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Патент USA US2404628

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July 23, 1946.
2,404,628 "
J. D. GRENKO Erm.
POLYMERIZATION 0F HYDROCARBONS
Filed June 1e, 1943
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JOHN o. GRENKO
’ LYNN
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ENToRs
2,404,628
Patented July 23, 1946
UNITED STATES PATENT OFFICE
POLYMERIZATION OF HYDRO CARBONS
John D. Grenko and Lynn R. Strawn, Port Arthur,
Tex., assignors vto The Texas Company, New
York, N. Y., a corporation of Delaware
Application June 18, 1943, Serial No. 491,320
`4 Claims.
(Cl. :E60-.666)
1
Y
This invention relates to the polymerization of
2
~
«
.
tion such as is necessary during take-off. In
other Words, during take-off it is desirable to em
hydrocarbons such as normally gaseous oleñns`
to produce nap'ntha hydrocarbons useful in the
ploy a rich mixture and for this purpose a naph
tha having a high content of aromatic constitu
ents is preferable to one having a high content
manufacture of motor fuel.
»The invention involves polymerizing normally
gaseous oleñns such as propylene and butylene
by contact with a solid polymerizing catalyst of
th'e alumina-silica gel type and more particularly
With a catalyst consisting essentially of a mix
ture of silica, alumina and zirconia such as de
of parafñnic constituents, the latter being useful
Where a lean mixture is employed as in cruising
operations.
.
.
A modification ofthe present invention in
pressure in the -range atmospheric .to 300 pounds
volves subjecting feed oleñns to contact with a
fresh, or freshly regenerated silica-alumina gel
polymerization catalyst at a moderate tempera
vture not in excessof about 560° F. underwhich
conditions the resulting polymer naphtha has a
relatively high content of saturatedv hydrocar
bons. The used catalyst preferably after being
in contact with oleñn feed hydrocarbons for not
more than about 5 hours under-the> aforesaid
moderate temperature‘conditions is then em,
ployed in a separate operation to effect'polymeri'
ization of feed olefins under more elevatedv tem
per square inch gauge.` It has been found that '
f by effecting the polymerization reaction with this
perature conditions so` as to obtain a polymer
' naphtha which is relatively rich in aromatic con
scribed in U. S. Patent No. 2,249,583. . More spe
ciñcally the invention involves eifecting the poly
merization with this type of catalyst under 4con
ditions such that a polymer naphtha relatively
rich in aromatic constituents is obtained.
'
In accordance With the invention the feed olefin
is subjected to contact with an alumina-silica
type catalyst- at a temperature Within th‘e range
about 580> to 700° F. and under apressure of about
150 pounds per squareA inch gauge o1' under a
type of catalyst within the temperature range in
stituents.
question the resulting polymer is unexpectedly
rich in aromatic constituents.
'I'he above mentioned patent broadly discloses
subjecting oleñns to-contact with a catalyst of
the type in question at temperatures ranging
from 200 to 650° E'. and under pressuresranging
The naphtha products obtained from
' eachoperation may be separately disposed of‘or
. may be blended all or in part for th'e purpose .of
producing’motor fuelY of predetermined charac
teristics.
l
_
,
Co-pending application, Serial No. 493,186, for
Polymerization of hydrocarbons, filed on July 2,
from 400 to 4000 poundsper square inch gauge. ,
1943, by Nelson B. Haskell and Charles J. Ran
Polymerization of oleñns such as propylene
with naturally occurring and synthetic aluminum '
dolph, Jr., describes more specifically the poly
merization of normally gaseous ole?ins under
silicates has also been described by Frederick H.
moderate temperature conditions with an alumi
na-silica gel type of catalyst so as to obtain poly
mer gasoline characterized by having a relatively
. Gayer in an article entitled “The catalytic poly
merization of propylene,” published in Industrial
and Engineering Chemistry, October,.1933, pages
high content of unsaturated hydrocarbons. ~ 'I'he
1122 to 1127. According to this author activated
Floridin and especially a synthetic alumina-on
co-pending application discloses effecting> the-re
silica catalyst are active in the polymerization of .
action at a temperature in the range about 425
to 560° F. during passage of the feed hydrocar
propylene to a liquid hydrocarbon mixture of
bons in gas ph‘ase through a contact mass of the
very high unsaturation. Elsewhere th'e author
points out that the polymer so obtained is pre
‘ about 0.25 to 0.55 pound of hydrocarbon ‘feed _per
dominantly composed of olefin hydrocarbons.
The present invention has to do, however, with
the discovery that by employing a reaction tem
perature about 580 to'600° F. and( above,Y the ’re
sulting polymer naphtha, mayA contain as much
catalyst employing a mass,y velocity in‘the’ra'nge
pound of catalyst per hour.
i.
As there disclosed
Lil the catalyst remains in contact with the hydro
carbons undergoing treatment for notlonger than
about 5 hours between catalyst- regenerations.
The present invention vinvolves a distinction
as 40 to 50% or more by‘weight of aromatic hy
since it’has to do with employment of a reac
drocarbons.
tion temperature substantially above 560° F. for
.
.
The production of naphtha rich in aromatic
constituents is advantageous from the standpoint
the purpose of producing polymer vnaphtha of
diiferent character, namely, rich in. aromatic con
of manufacturing aviation motor fuel useful
stituents. However,. it is Within the scope Vof
this invention to employ a two-stage operation,
`Where a high superchargingfrate is employed so
asto obtain a large power output Without detona
55
the >first stage involving the aforementioned
2,404,628
¿i
3
`moderate temperature reaction while the sec
alumina gel catalyst in the form of small gran
;ond stage involves the higher temperature reac
ules, particles, pellets or pills, etc.
The catalyst is continually fed into the upper
portion of the reactor ¿l through a conduit 5.
Provision may be made within the reactor ä for
maintaining the catalyst in the form of one or
more beds of desired depth. The catalyst moves
slowly and downwardly through the reactor from
the bottom of which it is removed through a
conduit 6.
`tion using partially spent catalyst from the mod
` erate temperature stage; In the higher _tem
` perature stage the used catalyst may be main
tained onstream for a substantial period of time
lof about five to eight `hours or ranging from a
lfew hours up to two or three days, thereafter
the catalyst is regenerated in the conventional
manner and re-employed in the moderate tem
Thus, as indicated, the feed hydrocarbon in
`this instance ñows countercurrently to the down
, perature reaction.
In practicing the process of this invention a
`catalyst may be maintained in a fixed bed, or
wardly moving body of catalyst. The polymer
"case the- feed olefin heated to the desired tern
ized hydrocarbons including unreacted hydro
carbons are continuously drawn off from the up
perature is continuously passed through the con
Ètact mass maintained at the reaction tempera
per portion of the reactor li through a pipe 'l
leading to a fractionator or fractionating unit 6.
lture, and the iiow of hydrocarbons continued
therethrough until the catalyst has become spent.
Thereupon the catalyst may be regenerated in
arate the product into a plurality of fractions
beds, within a reaction zone or zones.
In such f
Fractionation may be carried out so as to sep
including a gas fraction removed through a pipe
9, a polymer naphtha fraction through a pipe
lo and a heavy hydrocarbon fraction through a
pipe l l. The gas rfraction will comprise unre
` situ by the passage therethrough 0f oxygen-bear
ing gas so as to remove carbonaceous deposits
"upon the catalyst by combustion. Advantageous
acted olefin hydrocarbons which may be recycled
ly a plurality of reaction zones are employed
' Ã particularly Where the aforementioned two-stage 25 all or in part to the heater 2 or to the reactor 4.
A separate stream of feed olefin which may be
operation is employed. In this way when the
of the same character as that previously men
tioned is conducted fromY a source not shown
catalyst inthe low temperature stage has been
` onstream for 5 hours the feedstream may then
‘be diverted to an adjoining> reactor containing
through a pipe lâ'to a heater IB wherein it is
`fresh or freshly regenerated catalyst.A `During '
this period the offstream contact mass is em
i ployed for the higher temperature reaction until
l such time as it has become substantially spent,
heatedv to a temperaturein the range 560l to
'700° F. The resulting heated hydrocarbons
under a pressure of „about 1'50 pounds are passed
through a pipe Il to the lower portion of a re
when the feed stream is then diverted to another
actor !8 operating on the same principle as the
` low temperature reaction. i The completely spent
previously mentioned reactor t.
The used catalyst passing through the pipe 6
¿catalyst is then regenerated and thus placed in
to which reference has already been made passes v
` contact mass which may be partially spent in the
into the upper portion of the reactor lll and
reaction. The several reaction Zones are thus `40 provides the moving bedV or beds of catalyst con-V
tained within the reactor Ill.
`manifolded together by suitable pipe connec
‘ condition for employment inthe low temperature
The feed hydrocarbons likewise rise 'counter- Y
tions so that any one or more of the reactors
Y currently through the downwardly moving cata
i may be taken offstream either for use under dif
lyst maintained at the reaction temperature.
-The polymerized and unreacted hydrocarbons
are continuously drawn off through a pipe I9 to
a fractionator or fractionating unit 26. This
fractionator also may be operated to separate the
l ferent temperature conditions or for regeneration
I ofthe catalyst.
'
Instead of a fixed bed type of operation a mov
;able bed type of operation may be employed
wherein a body of catalyst movesV gradually
previously described three fractions.
`through the reaction zone either counter-cur
`
The polymer naphtha issuing from the frac
rently to or concurrently with a stream of feed
hydrocarbons undergoing-treatment. For exam
tionator 8 will be poor in aromatics or substan
ple, two reaction zones may be employed, the
ñrst being used for the low temperature reac
Ition, while the second is used for the higher
tially free'from aromatics, but relatively rich in
, temperature reaction.
saturated hydrocarbons, whereas the polymer f
naphtha issuing from the fractionator 2@ will
be relatively rich in aromatic vconstituents and
may be substantially free from saturated hydro
A body'of catalyst moves
I through the low temperature reaction Zone and
i the catalyst issuing therefrom is conducted to
carbon constituents.
the higher temperature zone. The spent catalyst
l issuing from this higher temperature zone is then
subjected to regeneration after which it is re
l turned for use in the low temperature reaction
1 zone."
60 The polymer naphtha may be drawn olf through
a pipe 272 while the heavier hydrocarbons are re
.
Y The >latter type of operation is illustrated by
means of a iiow diagram` shown in the accom
1 panying drawing to which reference will now be
' made for the purpose of further description of
theY invention.
A gas yfraction may be re
moved from the fractionator 2i) through a pipe
2l and the olefinic constituents thereof recycled
yall or in part to the polymerization reaction.
-
moved through a pipe 2S.
»
If desired the polymer naphtha products ob- `
tained from the two fractionating units may _be
drawn off all or in part toa receiver 2@ for the
purpose of blending to produce motor fuel of
As indicated in the drawing a stream of feed v
olefin such as propylene is .conducted from a »
I source not shown through a pipe I to a heater 2
`. wherein it is. raised to a temperature inthe range
,predetermined characteristics'.
Spent catalyst is drawn yoff continuously from
the bottom of the reactor lli through a 'conduit
V¢l25to 560° F. and under a pressure of abouty 150
‘ pounds; YThe 'heated hydrocarbon vapor,l is then
unit 3l from which it can be recycled through a n
>conduitt? to the reactor ii.
'
`1 conducted through a pipe 3 to the lower portion
of a vertical reactor 4 containing'a mass of silica
3o and may be passed to a catalyst regeneration
In' the'reactor >i8 the charging rate’ may be
maintained so that the massY velocity is within
V2,404,623
5
Y.
.
,
6
This example'likewise indicates that tempera
_
the range about .20 to 1.0 pound'of hydrocarbon
feed per pound of catalyst per hour.
While a moving bed catalytic operation is de
' tures of 423° F. and below are productive of poly
>mer naphtha products free or substantially free
scribed in connection with the drawing, never- ¿,
theless it is also contemplated that other means "
from aromatic constituents although such prod-,
uçts have a relatively high content of saturated
hydrocarbons. By increasing the temperature
of employing the catalyst may be utilized, as, '
for example, a catalyst in powdered form may
be injected into a body of the vaporized hydro
carbons undergoing treatment within the reac
polymer product is increased to 53%.
amount to from a fraction of a per cent to sev
tane number of about 78 to 80. 'I‘he addition of
3 ccs. of TEL raises the octane number to about
to 652° F., however, the aromatic content of the
'
The polymer gasoline rich in aromatic con
10 stituents which is obtained by employing a re
tion zone.
action temperature ranging from about 560 to
The catalyst may be used in the presence of a
700° F. is characterized by having a CFRM oc
small amount of moisture. For example, it may
eral per cent by weight of the feed.
In a fixed bed type of operation it may be
87.
Mention has been made of treating propylene,
but it will be understood îthat the feed to the
advantageous to condition the catalyst following
regeneration and this may be accomplished by
passing a stream of feed oleñn through the
process may comprise a mixture of olefin and
contact mass or bed at a temperature substan
non-olefin hydrocarbons such as obtained from
refinery sources,
Obviously many modifications and variations
of the invention, as hereinbefore set forth may
be made without departing from the spirit and
tially below the reaction temperature for a pe
riod of about 40 to 60 minutes. For example,
the catalyst employed in the low temperature
reaction may be conditioned by passing feed ole
scope thereof, and therefore onlysuch limita
iins at a temperature in the range 75 to 300° F.
through the contact mass for a period of about 25 tions should be imposed as are indicated in the
appended claims.
1 hour.
We claim:
In the following examples propylenewas sub
jected to polymerization by the action of the
catalyst of the character described in U. S. Pat
ent No. 2,249,583. Such a catalyst consists es
sentially of a calcined mixture of a major pro
1. A process for polymerizing propylene which
comprises passing propylene through a mass of
30
polymerization catalyst consisting essentially of
a calcined mixture of precipitated silica, alumina
and zirconia having approximately the compo
sition 100Si02í 2Al203: 12Zr02, said catalyst hav
ing been previously exposed for a short time to
mately the following composition: 100Si02,
35 feed olefin under polymerizing conditions at a
2A1203 and 12Z1'O2.
temperature of at least about 340° F. and not
The reactionwas carried out by continuously
in excess of about 560° F. maintaining a velocity
passing a stream of the propylene in gas phase
of flow through the contact mass such that the
through a contact mass of Ithe catalyst main
mass velocity through the catalyst is in the range
tained at a predetermined reaction temperature.
40 about .2 to .3 and effecting contact between pro
Example A
pylene vapor and catalyst at a temperature of
portion of precipitated silica and minor propor
tions of alumina and zirconia having approxi
T‘Èlìfp" Thiële’ MV Yield
Olefins
Aromatics
about 580 to 650° F., under a pressure of about X
saturates
415..."
0.5 0.549
31.4
22
580. _ _ ._
3. 5
. 526
37. 3
35
37
28
580 ..._
6.0
. 530
4.1.4
32
28
40
150 to 300 pounds thereby obtaining a polymer
naphtha' containing 40 to 50% and more by
weight of aromatic hydrocarbons.
2. A process for Í.polymerizing propylene .to
Vproduce naphtha rich in aromatics which com
prises passing propylene in a continuous stream
7
In the foregoing tabulation the temperature
represents the average reaction temperature of
the contact mass; time refers to the length of
through a mass of polymerization catalyst con
sisting essentially of. a calcined mixture of pre
time in hours that the contact mass has been
onstream; MV represents the mass velocity in
pounds of charge per pound of catalyst per hour;
yield represents the weight per cent of the poly- i
mer product, basis propylene feed; and oleiins,
aromatics and saturates represent the per cent
by weight of these constituents in the polymer
product.
As indicated by the tabulated data the product
obtained at a reaction temperature of 415° F. Vhas.
a relatively low aromatic content, namely, 7%,
and a relatively high saturated hydrocarbon con
tent, namely, 71%. By effecting the reaction at
a temperature of 580° F., however, the aromatic
content is materially increased to a value rang
ing from 28 to 37%.
34o___-_
jected to contact for a short time with a stream
of propylene gas under polymerizing conditions
at a temperature below about 560° F., main
taining the catalyst mass at a temperature of
about 580 to 650" F., and under a pressure of
about 150 to 300 pounds and maintaining a ve
locity of flow through the contact mass such that
the mass velocity through the catalyst is in the
range about 0.2 to 1.0 pound of hydrocarbon feed
per pound of catalyst per hour.
3. A continuous process for polymerizing pro
pylene which comprises passing a stream of hot
propylene vapor through a reaction zone main
v
tained at about 425 to 560° F., subjecting said'
vapor to contact therein with a catalyst consist
ing essentially of a calcined mixture of precipi
Example B
Teâlbïl’" Thlïlëf’" Mv Yield
cipitated silica, alumina and zirconia having the
approximate composition 100Si02: 2Al203:
12Zr02, said catalyst having been previously sub
tated* silica, alumina and zirconia having the ap
proximate composition liOOSiOz: 2Alz03: 12Zr02,
oiefius Aromatics saturates
y, .505
39.2
47
c
5a
423- _
1
.841
43. s
51
o
49
652- _ .__
a
. 31s
7o. 1
4s
53
1
removing from the reaction zone an eñluent hy
drocarbon stream comprising polymer naphtha
rich `in saturated hydrocarbons, removing >used
75 catalyst from said reaction zone, passing re
.movedoatalystto a separate reaction zone, pass
ing lthrough said .separate reaction zone a. >sepa.
matics, and blending polymer naphthaJ from both
said reaction zones to yform- motor fuel.
raf'terîstream .o_f v hotl propylene vapor, eñ‘ectîng
Contact between used catalyst and lseid Vseparate
¿stream .of propylene vapor at a temperature of
4. The method4 according .togclaim 3 in which
used catalyst is removed from seidA separate
zone, regenerated, and returned to said. lfirst
about 580 »to .650° F., removing from said sepa.
Arate
reaction
zone
an
eñìuent hydrocarbon
stream comprising polymer nalohtlnal rich ín aro
mentioned reaction zone.
JOHN D. GRENKO.
LYNN R. S’I‘RAWN.
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