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Патент USA US2404591

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July 23, 1946.
E. A. NARAGON
2,404,591
PREPARATiON 0F AROIA'I'IC HYDROCARBONS FROIHYDROCARBOK MIXTURES
I -
Filed June ‘6, 1944
2 sheets-sheet 1
ll
-
PAROMDTUIC _
‘
aHoIuGHqHYDROCABNS_
NPAR F I
RHlECYL3.E
AROMTICS
ERNEYANARAGON
IN ENTOR
HIS
BY ATTo'
I NEY
‘
2,404,591
Patented July 23, 1946
‘UNITED, STATES PATENT 0mm;
.
>' 2,404,591
' , PREPARATION oF AuoMA'rIo HYDROCAB
_ BoNs FROM HYDROCARBON MIXTURES
Ernest A; Naragon, Beacon, N. Y., assignor to The
Texas Company,iNew York, N. Y., a corporation: '
of Delaware
‘ Amica?oh We "1944, Serial No. 539,006
'
(Cl. 260—668)
,9, Claims.
the aromatic from the‘ wash solvent by di'stilla-' ‘
This invention relates to the preparation of
aromatic hydrocarbons from hydrocarbon mix‘
tures and particularly from naphtha, hydrocar
tion.
'
-
If it is not required to isolate the treated are?‘ .
bon mixtures.
The invention involves separation of aromatic ‘
hydrocarbons,_ particularly aromatics of higher
molecular weight than'toluene; from‘ hydrocar- _
matics, the wash‘solvent may have a boilingv
range withinthat of the’treated aromatics,}_ '
The wash solvent, may be a para?in'hydrq'oca'r-f
bon, mixture of para?ins', a""naphthene hydro-'f
carbon} mixture of lnar'phthenes, orl a‘ mixture 'Iof- -;
bon mixtures containing them and ‘converting
paraffin and ‘naphthene “hydrocarbons.
the separated hydrocarbonsinto aromatic hydro-'
IO.
The invention thus contemplates
carbons of improved ‘character ,for motor ‘fuel
the ‘_ dual
aluminum
capacity
halide-hydrocarborr'
oi reforming catalyst
-co_n'i1:v1exf.‘~
andlexe
in ‘
manufacture. "In accordance with the invention,v
aromatic hydrocarbons,‘ such as xylenesTor‘ arc-1
traction solvent‘. "Thus, aromatic‘ hydrocarbons,“
matic concentrates separatedfrom naphtha, are
I
'
"
v
r r
'
i
“
More specifically, an- aromatic hydrocarbon
such as ortho Xylene which‘ has’ ‘a; blending
I. M. E. P. (indicated mean effective pressure)
value of 0, is isomerized to give a‘ blending value
of 320 which is to be compared with a-‘similar
blending value of ‘about‘244‘ for iso-‘octané: Like; ,
wise, an aromatic concentrate, ‘boiling within ‘the
range of about 212-300" FQ, separated from by
droformed naphtha , and having a' blending ‘value
of about 1'70 may be subjected to the action" of
An effective catalyst forthis purpose is
employing”
version conditions so that‘the‘ dissolved- aromatic
hydrocarbons undergo isomerization, or "other re--'
forming‘ conversion reaction.‘ Thereafter“ the
converted hydrocarbons may be ‘separated ‘from
the complex veither by'di‘stillation or ‘by washing
with a suitable washjsolvent.
'It is contemplated that :the‘extraction and con-3
version reactions mayIbe‘ carried vout"‘sinuilto};
'neouslyT and in v a continuousfmanner ‘and {mi-a;
singlereaction‘ tower.‘_'
.
_‘th;e7other' hand} the ;
extraction and ’ conversion reactions may be-"c'a'r-v -
ried out in separate zones- aswill be hereinaite'r _
described,
an isomerizing catalyst so' as to- produce va prod
uct‘having a blending value of about 231. '
‘
the resulting extract,v comprising aromatics dis
solved ‘in complex, may'then be exposedto"cori-v
ing intoaromatics-which have avgreat‘er blending
_
7
maybe extractedfrom afaaphthagmixmre-‘anu ‘
subjected to the‘ action of an aluminum halide
catalyst so as to effect reforming or transform
value'for gasoline. '
‘
‘
I
alu-ir
_
‘_
the, accompanying drawingslillusl
trates a method ofio?peration‘ wherein aromatic;
hydrocarbons are continuously subjected ‘to con- i
tained by reacting aluminum chloride with kero
tact
with ‘the ‘catalyst under conversion condiéj
sene in the presence of hydrogen chlorideuat‘av
tions and the resulting aromatic products‘con?
temperature of about ZOO-250°
‘so' as‘topro a5 tinuously‘
displaced from thereaction zone“ either
duce a complex having a heat of hydrolysis of
with or 'without washing
around 290-330 small calories per‘gram ,oflcome
carbon such
pentane. ‘
minum halide-hydrocarbon" complex such as 'ob-i
plex.
"
1"
"I
The aromatic hydrocarbonsare subjected to -‘
the action of such complex catalyst in the pres-3
complexliquidrin anextraction' zone;
ence of hydrogen halide promoter at tempera 40 tioniwith}
and the resulting‘ extract solution lpassedtbma ;
tures ranging from' IOU-300° F. and preferably
separate reaction ,zone to _;e?ect‘_convers'ion_;_of
about 180-220° F. such that the hydrocarbons
dissolved aromatic hydrocarbons.“
undergo reforming, in which Visomeri‘zation is one
Figure 3" illustrates _ a‘, 1_thre_e’-stage: processv ’
of the principal reactions involved in increasing
wherein an aromaticucon‘centratei is obtained in ,
the blending value of the aromatic hydrocarbons 45an
extract stage, the resulting solutionbfrf-aro-j
undergoing treatment. ~
'
A complex'catalyst of the? foregoing character
is effective as a solventifor'extracting aromatic
hydrocarbons from mixtures containing them‘v 50
and, therefore,'may be used to selectively extract
aromatic hydrocarbons from paraffin hydrocar
bons so as to obtain an’ aromatic concentrate.
The dissolved aromatic hydrocarbons can be sep
arated or displaced from the complex by washing
with a saturated hydrocarbon boiling. either sub‘
stantially below'orabove the dissolved aromatic
hydrocarbons. .By using as the wash_;solvent a
hydrocarbonyboiling' outside-the range [of the
aromatic hydrocarbons, it~_is»possible’to separate
matics in- complex liquid passed" to-'a;"reaction'
stage ‘and'from there ‘toa'?nal’lstfage wherein the "
aromatic products are washed from thecomplex'?
Referring now to‘ Fig. :1,‘ an aromatic hydro-é’
carbon such as ortho xylene‘is conducted from‘:
a source hotshownthrough a pipe! and‘pas'sed
through a ‘heater or" heatexchanger 2 wher
it is heated to a temperature‘of about‘180l210‘f
55 The’hveatedstream'is-then’co d_ cted'throughi‘a:
pipe 3 to the lower portion of a ‘verticalreaction? ;
tower
4.‘
g
_
.
,.
_
The tower 4 contains-ai‘columnlof aluminum
.
chloride-hydrocarbon complex-‘having a vheat of
an hydrolysis of about 320'ca1ories. per'gram?of,com-,;: ,
2,404,591
A s
,
plex. Advantageously, the complex liquid column
is maintained in a'substantiallyr staticjcondition,
4
which is removed through a pipe 22 and a residual
fraction comprising high boiling hydrocarbons
without mechanical agitation, and ‘may have a
1 '-height ranging from about 10 to 25 feet.
which is removed through apipe 23; This latter
fraction may be recycled through a pipe 24 to
The feed hydrocarbons are injected into- the .
'. the reactor 4.
r
'
' bottom of the liquid catalyst columnin dispersed.
A continuous tower operation as illustrated in
form and the dispersed hydrocarbons tend to rise ‘ ;_‘Figure_ 1 may beTcarried out without the wash
through 1 the catalyst column ‘ by difference in :
density.
A
solvent, since the treated aromatics will rise
.
:through the foolumn-tof liquid by difference in
The catalyst column is maintained vat theyvfolre- " 10 density. ‘ The complex catalyst is thus main
tained saturated with aromatics and even though‘ 7
‘7 going reaction temperature of about ISO-210° F. 1
, e?ective for converting ortho xylene into'meta
saturated, retains substantial activity for isomer
izing and reforming aromatic feed hydrocarbons.
‘f ‘ and para xylenes as well as other valuable aro-'
‘
matic hydrocarbons.
'
' The saturated complex contains approximately
equal volumes of free aromatics and complex. '
A small amount of hydrogen chloride promoter
iswcontinuously added" from a" source not shown
,Referring now to Figure 2, 'a naphthalmixture
or a mixture of' aromatics and ,para?ins is con". ,_
‘ and introduced through a pipe 1 leading to the;
‘
‘
pipet:
'
~
7.
.
ducted'from a source'not shown through -.a pipe = V
The aromatic hydrocarbons-are‘ thus exposed ‘to
30 and a heat exchanger 3| wherein
the catalyst in the presenceof thepromoter which
latter-may amount. to from 70.5 to 5.0% or- from
about i2.'0?-to 3;0%'by weightriof the aromatic hy- "
The mixturethen ?ows through apipett-to
the bottomof an extractiontower~33vlwhereinit'
; drocarbonundergoing treatment. Make-up-alw
minum chloride maybe addedintermittently'or
continuously in small amount fso <as~_to_ maintain . .
the catalystliquid-at?the: predetennined-level of i
‘ activity.-_ The aluminum chloridemaybej added‘
3 as'a solution or- as aesuspension inva ‘portion of
A
1 the aromatic feed stream.
~
i-trisebrought _
20 to a temperature of: about 70-100“
is subjected to countercurrentcontact with a body
of aluminum chloride-hydrocarbon .- complex’v
characterized .by having a heat of hydrolysis of ;
about 290 to 330-calories per gram of complex
Thisv-complex-may'rbe; used. complex such asis
drawn off' from the subsequent conversion- re
action. It is introduced into the top of the tower:v
7
through a pipe 34.’
‘ carbon, suchasnormal pentana-is continuously '
; recycledgthrough-the» system as will bedescribed '
-
As' the feed hydrocarbons rise- through the
tower ‘33, aromatic constituents aredissolved-in '
and enters-the reactorl-4lthrou'gh a pipe‘ 8 com
the complex. The undissolved non-aromati'cghy
; municating- with the pipe’ 3; The pentane is in
drocarbons rise-to the topof the tower and'are
; troduced to thereactor-in the proportion of about, . continuously removed therefrom-lthrcughva pipe 7
.‘ 1v to'3~parts :by volume “of'pentanel-to one volume ‘
" of aromatic feed hydrocarbon; Thevpentane ,
35 and cooler 36.:
_
make-up-aluminum'chloride.
,
..
'
The complex-containing dissolved aromatic hy- ,
3 strearrn-also-maybe used for‘ introducing’ the
drocarbons is continuouslywdrawnofffrom the;
'
bottom/of the extractonthroughapipe 311 and
-;.The aromatic-'- hydrocarbons? andpentane-I rise
40 conducted through an exchanger or ‘heater 38 ‘
j through-the catalyst column-and accumulate in, v
wherein it'is. brought to a temperature of. about
the-top of-thereaction-vessel.
.
.
/
,
200°‘ F; The heated solution is then passedgintor
‘ liThe para?in- hydrocarbon may undergo'some
areaction
tower 4B. In the reactor. 40,- the arc-‘1.
f conversion but the extent of such conversion is
matic hydrocarbons thus-,remainin contact with r
‘ limited-due. togthe inhibitingireffect'eof the-'aro- f to. ;.4, , the catalyst in-the presenceof promoter for'a .
:matic hydrocarbonsipresent, . In other words,~
short period of timeas'in'the‘case of‘the reactor 7
‘ aromatic hydrocarbons’ Zsubstantially j inhibit
lLof Figure 1 so that the aromatic hydrocarbons.
isormerization of normal paraf?ns-under the conv undergo conversion;
‘
ditions: prevailing: within, the reactor :3.
.
'
A stream of parai?nhydrocarbon such'as pen- 7
The effluent : hydrocarbon stream '- containing
6:’)
iconverted 'aromaticsgis: continuously drawn .off . . '
‘ through a pipe I0 to a, fractionator or'strip'pcrgi l
is: removed. I
lthroughj a. pipe’ l’2-rand recycled .all orlin part
through apipe I3 communicatingwiththe pre-Vv
lviously‘mentioned pipe 3.
-
7
_
,
-
V
I
‘pipehl8i-and. may» be '- recycled all .or in ,part
I
,
I
1
r
, the products and recycled through a. pipe8. =
through the previously mentioned pipe 8. How
Referring to Figure 3,’ a hydrocarbon mixture‘
containing aromatics is drawn from a zone notv
;eVer-in the absence-of the wash solvent, the frac-V
ftionator »|5'may/ be by-passed‘ by conducting the
hydrocarbon stream from the stripper i I through v
' The residual hydrocarbon fraction’ comprising
~.
ii 1;
1tane fraction so-removedis conducted through a
g
I
The hydrocarbon products are‘ continuously.
drawnroif from the top of the reactor‘ through a
tionating systemsuch ‘as is: illustrated in Figure.
The fractionating system may comprise ._a
stripper for stripping the promoter whichis then
recycled through a pipe 'I3.Yas in Figure 1. Like
wise, the para?‘in hydrocarbon is separated from'
L ldttoja fractionator; l5.wherein apentane-frac
tion is continuously removed as a distillate frac
;tion ‘through a’ pipe [6 andcooler I1; 'I‘hepen-v
.
complex.
.‘The pipe til advantageously leadsto afrac-L.
> v‘hasbeen removed are conducted throughlapipe
p
ofr'theearomatic hydrocarbon product from the
_
pipe 4|;
The hydrocarbons from which.» the- promoter
pipe Hatoithe fractionator 2i.
reactor'AGY-V so as to subject the complex to. eon- ~
tinuous washing and thereby effect displacement
whereinithe promoter?is stripped‘ from the-hy
drocarbons; >The= . promoter-gas
tane-is likewise introduced continuously to the '
I
shown’ through a pipe 50 and heat exchanger 5|; ' The vheated mixture then passes into the bottom
through ‘a pipe 20, or from the stripper ii I through '
of an extraction tower 52"wherein it is subjected
to countercurrentcontact with a body of com
plex liquid as in the. case of extraction tower 33
pipe; Ma to a fractionator 2| wherein it maybe
of Figure 2.
aromatics is‘ conducted from the fractionator- Hi
' ‘separated'into fractions as desired; for example,
i
1 7
Temperature conditions are maintained so‘ as
'itlmay be separatedzinto a'i distillate fraction‘ 75 : to dissolve the aromatic hydrocarbons and thus‘
7
2,404,591; 1
6
5 ,.
bons.
>
-.
I‘
j
v
in thisigcase had a heat of hydrolysis‘ of about
The latter are continuously‘ ‘discharged.
298Icalories‘per-gram.I The» reactioniwas‘ carried‘
from the top of thetower through av pipe. 53 :and I
cooler/"54;; II
‘
portionstas’in Example I. The complex catalyst
extract‘ ‘them from J the ‘non-aromatic Jhydrocan-m ‘
out in thempresencelof
promoterat 'a temperature
thesame-amount
of 1803 F. .for a of
period"
:the'
'
The? resulting, solution’ of“ aromaticsin: com- 5
of 30 minutesfth'e: pressure ranging»froin~'12~to3 l
plex is drawn o? from‘the bottom/of the tower
about l??poundspersquareinchngauge?
52 throughva ‘pipe .55: to a reaction .vessel 56.‘
The hydrocarbons “were separated)» from '1 the' 1
Hydrogen chloride :promoter. may ,berintroduced
complex and vthe portion vfree .from “C5 vanddowér:i 1
from: asource not shown througha pipe 51-.‘
Thereactionlvessel 56 is ‘maintained at an ele-i 10> molecular. . weight hydrocarbons »had- the follow- vated temperature iadapted :toe?ect isomeriza- ‘
tion of aromatic hydrocarbons. 'The products of V
conyersion,iincluding catalyst, are continuously v
ing composition:
j
-
. .~
l ~
' ‘Per vcent byrvolume '
drawn off through the pipe 51 to awash towerf
58 wherein the mixture of complex catalystv and “
aromatic, hydrocarbons is subjected: to‘ ‘counter
currenticontact with a body-of paraffin hydro?’
carbons a, such as pentane.
Thus; the complex
mixture entersv the upper portion of thepwash
tower 58 while the streamlof 'normal‘pentane is 20
continuouslyl introduced :to. the to lower portion
‘Apparently, all‘ ethylbenzene r 1
‘
thereof. throughipipe 59;inlthe proportion of‘ about
1 to 3 volumes per volume-‘of complexmixture;
,Iril this tamper x'lyllériéf‘fboacéjl“
>
1
,'
_'
,
..
the jvfollowing volume percent com_ 7‘ '
aromatic" hydrocarbon- products - from the ‘com
plex catalyst; , z
' Mariam
,
about
Thelzwashing
1100:1509 is‘ so
effected.
as to. continuously‘
atla temperature,
displace-i
of
a
‘The 2 aromatic. products are. continuously, dis;
charged‘ through 1a pipe ‘60 - leading to‘: a fraction
Meta and pamiyhhés; ethyl‘ benzene
patingri'system“ such as described'in‘ Figure‘, 1-. r _
inlé ywasheds ‘complex substantially ‘free‘ from
aromaticsis drawn’ :o?.’ i through =a5pipe -;6I. and >
recycledrall orfin partthroughlaipipeh?z' leadingr i
tothert'opxof. thezextractorbl; Soniefof the com;
concentrate was mixed‘,' thcoiilple'x of ’
plex 'mayxbelrecycled directly. through‘acbran'chr . . '
about the same character‘ andin thef'sarnev 15m
portionsuas ExampleII; The reaction was" carried; :
pipe
{Int 6_3.to
orderthejréactor‘5?';
to maintain the‘
13,;activity hr the‘comA -.
'
cutvi'n the‘presencev of a similar amount ‘of pr
plex catalyst; additional aluminum lialideis added
moter at a temperatureiof 210°‘ Fkfor 30 niinut'es,_ .
>
the pressure rangingufrom about 20 to: 31§pounds=f
to the system jthrough a‘ pipe 6.4; such addition ,
being-made in somewhat. the. samem'annerias ;has 40 :The liquid productsiafter removal ofJCél and lo
~p ' >
promoter and wash solvent also as.:des‘cribed in“v
Figure 1.5.
-
I a
Y
1
'
l
>.
r
‘Example!
.
n.
‘
‘
‘hydrocarbons were of- the following composition.”
been described in. .connectionwith Figure 1... .
vProvision maybemade for recycling recovered ,
'
per-‘cent by Volume"
Hydrocarbons boiling below ‘benzene. ____ __'_
»
._
“A ‘quantity ‘ of] orth'o' xylene was charged ltd a’
reaction vessel, together with aluminum chloride; ‘
hydrocarbon‘ complex pinvthe proportion" of 2 vol-‘,5
umes' ’ of complex ~ to‘ '1 volume ‘‘of ‘hydrocarbon; " 50
Hydrogen chloride was added to'the extent of.2% .
by weight of the total charge; The resulting
mixture was “maintained ‘at a temperature of 210° ,
a In eachofthevrforegoing examples the hydroe.
Fr‘andunder-pressure'ranging from 43 to '10.
carbon products were separated from the'comple'x
pounds-for arperiod‘of about .30 minutes“ H'Ij'he.
by distillation at reducedpressure; It will be ob.- 7
complex catalyst was _-characterized ‘by having a _
heat
Theof‘ hydrocarbons
hydrolysis of about
were320
separated
calories vfrom
per gram;
the
served that in Example ,I the orthoxylene was H
isomerized to vproduce a substantial yield of a;
catalyst, and thatportion free froznCeand lower '
fraction comprising meta and para xylenes ‘and
ethyl benzene. In addition, thepe fraction ape
hydrocarbons was found toahavethemfollowing
composition:
V
I
V
/
"parently consisted principally/of Inesitylen‘e.‘ ‘ '
. Percent
'‘
y by
M volume
L‘
Hydrocarbons boiling below benZen6-_,______
Benzene;____________ ___ ____ __‘_:_'______,_____ a
'7 '
A
30.65
Toluene
Meta and__para xylenes,and
'
'- _,
ethyl benzenm---‘ _3.L
Orthp xylenle?'wrr-ir-r-r——?-'4-—:-—1P-€—~r—-—++—<—
(39.1112
Residue _____,_,-, ______________ --,-,__:--t-,--.-_
'1 Apparently’principally mesitylene
8 ..
1o
------
-
>
10.
It will be noted in the‘ case of Example ‘III that
the ortho xylene content of the concentrate was
reduced from 2lxfto “6% with'the formation'fojr?
benzene, ‘toluene, "meta and para xylenes and
mesitylenezetc.
>
'
V
‘
~
‘
"
=
‘
'
_
vIn the ‘following example orthov xylenelwas't‘
treated with a complex catalyst under ,‘substahJ
tially the same conditions as used in Example I
At the end “of the reaction, the reaction ‘mixture’
70 _of catalyst and hydrocarbons was subjected to ex- '
traction with normal pentane at aternpe'rature or "
about ‘70° F. so as to separate the aromatic hydro-J’
carbons vfrom "the complex"catalyst‘;v "The sepa'1
a-~reaction‘ vessel,':together with an- aluminum? rated‘ hydrocarbons after removal of ‘C5 and‘low'eri
chloride-hydrocarbon complex in the same‘pro-"75 hydrocarbons had the‘following' composition'z‘
A
- quantity
, ,
of “Erectile?!
ethyl benzene,
" was charged to '
2,404,591. 1; Y
Y
so
promoter-su?icient. tompre'vent. the complex from. becoming too vi'scousazi
‘ - 1 i
The ‘term “reforming” asused herein isfcon
templated as including reactions other than isom.- ‘ j ,
erizationsuch ascracking; alkylation, alkyl ex- '
change, etc. These rfeactionsmay occur simul
. taneously with i'somerization, although isomeriz‘a-l 1
tion is regarded as a principal reaction.
' Obviously many modi?cations and variations of' .
10 the invention as hereinbeforexset forth maybe
.Mention has been made of using aluminum
thereof,
made without
and departing
therefore;from
‘onlythe
such
spiritlimitations-v
and scope '7
chloride-complex as the catalyst. However, it is
contemplated thatother aluminum halide isom
1
should be imposed as ‘arfejindicated in-the ap-'
pended claims.
erizjation catalystssuch as aluminum bromide
Iclaim:
‘ _ may also be used. H “Other hydrogen halide pro
1 . may be employed. Such’other solvents may com-f
prise liqui?ed' normally gaseous para?‘in._hydro,-.v
carbons or normally liquid‘ hydrocarbons of higher
.
I
‘
'.
of
aromatic
an aromatic-rich
constituentsnaphtha
whichjcomprises
by isomerization
subjecting;
‘of a ‘fraction of said naphtha boilingin the range
of 'abouti-2l2'to 300°';F.'to. contact with: an alu-w
minum halide-hydrocarbon complex isomerizing“
molecular weight than pentana. Organic halides
catalyst having a heat, of hydrolysis int'he range “ '
such as CCli and CHCla. maybe used as, Wash
,
.
x
l; A process for: improving? the blendingvalue
moters besideshydrogenr chloride may be used.
Also other'wash solvents besides normal pentan'ev _
solvents.
.
-
' Reaction temperatures ,of. about 210° F. have
'beenementioned. in the examples but it neon: .
' of about 270~to 350‘ calories, and effecting said
contactrfor a short period, of'jtime at ai’temper'a- >
ture-in the rangeabout 180 to 300° ‘F. in metres-1 ‘
ence of a small amount of hydrogen halide ‘such’
templated that other temperatures may be 'em-;
that aromatic hydrocarbons containedi therein?
ployed, depending upon the activity of the'cata
undergo isomerizationto a substantialextent:
ly'st, the character of the aromatic hydrocarbons
2. A process‘ for-p»preparing-"aromatic'rhydro- '
undergoing vtreatment, andthe extent of conver
, sio'n desired; Thus, temperatures ‘ranging from‘ 30 carbon'sof improved .blendinglvaluei by isomer- 1
Iroom temperature‘ up to 300°"F.'may be employed,‘ .ization for the manufactureof motorxfuel which
althoughtemperaturesranging from 180 to about‘ .
comprises separating “from naphtha a , fraction 1»
220°F, are preferred.
rich in xylene‘ and" aromatics 70f 1 higher molecular
_
.
V
.
weight than toluene, subjecting said‘ fraction" to “
The'complex catalyst may havea heat of hy
.
contact‘ 'with :an‘aluminum halidef-hydrocarbo
complex isomerizing catalysti'having'a heat of”
drolysis Vranginggfrom .about'2?70 to 350 small .
caloriesrper' gram of complex, although aheatiof'
hydrolysis in“ the range ofaboiut‘ 2970'v to ‘1330’ .
calories and "effectingsaid'Jcontact-iora short . '
ferred.’ The activity of the, catalyst should bev
period of time at a temperature in the range '~
such that the e?luentjstrearn of hydrocarbons will
40 about 7180 to 220° F. in the presence'of a small _ 7
be substantially 'free from aluminumhalide.
‘ ‘ hydrolysis in the range of about 290 to 330 is pre- .
amount of hydrogen halide? such ‘that aromatic '- '
A reaction time of 30 minutes has been referred
to, in the examples, but a reaction time substan- ‘
hydrocarbons undergo isomerization toTa ‘sub
tially below this maybe used in a continuous ?ow
system in which ‘case the hydrocarbon residence
within the reaction tower may be a matter of
stantial extent.
several minutes.
'
"
‘
‘
.
3. A continuous process for isomerizing aro
45 matic hydrocarbons of higher'molecular weight
'
Complex catalyst will form in situ as a result 7
of 'reactionbetween added aluminum halide and a ‘
than toluene which comprises continuously in
jecting said aromatic hydrocarbons into the lower
portion of a vertical columnof aluminum chlo
ride-hydrocarbon complex catalyst, ‘ liquid having
small proportion‘ of’ the- aromatics undergoing
treatment. Therefore, the rate of halide addition ,50 a heat of hydrolysis in the range» of about 270 ,
to 350 calories, dispersing the injected hydro
is controlled by observing the heat ofhydrolysis
l ,of the complex catalyst fromtime to time during
carbons upwardly. through the column. in the
presence of hydrogen halide at. a temperature in ' .
continued operation. Provision is made for with
drawal ‘of a small portionof used complex from
the range of about 180 to 300° Fjsuch that sub- ~
the reaction tower. Advantageously, used com 65 stantial 'isomerization, :occurs' and continuously 1
plexis withdrawn from an upper portion of the
removing from the top of the column a hydro
tower while make-up aluminum halide is added
to the lower'portion. Provision is also made for
adequate space in the top of the reaction tower
carbon stream containing. .isomerized aromatic '
hydrocarbons.
may consist essentially of that formed by reaction
between the halide and aromatics. Sufficient
aluminum halide is added to the system to main
tain the complex at the desired level of‘activity,
i. e., having a heat of hydrolysis'in the range
.
i
V
v
.
.
v
.
_
than, toluene which comprises continuously in- ‘
Thus, while complex formed by reacting with ‘ '
kerosene has been mentioned at the outset, never
theless, it is contemplated thatwthe complex em
ployed inthe system during continued operation 66
vabout 290-330 calories.
r
matic hydrocarbons of higher molecular weight
to effect disengagement between thehydrocarbon'
phase and the catalyst phase.
‘
_
4. A continuous process for isomerizing aro
‘
It
alsocontemplated that provision may be
made for'effecting the extraction steps of Figs. 1
2 and, 3 in'the' presence'of a small amount of
jecting said aromatic hydrocarbons into the lower ~
portion of a vertical column of aluminum chlo
ride-hydrocarbon complex catalyst liquid having
a heat of hydrolysis. in therange of about 270 to >
350 calories, dispersing the injected vhydrocarbons
upwardly through the column in the presence of
hydrogen halide at a temperature in the range.
of about 180 to ‘300° F., simultaneously dispersing
upwardly through the column a 'low boiling sat
urated hydrocarbon so_as, tofacilitate displace
ment of aromatics from the ‘complex catalyst,
and continuously removing from the upper por
tion of the column a hydrocarbon stream con
taining isomerized aromatic hydrocarbons.
2,404,591
-
5. A continuous process for isomerizing aro
matic hydrocarbons of higher molecular Weight
than toluene which comprises extracting naphtha
containing said aromatic hydrocarbons with
aluminum halide-hydrocarbon complex having .
a heat of hydrolysis in‘ the range of about 2'70
to 350 calories, forming a solution of aromatics
in the complex, subjecting said solution in the
presence of hydrogen halide to elevated temper
10
said low boiling saturated hydrocarbon is normal
pentane.
‘
.
8. A continuous process for isomerizing aro
matic hydrocarbons of higher ‘molecular Weight
than toluene which comprises extracting naphtha
containing said aromatic hydrocarbons with
aluminum chloride-hydrocarbon complex having
a heat of hydrolysis in the range of about 270
to 350 calories, forming a solution of aromatics
ature in the range 180 to 300° F. for a ‘few 10 in the complex, subjecting said solution in the
presence of hydrogen halide to elevated temper
minutes time such that the complex effects sub
ature in the range 180 to 300° F. for a few min
stantial isomerization of aromatic hydrocarbons,
utes time such that the complex e?‘ects substan
washing resulting complex containing dissolved
tial isomerization of aromatic hydrocarbons,
isomerized hydrocarbons with a low molecular
weight saturated hydrocarbon so that aromatic 15 washing resulting complex containing dissolved
isomerized hydrocarbons with a low molecular
hydrocarbons are displaced therefrom and re
weight saturated hydrocarbon so that aromatic
moving the displaced hydrocarbons.
hydrocarbons are displaced therefrom and re
6. A continuous process for isomerizing aro
moving the displaced‘ hydrocarbons.
matic hydrocarbons of higher molecular weight
9. A continuous process for isomerizing aro
than toluene which comprises passing a naphtha
matic hydrocarbons of higher molecular weight
fraction rich in said aromatics and containing
than toluene which comprises passing a naphtha
para?inic hydrocarbons in countercurrent con
tact in an extraction zone with a body of alu
fraction containing aromatic and paraf?nic hy
drocarbons in countercurrent contact in an ex
minum halide-hydrocarbon complex having a
heat of hydrolysis in a predetermined range of 26 traction zone with a body of aluminum chloride
hydrocarbon complex having a heat of hydrolysis
about 270 to 350 calories, effecting said contact
in a predetermined range of about 270 to 350
at a temperature such that aromatics are dis
calories, effecting said contact at a temperature ‘
solved in said complex in preference to paraf?ns,
discharging undissolved para?ins, passing result
such that aromatics are dissolved in said com-'
arately discharging displaced hydrocarbons and
charging displaced hydrocarbons and complex
ing solution of aromatics in complex to a reaction 30 plex in preference to para?ins, discharging un
dissolved parai?ns, passing resulting solution of
zone, subjecting it therein to a temperature in
aromatics in complex to a reaction zone, sub
the range 180 to 300° F. in the presence of a
jecting it therein to a temperature in the range
small amount of hydrogen halide for a period
about 180 to 300° F. in the presence of a small
of time ranging from several up to about 30 V
minutes such that substantial isomerization of 85 amount of hydrogen halide for a short period
of time such that substantial isomerization of
said aromatics occurs, passing the so-treated
mixture of hydrocarbons and catalyst to a sep- , said aromatics occurs, passing the so-treated
of hydrocarbons and catalyst to a separatingv
arating zone, subjecting said mixture therein to
zone,
subjecting said mixture therein to counter
countercurrent contact with a low boiling satu
current contact with a low boiling saturated hy
rated hydrocarbon at a temperature in the range 40 drocarbon
at a temperature in the range of about _'
of about 100 to 150° F. such‘ that isomerized
100 to 150° F. such that isomerized aromatics
aromatics are displaced from said mixture, sep
are displaced from said mixture, separately dis
complex catalyst from the Separating zone, re‘ 45 catalyst from the separating zone, recycling dis
cycling discharged catalyst to said extraction
charged catalyst to said extraction zone and sup
zone and supplying make-up aluminum halide
plying make-up aluminum chloride to the ex
to the extraction zone to maintain the complex
traction zone to maintain the complex therein
therein at said predetermined range.
at said predetermined range.
> ' ‘ .
7. The process according to claim 6 in which ‘0 .
ERNEST A. NARAGON.
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