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Патент USA US2406081

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2,406,081
Patented Aug. 20, 1946 ’
UNITED; STATES " PATENT]
IPOLYMERIZATIONIdF owns,
HYDROCARBONS);
L, _,
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William A. La Lande, .Tr., andrllfeinz‘llleinemanm?Upper
tion, Philadelphia,
Darby, Pa., assignorsrtorPorocel
Pa, a,-,corporation~ (iorporaof.;Dela
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Application‘Novemberi'lglfi?, ,
Serial No. 562,405‘ ,
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9 Claims. (01. 260-68315)
Theipresent invention relates tothe polymeri
zation. of ole?ns, and more particularly to, the
polymerization ofv normally gaseous ole?ns to liq
uid' hydrocarbons comprising essentially aliphatic
1%»onless by weight. In'order to“ obtainrvthe'
most (ef?cient polymerization, the ole?ns; under-,;
going ‘conversion _ should: beisubstantially ifree: of;
moisture, ‘and thisvlmayljbe; accomplished byfdeér
hydrating ‘the olefins- in a conventional'manneri
polymers of copolymers suitable for use in the 5; with ‘dry-ing- agents? such as Activated Alumina;
manufacture of motor fuel‘.
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silica-gel», calcium‘ chloride and‘the like; 'While‘.‘
An» object of, this invention is the polymeriza
tion, of ole?ns'or of gaseous mixtures containing
ole?ns in the presence of a catalystv comprising
activatedbauxite to produce polymers boiling for: 1
the. most, part within, the gasoline’ boiling range.‘
A further object of this inventionl‘is the: poly
merization of- dehydrated gaseous ole?ns, partic
ularly the butylenes, at temperatures below 350
degrees F; in the presence of
' a'catalyst. compris-~ 15:
ing bauxite which hasbeen actiyatedby heating,
at, atempe'rature between ‘700, degrees and¢>180'0,
degreesR, and preferably between._1200 degrees
our-process is particularly, applicable to‘ the poly-v
merization of the: butylenes', especially isobutyl-r
ene, such process‘may also bejuti-lized in the con-'
version of'gaseous ‘mixtures including other. ole-'1 -
?ns-r such as ‘propylene, or- mixtures- of gases in--
cluding ethane, ethylenapropane, propylene, the'
butanes, ‘and the butylenes: Howevenrthe'presa
ence-of substantial quantities of gaseous: hydro
carbons other than‘v the :butylenesappearsto'havei
an adverseie?ect uponthe catalyst, and'thecon-f
version e?iciency ofvthe catalyst is substantially
decreased from that attainable“ with: the butyl=~
F. and. 1800 degrees Fl to a-Hresidual‘ moisture,
enes or isobutylene, .per se." jWhen, the gaseous;v
content ofnot more than 2% by weight, and; 20‘ mixture comprises the butylenes, or the butylenesi'
preferably 1% or less by weight.
.
with;variousproportions of other gaseous‘ hydro’
It has been proposed heretofore to crack or_
carbons, itis preferred to-ca-rry out the polymer‘
polymerize- hydrocarbon gases in thepresence of ‘3
ization under substantial superatmospheric pres-'
various adsorbent catalysts such‘ as fuller’s earth,
sure, for example, from 100 to~2~,000=pounds:'per1
acid activatede-bentonite, silica-- gel, activatedcan; 25 square,‘ inch. However, ' in- the polymerization of"
bon, alumina, and alumina» supported on’ silica.
'I-‘hesematerials, with the-exceptionof- alumina,
i$9buty1¢ne 01' copqlymerization? of isobutylene?
possess in varying degrees the ability‘to‘ catalyze
Willa-bummed’ or'butene‘2i the Operation may be‘
thepolymerization of ole?nsi, the, Catalytic e1?_
carriedrout at substantially atmospheric pressure,‘
ciency and catalyst life differing as between the 30' 01' higher pressuresrif desired-
materials.
Alumina, however, was found toliave"
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In carrying out our‘ process‘ We bring the gait“T
little or no-activity in ole?n-polymerization, even:
sous‘ ole?n‘ 01'‘ mixture‘ containing gaseous Ole?n“ ,
when employed under the most. favorable Com
into contact with thethermallyvactivated bauxite;
' ditions_
at temperatures not in excess of 350'degrees F.:
We have found that bauxite, when activated 35 #01‘ fliperiod of, time suf?cient' to‘e?ect polymer
under certain conditionais superior» to. the cata129301011 With>~ the production of liquid'hydrocar
lysts above mentioned, particularly with respect
bans comprising for the most part alipha'?op‘?y‘ ,
torrate of. decrease in efficiency, and totaluseful
mers‘boiling Within‘the motor'f‘uel‘range 01' hav
life. More speci?cally, we have found'that bauxing an” assay‘ distillation end‘ point not’ substan",
ite, when heated to a temperature between 700' 4° ?atly above 400‘ degrees’? The polymerization
degreeSR and 1300' degrees F‘ for Suf?cient time
of. isobutylene in the' presence of bauxitel‘of low,
to reduce its moisture content or “Volatile mat_
moisture content is initiated at ordinary tempera
ter" 150.6% by weight or less, exhibits to a marked
degree,,the ability, to catalyze the polymerization;
ature‘ ('70 degrees F. or lower) andsince the'reac
‘61011 is: exethermic; it may be necessary to‘ pro
vide cooling. of the catalyst to prevent‘the reac
or copolymerization of ole?ns to liquidwhydrocar- 45 tion temperature from reaching depolymeriza
bons; Even better results‘ are. obtained: in the‘
tion or decomposition levels- Ordinarily, a high
polymerization or copolymerization; . using‘ baux
degree of conversion may be obtained with cata
ite which has-been activated? at, 1200- degrees" F..
lyst temperatures of from-100' degrees 150-300
to 1,800, degrees F. to a residualimoisture content.
of not more than 2% by weight; andipref'erablyiwx degreesiF; precaution being taken to avoidw tem- 2'
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2,406,081
'peratures much in excess of 350 degrees F. The
bauxite may be employed in the form of granular
peratures, the polymerizationreactions being car
ried out at various temperatures to obtain liquid
hydrocarbon products. The length of time of
particles or pellets of desired size, or may be
utilized in ?nely divided condition wherein it is
suspended or'dispersed in the ole?ns. during the
conversion reaction and is removed from the re
each run was two hours, and the results obtained
are shown in the following table, the yields being
, expressed in weight percent of the isobutylene
action product upon completion of the reaction.
charged.
It is preferred, however, to utilize the bauxite in
the form of granules disposed as a bed through '
which the ‘ole?ns may be passed in order to‘e?ect
polymerization; which bed may be heated or
cooled as required to maintain it at the desired
conversion temperature. When, after prolonged? 11:;
7
Reaction‘
Percent conversion; bauxite activated at
,
'1
'
mp., ' 600°
F. ' 7002?‘.
8.57
6.0
g
v. M". v. M’.
de rees F.
use, the polymerizing e?iciency of the. bauxite has
decreased to a commercially uneconomical level,
the bauxite may be regeneratedby various m‘ethQ
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v.1vi’.
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146M571‘;
188%;1‘.
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v. if. v. M’,
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ods, the most simple and" inexpensive Tof which'is ' -- " '
heating in the presence of air; 'V'In‘lieuof thermal
regeneration per se, the spe t’ bauxite may be,
treated with steam or solvents and thereafter
subjected to heating at temperatures up to_-1800; -
The l% V. M. comprehends volatile matter or moisture in the
bauxite.
plishes
degrees complete
F. The reactivation
regenerationof usually
the bauxite
accom-j;
to.
100% of its original e?iciency.
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. » per hour through‘ a 200 gram bed of bauxite acti'-'
vated by heating at a temperature of 1200 de
velocity (volume of- gas pervolume of catalyst
per hour) employed -is not; particularly important,- ‘
grees F. The. conversion temperature Wasmain
tained, at 300 vdegrees
and 100%. conversion of
the isobutylene to liquid products was obtained‘
version is obtained regardless of'the space ve
for a period of 300 minutes! at which timethe
run was stopped, theve?iclency still being 100%.;
The stabilized product. contained 93% by volume,
of hydrocarbons boiling below'400 degrees F.,‘ and
‘ I locity. In the polymerization ofisobutylene, for
example, at 300 degrees‘ F. ' in the presence '1 of
bauxite catalyst,'100% conversion of the isobutyl
ene to liquid hydrocarbons is obtained with space
velocities up to 375 volumes of gaseous isobutylene
this productwhen hydrogenated at atmospheric,
pressure in theipresence of avcatalyst consisting
of nickel supported on kieselguhr at, a tempera
ture of 450 degrees F., had an octane number
per-[volume of bauxite per hour; . With increase
~ in space velocity’ from 375 r0440, the conversion
decreases progressively fromj100% to 90%,’v and
(motor method) ‘of 104, and with 2 cc. of tetra
with even‘ higher space velocities, the percentage
conversion vdecreases further. I
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ethyl lead added, had an octane‘number of 109.
' Our invention may be further illustrated by the
‘following examples, which, however, are not to .
product produced according to the present inven
Characteristic, ‘boiling data or the stabilized:
be construed as limiting the scope thereof.
tion are'shown in the following table. While most
of the product is suitable for hydrogenation to an’
.1. Isobuty1ene‘of‘_95% purity was passed at a l'
space velocity of 250 vols. per vol. of catalyst per‘
aviation gasoline’ blending stock, the small high
7 ’ h‘our through a bed of 200 grams of 6-14 mesh "
bauxite which ‘had been activated by heatingat
1200vdegrees F.‘ to a, moisture content of 1.18%
by weight. Y The polymerization'reaction terhpera- _.
ture was maintained at 275 degrees F. and total‘;
" condensation to liquid hydrocarbon products was
obtained; with no decline in catalyst activity durél
ing the run which produced 6 grams of liquid
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In carrying out the polymerization, the space
I since within certain limits a high degree of con
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4. lsobutylene Was passed at a. rate of 43 liters
products per gram of catalyst. . Distillation of the >
1 unstabilized'product' yie1ded'67% by volume of
hydrocarbons boiling between 72 degrees F. and
1 375. degrees F.,‘ 70%‘ of which distillate boiled :
_ 1 between 200 degrees F. and 250 degrees F. and
1 comprised mainly diisobutylene
’ § amounts of tri-isobutylene.
and minor
boiling end may be depolymerizeddover‘bauxite.
fuller’s earth, *or the like at’ elevated tempera-H‘
tures above about'800 degreesFi and recycled to’
the polymerization operation‘. v
' , Initial boiling point ________ __' _______ _i_°F_-_ 1180»
10%
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213
30% _______-i ________ __-_ _____ _.;____‘___.-.___._ 221
50% '_’_____'_ __________ _1_~_>_ _________ __'___.'__ 226V
70% ___L»_______ __. _______ __>___,___'_____ __V-_.- 233
80% ____r ____ -1 ____ _V____V__'_____; ______ __ 241
90% _________ _; ______ _-___-_ ____________ _‘__288»
End point ______________________________ __ 370
Per cent dist; __________________________ .__ 97
Per cent res ____________________________ _._
2
Spec. gravity__~____» ___________________ __ 0 7335
We claim:
' 1. The method of polymerizing normally gase
ous ole?ns to liquidhydrocarbons, which com
prises contacting saidiole?ns at a polymerizing‘
temperature below 350v degrees F. with bauxite
which'hasv been activated by heating at a tem
perature between-700 degrees F.‘ and 1‘800'deg'rees
F. to a residual moisture content of not more
1 isobutylene polymers and isobutylene-butene-l
than 6% by weight.
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'2; The method of polymerizing normally gase
1 copolymers, as‘ contrasted with 49 grams of poly
ous‘ ole?ns to liquid hydrocarbons, which com
§mers when isobutylene ‘alone was polymerized
prises contacting said ole?ns at a polymerizing"
temperature below 350 'degrees'F; with bauxite
which'has been activated by heating at a tem?
perature between 1200 degrees F. and 1800 ae-q
.grees 'F'. to a 'residual‘moisture content of not’
I under the same conditions. "
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.3. Isobutylene was passed‘ at a rate of 43 liters
‘per hourzthrough 200 gram beds of bauxite which '
' had been activated by heating at various tem-.
-'-more*tlian.2% by weight.
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2,406,081 ~
3. The method of polymerizing a normallygas
eous ole?n mixture consisting essentially of bu
tylenes to liquid hydrocarbons, which comprises
contacting said ole?n mixture at'a polymerizing
temperature below 350 degrees F. with bauxite
which has been activated by heating at a tem-'
perature between 700 degrees F. and 1800 degrees
1200 degrees F. and 1800 degrees ‘F. to-a residual
moisture content of not more than 2%“ by weight.
7. The method of polymerizing isobutylene to
liquid hydrocarbons, which comprises contacting‘
said isobutylene at a polymerizing temperature
below 350 degrees F. with bauxite which has been
activated by heating at a temperature of about
1200 degrees F. to a residual moisture content of
F. to a residual moisture content of not more
than 6% by weight.
4. The method of polymerizing a normally gas
eous ole?n mixture consisting essentially of bu
tylenes to liquid hydrocarbons, which comprises
contacting said ole?n mixture at a polymerizing
temperature below 350 degrees F. with bauxite
which has been activated by heating at a tem
perature between 1200 degrees F. and 1800 de
not more than 1% by weight.
10
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8. The method of copolymerizing a mixture of
isobutylene and normal butylene to liquid hydro
carbons, which comprises contacting said mixture
of isobutylene ‘and normal butylene at a poly
merizing temperature below 350 degrees F. with
15 bauxite which has been activated by heating at
a temperature between 700 degrees F. and 1800
degrees F. to a residual moisture content of not
grees F. to a residual moisture content of not
more than 2% by weight..
more than 6% by weight.
9. The method of copolymerizing a mixture of
said isobutylene at a polymerizing temperature 20 isobutylene and normal butylene to liquid hydro
below 350 degrees F. with bauxite which has been I carbons, which comprises contacting said mix
ture of isobutylene and normal vbutylene at a
activated by heating at a temperature between
5. The method of polymerizing isobutylene to
liquid hydrocarbons, which comprises contacting
polymerizing temperature below 350 degrees F.
700 degrees F. and 1800 degrees F. to a residual
with bauxite which has been activated by heating
moisture content of not more than 62% by weight.
6. The method of polymerizing isobutylene to 25 at a temperature between 1200 degrees F. and
1800 degrees F. to a residual moisture content
liquid hydrocarbons, which comprises contacting
of not more than 2% by weight.
said isobutylene at a polymerizing temperature
below 350 degrees F. with bauxite which has been
WILLIAM A. LA LANDE, JR.
activated by heating at a temperature between
30
HEINZ HEINEMANN.
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