically no shut 120 Vaporous reaction mixture, ?owing vaporous .re
downs for cleaning are necessary.
action e?luent to a separation zone in a restricted
3. Interior corrosion resulting from the intro
stream under such conditions that flow would
duction of air and atmospheric moisture and
eventually be stopped by clogging of the restricted
water as in other methods is completely elimi
path of flow by deposition of sublimed aluminum
nated.
25 chloride from said e?luent, periodically passing
4. The personal hazard from cleaningopera
said e?luent through an alternative path of ?ow
tions is greatly decreased.
5. The deposited material, which may still be
valuable as a catalyst, may be returned in its
entirety and without contamination to the cata
lyst chambers where it can be used again.
6. As compared with a method of removing the
deposits by circulating a special solvent in an
auxiliary closed system temporarily provided and
in which the special solvent passes through the
clogged equipment, the invention presents the
thereby isolating the deposited aluminum chloride
in said ?rst-named restricted path of flow from
contact with said e?luent, passing through said
30 isolated ?rst-named restricted path of flow in a
reverse direction and on to the inlet of said re
action zone a minor portion of vaporous feed
comprising normal butane under conditions ef
fecting sublimation of deposited aluminum chlo
ride and consequent freeing of said restricted
path of flow from clogging material, returning
said effluent to its thus-cleansed former path of
flow, and continuing during the entire series of
steps a continuous ?ow of the major portion of
advantages that the ?uid stream used in my in
vention for ?ushing the clogged equipment is a
part of the process flow, being the feed to the
system so that it passes to the converter and 40 said vaporous feed comprising normal butane and
carries the removed catalyst deposits thereto, and
hydrogen chloride without interruption of con
is much cheaper to use than it would be to circu
tinuity and without change in direction of flow
late a special solvent.
into and through said reaction zone.
The invention is particularly applicable to car
2. The process of claim 1 in which said first
rying out hydrocarbon conversions wherein the 45 named restricted path of flow is normally cooled
e?luent vapors contain a vaporized normally solid
to condense said vaporous reaction eii‘luent prior
catalyst which is normally deposited in solid form
to passage thereof to said separation zone, in
in subsequent lines and equipment. Normally
which at least two such normally cooled re
solid metal halide catalysts of the Friedel-Crafts
stricted paths of ?ow are provided, one being
type are especially troublesome. Particularly
cleansed by directing said minor portion of
troublesome are the aluminum halides, especially
aluminum chloride and bromide. Another sub
limable catalyst is zirconium chloride which is
becoming increasingly important in operations
where aluminum chloride has heretofore been
used. Numerous other readily sublimable metal
halides may be employed.
In some cases the vaporized component of the
eilluent that gives trouble by deposition in solid
vaporous feed therethrough and simultaneously
heating said path of ?ow which is being cleansed,
while another is being used in the normal man
ner for condensing said e?luent, and in which
the ?ow is switched after the clogging material
in the one is adequately removed.
3. 'The process of claim 1 in which said periodic
passing of effluent through an alternative path
of ?ow while cleansing said ?rst-named re-_
form in later equipment may be a material other 60 stricted path of ?ow is effected automatically in
than a catalyst, such as sulfur, etc. It may be
response to the attainment of a predetermined
a material being converted, e. g. naphthalene or
increase in pressure drop across said restricted
anthracene, or it may be a conversion product
path of flow caused by deposition of aluminum
or any other normally solid vaporous component
chloride therein.
of the e?luent which can be vaporized without 65
4. Apparatus for treatment of vapors which
decomposition and which it is desirable to return
comprises a treating chamber containing a
to the converter unit.
volatilizable treating agent, a vaporizer, a con
It will be obvious to those skilled in the art
duit for ?owing vapors from said vaporizer to
that numerous modi?cations may be made in the
one end of said treating chamber, a conduit for
illustrative embodiments described herein with
?owing treated vapors from the opposite end of
out departing from'the inventive concept which
said treating chamber into either of two con
is to be taken as limited only by the spirit or terms
densers, a conduit for flowing resulting con
of the appended claims.
densate from either of said condensers, a branch
While ordinarily the feed is in vapor form after
conduit leading from said ?rst-named vapor con
it traverses the feed heater 3 and as it is used to
duit for ?owing vapors to either of said con
" 2,405,364
7
.E‘densers'; a conduit for flow'ingtthese vapors from
said vcondensers back into said ?rst-named con
* duit'at a‘ pointtherein subsequent to said branch
conduit, means for supplying "cooling water to
‘either of said'condensers, and‘ means for supply
- ing' steam‘ to either of said condensers.
T‘ 5'. ‘A process for the vapor-phase-conversion of
8
halide from said‘e?iuent, periodically passing said
‘e?iuent through an alternative path of ?ow
thereby isolating the deposited metal halide in
said ?rst-named restricted path of flow vfrom
contact with said eiiluent, passing through-said
isolated ?rst-named restricted path of flow in a
reverse direction and on to the inlet of said re
action zone a minor portion of vaporous hydro
hydrocarbons which comprises passing a vapor
carbon feed under conditions effecting sublima
ous hydrocarbon feed through an elongated re
action zone containing a body of anhydrous nor 10 tion of deposited metal halide and consequent
freeing of said restricted path of ?ow from clog
mally solid volatilizable metal halide catalyst of
the Friedel-Crafts type' under conditions effect
ing’substantial ‘conversion ofisai'd' hydrocarbons
and concomitant“sublimation ‘ of‘ minor amounts
ging material, returning said e?iuent to its thus
cleansed former'path of ?ow,';andvcontinuing
during the entire series of steps a continuous
of = metal haiideifroi'nyv said‘ catalyst into the. 15 flow of the major portion of said vaporousieed
without interruption of continuity and without
j vaporous 'reactioniniixture; flowing vaporous re
change in direction of flow into and through said
Y action e?iuent to 'a’separationjzone in a restricted
istrean'i' under‘ such'con'ditions that ?ow'_ would
' eventually be stopped by ‘clogging of the restricted
j path"'of flow by. deposition of sublimed metal 20
reaction zone.
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‘HOWARD R. MARKLEY;
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