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Патент USA US2408188

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Sept. 24, 1946.
H. v. ATwELL
cmnALYsT~ MANUFAGTURE
Filed May 18, 1944
ON
Il
HAROLD
v. ATwELL .
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Hrs AT’rd N'EY
VE NTOR
Patented Sept. 24, 1946
2,408,187
' * UNITÈD „STAT
PATENT‘ÍoFFIcE >
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_ Íaiosnsi
CATALYST MANUFACTURE
~ - vliîlvarold
' ì ’ '
Atwell,- Beacon, N. Y., assignor to‘The
Texas Company, New York, N; Y,-,;a corporation
of Delaware. ,y d
` 1 @Application May
1_8, 1,944, seriam- .SSGßSQ-g, „
is claims.
(ci. 252-254)
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vessel and subjecting the entire mixture to vheat‘
ing :and stirring in a batch type of> operation..-
The present invention relates to catalyst manu- `
facture, and particularly'to ay .complex liquid'V
catalystformed’by'reacting a solid metal halide,
' The present' invention .involves 'a' substantial
improvement’ over the prior vart since it provides
such as aluminum chloride,- with a normally
liquid hydrocarbon in the presence of a promoter 5 for effecting solution of solid metal halidelin'äa
such as hydrogen halide. >
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solvent hydrocarbon under’conditions suchtthat
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substantially :no complex. formation»Y occurs -fand
then effecting reaction Abetween ».thefzdissolved
Complex .compounds 'formedf by 1. reacting a
metal halide with ar petroleum hydrocarbon in
the presence of a promoter are usefulas catalysts
halide» and Areacta'nt'"hydrocarbons ina separate
for elïecting catalytic conversion of'hydrocarbons 10 zone. `f @The invention* thus ¿permits segregating
the v‘conriple'x substantially las rapidly'.it is
such as conversion processes involving valkyla.
formed-and also permits" effecting contact be
tion and isomerization. >The metal halide ‘may
be> reacted with varioustypes of hydrocarbons
tween rthe" solvent f hydrocarbon' land> the solid
including oleñns,»paraflins, naphthenes, and aro
matics.' A mixture of reactant hydrocarbons
metal halidev _in the substantial absence» of
complex.
may be employed, as for~example,'kerosine or
some other fraction of petroleum.
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An advantage ofthe process of the present in
vention is thatfit avoids pumping and circula
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' In accordance with ìthe invention ytheA solid
metal halideï'is maintained’ in vay contact -zone
in lump or granular form. ' A stream of saturated
27o
C4 hydrocarbon in liquid phase is Vpassed through
the contact zone in‘contactvwith the'V solid metal
halide underconditions such as to effect solution
of a small amount ofthe'vmetal halide in" the
liquid stream. The ellluent stream from the con.lv
tact zone containing~ dissolvedmetal halideis
tioni‘of complex, Whichis particularlyv advantaá
geòus 'iromrvthe standpoint of reducing corrosion
arìd‘ei'osion of equipment'gf for example,` one
serious ‘difliculty'experien‘ced in pumping' 'com-Ly
'plex- withv a reciprpcatingitypeof pump isfth‘at
- theïcomplex penetratesA> thef'packingv glands; and
solidiñes therein ultimately causing" substantial
leakage'aswell as injury'to the pump.
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`lidvoreover, theu‘avoid‘ance 'of the presence of
complex'in the solution zone permits more ef
fective contact between _the solvent hydrocarbon
subjected to elevated temperature in the presence
of hydrogen halide‘and also in the presence of
the normally liquidireactant hydrocarbon in a 3.0 and `the solid metal" halide so that a uniform
second zone so as to effect complex formation:
betweenl the metal halide and the normally liquid
reactant hydrocarbon.
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' 'I‘he reactant hydrocarbon may lbe commingled -
rate of solution is realized.
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The invention also> involves a further advan
tage as regards'the preparation of complex from
a metal halide such as ~_ aluminum chloride.
with the C4 hydrocarbon stream prior- to, -_or 35 Aluminum chloride is relatively more _solublefin
subsequent to, its passage through the contact
butane than it is vin higher molecular Weight
hydrocarbons'. ' Thus' at a" temperature of about
zone, 'although the latter _is advantageous, as will
200° F. normalv butane dissolves about 1.75%
be explained later.V
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aluminum chloride by >Weight ofthe butane While
normal hexane at the same temperature dissolves
only about 0.33%. lNormal butane at a temper
ature ofl40° F. dissolves about 0.55% by Weight
of aluminum chloride YWhile normal hexane vat
The mixture of metal halide and reactant hy
drocarbons remain inthe second zone for suil‘i
cient time to permit.complexjfcrrnation.`
The resultingr __ mixturefofv hydrocarbons con
taininglcomple'x also undergoessettling so. as to
effect phase separation between complex andun
the sarnetemperature dissolves'only about 0.16%.
reacted hydrocarbons.; The hydrocarbon phase
comprising mainly C4 4hydrocarbons is*v drawn off
in.A acontinuous streamzand recycled through
y _ Consequently,reither normal or isobutane or a
mixture' of both is'used in the present invention
operation .isl conducted to effect substantial
to eiïectf'solution ofthe solid metal halide and
to transfer the dissoivedìmetal hande into the
"reactionl zone fory reaction with kerosirle4 in which
the halide is'much less‘soluble.
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L fThe invention also contemplates iortifying the
formation of complex».y
complex by subjecting it to‘contact with a stream u
theïcontact zone to dissolved additional metal
halide after which it-.again passes through the '
reactionand phase separation zones. The cyclic 50
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of.„`bu.ta`ne ,containing dissolved metal halide,
.. Complex compounds `have been prepared Áhere
tofore by chargingk aV quantity of hydrocarbon
oil, ¿metal halide,l andA promoter`fto a.. reaction
. 5.5
contact being continued until the complex has
extracted metalhalide Afrom the solvent hydro
2,408,187
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carbon to the extent desired, as will be described
later.
The resulting complex settles out and accumu
lates in the bottom of the vessel 3, while the bu
In order to describe the invention in more de
tail, reference Will now `be made to the accom
tane and unreacted kerosine accumulate as a
panying drawing which comprises a diagram of
vessel 3.
hydrocarbon layer in the upper portion of the
«
The butane may undergo isomerization so that
iiow useful in preparing a complex of aluminum
ultimately the C4 hydrocarbons in the circulat
chloride and kerosine hydrocarbons.
ing mixture will compriseganequilibrium'mixture
In the drawing the numeral- I rdesignates „a
pair of vessels packed with solidaluminum ,chloe
ride in the form of particles or lumps rangingl
from about 1A to 1%; inch in diameter. Two ves
of iso and normalbutane. The reaction condi
tions of time and temperature are such ‘that only
a very limited amount of the |butane enters into
sels are provided so that when one is onstream
complex formation with the aluminum chloride.
the other is offstream for recharging with fresh
The hydrocarbon phase separating in the ves
` sel 3 isl«continuously¿'drawn oiî through the pipe
aluminum chloride.
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9 and forcedï'byigthe pump I0 ‘through the pipe
The numeral 2 designates allieating zone which
may comprise a tubular heater wherein the mix
I I to the-heatiexchanger 4 wherein the tempera
ture of hydrocarbonsk and dissolved aluminun‘ry
tureI _of the; hydrocarbons may be reduced if de
chloride is raised to the temperature required _for
effecting complex formation.
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On the other hand, the heat exchanger 4 may
20 be bypassed as indicated. .
` YIt is contemplated maintaining a. relatively
The numeral 3 designates a reaction and set
tling vessel.
_ sired to a temperature in the range 150 to 200° F.
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The numeral 4 designates a heat exchanger;
through which the unreacted hydrocarbons are
recycled from the vessel 3 Vto either of the vessels I.
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short time.l of contact between hydrocarbons and
solid aluminum chloride in
aluminum chlo
ride vessels t so that' the action taking place
therein is essentially that of solution rather than
complex formation. Reducing' the‘ltemperature
An operation in which a butane: stream con,
taining kerosine is' circulatedithrough'the system
of the. recycled» hydrocarbons-in the exchanger 4
will be >described, ñrs't.
is a further means of'- inhibiting complex forma
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At the outset and’assuming'that'the-vessels»-I
tion in the-'vessel'|..
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are packed with solid aluminum chloride‘,'thesys-- 3.0.' 1 The circulation of hydrocarbons through the.
system is continued until substantially all ofthe
tem is filled wit-h a mixture -of butane-and kero'
kerosine present is converted to> complex. The
sine, the pressure being _suflicient to maintain the
compleximay‘be retained in the vessel 3 until the
butane in liquid phase. The> kerosine may
entire batch of kerosine charged is reacted. 0n
amount. to about l0 to 15% by volumeV of the
the other hand, the complex may «be drawn oiî.
butane. The butane and kerosine are drawn
continuously or intermittently if desired.
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from sources not shown through pipes 5 and 6
A modified form'of operation involves charg
respectively anddischarged into> pipe 'I vwhich
ing the system first withbutane a-ndthen adding
leads to the heater 2. The heater 2 is operated
the kerosine inl small amounts to thecirculating
so as to heat the hydrocarbon streamto a, tem»l
butane stream. In vthis type of operation theperature in the range 200 to 300o F. _ The> heated.
kerosine addition to the circulating stream. _may
stream passes through pipe B into» the *vessel` 3..
be regulated, so as‘to _provide approximately the
When the vessel 3 becomes filled with liquid, the
amount of kerosine required to; react withY the
overflow is conducted through- pipe S-by pump
dissolved aluminum chloride in thepstream. pass
I0 which discharges into pipe l-I ..
The pipe Il. communicates with the> heat ex-Í `~'45 ing rto the heater 2. Thismethod of operation
avoids- circulating unreacted- kerosine through
changer 4 which in turn discharges into pipe I2.
the aluminum chloride vessels I or at least-re
The. pipe I2 communicates with branch pipes
I3 and I4 leading to the vessels l.
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duces the amount so circulated to a minimum.
By circulating the» hydrocarbon stream in the
In this way the hydrocarbon stream is. vintro
duced to the top of either of: the. aluminum chlo `5`0 foregoing manner through the solution vessels
complex> formation therein can be substantially
ride vessels and ñows: downwardly therethrough
entirely avoided since under the conditions pre
discharging through pipes. I5 and i6 as the case
vailing therein butane- does- not enter into com
may be».y which in turn communicatewith thepre
viously mentioned pipe 1.
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plex readily.
Once the system. has. become ñlled with> hw 55 i The complex formed.. in the. vessel 3 may be
drawn off through a, pipey I1 to atower I8 for the
drocarbon liquid, the introduction of further
purpose of fortifying it with additional aluminum
hydrocarbons may be discontinued. Under such
chloride. The complex is advantageously dis
conditions the butane and unreacted kerosine are
posed as a static column of liquid in the tower I8.
continuously recirculated through the. system un
til substantially all. of the kerosine present: is 60 A stream of butane containing` dissolved alumi
num chloride isvdrawn oiiv from the Vessels I` and
converted to complex. In actual operation it is
vconducted through pipe I9 which terminates in
contemplated that the effluent stream from the
a suitable distributor 20 positioned within the
aluminum chloride. vessels l will contain a small
bottom of the tower.
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amount of dissolvedvalurninum chloride and will
be substantially free from complex.- Any required < 65 The butane stream is thusv dispersed within the
static column of liquid and rises upwardly there
makeup promoter is added toYL this stream either
through. In doing so thecomplex extracts alu
prior to or subsequent to its passage to the heater
minum chloride from the butane stream until the
2. The heating temperature. and the amount of
complexv becomes saturated.
promoter are correlated to eiîect substantially
complete reaction between the dissolved alumi- `
num chloride and kerosine hydrocarbons. The
reaction to` form complex takes place substan
tially entirely in the. vessel 3 Whichis. of suffi;
In this way a complex suitable’as an isomeriza
tion catalyst may be prepared: For'example, -a
complex catalyst effective for isomerizing normal
butaneY is characterized' by havingl a heat of hy
drolysis of about 300- tol 330 small calories per
.cient capacity to permit a substantial reaction
T5 gram of complex. The complex leaving the-»ves
time, namely, about 30 to 60 minutes.
2,408,187
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sel 3 may have a heat of hydrolysis of only about
200 to 280 calories. Consequently, its heat of
` recyclingv said hydrocarbon phase to the contact
zone, and >continuing the cyclic operation to eiîect
substantial conversion of kerosine hydrocarbons
to aluminum chloride-hydrocarbon complex.
hydrolysis may be raised by fortifying in the tower
I6 as already described. >This fortifying action
2. A method of preparing a complex catalyst
is advantageously carried out at a temperature .
of about 200° F.
formed byreacting aluminum chloride with kero
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sine in the presence of hydrogen halide which
During the fortifying action the effiuentstream
comprises maintaining in a contact zone alumi
of butane may be discharged from the tower I8
through a pipe 2| and passed all or in part to
num chloride in solid granular form, circulating
pipe 22 communicating with the previously men 10 through said contact zone in contact with the
solid halide a stream of liquid hydrocarbons com
tioned pipe H.
prising a major portion of saturated aliphatic C4
'I'he fortifying stream of butane and dissolved
hydrocarbon vand a minor portion of kerosine,
aluminum chloride may be passed through the
eiîecting contact between solid halide and hydro
heater 2 prior to introduction to the tower I8 in
order to maintain the required temperature con 15 carbons under conditions of time and tempera
ditions in the tower I8.
ture such that solution of a small amount of
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The collecting and fortifying of the complex
may, if desired, be carried out in a single chamber
' aluminum chloride in C4 hydrocarbonsk occurs`
without substantial complex formation, passing
said stream of solution to a reaction zone, sub
While specific mention has lbeen made of form 20 jecting it therein to elevated temperature in the
or vessel.
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Vrange of about 200 to 300ov F. and in the presence ,
'ing a complex from aluminum chloride, it is con
of hydrogen halide such that dissolved aluminum
templated that other solid metal halides of the
Friedel-Crafts type, such as aluminum lbromide
and zirconium chloride,.may be used. Likewise,
other hydrocarbons or hydrocarbon mixtures than
chloride reacts with kerosine hydrocarbons to
.form complex, separating resulting complex fromV
the unreacted hydrocarbons including C4 hydro
carbons, recycling the hydrocarbons from which
complex has been separated to the contact zone;
and continuing the circulation of hydrocarbons
` kerosine may be used. However, from the stand
point of making a complex catalyst effectivelfor
isomerizing normal parañins such as normal bu
to effect substantial conversion of said kerosine K
1 tane, it is desirable to employ a non-aromatic
hydrocarbon.
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Obviously many modifications and variations
of the invention as above set forth may be made
without departing from the spirit and scope
thereof, and therefore only such limitations
should be imposed as are indicated in the ap
pended claims.
I claim:
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1. A method of preparing a complex catalys
formed by reacting aluminum chloride with kero
sine hydrocarbons in the presence of hydrogen
halide which comprises maintaining aluminum
chloride in solid granular form in a contact zone,
passing a saturated aliphatic C4 hydrocarbon in
hydrocarbons to complex.
3. A method of preparing a complex catalyst
formed by reacting aluminum chloride with Akero
sine in the presence of hydrogen halide which
comprises maintaining in a contact zone alumi
num chloride in solid granular form,r circulating
through said contact zone in contact with thev
solid halide `a stream of saturated aliphatic C4
hydrocarbons in liquid phase, effecting contact
between'solid halide and C4 hydrocarbons under
conditions of time and temperature such that
solution of a small amount of aluminum chloride
in C4 hydrocarbons occurs without substantial
complex formation, thereafter vpassing the circu
liquid phase through- the contact zone in contact
lating stream containing dissolved aluminum
with said chloride, eiîecting solution of a small
amount of chloride at a temperature below about
200° F. in the C4 hydrocarbon under conditions
such that substantially no complex formation 0c
curs, passing the resultant solution to a reaction
chloride to a reaction zone, adding to the stream,
passing to said reaction zone a small amount of
kerosine, subjecting the dissolved chloride to con
tact with the kerosine in the presence of hydrogen
hydrocarbons removing from the reaction zone
carbons to complex.
halide at elevated temperature Vsuch that dis
zone, subjecting the dissolved chloride to contact 50 solved aluminum chloride reacts With kerosine to
form complex, separating resulting complex from
in said reaction zone with said kerosine hydrocar
the unreacted hydrocarbons including C4 hydro
bons in the presence of hydrogen chloride at a>
carbons, recycling the hydrocarbons from which
temperature in the range about 200 to 3009 F.
complex has been separated to the contact zone,
such that dissolved chloride enters into complex
formation with kerosine hydrocarbons, separating 55 and continuing the circulation of hydrocarbons
to effect substantial conversion of kerosine hydro
resulting complex from C4 and unreacted kerosine
a hydrocarbon phase consisting mainly of C4 hy
drocarbons and substantially free from complex,
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HAROLD V. ATWELL.
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