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Патент USA US2404499

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july 23» 1945-
J. c». lvERsoN
2,404,499
ISOMERIZATION OF HYDROCARBONS
Filed May 30, 1942
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JOHN o. lv RsoN
ATTORNEY
2,404,499
Patented July 23, 1946
UNITED STATES
PATENT- OFFICE y
2,404,499
ISOMERIZATION OF HYDROCARBONS
_John O. Iverson, Chicago, Ill., assignor to Univer
sal Oil Products Company, Chicago, Ill., a cor
poration of Delaware
Application May 30, 1942, Serial> No. 445,145
13 Claims. (Cl. 260-683.5) y
l
»
This invention relates to a process for the
s
2.
A
Y
strictly thermal or high temperature thermal
isomerization of paraii'in hydrocarbons and par
catalytic methods.
ticularly those of normal or mildly b-ranched
structure to produce more highly branched
isomers therefrom.
more or less readily brought about by lContact
with such metal halides as aluminum chloride
While the process is particularly applicable to
the isomerization of individual hydrocarbons such
as normal butane representing normally gaseous
isomerizable parafilns and normally liquid paraf
v
.
The isomerization of parañin hydrocarbons is
and aluminum bromide. Alternative metal hal
ides not necessarily of equal efficiency include
zirconium chloride, zinc chloride, ferric chloride
or their bromides, or mixtures of these With each
fin hydrocarbons such as pentanes and hexanes, 10 other or With aluminum halides. These halides
may be used in a variety of Ways for the isomer
the process of the invention may be applied to the
treatment of hydrocarbon mixtures comprising
both parailins and naphthenes such as, forex
ample, straight-run petroleum fractions of gaso
line boiling range, valthough other types of hydro 15
carbon conversion reactions in addition to isomer- «
ization will take place in such treatments. As a
result of these treatments the antiknock prop
ization of hydrocarbons. One of the oldest ‘and
simplest methods consists in rellluxing the liquid
in the presence of granular and finely `divided
metal halides preferably With the addition of small
amounts of Water or hydrogen halide, the lower
boiling isomerv being taken overhead and con
densed. Other methods employ aluminum` chlo
erties of the gasolines charged are improved by
ride, for example, supported on `relatively inert
The isomerization of paraflin and naphthene
hydrocarbons to produce’more highly branched
the hydrocarbon containing dissolved or entrained
20 granular materials over which the hydrocarbon
the sum total of the reactions taking place.
or hydrocarbon mixture to be isomerized is passed
More speciñcally the present invention is con
in liquid or vapor phase along with the hydrogen
cernes with a mode of operation which involves
halide. More recent developments in continuous
closely cooperating steps, the process being par
processes have involved the passage of hydrocar
ticularly suitable for use in connection .Withgran-k
ular metal halide catalysts of the Friedel-Crafts 25 bons to be isomerized through beds oi granular
aluminum chloride and the further passage of
type such as aluminum chloride.
aluminum chloride into a reactor after the addi
tion of a hydrogen halide. In a packed reactor,
structure is becoming increasingly important in 30 this operation serves to maintain a definite
amount of active metal halide on the surface of
connection with petroleum refining. The isomer
the packing. The present process is concerned
ization of normal butane is important in view of
with improvements in this type of operation so
the fact that isobutane is considerably more re
compounds or compounds with more condensed
active than normal butane and can, for example,
that some of the operating diii'ìculties commonly
be more readily alkylated with oleiins such as 35 encountered are obviated.
In one speciñc embodiment as applied to nor
butenes to produce octanes of high antiknock
mal butane representing saturated isomerizable
value.v Butenes formed by the dehydrogenation
hydrocarbons the present invention comprises
of isobutane yield octenes which When hydrogen
passing said normal butane and hydrogen chloride
ated yield octanes of higher antiknock rating than
those produced by subjecting normal butane to a 40 through a stationary bed of granular aluminum
chloride under a temperature and pressure ade
similar series of steps. Normal butane generally
quate to effect isomerization while simultaneously
occurs in larger amounts than isobutane so that
introducing a portion of the cooler normal butane
its isomerization is frequently necessary if the
charge at spaced points in the aluminum chloride
greatest possible utilization must be made of the
gaseous products from petroleum distilling and 45 bed to control undue temperature rise therein,
cracking operations.
v
-
In the case of normally liquid hydrocarbon mix'
ilures such as straight run gasoline fractions either
passing the products from the aluminum-chloride
contact into contact with granular absorbent ma
terial for the removal of aluminum chloride con
tained in products While introducing further
of close cut or rather WideV boiling range proc
esses involving isomerization of paraffins are of 50 amounts of cooler butane charge at spaced points
in the absorbent material to control temperature
deñnite Value in that the treated fractions have
therein, fractionating the products from contact
increased antiknock rating so that the process
with the absorbent to produce hydrogen chloride,v
ovlTers a means of greatly improving the quality
isobutane and normal butane, recycling said hy
of gasolines Without the excessive losses frequently
encountered when fractions are reformed by 65 drogen chloride to commingle with normal bu
2,404,499 '
3
tane charge, recovering said isobutane and re
cycling said normal butane to further isomer
Vizing treatment.
In its broader aspect the feature of employing
portions of hydrocarbon charge at a temperature
lowerthan that obtaining in isomerizing reaction
zones to counteract the tendency for undue tem
peratures `rises `in .isomerizing- _reactors is 1appli-
passes through line 9 containing valve I0 and
line 9’ containing Valve Ill' to -contact with gran
' ular aluminum chloride contained in catalyst
chamber I3 while a substantially equal portion
passes through line I I containing valve I2 into
and through the granular catalyst contained in
catalyst chamber I4. In this strictly parallel op
eration of the two catalyst chambers the'eii‘luent
cable to any type .of continuous flow isomerizing
materials `from chamberfIS pass through line I5
process such as, for example, a process in which 10 containing valve I5 while those from chamber I4
isomerization is effected by merely passing the
pass through line I1 containing valve I 8, the
hydrocarbon charge mixed with a hydrogen hal
streams combining in line I9 containing valve
ide through a stationary bed ofVv granular ymetal
2D «and passing to Vthe succeeding chambers con
halide either alone or on a support,~or.in_processes
where isomerization is effected '.by the uselof _rela
tively finely divided catalyst which is carried up
` l Wardly through a reaction zone by lan ascending `
taining granular material. In case it is desired to
1.5 .operate the twocatalyst chambers in series, the
-eiliuent materials from chamber I3 may be 'di
Verted through line 33 containing valve 34 with
>valve I6 lclosed and pass through line 31 contain
stream of vapors of hydrocarbons followed by sep
aration of hydrocarbons and powdered catalyst
ing .valve .38 through line 25 containing valve 25
with return of the latter yto further catalytic use 20 and leading to line I I and thence through cham
. either with or without intermediate regeneration.
The features of the present invention and par
ticularly the use of relatively cool charge to con
trol temperature in theisomerizing zones will be
more fully described in connection with the a+
tached drawing which shows diagrammatically
by the Áuse of conventional ñgures in general side
elevation an arrangement of apparatus in which
the'process may be conducted. The description
of the operation'is given in connection with the
. treatment of normal lbutane in the interest of
ber I4 with valves 36 and 24 closed so that the
total eñ‘iuent materials passthrough line I] con
taining valve I8 to line I9. When chamber I4
is to be used as the ñrst ofthe series the chargev
is introduced through line I I containing Valve ,I2
with valve 25 closed and the e?liuent materials
from chamber I4 _pass through line 35 contain
ing valve 3S with valves I8 and 34 closed and
thence through line 31 containing valve 38 to
line 23 containing valve 24 and into catalyst
chamber I3 by way of >line 9’ with valve I 0"
` simplifying the description and making it more
closed.- The eñluent materials in this case pass
I readily understandable though it is to be under
through line I5 containing valve I6 with valve 34
stood that a similar characteristic flow may be
closed into line I 9.
,
used on other individual hydrocarbons or on hy 35
To eiiect cooling of the reaction zones an un
1 drocarbon4 mixtures particularly those represent
3 ed by 'hydrocarbon fractions of gasoline boilingv
heated portion of the charge passes through line
2i containing Valve 22 and may be then passed
through line 2l containing valve 28 to interme
Referring to the drawing normal butane is in
diate points ,in the `catalyst chambers by way of
troduced to the plant b-y Way of line I contain 40 line 29 containing valve 39 and leadingv to cata
` ing Valve 2 -leading t0 a charging pump'3 which
lyst chamber I3 or line 3| containing valve 32
. discharges through -line 4 containing valve 5. Re
and leading to catalyst chamberk III. The cool
cycled normal butane‘enters line I from line |23
ing _or “quenching” fluid is .shown as being intro
` containing valvev I'24 as will be subsequentlyde
duced at _one `single point in each chamber al
scribed. In accordance lwith the present inven 45 though >it is comprised within the scope of the
` tion `the `main portion ofthe char-ge to the isom- ‘ invention to introduce the .cooling material at
er'izing plant is'heated and passed to contact
any point or plurality kof points which are found
` with granular aluminum chloride while a minor
necessary to produce the best results. To provide
i portion is reserved .for effecting cooling in _the
for intermediate cooling between chambers when
isomerizing zone wherein there is a tendency for 50 they .are used in series, a regulated portion of
temperatures to Vrise unduly due to the eXo
-cooling fluid may .be _introduced either through
thermic vnature of the isomerization reaction.
valve 2I’ .into line 23 :or line 25 with valve 28
Thus, the major portion of the charge is passed
closed.
«
from Aline 4 through line 6 containing valve 'I and
In the second stage of the isomerizing process
l through a suitable heater 8 in which the charg 55 the _partially isomerized Ämaterials lfrom the ñrst
ing material is brought to an optimum tempera
zone in which they were contacted with alumi
ture for its isomerizing treatment. Unheated
num chloride are passed to a secondary treating
portions of 'the charge are passed through line
zone containing granular and preferably absorb
2| containing valve 22, and line 53 containing
ent material such as, for example, porous refrac
valve 54 for cooling purposes as will be described 60 tories, granular aluminas, such as bauxite clays
1in proper sequence. Provision is «made for pass
' either raw or acid treated, kieselguhr, etc, In
ing a portion of the original charge through a
Ithis stage further isomerizing action may occur
¿secondary heater 5I” in line 5I so that this por
as the partially converted hydrocarbons contact
tion of the charge may carry additional heat to
the absorbent which has taken up any aluminum
the stream of hydrocarbon material from the 65 chloride .carried over from the ñrst zone and at
`catalyst supply chambers I3 and I4 and permit
the same time metal halide-hydrocarbon com
_substantially ‘vapor phase operation in the reac
plexes are absorbed and removed from the reac
tion chambers 45 and ‘46 >while a substantial
tion products. Thus, in the ordinary operation`
amount -'ofxliquid‘phase ismaintained in the cat
of the process products of the primary isomeriz
„ alyst -supply chambers.
70 ing zone pass through _line I9 and valve 20 into
-The embodiment ofthe invention contemplates
chambers containing granular absorbent mate
1the use of lisomerizing reactors either in parallel, _> rial, these chambers being used in parallel, se
‘series or series-parallel connection. ThuS, in
ries or series-parallel connection as in the case
`parallel operation of reactors containing alumi
of the primary chambers, and .being provided
num chloride the >portion ofV the heated.> Charge 7.5 with means for temperature control by the in
range.
'
2,464,4ee
troduction our unheatedïcharge.
produc-tsv
from _line |,9Vmay be introduced by-'way of line
4| containing valve 42 to a packed chamber 45,
and another portion >of _the primary reaction
products may be passed'through line 43 contain
ing valve 44 to packed' chamber 46. ,A line' 39>
6
phase in the primary zone andvapor phase in
secondary zone.' In the caseof normal butane‘
satisfactory isomerization may be effected in theI
`setup of the present character by passing the"
normal butane through the aluminum chloride
catalyst chambers in substantial liquid phase and >
eiïecting isomerization in the succeeding second
containing valve 40 is also provided for the di
version or bypassing of a portion of the original
heated charge to the secondary reaction cham
ary zone in vapor phase. In the case of normally
liquid isomerizable hydrocarbons substantially
liquid «phase conditions may be maintained
bers as a means of temperature control therein.
When chambers 45 and 46 are operating in par-_
allel, the efliuent materials from chamber 45V will
follow line 41 containing valve 48 while those
throughout the primary and secondary zone. In
the case of normal butane temperatures of from
approximately 150 to 200° F. may be maintained
in the primary zone under pressures ofthe order
of 250 to 350 pounds per square inch while slight
from -chamber 46 follow line 49 containing valve
50, the two streams uniting in line 10 containing
valve 1| and passing to the succeeding fraction
ly higher temperatures of the order vof 200 to
220.D F. and the same or slightlyA lower pressure ls
ating zone. When the packed chambers are uti
used in the second zone.. The amount of hydro
lized in series with chamber 45 as the nrst cham
gen chloride present at any stage of the isomeri
ber the effluent materials from this chamber will
pass from line 41 through line 64 containing valve 20 zation may be varied to control the rate and
character of the reactions. As a rule, amounts>
65 with valves 48 and 61 closed and follow line
of from about 1 to about 20 mole per cent of
68 containing valve 69 and line 56 containing
lvalve 51 to enter line 43, withvalves 44 and 55
hydrogen chloride in respect to the hydrocarbon
. with valves 50 and 65 closed and through line 68v
are fractionated to recover those of desired char-.
or hydrocarbon mixture undergoing isomerization
closed. When chamber 46 is to be used as the
first in a series the eilluent materials will pass 25 may be used.
Following the isomerization stages the products
from line 49 through line 66 containing valve 61
acteristics, hydrocarbon recycle stocks and hy
containing valve 69 to now through line 54' and
valve 55 into line 4| with valves 42 and 51 closed.
In this case the total effluent materials will pass
through line 41 containing valve 48 into line 16.
drogen chloride. Thus, the total products from
the secondary isomerizing zone may be caused
to pass through condenser 'l2 wherein substan
tially complete liquefaction of all products isy ob
For cooling purposes in the secondary zone
tained and the liqueñed material passes through
containing granular material line 5I containing
valve 52 leading through heater 5|" and line 5|'
line 13 containing valve 14 to a receiver 15 pro
containing valve 52’ serve to admit heated 0r
cooler charge to line 4| or line 43. Line 53 con
taining valves 53’ and 54 permits the passage
of cooling fluid to line 58 containing valve 59
vided with a gas release line`16 containing a valve
To permit intermediate cooling between charn
dividing‘the lower section from the small upper-
11 for the’removal of uncondensed‘gases.
In the next step the hydrogen chloride is re
covered for reuse by a convenient means such as
distillation under relatively high pressures above
which has branch lines 6|] containing valve 6|
leading to an intermediate point in chamber 45 40 300 and usually of the order of 450 pounds »per
square inch. Thus'a pump 80 takes suction on
and branch line 62 containing valve 63 leading
the liquid material in receiver 15 by way of line
to an intermediate point in chamber 46. Again
18 containing valve 19 and discharges through
these single points of introduction are merely
line 8| containing valve 82 into a high pressure
to illustrate any single or any multiple points
fractionating column 83 containinga plate 84
which may be used as circumstances may require.
section. The vapors of hydrogen chloride andv
some light hydrocarbons pass through line 85
containing valve 86 and reflux is condensed dur
containing valve 51.
,
In the preceding description the ilow through 50 ing passage through overhead condenser 81 after
which hydrogen chloride passes through line 88
the catalyst chambers and packed chambers has
containing upstream pressure control valve 89,
been indicated as being upward but dovvnflows
line 88 leading to an intermediate accumulator
may also be used without departing from the
90 for the intermediate storage of hydrogen chlo
scope of the invention.
.
The preferred arrangement of the isomerizing 55 ride and whatever hydrocarbons have passed
overhead as vapor. From receiver 90 hydrogen
zones permits considerable ñexibility in opera
chloride is passed through line k9| ycontaining
tion. Thus the major amount of isomerization
' valve 92 to line 93 leading to line 6 and thence
may be brought about in the primary zones des
to the primary isomerizing step. Hydrogen chlo
ignated as “catalyst chambers” in contact with
ride suñicient to make up any incidental losses
granular aluminum chloride catalyst in the pres
in the processing is admitted from line 93 con
ence of hydrogen chloride; or the aluminum chlo
bers when they are used in series line 53 leads
to both line 54’ containing valve 55 and line 56
taining valve 94 as required.
ride in the primary zone may serve in the absence
of added hydrogenI chloride merely as a source
.
chloride is admitted only to the packed reaction
of supply of catalytic material to be deposited
on granular materials in the second zones desig
. '
To provide for operation in which hydrogen n
65 chambers line 9 | ' containing valve 92' is provided
to permit the recirculated hydrogen chloride and
any hydrogen chloride introduced from iline 93
chloride is introduced to assist in the isomerizing
to be introduced into line 5| ahead of Secondary
action. The choice of operating procedure will
heater 5|” and thence to the packed chambers.
depend upon the character of the hydrocarbon
The bottoms from fractionator 83 pass through
or hydrocarbon mixture which it is desired to 70
nated as “packed chambers,”` towhich hydrogen
isomerize. Similarly both temperature, pressure
and flow rate may be varied in the primary and
secondary zones so that substantially vapor phase
conditions may be made to obtain in both zones,
liquid phase conditions in both zones or liquid 75
line 95 and a cooler 95' and are then split into
a stream passing through line 96 and valve 91
and leading to line 10 to increase the'amount
of liquid and promotev more effective condensa
tion in condenser 12. `The main stream of bot
2&4045499,
toms.. isfpassed. through. >line 90 .containing valve.
mannerA with Y an overall. _yield of; riso-,butane ~ from.z
normal butane of 90 perk cent,"V the plant pro-._v '
duces4 a yield of f5`20barrels of iso-butane per
. 90 to'l a' treating >stage’designated as |00 where
it is treated to remove any traces of hydrogen
chloride, aluminum chloride or aluminum chlo
stream
ride complexes preferably by contact withY alka
line material such as aqueous caustic soda, be
Thus the treated materials from Zone
|00 Ypass through line |0| containing valve |02 10
and enter the isobutane fractionator |03 designed
to effect a substantially accurate separation of
this hydrocarbon. The vapors from fractionator
_|03 pass through line |04 containingr valve |05
and are liquefied during passage through con
,
.
.
l. A process for the isomerization of normal»
butane which comprises passing a portion of a
fore` the ñnal fractionation to produce isobu
tane and normal butane and separate heavy ma
terials.
day.
I claim as my invention:
normal butane charge mixed with hydrogen
chloride through a stationary bed of granular
aluminum chloride ata temperature and pres
sureV adequate to effect isomerization while simul
taneously introducing vfurther portions of the
normal butane chargent spaced points in the
aluminum chloride bed to control the tempera
15 ture therein, passing the products from the
denser |06 after which `they pass through line
aluminum chloride bed'into contact with granular
I06’_ to a. receiver |01. To assist in controlling
absorbent material while introducing further
the fractionation in fractionator |03 a controlled
portions of the butane charge at spaced points'`
portion of the condensed liquid. is returned to a
in the absorbent material. to control the tem
point `’near the top of the fractionator by a pump 20 perature therein, fractionating the products re
||Il which takes suction in on line |08 by way of
sulting from contact with the absorbent to re
lineIIlS’ and discharges through line ||| con.
cover hydrogen chloride, isobutane and normal>
Vtaininglvalve ||2, the main portion of the iso.
butane, recycling said hydrogen chloride to com
butane as a product of the process following line
mingle with the normal butane charge, recover
|08 and valve |09 to storage or use in other 25 ing said isobutane and recycling said norma
processes.
butane to further isomerizing treatment.
f
The bottoms from fractionator |03 consist
2. A process for the isomerization of normal
ing largely of normal butane together with some
butane which ,comprisesr passing. a portion of
heavier hydrocarbons pass through line | I3 con
a normal butane charge mixed with> hydrogen
taining valve | I4 to a fractionator ||5 operated 30 chloride through a stationary bed of granular
to effect the separation of normal butane. Thus
aluminum chloride at a temperature of from
the vapors of this compound pass through line
about 150 to about 200° F. and a pressure of from
I I6 containing valve I |`| andare liqueiied by pas
about 250 to about 350 pounds per squarev inch
sage through condenser IIB after which they
to effect isomerization while simultaneously in
flow through line ||8’ to a receiver ||9. Again
troducing further portions of the normalV butane
to assist in controlling the fractionation in frac
charge at spaced points in the aluminum chlo
tionator ||5 pump |25 takes a portion of the
ride bed to control temperature therein, passing
liquid from receiver ||9 by way of line |20 and
the products from the aluminum chloride bed
line |20' and discharges it through line |26 con
into contact with granular absorbent material
taining valve |21 into a point near the top of the 40 at a temperature of from about 200 .to .about
fractionator. The production of normal butane
220° F. -and under a' pressure corresponding to
follows line |20 containing valve |2| to recycle
substantially vapor phase 'conditions while in
pump |22 which discharges through line |23 con
troducing further portions of the butane chargeV
taining valve |24 into line I to commingle with
at spaced points in the material to control tem.
the fresh charge. Hydrocarbons heavier than 45 perature therein, fractionating the products _from
normal butane are withdrawn as bottoms from
contact with the absorbent under a pressure substantially in excess of 300 pounds per square
inch to recover hydrogen chloride, isobutane and
fractionator | I5 through line |28 and through
a. condenser |29 and are then removed through
line |30 containing valve |3| to a suitable
storage.
f
,
The following example is given to show typical
charge rates, yields and operating conditions
used in a process of the present character
though without the intent of correspondingly
limiting the scope of the invention.
The process is used to isomerize normal butane
and the-total combined feed to the process in
cluding fresh and recycled butane is 1,078 barrels
per day. 0f this materialr 269 barrels are pre
heated to a temperature of 190° 1*". and passed in
50
normal butane, recycling said hydrogen chloride
to commingle with the normal butane charge,
recovering said isobutane and recycling said
normal butane to further- isomerizing treatment.
3. A process for the isomerization of normal
butane which comprises passing a portionof
a normal butane charge mixed with hydrogen
chloride through a stationary bed of granular
aluminum chloride at a temperature of from
about 150 to about 200° F. and a pressure of
from about 250 to about 350 pounds per square
inch to effect isomerization while simultaneously
series through catalyst Supply chambers con
introducing further portions of the normal
taining granular aluminum chloride. 695 bar
butane charge at spaced points in the aluminum
rels of the combined feed and 14,600 pounds of
chloride bed to control temperature therein, pass
hydrogen chloride are passed through the main
ing the products from the aluminum chloride
(25
heater preceding the packed reaction chambers
bed into contact with granular absorbent ma
and heated to a temperature of 275° F. 114
barrels per day of the combined feed at a tem
perature of 157° F. is injected into the reactors
which are used in parallel to oii'set the tendency
toward temperature rise due to the exothermic
character of the i'somerizing reaction. A pres->
sure of 250 pounds per square inch is maintained
. upon both the saturators and the reactors and
the hourly liquid space velocity per volume of
reactor packing is 0.25. ` In operating in this
terial at a temperature ofv from about 200 to
about 220° F. while introducing further portions
of the butane charge at spaced points in the
absorbent material to control temperature there
in, fractionating the products from contact with
the absorbent under a pressure substantially in
excess of 300 pounds per square inch to recover
hydrogen chloride, isobutane and normal butane,
recycling said hydrogen chloride to commingle
with the normal butane charge, lrecovering said
2,404,499
10
ular absorbent material While introducing fur
ther portions of said fraction at a lower tempera
ture at spaced points along the line of flow
isobutane and recycling said normal butane to
further isomerizing treatment.
4. A process for the isomerization of normal
butane which comprises passng a portion of
through the absorbent material tocontrol tem
perature therein, fractionating they products from ,
a normal butane charge mixed With hydrogencontact with the absorbent to separate -hydrogen
chloride through a stationary bed of granular
chloride, a treated fraction of improved anti
aluminum chloride at a temperature of from
knock value and a higher boiling fraction, re
about 150 to about 200° F. and a pressure of from
cycling said hydrogen chloride to commingle with
about 250 to about 350 pounds per square inch
to effect isomerization with a substantial amount 10 the charge, recovering said treated fraction andV
recycling said higher boiling fraction to further
of said butane in liquid phase While simultane
ously introducing furtherV portions of the normal
treatment.
Y
.
'7. A process for isomerizing saturated hydro
carbons which comprises heating a portion of the
butane charge at spaced points in the aluminum
chloride bed to control temperature therein,
passing the products from the alumium chloride
bed into contact with granular absorbent ma
terial at a temperature of from about 200 to
saturated hydrocarbon charging stock to isom- ì
erizingtemperature, passing the thus heated hy
drocarbons' together with a hydrogen halide v
about 220° F. and under a, pressure correspond
ì ing to substantially vapor phase conditions while
through a stationary bed of granular metal halide
a pressure substantially in excess of 300 pounds
per square inch to recover hydrogen chloride.
bed hrough a body of solid absorbent material
while introducing an additional portion of said
charging stock to at least one intermediate point
isonierizing catalyst under isomerizing conditions,
introducing further portions of the butane charge 20 simultaneously introducing another portion of
said charging stock to at least one intermediate
at spaced points in the absorbent material to
point of said bed to control the temperature in
control temperature therein, fractionating the
the bed, passing the products from the catalyst
products from contact with the absorbent under
isobutane and normal butane, recycling said hy
drogen chloride to commingle With the normal
butane charge, recovering said isobutane and
recycling said normal butane to further isomeriz
of said body to control the temperature therein, ,
and fractionating the products discharging from
said body to separate isomerized hydrocarbons
30 therefrom,
ing treatment.
3. A process for isomerizing paraiiinic hydro
5. A process for the isomerization of a normal
carbons which comprises heating a portion of the
paraiiin hydrocarbon which comprises passing a
paraiiinic hydrocarbon charging stock to isom
portion of the charge of said hydrocarbon mixed
erizing temperature, passing the thus heated hy
with hydrogen chloride through a stationary bed
of granular aluminum chloride under a temper
ature and a pressure adequate to eiïect isomeriza
35 drocarbons together with a hydrogen halide
tion while simultaneously introducing further por
tions of the hydrocarbon charge at spaced points
through a stationary bed of'granular metal halide
isomerizing catalyst under isomerizing conditions,
simultaneously introducing another portion of
in the aluminum chloride bed to control temper- "
said charging stock to at least one intermediate
ature therein, passing the products from the alu-_ 40 point of said bed to control the temperature in
the bed, passing the products from the catalyst
minum chloride bed into contact with granular
bed through a body of solid absorbent material
absorbent material while introducing further
while introducing an additional portion of said
portions of the hydrocarbon charge at spaced
charging stock 'to at least one intermediate point
points in the absorbent material to control tem
perature therein, fractionating the products from
contact with the absorbent to separate hydrogen
chloride, a lower boiling isomeric hydrocarbon
fraction and unconverted normal parail‘ìn hydro
45
therefrom_
characterized in that said charging‘stock com
aluminum halide.
6. A process for treating a gasoline fraction
under a temperature and a pressure adequate to
eiîect a substantial increase in the antiknock
value thereof While simultaneously introducing
further portions of said fraction at a lower tem
perature at spaced points in said bed to control
,
10. The process as deñned in claim 7 further
characterized in that said catalyst comprises an
isomerizing treatment. `
stationary bed of granular aluminum chloride
'
prises a naphthene hydrocarbon.
unconverted paraffin hydrocarbon to further
bons to increase the antiknock Value of said frac
tion which comprises passing a portion of said
fraction mixed with hydrogen chloride through a
`
9. The process as defined in claim 7 further
carbon, recycling said hydrogen chloride to com
mingle with the paraffin hydrocarbon charge, re
covering said isomeric fraction and recycling said
composed predominantly of saturated hydrocar
of said body to control the temperature therein,
and fractionating the products discharging from
said body to separate isomerized hydrocarbons
55
-
11. The process as defined in claim 8 further
characterized in that said catalyst comprises an
aluminum halide.
12. The process as deiined in claim 7 further
characterized in that said catalyst comprises
aluminum chloride and in that said hydrogen
halide in hydrogen chloride.
13. The process as defined in claim 8 further
characterized in that said catalyst comprises alu
minum chloride and in that said hydrogen halide
temperature therein, passing the products from 65 is hydrogen chloride.
the aluminum chloride bed to contact with gran
JOHN O. IVERSON.
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