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Patented Dec. 24, 14946
’ 2,413,105
UNITED STATES." PATENT OFFICE
ALKYLATION OF HYDROCARBONS
George B. Hatch and Ernest F. Pevere, Beacon,
. Louis A. Clarke, Fishkill, and Frank H. Bruner.
Beacon, N. Y., assignors, by mesne assignments,
to The Texas Company, New York, N. Y., a cor-y
poration of Delaware
Original application August 30, 1939, Serial No,
292,582. Divided and this application January
7, 1941, Serial No. 373,416
10 Claims. (Cl. 260-—683.4)
.
2
-
'l
.
Cs and C4 ole?ns, for the production of high
This invention relates to the alkylation of hy
anti-knock gasoline hydrocarbons.~- .
'
drocarbons and particularly to the alkylation of
In carrying out the alkylation treatment in a
isopara?ins with ole?ns in the presence of a liquid
continuous manner it is usual to'pass the hy-v
or ?uid catalyst for production of gasoline, and
drocarbons to a tower or reaction vessel wherein
has to do particularly with the operation of an (1 ‘they
are subjected to alkylation whilein ‘con-f, .
alkylation process.
tact with .an alkylation catalyst, such as con-‘
The present application is a division of Serial
centrated sulphuric acid, under predetermined _ _
. No. 292,582, ?led August 30, 1939, for Alkylation
conditions of temperature and time of; reaction,
of hydrocarbons, now Patent No. 2,267,097, dated
conccntration of acid, and ratio‘ of acid to hydro:
10
December 23, 1941.
carbons.
The invention has to do with an alkylation
are introduced to a reaction vessel and therein
subjected toalkylation in the presence of a cat
alyst such as concentrated sulphuric acid, hy
I
I 5
‘ drocarbons, as well as unreacted. hydrocarbons,
and an'acid layer comprising usedacid.
alysts, either with or without a promoter. Ac
cording to the invention a mixture of hydrocar
bons and catalyst is continuously ‘withdrawn
from one portion of the reaction vessel and re
.1
The reacted mixture is drawn offin a continu
ous stream and introduced’ toa 'settlingves'sel;
where strati?cation occurs, with the formation
of a hydrocarbon layer comprising alkylatedihy
process wherein ole?n and paraf?n hydrocarbons
* drated borontri?uoride and other alkylation cat
,
I
All or ;
a portion of the used acid may be recycled to
the reaction vessel, while the hydrocarbon, layer a
20
is subjected either to further contact with the
catalyst in a subsequent stage, or else neutral
cycled to another portion under conditions of
ized and fractionated to remove the unreacted.
high velocity ?uid flow so asto impart a high
hydrocarbons, such as isopara?ins, whichare re- _
‘degree of agitation or turbulence to the ?uid
turned to the system for alkylation with addi
contents of the vessel.
Thus, a stream of hydrocarbons and catalyst 25
A portion- of the reacted mixture drawn off
comprising products‘of reaction may be contin
from the reaction vessel may be recycled directly
uously Withdrawn from the top or upper por
to the reaction vessel without subjecting it to‘
tional
tion of a vertical reaction vessel and a prede
termined portion thereof recycled to. the reac
tion vessel. That portion not recycled is sub
jected to settling so as to stratify and form a hy
drocarbon layer and a catalyst layer. The by
drocarbon layer is removed and subjected to such
further treatment as may be desired, while the
catalyst layer is withdrawn and at least a por
tion thereof also recycled to the reaction vessel.
An important object of the invention involves
withdrawing from the bottom or lower portion
of the reaction vessel a portion of the liquid con
tents and returning this withdrawn liquid in, a
stream or streams ?owing under high velocity'so
as to impart suf?cient agitation to the contents
of the reaction vessel in order .to'avoid forma
tion of relatively stagnant pools of liquid cata
ole?ns.
>
settling, as above described.
30
r
,_
.
.
.
In such an operation there is a tendency for '
settling or‘ strati?cation to ‘occur within there
action vessel, due to the difference in specific".
gravity between the hydrocarbons and the alkyl~
ation catalyst, for example,’ concentrated sul
35 phuric acid. As a result; the acid tends ~to be'
concentrated in the bottom-or lower portion of 1
the reaction vessel, due to settling. ‘Relatively
stagnant pools of acid may-"thus; accumulate
within the lower portion of the vessel, and this
40 is undesirable, from the standpoint of realizing,
the most e?icient use of the catalyst and also the
avoidance of either under or o'ver-treatment’of
.certain constituents'of the hydrocarbons.
Accordingly, the present invention involves re
ducing the amount of settling and concentra
45
lyst within the vessel.
tion of acid within the reaction vessel by continu; f
vIn an alkylation process it ,is essential to I
ously removing some of the concentrate from the
achieve this object in order to realize e?icient
lower portion of the vessel, mixing with feed hy~f
use of the catalyst, as well as to avoid catalyst
drocarbons and introducing‘the mixture‘to an~
deterioration, and also/in/o der to avoid over
other portion of the vessel in a highlyturbulent.
treating certain constituen s and under-treat 50
state.
It also involves maintaining efficient agi-,
ing other constituents of the hydrocarbons un
dergoing treatment.
a
The invention is of particular application in
the alkylation of low-boiling isopara?lns, such
as isobutane or isopen'tane, with ole?ns, such as 65
tation within the vessel.
1 -.
I
p
.
v
.
The invention 'will be understood more fully
by reference to the ?gures of the accompanying . .'
drawing.
_
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~
1
i.
.
3
2,413,105
The drawing illustrates, in each ?gure, a
single reaction unit comprising reaction and
settling vessels, although it is contemplated that
a plurality of such stages may be employed, using
in each stage the method or methods of recycling
described herein.
As indicated in Fig. 1, the reaction vessel com
prises a tower | and wherein the ole?n and iso
para?ln hydrocarbons are subjected to contact
with a catalyst, such as 'concentrated'sulphuric
acid. The liquid mixture of unreacted hydro
4
,
controlled ori?ce 22, controlling the proportion of
the drawn-off mixture passing to a settler 23,
similar to the settler 3 described in connection
with Fig. 1.
That portion of the withdrawn mixture not
passing to the settler 23 ?ows through a pipe 24
communicating with the suction side of a pump
25 and by which means it is reintroduced to the
I lower portion of the reaction vessel 20.
Catalyst with some hydrocarbon accumulating
in the bottom of the reaction vessel 20 is with
carbons, alkylate and catalyst, accumulating in
drawn through line 26 by a pump 21, which dis
the top of- the vessel, is continuously drawn o?
charges this liquid through a nozzle or nozzles
through a conduit 2, leading to a settler 3. . _
28, discharging into the upper portion of the
The settler 3 is advantageously of conical
reaction vessel 20.
shape, as indicated, so as to facilitate removing
Feed hydrocarbons, together with recycled iso
the separated catalyst from the hydrocarbons as
para?in hydrocarbons, are introduced to the
rapidly and as completely as possible and there
suction side of the pump 21 through a pipe 29.
by to reduce to a minimum the time of‘c‘ontact‘
Used catalyst, withdrawn from the bottom of
between catalyst and hydrocarbons after intro 20 the settler 23, together with any makeup catalyst,
duction to the settler.
is conducted by a pipe 3|! communicating with
The conduit 2 contains an ori?ce or ‘valve 4
the pipe 26, leading to the suction side of the
adapted- to control the amount of liquid mix
pump 21.
.
ture passing to the settler 3. That portion not
Thus, one feature of the method of flow 11
passed to‘ the settler 3 is by-passed through a 25 lustrated in Fig. 2 involves the realizing of
conduit 5, communicating with a recycle pump‘
countercurrent flow within the vessel between the
6. The pump 6 discharges'through nozzles ‘I,
recycled liquid discharged through the nozzles 28
which in turn discharge into the bottom of the
and the recycled liquid introduced to the lower
reaction vessel I.
portion of the vessel by the pump 25.
The feed hydrocarbons, together with recycled 30 In Fig. 3, fresh feed from line 39, recycle cat
isoparaf?n, hydrocarbons, may be introduced to
alyst from line 35, fresh catalyst from line 31,
the suction side of the pump through a pipe 8.
and catalyst-hydrocarbon mix from line 38 are
In operation a stream of liquid mixture is
mixed and forced by pump 36 through mixing
continuously withdrawn from the lower portion
nozzles 40 into reaction tube 4|, which discharges
of the reaction“ vessel I through a pipe 9 con
into the upper portion of secondary reaction
taining a controlled ori?ce Ill. The pipe 9 com
vessel 3|. A controlled proportion of reaction
municates with the conduit 5 previously men
products is continuously withdrawn from an in
tioned, so that the liquid mixture withdrawn
termediate point of vessel 3| by line 32 containing
through the pipe 9 is conducted to the suction
ori?ce 33. Pipe 32 preferably discharges from
side of the pump 6 and there commingled with 40 vessel 3| at a point varying from about one
fresh feed hydrocarbons and recycled isopara?in
half to three-quarters of the height of the vessel.
hydrocarbons prior to passage through the
The withdrawn liquid is passed to a separator
nozzles into the bottom of the vessel I.
34, by which means the hydrocarbons are sep
The used catalyst withdrawn from the settler
, arated from the used catalyst. The used catalyst,
3 is passed, all or in part, through a conduit
all or in part, is returned by pipe 35 to the
II, also communicating with the suction side of
suction side of a recycling pump 36.
the pump 6. Fresh catalyst, added as makeup,
The suction side of the pump 36 also com
may be introduced through a pipe l2, com
municates through a pipe 38, with the bottom of
municating with pipe ||, previously mentioned.‘
the reaction vessel 3|, thereby drawing off such
The circulating stream of hydrocarbon and .1 O portion as may be desired of the liquid mixture
catalyst passing through the pump 6 may contain
accumulating in the bottom of the vessel.
a ratio of catalyst to hydrocarbon of about 1:1
by volume. Where ,the catalyst is sulphuric
acid the concentration is maintained in the
range of about 90 to 100% H2804.
The ratio of circulated hydrocarbon to fresh
feed hydrocarbon is maintained high and may
range between about 5:1 and 100:1, and pref
erably between about 10:1 and 30: 1.,
The-ori?ces 4' and III are regulated so that
the recycled hydrocarbon catalyst mixture pass
ing through the pipe 9 is su?lcient to prevent
The recycled hydrocarbons, feed hydrocarbons,
and the recycled catalyst, together with makeup
catalyst, etc., are brought into intimate contact
by pump 36 and forced through nozzles 40,. as
previously described, into tube 4|, which is a
relatively long conduit of restricted cross
sectional area, and therefore adapted to prolong
the e?ect of agitation and turbulent ?ow as the
?uid discharged through the nozzles 40 rises
therethrough.
A ‘certain amount of settling is permitted in
formation of a pool of separated catalyst in the
the reaction vessel 3| so as to permit drawing
lower portion of the'reactor; This, of course,
off a stream rich in hydrocarbons through the
depends upon a number of factors, including 65 pipe 32, while recycling through the pipe 38 a
the efficiency of agitation, catalyst ratio, and
mixture richer in catalyst.
nature of catalyst. In general, the proportion
While single stage operations have been illus
withdrawn through pipe 9 is less than the over
trated in the ‘drawing, it is contemplated that
flow through pipe 2, and may comprise about,
the methods of ?ow described may be used for
70 multiple stage operations and, in which case, the
5—75% of the latter.
Fig. 2 likewise shows a reaction vessel 20 pro
feed hydrocarbons may be introduced in part to
vided with" an over?ow pipe 2| through which
each stage or to as many of the stages as may
the mixture of unreacted hydrocarbons, alkylate
be desired.
and catalyst accumulating in the top of the vessel
Obviously many modi?cations and variations
is vdrawn off. The pipe 2| is provided with a 76 of the invention, as hereinbefore set forth, may
2,413,105
tling zone where remaining catalyst is settled '
be made without departing from the spirit and
from hydrocarbons.
4. The method according to claim 3, wherein
scope thereof, and only such limitations should ‘
be imposed as are indicated in the appended
claims.
We claim:
the catalyst is strong sulfuric acid of about 90
10()% strength.
-
1. In the continuous alkylation of an isopara?in
the said second zone comprises a chamber of
with an ole?n in the presence of an immiscible
enlarged cross-sectional area over the cross-sec
alkylation catalyst of greater density than the
hydrocarbons undergoing treatment, wherein the
feed hydrocarbons are continuously introduced
tional area of the said ?rst zone and into which
chamber the stream of emulsion from theisaid
?rst zone enters at an upper portion thereof, and
the stream of mixture richer in catalyst is with
drawn from a lower portion of said chamber,
into a closed circuit containing recirculating
emulsion of mixed catalyst and hydrocarbons
undergoing reaction and constituting an alkyla
while‘ the stream of mixture richer in h’ifdrocar»
tion reaction zone, and a portion of the recircu
lating emulsion stream is continuously diverted
to a separating zone where catalyst phase is set
'
5. The method according to claim 3, wherein
-
bons is withdrawn from an intermediate‘ portion
5
s-a I
thereof.
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,_
,
6. The method according to claim 3, wherein
the
remaining catalyst settled from hydrocarbons
are continuously discharged from the separating
in
said
second settling zone is separated from the
zone, and at least a portion of the eparated cata
as rapidly and completely as pos
lyst phase is recycled to the alk lation reaction 20 hydrocarbons‘
sible
to
thereby
reduce to a minimum the time
zone, the improvement which comprises removing ‘ of contact between
catalyst and hydrocarbons
the separated catalyst from the separating zone
after separation from the emulsion.
as rapidly and completely as possible to thereby
tled from hydrocarbon phase and both phases
reduce to a minimum the timeof contact between
catalyst and hydrocarbon after separation from
the emulsion.
I
7. In the continuous alkylation of a low-boiling
25 isopara?in with an ole?n in the presence of an
immiscible alkylation catalyst of greater density
than the hydrocarbons undergoing treatment, the
,
2. In the continuous alkylation of an isopara?in
with an ole?n in the presence of strong sulfuric
process which comprises continuously feeding the
hydrocarbons into a ?owing emulsion stream of
acid of about 90-100% strength, wherein the feed
hydrocarbons are continuously introduced on the
mixed catalyst and hydrocarbons undergoing
reaction, passing the ?owing stream through a
suction side of a recirculating pump into a ?ow
restricted ?ow passage with turbulent ?ow under
ing stream of emulsion of mixed acid and hydro
alkylating conditions, then introducing the stream
carbons undergoing reaction, the flowing stream
into the upper portion of an enlarged secondary
is forced with turbulent flow through a restricted
reaction chamber providing relatively quiescent
flow passage under alkylating conditions, and the 35 ?ow where additional reaction time is provided
mixture then passes through an enlarged ?ow
and partial settling of catalyst from hydrocar
passage, from which a portion of the acid and
hydrocarbons is returned to the suction side of '
bons occurs to form a‘ lower mixture richer in cat
reduce to a minimum the time of contact between
bons and passing said stream to a quiescent set- -
alyst and an upper mixture richer in hydrocare
the pump for recirculation through the system
bons, continuously recycling from said enlarged
40
and a portion of the acid‘and hydrocarbons is
chamber a stream of the mixture which has only
diverted to a settling zone where acid is settled
partially settled and which is richer in catalyst but
from hydrocarbons, and'settled acid is withdrawn
which has not formeda settled catalyst layer to-_
from said settling zone and at least a portion
the said restricted ?ow passage to form the flowing‘
thereof is recycled to the recirculating emulsion ~ emulsion stream into which the feed hydrocarbons
stream, the improvement which comprises remov 45 are introduced, and continuously diverting from
ing the settled acid from the settling zone as
an intermediate portion of said enlarged cham
rapidly and as completely as possible to thereby
ber a stream of the mixture richer in hydrocar
acid and hydrocarbons after separation from the
emulsion.
50
.
tling zone where remaining catalyst separates
3. In the continuous alkylation of a low-boiling
from the hydrocarbons.
8. In an alkylation process in'which an emul
isopara?in with an ole?n in the presence of an
sion of reactive hydrocarbons‘ and strong mineral -' ~
immiscible alkylation catalyst of greater density,
acid is maintained and circulated in a circulatory
system comprising a reaction zone and a primary
‘ than the hydrocarbons undergoing treatment, the
process which comprises maintaining two zones 55 settling zone, the improved method which com
of reaction in series, the ?rst of which comprises
an initial zone of reaction‘ wherein feed hydro
prises partially settling the emulsion entering said
primary settling zone to form an upper layer of
emulsion which is rich in hydrocarbons and a
carbons are introduced into a ?owing stream of
emulsion of mixed catalyst and hydrocarbons
lower layer of emulsion'which is richer in acid,
undergoing reaction and the mixture is agitated 60 recycling the said lower layer of emulsion to the
under alkylating conditions, and the second of
reaction zone before a settled acid layerv has
which comprises a secondary relatively quiescent
formed therefrom, separately withdrawing the
reaction zone into which emulsion from the ?rst
said upper layer of emulsion from the said pri-'
, 'zone flows and wherein partial settling of the
mary settling zone and diverting the same to a
emulsion occurs forming a lower mixture richer 65 secondary settling zone wherein substantially
in catalyst and an upper mixture richer in hydro
‘complete separation of acid from hydrocarbons is
carbons, continuously recycling from the said
effected;
second zone a 'stream of the mixture which has
only partially settled and which is richer in cata
lyst but which has not formed a settled catalyst 70
, layer to the said ,?rst reaction zone to provide
the said ?owing stream of emulsion therein, and
continuously withdrawing from the said second
zone a stream of the mixture richer'in hydro
carbons and passing said stream to a second set- 75'
1
1
‘
i
9. In the continuous alkylation of a low-boiling
isopara?in with an ole?n in- the presence of an
acid alkylation catalyst of greater density than
the hydrocarbons undergoing, treatment, the proc
ess which comprises maintaining two zones in se
ries, the ?rst of which comprises anrinitial zone _
of reaction wherein feed hydrocarbons are intro
a ‘ I -
7
2,413,105
duced into a ?owing stream of emulsion of mixed
catalyst and hydrocarbons undergoing reaction
and the mixture is agitated under alkylating con
ditions, and the second of which comprises a, sec
ondary reaction zone into which emulsion from
8
zones of agitated reaction, partial settling and
more complete settling in series; continuously
feeding the isoparaf?n and ole?n into the agitated
reaction zone containing an emulsion of hydro
carbons and alkylation catalyst under alkylating
the ?rst zone flows and wherein partial settling
conditions,
passing emulsion from said reaction
of the emulsion occurs, forming a lower emulsion
zone to the partial settling zone where incomplete
richer in catalyst and an upper emulsion richer
settling of emulsion occurs, recycling partially but
in hydrocarbons, continuously recycling a stream
incompletely
settled emulsion from one elevation
of the emulsion richer in catalyst before the same 10 of said partial settling zone to said reaction zone
has separated into a settled acid catalyst layer
before the said emulsion has separated into a
from the said second zone to the said initial re
settled
catalyst layer, passing additional emulsion
action zone to provide the said ?owing stream of
from a different and higher elevation of said par
emulsion therein, and continuously withdrawing
tial settling zone to said more complete settling
from the said secondary'reaction zone a stream 15 zone where a separate hydrocarbon phase is
of the emulsion richer in hydrocarbons and pass
formed, and recovering alkylate from said hydro
ing said stream to a settling zone where remain
carbon phase.
ing catalyst is settled from hydrocarbons.
GEORGE B. HATCH.
10. Process for the continuous alkylation of an
ERNEST
F. PEVERE.
isoparaiiin with an ole?n in the presence of al 20
LOUIS A. CLARKE.
kylation catalyst which comprises maintaining
FRANK H. BRUNER.
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