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Патент USA US3046326

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July 24, 1962
D. A. GUDELIS
3,046,316
TETRAPROPYLENE QUALITY IMPROVEMENT
Filed NOV. 30, 1959
PROPYLENE
PROPANE
FEED
2
‘ -- REACTOR
FLASH DRUM L-~
H2 GAS
DEPROPANIZER 7-
FRACTIONATOR r“
FRACTIONATOR1——
I3
BOTTOMS
DAVID A. GUDELIS
'
INVENTOR
BY
C17; H ' M ATTORNEY
United States Patent O?ice
l
_
3,046,316
TETRAPRQPYLENE QUALHTY IMPROVEMENT
David A. Gutielis, Sarnia, Gntario, Canada, assignor to
.Esso Research and Engineering Company, a corpora
tion of Delaware
Filed Nov. 30, 1959, Ser. No. 856,167
12 'Claiins. (Cl. 260-671)
3,046,316
Patented July 24, 1962
2
pound of catalyst and the polymerization reactor is
maintained at temperatures between 200° and 600° F.,
preferably 300° to 450° F. and more preferably between
320° to 400° F., and at pressures of 300 to 1000, pref
erably 500 to 800, p.s.i.g.
A typical polymerization product will comprise tetra
mer in an amount from 10 to 30 volume percent on total
polymer in a single pass process. By recycling lower boil
This invention relates to the preparation of improved
ing polymer the yield of C12 polymer can be increased to
ole?n alkylation feeds for use in the preparation of alkyl 10 about 90 L.V. percent on the net polymer. The tetramer
aryl compounds known as detergent alkylates. In par
fraction employed for alkylation is essentially one of
choice depending on its effect on the detergent product;
ticular, this invention relates to the preparation of superior
however, a typical suitable tetrapropylene fraction which
Cit-C24, especially C12~C15, polypropylene alkyiation feed
may be employed to produce highly desirable alkyl
stocks and to their use in the alkylation of aromatic hy
benzene products will boil in the range of 365 °—430° F.
dlocar‘oons to improve alkylate quality and to reduce
catalyst consumption in the alkylation reaction. More
at atmospheric pressure.
The polypropylene thus produced is then reacted with
particularly, this invention relates to an improved method
of polymerization for improving the quality of C12 01'
benzene or similar aromatics in the presence of AlCl3.
One of the most suitable commercial processes comprises
tetrapropylene rich fractions for use in alkylation re
actions with benzene by introducing hydrogen gas to the 20 the use of AlCl3 in the form of a dispersion or sludge with
tetramer producing polymerization reaction.
By tetrapropylene, tetramer, or C12 polypropylene frac
high molecular weight hydrocarbons. In order to provide
ing in the range of about 340° to 450° F. Such a frac
a‘ high selectivity to monoalkyl benzene compounds as
compared to di- and polyalkylated benzene a high ratio
of benzene to ole?n feed, e.g. tetrapropylene, is employed.
tion will usually contain a major proportion of C12 poly
mers with lesser amounts of lower and higher boiling poly
benzene to tetramer.
tion is meant a propylene polymer fraction generally boil
mers.
These ratios may be in the range of from 2 to 20:1 of
The alkylated benzene is then fractionated into a light
alkylate, heavy alkylate and detergent alkylate.
The
This invention preferably comprises the simultaneous
introduction of hydrogen and a propylene comprising feed
detergent alkylate may have a boiling range of, for ex
stock to a tetramer producing polymerization reaction to
form a superior ole?n alkylation feedstock and the prepa-‘
ample, about 415° to 610“, preferably 500° to 610°, F.,
at atmospheric pressure, although this may vary depend
ration of C12 alkyl benzene from such feedstock.
ing on the particular speci?cations of the various detergent
The alkyl aryl sulfonates which are built up to form
commercial water soluble detergents are themselves pre
with ole?n polymers in the presence of a Friedel-Crafts
manufacturers.
An important cost factor to the manufacturer of alkyl
ated benzene is the amount of AlCl3 that is required to
catalyze the reaction. It is a primary object of this in
vention to provide an improved polypropylene feedstock
for this alkylation reaction so that the amount of alkylation
catalyst, e.g. AlCl3. In this alkylation reaction it has
catalyst required is substantiallyv decreased over prior art
pared by sulfonating alkyl substituted aromatic hydro
carbons. The alkyl substituted aromatics in turn are gen
erally prepared by alkylating an aromatic hydrocarbon
been necessary to employ up to 6 to '7 weight percent 40 processes. It is a further object of this invention to pro
vide a process for the preparation of alkyl benzene suitable
of A1013 based on total tetramer feed. The alkyl benzene
for detergent manufacture wherein relatively small quanti
is subsequently reacted with sulfuric acid to form a sul
ties of alkylation catalyst are required.
fonic acid which is neutralized with caustic to form the
It is known that the polypropylenes and especially tetra
sodium alkyl benzene sulfonate. The sulfonate detergent
propylene fractions employed for the alkylation of hen
in commercial practice is of course combined with various
detergent builders such as sodium sulfate, carboxy methyl
cellulose, various sodium phosphates and the like.
The monoole?ns employed as feed in the preparation of
zene may at times contain inhibiting materials which de
the alkylate are preferably a tetrapropylene fraction or a
terials are essentially CnH2n_2, CnH2n_4, CnH2n_6 type
C12 ole?n rich fraction although C9—C24 polypropylenes
crease‘ the eiiiciency of the AlCl3 catalyst to a substantial
extent. It has now been found that these inhibiting ma
50 polymers which are formed as a result of conjunct poly
may be used. As feed for the polymerization plant it is
merization occurring alongside the regular polymerization
preferable to employ a light gaseous ole?n which is pre
reaction. It is inherent of the polymerization mechanism
dominantly propylene and propane. This ole?n feed may
that at any given reaction conditons three types of poly
also include small, amounts of butane, ethylene and
merization reactions can occur. The product of the ?rst
ethane, i.e. up to a total of about 15 weight percent. 55 type which may be termed “true” or “homo-polymer
However, it is preferred that the feed be free of C4 un
ization” consists of ole?ns which are an integral multiple
saturates.
of the propylene monomer, e.g. C6, C9, C12, C15, etc.
Tetramer may be produced as a by-product of gasoline
The product of the second type may be called “hetero
manufacture by fractionation of the polymer product or
polymerization” and consists of ole?ns which are not an
in a process designed speci?cally for the production of 60 integral multiple of the monomer, e.g. Cq, C8, C10, 011,
tetramer in which case the conditions of polymerization
etc. This type of polymerization creates no particular
are generally milder and designed to maximize C12 poly
problem. The third type of polymerization can be named
propylene by recycling light polymer boiling below C12.
“conjunct polymerization.” The latter yields a mixture
Thus, the polypropylenes are produced in a polymeri
of products consisting of mono-, di-, etc. ole?ns, para?ins,
zation plant which comprises a reactor packed with phos 65 cycloalkanes, cycloalkenes, cyclodienes, and aromatic
phoric acid on kieselguhr or other conventional carriers.
hydrocarbons. ‘It is therefore an object of this invention
Generally the phosphoric acid is present in amounts of
to hold to a minimum the formation of such conjunct
50 to 90 wt. percent calculated as P205. This general
polymers, e.g. CnH2n_2 polymers, in tetrapropylene poly
process is well known in the art and usually referred to as
merization.
It has now been found that conjunct polymerization
U.O.P. polymerization. In carrying out a polymeriza 70
with its production of Gui-12,14 polymers is suppressed by
tion of this type the propylene feed is passed into the re
introducing hydrogen gas into the polymerization reaction.
actor at a rate of about 0.10 to 0.50 gallon per hour per
4
3
mass spectrometry to determine the HDI for each frac
tion. The tetramer fractions are then alkylated with
‘More particularly, it has now been found that a superior
ole?nalkylation feedstock can be prepared by introducing
hydrogen at a rate of about 2 to 100, preferably 30 to 70
benzene in a conventional alkylation reaction as herein
mole percent, based on propylene in the hydrocarbon
feed, into the polymerization reaction maintained at a
temperature of about 200° to 600°, preferably 320° to
before described. The amount of catalyst required for
400° F., and under a pressure in the range of about 300
to 1000 p.s.i.g. By maintaining hydrogen in the reactor
in accordance with this invention dehydrogenation re
actions during polymerization are repressed. 'Tetramer 10
thus produced provides an ole?n polymer feedstock for
each fraction based on weight of tetramer is ascertained.
The results obtained and the conditions of alkylation are
set forth in Table I.
Table I
EFFECT OF HDI ON CATALYST CONSULIP'I‘ION
Pressure, p si 9
alkylation reactions which produces alkyl aryl compounds
of outstanding quality and reduces catalyst consumption
800
800
Temperature, ‘’ F _________________________________ __ 360
800
350
Tetramer HDI ____________________ __
in the alkylation reaction. The process of this invention
eliminates the need for separate treatment of the tetramer 15
such as hydro?ning subsequent to polymerization. By
controlling the rate of hydrogen input to the polymer
Wt. percent of A1013 consumption___
Percent increase __________________________________ __
EXAMPLE 2‘.
To determine the effect of introducing hydrogen gas
ization reaction and the conditions of such reaction to
inhibit the formation of undesirable unsaturates, e.g.
‘directly into a tetramer producing polymerization reac
conjunct polymers of the type CnH2n_2, the mono-ole?n 20 tion tests were conducted both with and without hydro
gen. The propane diluted propylene comprising feed
content of the alkylation feedstock can be raised without
stock was the same in all tests. In each case the propylene
the‘loss of ole?n to saturates that is incidental to known
processes for hydro?ning a polymer fraction.
feedstock was diluted with propane prior to polymeriza
For in
tion in a propane to propylene ratio of about 2:1. The
the polymers produced in the polymerization of propylene 25 polymerization catalyst employed in each test was a solid
type phosphoric acid catalyst, i.e. kieselguhr impregnated
are saturated polymers. It has been found that the in
with a phosphoric acid mixture having the following
troduction of hydrogen gas to the reaction zone in accord
typical composition:
ance with the process of this invention does not noticeably
:‘Wt. Percent
increase this loss to saturates. On the other hand it
62
has been found that a hydro?ning of the unsaturated poly 30 P205 ___________________________________ __
stance,‘ a small amount, e.g. about 2 to 5 L.V. percent, of
mer after polymerization su?icient to convert the Cnl-I2n_2
polymer to CDHZD polymer results in a loss of unsaturated
SiOz
___________________________________ __
H2O
polymer‘tolsaturated‘polymer in the range of about 15
_
__ _ __ _
_ _ _ __
Free ‘P205
32
_
__
7
14-18
to 25 L.V. percent. Conjunct polymers of the type
In the tests employing hydrogen the hydrogen was intro
CDHMHZ may be referred to as “hydrogen de?cient” poly 35 duced into the reaction at ‘a rate of 0.6 mole of H2 per
mers. The presence of such polymers in a tetramer frac
mole of propylene. The ‘conditions and results of these
tion may be detected by low voltage mass spectrometry.
Under this method, if the ionizing voltage is selected at
tests are given in Table II.
a relatively low value, only the molecule ions of com
Table II
pounds having an ionization potential at or below the 40 PROPYLENE POLYMERIZATION WITH AND WITHOUT
selected voltage are formed and the distribution of
HYDROGEN INTRODUCTION
CnHZn and CnH2n_2 compounds determined. See “Low
Voltage Techniques in High Molecular Weight Mass
Spectrometry,” by H. E. Lumpkin, Analytical Chemistry,
Run Number
1
2
3
Vol.30, No. 3, pages-321 to 325, March 1958. With this 45
vdistribution available it became possible to qualitatively
Pressure, p.s.i.g _____________ __
800
800
Temperature, ° F ____ __
450
495
characterize a tetramer fraction as to its content of
Conversion, wt. percent"
Without Hg:
Tetralner Analysis, L.V. percent
CnH2n_-2 polymers. A unit of measure termed the hy
drogen de?ciency index, hereinafter referred to as the
“HDI,” has proven a practical means for characterizing 50
arparticular tetramer fraction with regard to this factor.
Space Velocity, g.p.h./1 _
0.
D1121; ______________________________ __
OnH2n—Z-CnH2u-4
CnH2u—e
The “HDI” of a particular tetramer fraction is determined
Tetrarner HDI
fromlow voltage mass spectrometry readings by taking
a simple ratio of the isotope corrected peak heights shown
for Chi-12,, and CnI-I2n_2 compounds according to the for 55
mula:
Tetramer and Benzene-——
Wt. percent A1013 Consumption Z..._
Bythe process of this invention an alkylation tetramer
feed can be prepared which has a low HDI and cor
respondingly resultsin a considerable saving of catalyst
inthe‘alkylation reaction. Furthermore, by preventing
_ _ _ _ _ _ _ _ _ __
79.1
93.2
83. 1
77. 9
G. 2
0. 6
0. 0
14. 1
2. l
0. 7
17. 6
3.1
1. 4
10. 0
20.0
31. 2
3. 2
5 0
7.0
89. 7
8- 5
1.0
0.8
14.0
82. 3
13. 6
1. 9
2.2
22. 7
3. 9
5. 2
lkylating
With Hz!
Tetrainer Analysis,» L.V. percent—
0.1112
CnH2n~2
OnHZn-4
CnHzn-u“
Tetramer HDI
Catalyst Requirement for Alkylating
The HDI of an ole?n feedstock to an AlCla catalyzed
alkylation reaction has hen found to be directly related to 60
the catalyst vconsumption therein.
___ _ __ _
Catalyst Requi rnent f
0. 10
79.8
Tetramer and Benzene——
Wt. percent A1013 consumption L.-.
2. 8
1 G.p.h./lb. ='U.'S. gallon per hour/pound of catalyst.
2 Based on weight of tetramer feed.
The invention may be more easily understood by refer
65 ring to the accompanying drawing which sets forth a sim
the formation of hydrogen de?cient polymers during the
pli?ed ?ow plan for carying out one embodiment of this
polymerization reaction the ‘total tetramer yield is higher
invention.
than'that realized fromhydrogenating the tetramer after
~
EXAMPLE ‘3
polymerization. A phosphoric acid polymerization cata
lyst is not a hydrogenation catalyst and, therefore, does 70 A propylene-propane comprising stream is introduced
not promote hydrogenation of the product by the H2 pres
via line 1, passed through preheater 2' maintained at a
ent inthe reaction zone.
‘temperature of about 320°~450° F. into reactor B. H2
gas from line 3 which may be combined with vH2, propane
EXAMPLE 1
and unreacted propylene recycle from line 6 is passed
Various tetramer fractions are analyzed by low voltage 75 through preheater 4 directly into reactor B. Reactor B
3,046,316
6
contains a U.O.P. solid type phosphoric acid catalyst con
taining about 62 wt. percent of P205 and is maintained
prising feedstock consisting essentially of propylene and
propane and about 0.3 to 0.7 mole of hydrogen gas per
mole of propylene in said feedstock into a reaction zone
at a temperature of about 320°—450° F. under a pressure
of about 300-1000 p.s.-i.g. The space velocity is main
tained at about 0.1 g.p.h./lb. The entire effluent from
containing a solid phosphoric acid polymerization cata~
lyst maintained at a temperature in the range of 300° to
450° F. and a pressure of 500 to 800 p.s.i.g., and recov
reactor B is removed via line 5 from whence it passes to
?ash drum C where most of the propane, hydrogen and
ering said ole?n, the ole?n recovered from the improved
unreacted propylene in the stream are ?ashed off and re
process having a lower HDI than the ole?n recovered
cycled to line 3 via line 6. From C the polymer-rich
from the unimproved process.
e?luent is removed via line 7 and passed to depropanizer 10
5. A process in accordance with claim 4 wherein said
D where the remaining gaseous components are separated
ole?n is a C12 to C15 ole?n.
from the liquid polymer and vented via line 8 or re
6. A process in accordance with claim 4 wherein the
cycled to line 1 via lines 18 and 10. The liquid polymer
mole ratio of said propane to said propylene is in the
effluent from D is removed via line 9 and passed to ?rst
range of 0.5-4: 1.
~
fnactionating zone E Where it is separated into two 15
7. A process in accordance with claim 4 wherein said
streams. The light polymer C5—C11 is taken overhead
catalyst is phosphoric acid on kieselguhr.
through 10 and may be blended into gasoline or recycled
8. A process for producing an ole?n polymer boiling
back into polymerization reactor ‘B via lines 10 and 1.
in the range of 365° to 430° which comprises simul
taneously introducing an ole?n containing feedstock con
The C12 rich fraction is removed from ‘E via line 11 and
passed to second f-ractionator F where a tetrarner fraction 20 sisting essentially of propane and propylene and about
0.3 to ‘0.7 mole of hydrogen gas per mole of propylene
of the desired boiling range is taken overhead via line 12
and passed to the alkylation unit. High boiling bottoms
in said feedstock into a reaction zone containing a solid
are removed from F via line 13.
phosphoric acid polymerization catalyst at a temperature
‘
in the range of 320° to 400° F. under a pressure of 500
to 800 p.s.i.g. at a rate of about 0.1 to 015 gallon per
It is to be understood that various modi?cations of the
process ?ow pattern may be made ‘which fall ‘within the
scope of the invention as ‘claimed. ‘For example, the
hour per pound of said catalyst and recovering from said
zone ‘said ole?n polymer, the ole?n polymer recovered
from the improved process having a lower HDI than
the ole?n polymer recovered from the unimproved
material recycled via lines ‘6, 8 and 10 may be introduced
directly into reactor B.
The tetramer fraction removed is. alkylated with ben
zene at a temperature of about 55° F. and a pressure of 30 process.
about 20 p.s.i.g. employing AlCla catalyst. The amount
9. A process in accordance with claim 8 wherein said
of AlCl3 used up in effecting this alkylation is found to
catalyst consists essentially of phosphoric acid on
be 2 to 3 wt. percent based on total polymer fed to the
kieselguhr.
>
10. In a process of alkylating benzene by the reaction
alkylation reaction.
The above conditions represent preferred conditions 35 of a C9~C24 ole?n with benzene in the presence of alu
minum chloride catalyst wherein- said ole?n is a poly
and may be altered slightly to suit the needs of any par
merization product prepared by introducing a propylene
ticular plant design. For ‘further detailed and general
feedstock comprising at least 85 Wt. percent propane and
propylene in a molar ratio of between !0.5—4:1 into a
information as to the alkylation process per se reference
may be had to the patent issued to W. J. Paltz, US.
2,667,519.
reactor containing a solid phosphoric acid polymerization
_
The term “gph.” used herein refers to gallons per hour.
The term “s.c.f.” used herein refers to standard cubic
feet.
What is claimed is:
1. In a process for producing a C9 to C2:: ole?n by a 45
polymerization of propylene which comprises introduc
ing a propylene feedstock comprising at least 85 wt.
percent propane and propylene in a molar ratio of be
tween 0.5-421 into a reaction zone containing a solid
phosphoric acid polymerization catalyst and maintained
at a temperature in the range of 200° to 600° F. at a
pressure in the range of 500 to 800 p.s.i.g. and recovering
catalyst maintained at a temperature in the range of 200°
to 600° F. and a pressure of 500 to 800 p.s.i.g. and re
covering said ole?n therefrom, the improvement which
comprises introducing into said reactor during said poly
merization 0.3 to 0.7 mole of hydrogen gas per mole of
said propylene, recovering said ole?n from said reactor
and employing said ole?n to prepare alkyl benzene in
the presence of aluminum chloride catalyst, the ole?n
recovered from the improved process having a lower
50 HDI than the ole?n recovered from the unimproved
process.
11. A process in accordance with claim 10 wherein
said temperature is in the range of 320° to 400° F.
said ole?n as product therefrom, the improvement which
12. A process in accordance with claim 8 wherein a
comprises maintaining in said reaction zone during such
polymerization about 0.3 to 0.7 mole of hydrogen per 55 light ole?n polymer produced in said polymerization re
action is recycled to said reaction zone, said light ole?n
mole of propylene, the ole?n recovered from the im
polymer containing less than 12 carbon atoms.
proved process having a lower HDI than the ole?n re
covered from the unimproved process.
References Cited in the ?le of this patent
2. A process in accordance with claim 1 wherein said
60
ole?n is a C12 to C15 ole?n.
UNITED STATES PATENTS
3. A process in accordance with claim 1 wherein said
temperature is in the range of 300° to 450° F.
4. A process for producing a C9 to C24 ole?n which
comprises simultaneously introducing a propylene com
2,446,619
2,477,382
2,786,878
Stewart et al. ________ _._ Aug. 10, 1948
Lewis _______________ __ July 26, 1949
Arundale et al. _______ _ .Mar. 26, 1957
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