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Патент USA US2405968

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Aug 20,1946.
:c. ‘s. LYNCH ETA;v
Filed May 25; 1945
. ,72
7'0 sums/4125a
M11522 ’
Patented Aug. 20, 1946
2,405,968 ‘
Charles S. Lynch, Plain?eld, and Howard G.
Codet, Mountainside, N. J., assignors to Stand
ard Oil Development Company, a corporation
of Delaware
Application May 25, 1943, Serial No. 488,344
6 Claims. (C1. 260--683.4)
The presentinvention relates to improvements
in the art of alkylating ethylene mixed feeds, and
more particularly, it relates to a continuous op
eration of catalytically alkylating ethylene with
it is associated as it is fed to the systemlbefo're
isoparaf?ns in which the ethylene feed stock is
contacting the catalyst in the alkylation proc
ess. ,In other words, in a commercial re?nery the
normal C2 or ethylene fraction will be associated
with neighboring hydrocarbons and hydrogen.. In
mixed with other hydrocarbons and gases and in
which theralkylation is accomplished in a man
ner which is cheaper than has been possible here
>_ _ Recently it has been found that , ethylene may 10
be alkylated with isobutane to form hydrocarbons
boiling within the gasoline range, of high octane
ert, and if they ?ow through the systeméwith the
ethylene during the reaction, they willleventually
been-found in connection with these researches
' paraffin and the ole?n with aluminum chloride for
other words, the C2 hydrocarbons will contain‘in
addition to the desired Qle?n, methane, ethane,
and hydrogen. The para?ins, of course, are in
number, incIudingZB-dimethyl butane. It has
' that the catalyst prepared by contacting the iso
Our present invention relates to that phase-of
the above indicated process which includes sep
arating the ethylene from ‘the gases'with which
have to be eliminated and their'processing' and
15 elimination uselessly, ' o'fjcourse, requires ; addi
"an extended period of time is a brown mobile ‘ tional facilities and utilities.
In brief compass, we have devised a-procefss
liquid which apparently is an aluminum chloride
'for eliminating the unwanted’ hydrocarbons in
hydrocarbon» complex, which is an active cata
' lyst’possessing a long life and is otherwise satis 20 the ethylene feed, in a relatively simple andex
peditious manner as will more fully appear. here
factory. It has furtherbeen found in connec
tion with these prior researches that the alkyla
In the accompanying drawing we have shown
tion may be carried outat ordinary atmospheric
a?oW, plan indicating a continuous process for
temperatures or above. For example, the alkyla
alkylating ethylene with isobutane, including the
tionmay be carried out at temperatures from 25 features
hereinbefore mentioned.
65‘*-200_° F. with a range of 90—l25° F. preferred.
Referring in detail to the drawing, we shall
It has further been found that a small amount
describe a preferred method of alkylating ethylene
of volatile halide incorporated with the isobutane“
with isobutane in the presence of aluminum chlo
feed greatly improves
the quality and the yields.
Thus, from 1 to 15% of, ethyl chloride or methyl 30 ride hydrocarbon complexso that a vbetter un
derstanding of our invention may be had.
chloride based on the isobutane or other isoparaf
I_ is a reactor which, as indicated in the draw
?n greatly increases the efficiency of the process.
ing, may be an elongated, cylindrical vessel packed
About 5-10 volume per cent of ‘ethyl chloride
with a material such as Raschig rings. Super
gives the best results. Further, it has been found
posed on reaction vessel I is a settler 2 carrying
that pressures of from 100-1000 lbs/sq. in. give
i) a pressure gauge 3 disposed in a ventline 5 carry
good results with pressures ‘of the order of 200
ing a liquid level control valve l0. Disposed at
'300 lbs. preferred. The researches have also re
the side of the reactor I is a vessel or receptacle
“vealed that ._ the fresh feed to the reaction zone
should have an excess of the isopara?in, that is
20 in which is contained aluminum chloride,and
‘ to‘ say, best results are obtainable when the fresh 40
feed 'pcontains 3 mols of isopara?in to each mol
of ole?n. With respect to the amount of alu
“minum' chloride, it has'been found that by main
taining from _3 to 100, and preferably’ about 20
weight 'per cent of aluminum chloride in the
reactor" gives ‘optimum results. Under the con~
ditions stated, numerous runs ‘have demonstrated
that when Working at its best, the foregoing proc
through this container where it absorbs or other
wise acquires aluminum chloride and then‘flows
into the reactor. The ethylene feed'enters ‘the
system through a line 25 and the isobutane en
ters through line 28, the latter being in_a liquid
45 condition. At the start of the operation, the iso
' butane is ?rst introduced into the empty system
through line '28, flows through a scrubber 30,
thence is withdrawn through line 32 and pumped
by pump 35 through line 36 into reactor l until
the column is nearly ?lled with lique?ed isobu
ess is adapted to produce an alk'ylate over 60
volume per cent of which contains Cs hydrocar
bons; including 2,3-dimethyl ‘ butane. 2,3-di
tane. The ethylene feed is introduced through
methyl‘butane is a hydrocarbon which has a high
line 25 as a gas to scrubber 30 where it is ab
'octane number but is particularly valuable be
' cause of its excellent rich mixture performance
~ in a supercharged engine. ‘
the feed stock, as will subsequently appear, passes
sorbed and, passes via line 32, pump 35 and line
36 into the reactor l until the isobutane is about
half saturated with respect to ethylene. The eth—
ylene and isobutane pass upwardly to settler 2
and then are withdrawn through recycle line 40
and returned to the tower 30 for recycling via
line 32, but now the recycle stream passes through
line 38 and thence through the aluminum chlo
ride receptacle 20 and thence passes into the
tower 1.
After the'passage of 3-4 hours, the aluminum
chloride will have reacted with the hydrocarbons
to form the aforementioned aluminum chloride-"i.
hydrocarbon complex, which is the active catalyst
for the alkylation process, and 'after"‘this“"‘in
duction” period during which-thematalyst is
formed, product may be withdrawn through line
12 and delivered to fractionatingand- distilling
equipment (not shown) to recover the desired
products. There will come atime when .the ma
entering feed While the other components pass
up the tower and may be withdrawn through a
vent pipe 50. It is obvious that this is a desirable
method of operating since the removal of hydro
gen, methane, ethane, and the like, at the begin
ning of the‘ operation, makes it unnecessary to
circulate these inert materials'through the whole
system, including the fractionation and distilla
tion equipment in which the product stream‘ 12
is subsequently treated. Thus, by scrubbing the
fresh feed with a recycle stream saturated with
respect to the‘ unwanted components of the eth
~ylene..fresh’-feed, we“ are able to reject at once
:from thesystem-dnert materials, such as meth
rrane,'tethane,'hydrogen, and the like, in a simple
and expeditious manner.
. Our process possesses particular utility in the
processing of an ethylene feed stock which con
terial recycled through 20 must be directed to
tains a. minor quantity of ethylene, say from
another container 20a which containstfreshlalu
minum chloride, the latter container being sim 20 30-40%, such as is obtained, for example, in
.steam cracking of hydrocarbons. However, tour
=ilar-,,in. construetionill, [and .-thence passed .into
could be used<for.feed' stocks containing
.the reactor has-“before. The containerl? is
as low as 10% ethylene in the feed entering
thoroughly “cleaned ;and recharged with. alumi
through line 25' and this-lowconcentration of
numzchlor-ide .-for subsequent use-inv the process.
would be highly impractical in an al
.Imotherwords, the preferredmethod of operat .25 ethylene
where a large preponderance of
.ing .thenprocess is to “provide two or'more con
inert material continuously passed through the
:tainers-Miand ZOaandafter one has been in .use
system. The temperature of theliquidrin- the Ire
vfor some time, it willbe withdrawn vfrom the cir
cycle stream is from 50° to 200° F., preferably
.».culating_ system, "thoroughly cleaned and’ re
.charged' "with . fresh ~zaluminum chloride. .The 30 from 75° to 125° _F.,vand the/pressure is from'100
to 11000 lbs/sq. in., preferably from'200-to; 300
.other container will imeanwhile bev on stream.
lbs/sq. in.
_» ' .
-Theuseof itwoi-or more-containers 20 maintains
In operating our process, as in the previous de
continuityot operation even. though itis neces
velopment of this process, wemaintain-a-molec
:sary tosaddlaluminum chloride periodically to
ular excess of isobutaneover the ethylene, Pref
the system. to maintain. the , catalyst activity as
erably we maintainv 3 to 100 mols of isobutane per
previously indicated. It: will. benoted thata por
mol of ethylene in-the reaction zone. The re
..tionof thelrecycle. product in line.32 may- bypass
cycle ratio, i. e., theratio of recycledlproductrto
-.-the.container_2>0 or slim-and passydirectlyinto the
fresh feedis from 1 to 30 volumesofrecycle-prod
reactor 1 gthroughzline??. ‘We-maintain a con
per volume of .fresh feed (i. e.,‘newly added
sumption. .of.,aluminum<- chloride _ in - our process 40
ethyleneand isobutane, disregarding the unde
varying from 0.04 to 0.08 lb. of AlCls per, gallon
sired constituents in the ethylene feed). When
. of-alkylate.
operating at its best, verylittle catalyst isin the
. Thereis .another.,.point. with. respect to the op
recycle stream,
less than “0.04 weight per
. erationoL-the , process .and .itis this, .viz.,_that
when the reactorlbecomes ?lled with catalyst, the 1.A St cent when. operatingat 110°. F.
wexcess .passesdntosettler v2, iirom which .it may
be- withdrawn byidraweoff ,pipe .8. ~ Actually, .hoW
> -
We. have described in detail the'application of
. our. invention .to .they alkylation- of ethylene and
isobutane. It is to be understood'that‘ thesame
principle may apply to thealklation of. propylene
50 .or.butylene where the propylene or butylene feeds
are mixed or'diluted with relatively large-‘quan
. .Except for .the manner cry-introducing the feed
titiesof other. gaseous materials. The removal
stocks; , we .haveindicatedthe . development. of the
propane in the scrubbing stepispossiblewhen,
.alkylationprocessup to thetimeof ourinven
as is usuallythe case,.:the pressures»;exceed..l25
_~..tion, .whichjinvention will?nowxbe described .in
detail. ...Heretofore,.inoperatingrthe process de 55 lbs/sq. in. in the system.
- ‘What we claim is:
.scribed,,the ethylenefeed and the isobutane feed
1. In the continuous alkylation of~olefins with
arehot fed to the system inthe manner we have
isopara?ins conducted in the preesnce of an alu
indicated-in.thedrawing vbut. are changed di
minum chloride-hydrocarbon complex formed in
rectlyto the reactor, andtherefore our improve
situ during the operationof the process, the im
ment comprises, principally, the. interposition » of
provement which comprises ?rst forcing a mixed
. the scrubber 30 into the system. .The mixed feed
feed containing a minor proportion of ethylene
. entering thesaid scrubber-at 25contains hydro
with an isopara?in through a reaction zone con
gen, .methane, ethylene,.>and ‘possibly ethane, and
taining the. said aluminum chloride-hydrocar
contacts.- therein .the .isobutane which enters
bon complex,‘ permitting the feed stock and the
through;.1ine..28. .The isobutane becomes satu
catalyst to'remain incontactvwith each other for
rated, of,.course, with respect. tov hydrogen, meth
a su?icientperiodof- time toe?ect the‘desired
.ane, ethylene, and ethane. The ethylene in the
conversion, withdrawing a product stream, si
- course ofQthereactionis continually removed in
multaneously withdrawing a recycle stream con
reactor I, but thehydrogen, methane and ethane
.are unchanged-and consequently the recycle ~ taining iscbutanev and small vamount of alkylate,
passing the recycle stream into a scrubbing zone,
.stream in‘ 40 entering scrubber 30, after the proc
everrthe: system maybe. operated .1‘00hours or
more~..before!it. islnecessary to withdraw spent
catalyst .throughpipe- 8.
, esshas been in operation for a su?icient period
forcing the mixed feed containing a minor pro
portion of ethylene .in countercurrent contact
of time,>=is.saturated with respect to all of the
with the recycle stream whereuponthe recycle
>.components entering 25, except ethylene, and
hence-onlythe-ethylene is dissolved out of the 75 stream becomes saturated .with. undesired/x com
ponents of the mixed feed containing ethylene,
withdrawing the recycle stream enriched with
ethylene from the scrubbing zone and returning
the same with added isobutane to the reaction
zone, continuing the ?ow of materials in the
manner indicated, thus causing mixed ethylene
feed, after the recycle stream has become sat
urated with undesired components of the fresh
bing zone whereby substantially only ethylene is
dissolved in said recycled product, withdrawing
the undesired components of said hydrocarbon
stream from said scrubbing zone, conducting the
recycled product containing dissolved ethylene
with added isobutane to a reaction zone contain
ing the said hydrocarbon-A1013 complex catalyst,
permitting the ethylene and isobutane to contact
feed, to contact said recycle stream whereby said
each other and the catalyst at elevated tempera
undesired components are rejected by the recycle 10 tures
and pressures.
stream in the scrubbing zone and are adapted
method of claim 2 in which the tem
to be withdrawn from the scrubbing zone and
perature in scrubbing zone is from about 75 to
thus separated from the desired ethylene dis
200° F.
solved in said recycle stream.
claim 2 in which the pres
2. In the continuous alkylation of ethylene with
sure in the scrubbing zone is from 200 to 400
isobutane in a, continuous operation employing a
lbs/sq. in,
hydrocarbon AlCls complex catalyst, the improve
ment which comprises feeding a hydrocarbon
stream containing ethylene and undesired com
ponents to a scrubbing zone, feeding a recycle
product stream substantially saturated with re
spect to undesired components of the feed to said
scrubbing zone, contacting said hydrocarbon
stream with said recycled product in said scrub
5. The method of claim 2 in which the ethyl
ene feed contains from 50 to 90% hydrocarbons
other than ethylene.
6. The method of claim 2 in which the A1013
consumption is from 0.04 to 0.08 lbs. AlCls per
gallon of alkylate produced.
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