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Sept 17, 1946-
B. l.. EvERlNG Erm.. l `
2,407,873
POLYMERIZATION OF CIAJEFINvS v
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Sept. 17, 1946*.-
2,407,873
B. L. EVERING ETAL
POLYMERIZATION OF OLEFINS
Filed Noi. 13, _1945
2 sheets-sheet 2
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2,401,873
Patented Sept. 17, 1946
UNITED STATES; PATENT’ OFFICE A
2,407,873
PÜLYMERIZATIÜN OF OLEFINS
Bernard L. Evering, Chicago, Ill., Edmond L.
d’Ouville, Pittsburgh, Pa., and Don R. Carmody,
Newton, Iowa, assignors to Standard Oil Com
pany, Chicago, Ill., a corporation of Indiana
Application November 13, 1943, Serial No. 510,112
`11 Claims. (Cl. 26o-683.15)
l
2
This invention relates to the polymerization of
oleñns and particularly normally gaseous oleñns
hydrocarbon for making the complex We effec
such as butenes by means of a liquid aluminum
ln other Words, when a complex is prepared by
halide-hydrocarbon complex catalyst and it per
tains more particularly to a particular catalyst
employed and the method of preparing, fortify
ing
a continuation-impart
and using said catalyst.
of our This
copending
application
applica
tion Serial No. 287,089, now Patent No. 2,354,652,
issued August 1, 1944.
When hydrocarbons are isomerized by means
of aluminum halides such as aluminum chloride
and aluminum bromide in the presence of hydro
gen chloride a liquid aluminum halide-hydro
carbon complex is formed Which itself is an actï'e
catalyst for promoting isomerizatiou. After this
catalyst is relatively spent for eifecting isomeriza
tion it is still active for the alkylation or poly
merization of oleñns and even if the catalyst is
tively limit the hydrocarbon ' content thereof.
continuously adding an olefin, this olefin is con
tinuously absorbed or combined inthe complex
until the aluminum chloride content thereof
reaches extremely small proportions.. We have
found that the aluminum chloride content of the
complex should-be upwards of `50% and should
preferably be within the approximate range of
to 80%. A complex prepared from an aro
matic-free distillate from a Mid-Continent crude
and anhydrous aluminum chloride may for ex
emple have approximately the following analysis:
Weight per cent
Aluminum _____________________________ „12.5
Chlorine ________________________________ __
44
Hydrocarbon __________________________ __ 43.5
In an effort to ascertain the chemical struc
relatively spent for alkylation of oleñns with
isoparaiîins it is still relatively active for effecting
cleñn polymerization.
ture of the complex a portion of it was carefully
An object of this invention is to provide a
process in which an aluminum chloride-hydro
in a water reflux condenser, a solid carbon
carbon complex which is relatively spent in one` ~\
reaction may be used as a catalyst in another reac
tion. A further object is to provide a method and
means for effectively utilizing such complex until
it is substantially completely spent. A further
object is to provide an improved method and, f'
>means of contacting olefins with an aluminum
chloride-hydrocarbon complex for producing vis
cous hydrocarbons of high molecular Weight.
Other objects Will become apparent as the detailed
description of the invention proceeds.
It has long been known that oleñns could be
polymerized With aluminum chloride (U. S.
1,385,620) and it has been proposed that such
polymerization be effected by means oi a suspen
sion of anhydrous aluminum chloride in petro- ‘i
leum ether (U. S. 1,745,028). When anhydrous
aluminum chloride is thus employed for effecting
polymerization a complex is formed with the oleñn
and it has been suggested that this complex itself
acts as a polymerization catalyst by absorbing the
olefin. In such cases it was deemed necessary to
hydrolyze the resulting liquid in order to obtain
the desired polymer. Our invention is an im
provement over these known processes.
decomposed by addingV Water drop by drop With
constant stirring. The products were collected
dioxide-acetone tower, a gas absorption tube to
remove hydrogen chloride, and a permanent gas
collector. The hydrocarbon layer was extracted
with ether and the ether distilled from the hy
drocarbon layer. The 45 volume percent over
head from the distillation of the hydrocarbons
had the following characteristics:
Boiling range _____________ _`_ ____ __ 1421°-553° F.
Refractive index_ __ ________ -_ N2"D 13820-15377
The distillation revealed plateaus at 300° F. and
again at 440° F., which fractions Were character
ized by pronounced terpene odors. The fraction
showed varying degrees of unsaturation.
The activity of the aluminum chloride-hydro
carbon complex is dependent upon the nature
of the bound hydrocarbon as well as the amount
thereof. Complexes of little or no catalytic
activity yield on hydrolysis a coke-like hydrogen
deficient organic material which is often insoluble
in organic solvents. Active complexes on the
other hand yield on hydrolysis a hydrocarbon or“
the lubricating oil viscosity range, e. g. with a
molecular Weight oi about 300 to 500 and with
an average of more than 1 double bond, gener
The aluminum chloride-hydrocarbon complex 50 ally 2 to âdouble bonds per molecule. For a
catalytically active complex it is important that
of our invention is preferably initially prepared
the hydrocarbon constituent Which'is liberated on
by reaction of aluminum chloride with a satu
rated hydrocarbon instead oi an olefin and the
saturated hydrocarbon is preferably substantially
hydrolysis have a certain minimum hydrogen
to-carbon ratio in relation to the total aluminum
free from aromatics. By employing a saturated 55 chloride content of the complex. There should
2,407,873
3
4
be no less than 1.0 mol of aluminum chloride for
each double bond in the hydrocarbon obtained on
Y produced in the isomerization step with an ex
traneous olefin or for Íeffecting polymerization
hydrolysis. Catalysts which contain about 2 mols
of extraneous oleñns. By initially preparing the
of `aluminum chloride per double bond are very
complex in the substantial absence of olefins we
avoid the danger of employing a complex hav
.suitable for polymerization. Catalysts have been
used for isomerization in which the aluminum
chloride ratio was as high as 10 mols of aluminum
chloride per double Ábond in the oil produced on
hydrolysis. Our preferred catalyst is one which
ing an excessive hydrocarbon content and assure
the production of the most suitable type of com
plex for effecting polymerization. Once the com
_plex is formed its activity may be maintained by
contains from 1.0 to 5 mols of aluminum chloride 10 merely supplying make-up aluminum chloride,
preferably .to a portion of the complex which is
hydrolysis of the complex. The number of double
`withdrawn from the system and before that com
bonds can be determined by hydrogenation or
plex isreturned to the system or charged to a
per double bond in the oil which results from the
»
.
subsequent conversion zone. The complex from
Our active complex catalyst is a rather viscous 15 the isomerization system maybe employed for
liquid khaving a specific gravity in the'general
alkylation and then for polymerization or if de
vicinity of 1.5 and it is not appreciably soluble in
sired the complex may be sent directly from the
hydrocarbons. When a hydrocarbon charging
isomerization to the polymerization system.
stock is introduced at the rbase of a column of such
Our invention- will lbe more clearly understood
complex under sufficient pressure to maintain 20 from the following detailed description read in
substantially liquid phase conditions the hydro
conjunction with the accompanying drawings
carbon becomes intimately dispersed in the col
which form a part of this specification and in
umn of complex so that the presence of a second
which
phase is not readily discernible. On continued
Figure 1 is a schematic ñow diagram illustrat
introduction, however, we have found that a clear 25 ing the integration of the polymerization process
hydrocarbon liquid separates from the top of a
with isomerization and/or alkylation, and
complex column as a _separate and distinct phase.
Figure 2 is a iiow diagram illustrating a com,
This product liquid may' mechanically entrain
mercial application of‘our polymerization process
some of the complex but entrained material may
per se.
be separated out in a settler and returned'to the 30
Referring to Figure 1, isomerization is effected
column or adsorbed on a coke filter. For effec
in system I0, alkylation in system II and poly
other methods.
v tive conversion the column -shoruld be at least 5
merization in system I2. The charging stock for
feet in height and should preferably be l0 to 30
the isomerization may be normal butane, normal
feet in height. „By using a column of complex
of proper activity and height the losses of alu
minum chloride by solution in the effluent p-rod
uct stream is substantially eliminated. We prefer
pentane, hexanes, heptanes, octanes or alight
35 paramnic naphtha, preferably a straight-run
naphtha having an end point not substantially
higher than about 150 to 160° F. Such charge is
to avoid the introduction of solid aluminum chlo
introduced to the isomerization system through
riderper se into the column but any small amount
line I3, hydrogen chloride is introduced through
of aluminum chloride which may reach the col 40 line I4 and aluminum chloride through line I5.
umn as make-up catalyst is quickly taken up by
The aluminum chloride and hydrogen chloride
the complex and thus utilized in maintaining the
react with a portion of the charge to form the
aluminum chloride content of the complex at the
complex as hereinabove described and 'this com
desired level.
‘
.
plexthen elîects conversion of the remainder of
Glenn-containing gases _ from any suitable 45 the charge at temperatures of about 100° F. to
source may be employed in our process. These
250° F. or higher and at pressures from about 100»
may be gaseous oleñns containing 2, 3 or 4 carbon
pounds per square inch to 1000 pounds per square
atoms per molecule or a mixture of any two or
inch, for example,` about 450 pounds per square
more of such oleñns. Also, we may use the
inch, the pressure preferably being sufficient to
dimers, trimers and higher polymers as charg 50 maintain the reactants in liquid phase conver
ing stock for the polymerization. Dilution with
sion conditions. The contact time~ may Vrange
paraflinic hydrocarbons is not objectionable and
from about 1 to 120 minutes depending upon
in fact is highly beneficial in that such saturated
the other conditions of the reaction. As the re
hydrocarbons serve to dilute the polymerization
action progresses a liquid complex is continu
products and thus make possible the continuous
ously formed.- This complex is withdrawn with
removal of polymerization product from catalyst
the hydrocarbons through line I 6 to separator
complex. A feature of our invention is the facil
I1. In separator I1 the liquid complex settles
ity with which oleñns may be polymerized from
out and is withdrawn through line I8. The
conventional refinery streams of Ca or C4 hydro
isomerization reactor may be of the type illus
carbons such, for example, as streams contain 60 trated in our copending application but it is
' ing normal and isobutane, butene-l, butene--Z
preferably a tower-type reactor wherein the hy
and isobutylene or streams containing propane
drocarbons pass as a dispersed phase upwardly
and propylene or mixtures of said streams. By
>through a column of complex and where make-up
regulating the polymerization conditions We may
aluminum chloride is continuously introduced
obtain polymers of _the gasoline boiling range, 65 into this column either as a solution in a part of
the incoming charge or in admixture with re
heavier polymers.
cycled complex.l
polymers of the lubricating oil range or even
Another feature of our invention is the multiple
use of our improved catalyst complex. It may
ñrst be employed for the cracking, dispropor
tionation orisomerization of saturated hydrocar
The products from separator I'I pass through
line I9 to a stripping andfractionation system
70 20 from Wh'ich hydrogen chloride may be re
turned by line 2 I to the isomerization system. A
bons, this step being an ideal method of prepar
ing the complex in the first place from aluminum
chloride. The complex may then be employed
either for promoting alkylation of the isoparañins 7 5
light'isomerizaticn product‘such as isobutane
may be withdrawn through line 22 and a, further
light product may be withdrawn through line 23
and a heavy product through line 24. This frac
12,407,873
6
tionation system forms no part of our `present
invention and therefore requires no detailed de
scription but it should be understood that such
system includes separation and recovery of hy
drogen chloride and the various hydrocarbon
tion reactions they are :still highly effective for
effecting olefin polymerization.
The catalyst complex introduced into polymer
izer I2 through line 45 may be fortified by alumi
num chloride introduced through line 4B, such
amount of aluminum chloride being employed
components which are discharged from separa
that the resulting complex will have an alumi
tor I 1.
num chloride content of about 40 to 80%, gener
A part of the complex leaving the bottom of
ally about 50%. Usually the complex will con
separator Il through line I8 may be recycled
through line 25 to the isomerization system, a l0 tain sufficient hydrogen chloride for polymeriza
tion reaction. Any additional small amounts of
part or all of it may be introduced through line
hydrogen chloride may be introduced through
26 into alkylation system I I and a part or all of
line lil. An olefin charging stock is introduced
it may be introduced through line 21 to polymer
through line 43. This olefin charging stock is
ization system I 2. Into the alkylation system
preferably a refinery gas stream rich in isobutyl
We may also introduce make-up aluminum chlo
ene and normal butenes but also containing con
ride through line 28, hydrogen chloride through
siderable amounts of corresponding paraffin hy
line 29, an olefin or aromatic hydrocarbon
drocarbons, i. e. butane and isobutane. Alter
through line 3.0 and an isoparafün hydrocarbon
natively, th'e charge may consist essentially of a
through line Si. The isoparafñn may come from
an external source 32 or from the isomerization
system through line 33. rI‘he alkylation reaction
may be effected at temperatures from about 0
to 212° F. depending on the olefins used, and un
der pressures from about 0 to about 1000 pounds
per square inch gauge. The isoparafñnic hydro
carbons should be present in amounts equal to
‘and preferably in excess of the oleñnic hydrocar
bons. The ratio of isoparafñn to olefin charged
(external ratio) may vary from about 1:1 to 6:1
or more. Intimate Contact between the alumi
num chloride-hydrocarbon complex and the hy
drocarbon feed stocks may be obtained by rapid
mixture of propane and propylene or it may con
sist of a mixture of hydrocarbons of from 2 to 5
carbon atoms at least a substantial portion of
which is oleñns. In the speciñc example here
inafter set forth the olefin charge consists of a
butane-butylene stream containing about 15%
isobutylene, 25% normal butenes, 55% butanes
and the remainder Cs and C5 hydrocarbons.
The conditions in polymerizer I2 may be varied
depending upon the type of olefin charged and
the products desired. In the polymerization of
these gaseous olefins to gasoline type or lubricat
ing oil type fractions we may use temperatures
of about 0° to elif)n F. and pressures sufficient to
keep the reactants in liquid phase. Predomi
stirring or by mixers or circulating systems or by
tower-type reactors. Examples for 'more specific
operating conditions are set forth in United 35 nantly gasoline type fractions may be produced
at the higher temperatures and heavier lubricat
States Patents 2,303,560-1-2.
ing oil fractions will predominate in the product
The reaction mixture is withdrawn from alkyl
when the lower temperatures are used. For
ation system II through line 35i to separator 55
heavy products the polymerization may range
wherein the complex is separated from hydro
from 40° to 0° F. or even lower, but for our pur
carbons. If the catalyst is not spent with regard
poses the best temperatures are in the general
to alkylation it may be Withdrawn through line
vicinity of about 20° to 30° F. Intimate contact
35 and at least a part of it may be recycled
between the oleñnic feed gas and lthe catalyst
through line 3l to the alkylation system. It is
may be obtained by the use of mechanical stir
possible to res-tore a part of the activity of the
rers or circulating systems but remarkably supe
complex by addition of aluminum chloride and
rior results are obtainable by the use of a simple
it is thus possible to use complex from separator
tower type reactor as will be hereinafter de
3b in isomerization chamber I@ by returning it
scribed in more detail. The temperature may be
through line 33 and line 25.
maintained by the use of suitable cooling coils.
The hydrocarbon product of the alkylation re
The aluminum chloride complex andthe poly
action :is Withdrawn from separator 35 through
merized hydrocarbons may be withdrawn through
line 39 to fractionation system ¿i0 from which
line d!! to separato-r 50 from which complex may
material lighter than isobutane 4may be removed
be withdrawn through line 5I and either re
through line di, isobutane ‘for recycling may be
cycled through line 52 or be Withdrawn from
withdrawn through line 112, a .light `alkylate may
the system through line 53, a part usually being
be withdrawn through line ¿i3 and a heavy prod
recycled for further fortification for use with
uct through line Mi. It should be understood
aluminum chloride and another part being With
that any type of stripping, fractionation and re
drawn.
covery system may be employed.
The polymerized hydrocarbons are Withdrawn
The catalyst from the alkylation reaction may
no longer be effective for promoting the reaction 60 from the separator through line 54 and a part
of them may be recycled through line 55 to the
between olefin and isoparaffin and yet may not
polymerization reactor or system I2. The re
be spent as regards further catalyst activity. For
this reason a part or all of it may be withdrawn
from separator 35, line 33 and line A15 to poly
merization system I2 wherein olef'lns are poly- ‘
merized to form hydrocarbons suitable for use as
gasoline ‘or as lubricating oil depending upon the
conditions maintained in the polymerizer.
The
complex withdrawn from separator 35 may con
tain slightly more or slightly less bound hydro
carbon than the catalyst withdrawn from sepa
rator Il but generally speaking complexes from
these Sources are quite similar in composition
mainder may be introduced into a fractionation
system ë-â from which unreacted light gases are
withdrawn through line lil, low boiling liquids
through line 53, light polymer through line 59
and heavy polymer through line §93. Here again
it will be understood that any type of fractiona
tion stripping and product recovery means may
be used. If the fraction withdrawn through line
558 consists essentially of isobutane this fraction
may be introduced to alkylation zone I i through
line 3l and if it is predominantly normal butane
it may be charged to isomerization system I0
Vand activity. Although these vcomplexes Vmay be
relatively spent for the isomerization and 'alkyla 75 through Eline I3. Other methods of utilizing vari
V2,407,873
7
8
`ous products will be apparent to thoseskilled in
the art from the above description.
An outstanding feature of our integrated proc
mixerßl or through line ‘l0 to the top of tower
62. Spent caustic is removed from the system
through line 'i I.
The neutralized butane-butylene stream then
ess as herein described is the multiple use of our
speciñc type of improved aluminum chloride
hydrocarbon complex. This complex is prefer
5 passes by lines 72 and 12a or 12b into one or
both of the calcium chloride dryers 13 and 13a.
The dried stream leaves the top of the dryers
ably initially prepared by a reaction such as
isomerization which involves a saturated hydro
carbon so that the resulting complex will contain
«not more than 50% and preferably yonly about
20 to 45% of bound hydrocarbon. This bound
through line 'id at a pressure a little over 200 .
pounds per square inch and passes through heat
exchanger 'l5 wherein it is cooled from about
100D F. to about 70° F. The stream is then
joined by recycled product stream from line 16
hydrocarbon, While derived from saturated hy
drocarbons, is unsaturated in character. The
which brings the resulting temperature down to
character of the bound hydrocarbons from the
about 40° F. The mixture next passes through
-isomerization or alkylation complex should be 15 cooler Tl which lowers the temperature of the
such that on hydrolysis of the complex it will
stream to about 0° F. About 0.86 pound per hour
yield a viscous oil of about 300 to 500 molecular
of anhydrous hydrogen chloride is then intro
weight which is characterized by limited unsat
duced to the stream through line i8 and the
uration, our preferred catalyst for polymeriza
stream is introduced through branch line 19a,
tion containing about 2 mols of aluminum chlo 20 10b and/o1' line 19e into polymerization towers
ride per double bond in the oil which results
80d, 80h, and/or 00e, respectively. Each of these
from complex hydrolysis.
towers is about 41/2 feet in diameter by about
The activity of our complex may be measured
121/2 feet in height and each is provided with
by its heat of hydrolysis. In the case of alumi
cooling coils tía, Sib and 0|c for removing
num chloride complexes the activity for isomer 25 103,000 B. t. u. per hour. The cooling is effected
ization or alkylation should be within the ap
proximate limits of 60 to 75 large calories per
b-y vaporization oi propane or other suitable re
irigerant Within the cooling coils, the refriger
ant vapors being returned by lines 32, 82a, 82h
and 02e and line 83 to knock-out drum 84, then
. gram atom of active aluminum; for polymeriza
tion the activity should be Within the approxi
-mate limits of 50 to 67 large calories per gram 30 to compressor 85, condenser 86 rand refrigerant
atom of active aluminum.
In the case of alumi
holding drum 87. A part of the refrigerant from
the holding drum passes by lines 88 and 89
num bromide complexes the activity should be
within the approximate limits of 67 to 82 large
calories per gram atom of active aluminum for
through cooler 1l and thence by lines 90 and 83
isomerization or alkylation and within the ap- .
proximate limits of 57 to 75 large calories per
gram atom of active aluminum in the case of
polymerization.
The expression “active alumi
to knock-out drum 04. The remainder of the re
frigerant passes by line 0i and lines 02a, 92h
and 92e to inlet ends of coils Bla, Bib and ßlc.
Before initiating the polymerization each of
the reactors is charged with an aluminum chlo
num” means the aluminum content of the hy
ride-hydrocarbon complex which has preferably
drolizable aluminum compound in the liquid 40 been prepared by reaction of aluminum chloride
complex material; inactive aluminium compounds
with a saturated light hydrocarbon in the pres
such `as oxides or hydroxides are thus not in
ence of hydrogen chloride as hereinabove de
cluded by the expression “active aluminum.”
scribed so that said complex will have a hydro
Since our invention is primarily concerned
carbon content of about 20 to 60%.. A heat of
with` oleñn polymerization we will now describe 45 hydrolysis within the approximate range of 50
an example of a commercial application of the
to 67 large calories per gram atom of active yalu
invention in a plant for producing 800,000 gallons
minum will on hydrolysis yield an oil of about 300
per year of a butene polymer having a viscosity
to 500 molecular weight there being about 1 to 5
of the order of ’700 to 1800 seconds Saybolt uni
mols of aluminum in the complex per double
versal viscosity at 210° F. The charge in this
bond of the oil thus produced on hydrolysis. The
case is a reñnery butane-butylene stream of ap
complex can be prepared from the butane-butyl
proximately the following composition:
ene charge itself provided that proportions and
complex-forming conditions are employed to in
Mol
per cent
Volume
per cent
sure a complex of the above characteristics but
55 we prefer to prepare the initial complex by treat
ing pentane, light naphtha or similar hydrocar
Propylenc ___________________________________ __
0. l
0. 1
Propane__ ._
0.7
0.7
Isobutane_ _
Butylcnes__
Normal butane..
'
_
_
46. 7
47. 2
_.
_.
4l. 2
8. 9
40. 3
8. 8
Pentanes ____________________________________ __
l. 7
2. 0
Amyleucs ___________________________________ _ _
0. 7
0. 9
bons with aluminum chloride in the presence of
hydrogen chloride.
Each reactor is about one-half iilled with such
60 complex and the charging stock is dispersed into
the base of the complex by suitable distributors
so that the charging stock passes upwardly as a
Of the butylenes about 36% is isobutylene, 26%
dispersed phase in the column of complex. The
temperature in the reactors is maintained within
butene-l and 38% butene-2. About 685 barrels
per day (about 1200 gallons per hour) of this 65 the relatively narrow limits of about 20 to 30° F.
charging stock is introduced by pump 6| at about
although this temperature may be as high as 40°
260 pounds pressure into caustic tower 62 which
F. if larger amounts or lower viscosity products
may be about 2?/2 feet in diameter by about 12
may be tolerated and may be lower than 20° F.
feet high. 41 barrels per day of 10% aqueous
if heavier products are desired. 'I‘he feed inlet
sodium hydroxide is introduced by pump B3 to 70 temperature may be approximately the same as
line 64. The overhead streamqleaves tank 62
the average reactor temperature, theV pressure
through line 65, is admixed with caustic from
should be sufficient to maintain liquid phase con
line 66, passed through mixer Sl and introduced
version conditions and may be of the order of `100
into caustic settler S8. The settled caustic is re- ~
`turned >by pump 69 either through line 66 toV
to' 500, for example 185 pounds per square inch.
The space, velocity maybe ofthe order of 'about
amers,
Si
cosity of about 50 seconds Saybolt at 100° F., an
0.1 to 10, for example 2`volumes of inlet stream
(including recycled material) per volume of com
A. P. I. gravity of about 43 and a flash of 130° F.
The heavy polymer which is withdrawn from
the base of the tower at the rate of about 60 to
plex in the reactor per hour. Relatively low
space velocities (.1 to 2) may be necessary with
65 barrels per stream day is forced by pump |22to cooler |23 and thence to storage. .This heavy
polymer has the following characteristics:
relatively inactive catalyst, and relatively high
space velocities (2-10) with catalyst of high ac
tivity, assuming a column height of about 5 to 20
feet. An amazing feature of this system is the
Viscosity __________ __ 900 sec. Saybolt at 210° F.
remarkably effective conversion which is effected
Gravity A. P. I __________________________ _.. 29
without any mechanical mixers, stîrrers or circu- 10 Pour _______________________________ __ +35° F.
lators the charging stock and diluted products
Flash ___________________________ __ S50-400° F.
being lighter than the complex passes upwardly
To maintain the catalyst at the desired activ
therethrough and leave the top of the reactors
ity in this process complex from storage tank 96
through line 03 to settling tank 00. This tank
or complex withdrawn from the reactors through
may be maintained at a pressure of about 175 15
lines |25a., i255, l25c, lines |26 and |21 is intro
pounds per square inch and a temperature of
duced through line |28 to fortification tank |29
about 30° F. The complex which settles out in
into
which powdered aluminum chloride is added
this tank is Withdrawn through line 95 to catalyst
from
source |30. The added aluminum chloride
storage drum 90. About 2500 barrels per day of
is intimately mixed withthe complex so that the
the product leaving the top of tank 94 is recycled
20
aluminum chloride content thereof will be in
creased to such an extent that when this fortified
complex is returned to the polymerization re
scribed. `The remainder of the product stream
actors it will maintain the aluminum chloride
passes through line 08 to settling drum 99 from
content
of the complex in said reactors within
which additional catalyst is‘separated and re 25 the desired
range of about 40 to 80% or prefer
turned through line |00 to storage drum 90. The
ably about 45 to 55%. About 2 to 10, for »example
through line 76 by means of pump 97 for admix
ture with the incoming stream as hereinabove de
product stream next passes through lines |0| and
about 6 pounds of aluminum chloride is usually
|0|a or |0|b to clay towers |02a andl |021) which
required per barrel of total polymer produced.
operate at pressures of about 165 pounds per
In this particular case about 25 pounds per hour
square inch. The products leaving the clay 30 of aluminum chloride is introduced into the forti
towers through line |03 pass through heat ex
fying chamber along with an equal or greater
changer '15 wherein they are heated to about 70°
F. and then passed through heater |04 wherein
amount of complex and the resulting mixture in
the form of a viscous complex or paste is intro
they are heated to about 270° F. at which tem
duced by pump |31, line |32 and branch lines
perature they are introduced into flash drum |05 35 133e, |335 and _|33c to reactors 80a, 30h and 80e
which operates at aboutV 135 pounds per square
respectively. Instead of adding the make-up
inch. This tower is provided with a heater |05
aluminum chloride in fortified complex it may be
for maintaining a tower bottom temperature of
added by making new complex with substantially
about 335° F. The overhead which leaves the
equal amounts of aluminum chloride and poly
tower at about 300° F'. is cooled in cooler |01 and 40 mer (such as heavy polymer produced in our
introduced into butane surge drum |08 at about
process) the latter being introduced through line
100° F. About 543 barrels per d_ay of butanes with
|30. By simply fortifying the complex, however,
residual butenesare introduced from the base of
we not only minimize the necessary amount of
this surge drum through line |00 to an alkylation
added aluminum chloride but we obtain better
system. Any gases purged from the top of the 45 control.
,
surge drum through line ||0 may be combined
It
should
be
noted
that
aluminum
chloride
per
with gases discharged from the top of catalyst
se is not the effective catalyst in our polymeri
storage drum 90 through line |||,` scrubbed with
spent caustic and then introduced into a fuel gas
line.
`
"
`
’
zation reactorand we prefer to avoid any intro
50 ductionv of solid aluminum chloride into the re
actors, the make-up being added in the form of
fortified complex which in turn equalizes with the
The bottoms from flash drum |05 are heated
preferably in a Dowtherm system a diphenyl or
diphenyl oxide being heated in furnace ||2 to a
temperature , `of about 500° and >then passed
complex in the columns of catalyst in the re
actors. Should any small amounts of entrained
uncombined aluminum chloride actually enter
through exchanger‘l I3 and returned to the fur 55 or
the reactor it quickly becomes associated with
nace at approximately theV same temperature.
the complex' therein. The remarkable advan
The stream which passes through exchanger | |3
tages oifered by our system are due in large meas
is then heated to about 500° F. which steam is
ure to the use of our particular catalyst complex
introduced through line H4 t0 stripping tower
H5 which may be about 2 feet in diameter to 60 as distinguished from the use of solid aluminum
chloride. In other words, we obtain la control of
about 24 feet in height, which may operate at \
reaction and product produced which would be
about 5 pounds per square inch gauge with a bot
impossible in the case of solid aluminum chloride
tom temperature of about 450° F. and a top tem
catalysts, wherein such difficulties as hot spots,
perature of about 500° F. 152 pounds per hour
dead spots, channeling, plugging, etc. are always
of 110 pounds steam is introduced at the base of
this stripper through line H0. To‘the overhead
from the stripper 'about .4 pound'per hourof
encountered,
Another feature of our invention
< is the use of a relatively stationarycolumn of
liquid complex in the reactor, the passage of dis
ammonia is added through -line Il] and theover
persed charging stock continuously therethrough,
head stream then passes through cooler ||8 «to
separating drum H9 from thebottom of `which zo and the maintenance of substantially constant
complex activity by carefully controlling rates of
water is withdrawn through- line |20 and from
adding make-up and withdrawing relatively
the side of which a light polymer stream is with
spent complex.
`
`
drawn through line |2|. This light polymer
The nature of the conversion and of the pro
stream may amount to about 35 to 40 barrels per
stream day and is characterized 'by a‘Saybolt vis
75
duced products can be `controlled by regulating
.f
Y
-v
y
-
-
11
,
.
the space velocity, the height of the columnof
complex and the activity oi the complex to obtain
understood that this example is-by way of illus'
tration and not by way of limitation. Various
any desired extent of olefin clean-up. By using
modifications of apparatus and alternative oper
a relatively high column and/or a suiiiciently low
ating conditions will be apparent from the above
spacevelocity the oleñn clean-up may be almost Ul detailed description to those skilled in the'art.
quantitative with a relatively active complex.
We claim:
Y
l
Byusing higher space velocities and relatively
1. The method of utilizing aluminumY chloride
short column oi complex, particularly with rela
in catalytic hydrocarbon reactions which com'-v
tively "inactive complex, the-oleñn clean-up may v prises first contacting it with a substantially aro
be relatively small and the polymerization will be 10 matic-free normally liquid saturated hydrocar
relatively selective, i.` e., will be largely limited
bon fraction under conditions for effecting isom
tothe ‘polymerization of isobutylene. The fol
erization of said hydrocarbon fraction and the
lowing table will illustrate how the polymeriza
formation of an aluminumY chloride complex
tion and the nature of polymerized products vary
which on hydrolysis would yield a hydrocarbon
with different percentages of olefin clean-up in
oil of lubricating oil viscosity and which complex
the case of speciñc oleflnic gas hereinabove den
contains from about 1 to 5 mols of aluminumchlo
scribed whereinothere are about 2 parts of normal
ride per double bond in the oil which would re
butenes to about 1 part of isobutenes and where
sult from said hydrolysis, Yseparating said alumi
the complex contains in the general vicinity of
num chlorideV complex from isomerized hydro
50% by weight of bound hydrocarbon.
carbons, and subsequently treating normally gas
eous oleiins in the presence of said aluminum
Selective polymerization of isolanti/Iene
Vchloride complex under conditions for effecting
polymerization of said gaseous olefins.
Y' .
W cight
ÑVeight
2. The method of converting normally gaseous
Per
cent
Per cent
Per cent
1
clean-up
of i-Ql:
of n-QF
reacting
polymer
polymer
20
40
60
80
44
69
88
97
7
24
44
71
78
62
52
44
22
38
48
56
of ole?ins
reactmg
Pi‘ìëîîlt
Pâfáeït
25
oleflnic hydrocarbons to hydrocarbons of higher
molecular weight which comprises contacting said
oleñnic hydrocarbons under conditions for effect
ing polymerization with an aluminum chloride
30
complex originally formed during the isomeriza
tion of normally liquid saturated hydrocarbons by
contact with an aluminum chloride catalyst under .
The heavy polymer which may have a viscosity
range from 700 to 1800 seconds Saybolt at 210° F.
is extremely valuable for a large number of spe~
cial applications. It is a particularly valuable
component of specialty or premium lubricants
and coating compositions. It is likewise valu
able for the preparation of lubricant addition
isomerization conditions, said complex being- one
which on hydrolysis would yield a hydrocarbon
oil of lubricatingy oil »viscosity and which contains
from about _1 to 5 mols of aluminum chloride per
double bond `in the oil which would result from
said hydrolysis.
_
, Y.
'
_
_
.
,
.
1
Í
3. `The method of utilizing aluminum chloride
in hydrocarbon conversion processes which meth
agents which may be prepared by treating said
polymer with oxygen, sulfur, chlorine, phos 40 od comprises treating parañinic hydrocarbons
phorous, etc. or compounds thereof.
with an aluminum chloride catalyst., in the pres
ence of hydrogen chloride 'to effect an> isomeriza
The light polymer likewise has Valuable proper
tion reaction and to produce a complex of lowered
ties which cannot be duplicated by natural pe
troleum oils and for example a fraction having
activity forthe isomerization reaction, said com
the following specifications is outstandingly su 45 plex beingronde which on hydrolysis would yield
a hydrocarbon oilofV lubricatingoil.viscosity and
perior as an ice machine oil, air compressor lu
bricant and a variety of other uses. '
which contains from about l to 5 mols? of alumi
num chloride. per double bond. in the oil which
<Viscosity at 100° F_____ __'_____ '7.5-9 centistokes
would result from said hydrolysis, and subse
PourfF ______________ __Y__V___V„ -85 max.
quently contacting said. catalyst of lowered isome
Carbon residue ______________ _,001 max.
verizatiron activity with a hydrocarbon _stream conf
Color, NPA _________________ __ 2 max.
Neutralization No., mg.
KOH/gm _______________ __`__ 0.05 max.'
Flash, °F ___________________ __ 180 min.
Dielectric strength __________ __ 25,000 max.
sis’ting substantially entirely of normally-gaseous
hydrocarbons containing oleñns under >conditions
forl effecting the production therefrom of normal
5% Iilìy liquidO hydrocarbons of branched-chain, struc,
ure.
A-remarkable and unpredictable advantage of
fered by our polymerization process is the large
yield of polymer obtainable from a'given amount
of catalyst. Based on fresh feed the aluminum
chloride requirements are only about 1% by
weight and the hydrogen chloride requirements
are only about .01% by weight or less. We may
obtain upwards of 20 gallons of polymer per
pound of aluminum chloride with our process
while processes employing solid aluminum chlo
ride as a catalyst produces only about 2 to 3
gallons of polymer per pound of aluminum chlo
ride. Furthermore, our process is remarkably
simple in Yoperation and is free from most of the
troublesome-operating difliculties which inevita
bly arise from the use of solid aluminum chloride
catalyst.
While we have described in considerable detail
,
.
v
.,
.
`
`
4. The method of utilizing aluminum 'chloride
in catalyticîhydrocarbon reactions which. com
prises iîrstV contacting it‘with a substantiallyaro
matic free normally liquid saturatedhydrocarbon
fraction under conditions for effecting isomeriza
tion of said hydrocarbon fraction and the forma
tion> of ,an> aluminum chloride complex, separat-.
ing said aluminum chloride complex from isomer
ized hydrocarbons, subsequently treating a mix
ture of isoparañìns with olefìns in the presence
of said aluminum chloride complexunder condi
tions for effecting alkylation, and contacting ole
ñnic hydrocarbons with a substantiallyspent cat
‘alyst from the alkylation system under conditions
for effecting polymerization of said voleflnic hy
drocarbons.V
Y
Y
i
-
.
I
».
Y
~
v
K 5. The method of polymerizing normally gas
eous oleiins which comprises continuously pass
a speciíic example of our invention it should be 75 ing said oleiins upwardly in the liquid phase
131
14
through a column at least ilve feet in height or
therein, `returning an aliquot portion of the with
catalytically active liquid aluminum chloride ali
phatic hydrocarbon complex in a polymerization
zone, said complex .being immiscible with hydro
finery gas stream, treating another portion. of the
drawn stream in substantial amounts as the re
cycle stream ior admixture with the incoming re
carbons and polymer products and having an alu UK withdrawn stream to remove catalyst containi
nants therefrom and fractionating said last
minum chloride content in the range of about
named portion or the product stream after the
40% to about 80% by weight and at least one
treating step.
mol AlCls per double bond in the oil which results
7. The method of polymerizing normally gas
from hydrolysis of said complex, continuously in
eous oleñns from a hydrocarbon stream contain
troducing with said oleñn's a substantial amount 10 ing said olelins in admixture with normally gas
of liduelied normally gaseous parai‘lin hydrocar
bons for lowering the viscosity and density ci
polymerization products by dilution and thus ía
cilitating their separation from the heavier com
plex in which hydrocarbons are substantially in
soluble, maintaining the column at substantially
constant polymerization temperature by precool
ing the introduced hydrocarbons to a temperature
below the polymerization temperature and by ab
stracting heat from the column by indirect heat "
exchange with a coolant circulated through the
polymerization zone, continuously separating di
luted products from complex in the upper part of
the polymerization zone, continuously remo-ving
\ cous paramn hydrocarbons which method com
prises continuously distributing said stream in
liquid phase at a lowpoint in a column of active
liquid aluminum chloride-aliphatic hydrocarbon
complex, said complex being immiscible xwith hy
drocarbons and polymer products, containing in
its composition amounts of hydrocarbon constitu
ents in the range of about 20% to about 50% by
weight, being one which on hydrolysis would yield
a hydrocarbon oil of lubricating oil viscosity and
further characterized by having from about l to
5 mols of aluminum chloride per double bond in
the oil which would result from said hydrolysis,
passing said distributed stream upwardly through
separated diluted products from the upper part '
at least about 5 feet of said column of said coni
of »the polymerization zone at a point spaced from
the column of complex whereby the bulk of the
complex is retained in the polymerization zone
and employing a space velocity, column height
plex under conditions for effecting polymeriza
and complex activity in the polymerization zone ‘
continuously separating polymerization products
for effecting an olefin clean-up within the range
of about 40% to at least about 80%.
diluted with unreacted paraflin hydrocarbons
from the bulk of the complex in the upper part
of the polymerization zone, continuously with
6. The method of producing polymers of lubri
cating oil viscosity from oleñns higher boiling .Y
tion as the main reaction, continuously removing
heat from said column by passing a coolant in
indirect heat exchange relationship therethrough,
drawing a stream of diluted products from the
stream consisting essentially of paralîñns and o e
upper part of the polymerization zone ata point
spaced from the top of the column of complex
whereby the `bulk of the complex is retained in
ñns higher boiling than ethane and lower` boiling
than pentane to remove other components there
the polymerization zone, treating a minor por
tion of the withdrawn product stream to remove
from, combining said treated stream with a re
cycled stream hereinafter defined, cooling said
any entrained catalyst material therefrom, frac
tionating the treated products to obtain at least
combined. stream to a temperature below the tem
one fraction of lubricating oil Viscosity, and re
than ethylene and lower boiling than amylene '
which method comprises treating a refinery gas
cycling a major portion of the withdrawn product
introducing the cooled stream at the base of a 45 stream prior to the treating step to said low point
in said column of active complex in said poly
polymerization zone containing a column at least
merization zone.
about iive feet in height of active liquid aluminum
8. The method of polymerizing olefms contain
chloride-aliphatic hydrocarbon complex, said
ing more than two and less than five carbon
complex being substantially immiscible with hy
drocarbons and polymer products and containing 50 atoms per molecule from a liquefied gas stream
consisting essentially of a mixture of said 01e
in its composition an amount of hydrocarbon
iins with normally gaseous paraffin hydrocar
constituents within the approximate range oi'
bons containing more than two carbon atoms
about 20% to about 60% by weight, said complex
per molecule which method comprisesV cooling
being further characterized by containing at least
one mol AlCla per double bond in the oil which 55 said liquefied _stream to a temperature below
the temperature employed for effecting polymer
results from hydrolysis of said complex, dispers
ization, introducing the cooled stream at the .base
ing .the cooled stream at the base of said column
of a column at least five feet in height of an
and passing said stream upwardly as a dispersed
active liquid aluminum chloride-aliphatic hy
liquid phase through said column, removing heat
from said column by indirect heat exchange of 60 drocarbon complex which has a hydrocarbon
content in the range of about 20% to 60% by
complex in the column with a coolant circulated
weight, which is immiscible with hydrocarbons
therethrough and effecting said heat removal at
and polymer products and which on hydrolysis
a rate to maintain the column at a substantially
would
yield a hydrocarbon oil of lubricating oil
constant polymerization temperature, maintain
ing a pressure in the polymerization zone sufli 65 viscosity and which contains about 1 to 5 mols
of aluminum chloride per double bond in the oil
cient to maintain the hydrocarbons in liquid
which
would result from hydrolysis, passing the
phase, employing a space velocity in the range of
introduced stream as a dispersed phase upwardly
about .l to l0 and sufficient to obtain an olefin
through said column of active liquid complex in
clean-up of at least about 40%, separating prod
ucts diluted with unreacted normally gaseous 70 a conversion zone under a pressure suücient to
maintain liquid phase conversion conditions and
parañins from the bulk of the complex in the
at a temperature and rate for effecting polymer
polymerization zone and continuously withdraw
ization
as the main reaction, removing heat from
ing a diluted polymer product stream from the
the column of complex by indirect heat exchange
upper part of the polymerization zone at a point
spaced from the top of the column of complex 75 of complex in the column with a circulating cool
perature employed for effecting polymerization,
15
azione@
ant, separating liquid polymerization products di
luted with said normally gaseous parafûnic hy
drocarbons from the bulk of the complex material
in the conversion zone, withdrawing a diluted
liquid product stream from the upper part of the
conversion zone to a settling zone, removing fur
ther amounts of complexfrom the diluted liquid
product stream in said settling zone,‘_treating at
16
product and Which contains at least 20% >but not
more than 50%` of hydrocarbon constituents in
its composition, and at least one'mol AlCl3 per
double bond in the oil which results from hy
drolysis ‘of said complex, passing said dispersed
stream upwardly through said column under
polymerization conditions which include a pres
sure sufficient to maintain the hydrocarbons in
least a portion of the diluted liquid product
liquid phase, a polymerization temperature and
stream from the settling zone to remove residual 10 a space velocity and column height sufficient to
amounts of catalyst material and fractionating
eiîect an olefin clean-up within the range of about
said treated portion of the product stream.
40% to at least about 80%, abstracting heat from
9. The method of claim 8 which includes the
said column by passing a coolant in indirect heat
steps of separately withdrawing a major portion
of the diluted product stream from the settling
zone,' cooling said major portion and recycling
said major portion to the base of the column
of active liquid aluminum chloride-hydrocarbon
complex.
exchange relationship therethrough, continu
ously separating diluted polymer product from
complex in the upper part of the polymerization
zone, continuously withdrawing a stream of di
luted polymer product from an upper point in
the polymerization zone which is spaced from the
10. The method of obtaining viscous hydro
column of complex, treating atleast a portion
carbons from butylenes which method comprises
of the withdrawn product stream to remove cat#
cooling a liquefied dry :butane-butylene stream
alyst contaminants therefrom and fractionating
containing substantial amounts of butanes, nor
said treated portion to obtain at least one viscous
mal butylenes and isobutylene to a temperature
liquid fraction.
’
'
'
below the temperature employed for eiïecting 25
l1. The methodrof claim 10 which includes the
polymerization, contacting the cooled stream in
steps of recycling a major portion of the with
a polymerization zone with a mass of active liquid
drawn Yproduct stream and returning it to the
aluminum chloride-aliphatic hydrocarbon com
polymerization zone in admixture with the lique
pleX, eiïecting said contacting by -continuously
ñed .loutane-butylene stream.
'
‘
'
dispersing said cooled stream at a low level in 30
a column at least ñve feet in height of such ac
tive liquid complex which is immiscifble with said
stream and with the polymerized hydrocarbon
BERNARD L. EVERING.
EDMOND L. D’oUvlLLE.
DON R.` CARMODY.
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