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Jan. 1s, 1949'.`
_
_w. N. FENNEY
2,459,636
ALKYLATION METHOD AND APPARATUS
_
76
13.5.\
`..«
INVENToR.
BY
„nl
.
Jan. 18, 1949.
9v, N, FENNEY
»
_
2,459,636
ALKYLATION METHOD AND APPARATUS
Filed April 25, _1945
,
46
,
2 Sheets-Sheet 2
4g_ a
Il,
l
rrr- y
' 5/ v
/l
50.,
‘Patented Jan. 18,1949-
'
- 2,459,636
j UNi'raD STATES ,PAT amori-‘léa
2,459,636
ALxm'rIoN METHOD AND APPARATUS
AWilliam N. Fenney, New York, N. Y., assignor to
The Texas Company, New York, N. Y., a cor
poration of Delaware
Appucatmn April 25, i945, serial No. 590,214
9 claims. (c1. 26o-essa)
,
l
.
This invention relates to the catalytic a1kyla~tion of a hydrocarbon or other organic compound
having a> replaceable hydrogen atom with a suit
able allrylating agent, such as an oleiln, for the
mixer such as the Stratco reactor, have been used
in this process. In these various processes, it is
an objective to preferentially react the olefin _with
production of gasoline hydrocarbons of high anti
knockV value suitable for aviation gasoline and
and minimize side reactions of the olefin with
the isoparaflin to produce the desired alkylate
' itself and with
thecatalyst, which side reactions
motor fuel, or for the production of valuable
cause deterioration in quality and yield of the
alkylated organic compounds for other purposes.
product and reduce catalyst life.
,
One of the principal objects of the invention
; In order to accomplish this objective, it is cus
is to provide an improved method of carrying out 10 _tomary tc use affeed
in which the isoparañin is
the alkylation operation to increase the selec
"in substantial molar excess of the olefin, and also.
tivity of the desired alkylation reaction and mini
to recycle hydrocarbon products or an emulsion `
mize undesired side reactions, to thereby produce
of catalyst with hydrocarbon products in order
high yields of a superior quality of alkylate and
to build up a very high ratio of isoparaiiin to
increase catalyst life.
oleiln at the point of contact of the oleñn with
A further object of the invention is to __eifect
the alkylation catalyst. Efiicient agitation of the
multi-point dispersion of the oleiln or other
reaction mix is also employed. In the various
alkylating agent in the reactionmixture in a
types of reactors customarily used, the olefin is
simple and economical manner to prevent local
introduced from a relatively‘large pipe opening
accumulation of the alkylating agent in and local
at one point or localized area, or at two or three
overheating of any increment of the reaction mix.
Another object of the invention is to provide
more effective reaction conditions by combining
highly efficient agitation of the reactionmix with '
rotary multi-point dispersion of the alkylating
agent in the agitated mix, and also prompt re-v
frigeration of the mix containing dispersed alkyl
A p ating agent immediately after introduction-.bf the
latter to remove the heat of reaction as fast as
it is liberated.
.
Still another object of the invention is to pro
vide improved alkylation apparatus for carrying
out the above method and accomplishing the
foregoing objects, wherein the apparatus is simple
and economical in construction, readily controlled
and highly eñicient in operation, and is provided
with a rotaryl agitator and dispersion member
for dlspersing the alkylatingagent inthe reaction
points at the most, of any reactor system; and
reliance has been placed on eiiicient agitation or
rapid circulation of the hydrocarbon-catalyst mix '
past the zone of olefin introduction. While good
operation has been secured, particularly where a
very high isoparailln or isobutane concentration
of about '6G-70% or more by volume has` been
maintained in the hydrocarbon phase of the re
action mix, there are still some side reactions
30 which‘show up largely in reduction in yield and
quality of the alkylate and in catalyst deteriora
tion, thereby` increasing the cost of the process
per unit volume of alkylate and finished l100
octane gasolineproduced. Further, the necessity
3.
for maintaining the very high isobutane concen
tration in the reaction mix represents one of the
' most expensive items of the process, since exten
sive fractionating equipment of high installation
.and operating cost is required for separating iso
Other objects and advantages of the invention 40 butane of the necessary purity for recycling to
mix.
'
-
‘
will be apparent from the following descriptionwhen taken in coniunction with the accompany
ing drawing and appended claims.
Various catalytic alkylation processes for alkyl
atingan isoparaflin with an oleñn or other suit
able alkylating agent for the production of gaso~'
line hydrocarbons of high antiknock value are
known. These involve the use'ofcatalysts such
as strong sulfuric acid, hydroñuoric acid, a forti
iied aluminum halide-hydrocarbon complex. BF;
water complex and the like.
The best known »
- process which is now widely used on a commer
the reaction zone. Consequently, improved meth- `
ods for increasing the selectivity of- the alkylation
4reactibn and minimizing undesired side reactions,
while at the same time enabling lower isoparañln
' concentrations to be employed »in the hydrocarbon
phase of the reaction mix and still obtain ceiling
or high quality alkylate, had remained ade
sideratum.
-
‘
.
’ It has heretofore been proposed to introduce the
oleñn or other alkylating'agent into the reaction
mix by so-called “multi-point” injection, wherein
the oleñn is added from a large number of small
openings or jets which> are widely spaced from
each other throughout a substantial portion of
reactor, Jet type reactor, and propeller type of 56 »the
reaction zone,'in order to avoid local accumu
cial scale is the sulfuric acid. alkylation process.
Various'reactors, such as the pump and time tank
9,459,680
3
lation. while this is effective ro
intended, rather complicated and -
`
- - -
weon
structions of distributors and piping are required.
It has also been proposed to combine this' multi
4
meral 2l. While Pig. 1 shows four such members
within the reaction zone 20 confined by tank Il.
Nitis to be understood that this is merely for pur
point-,olefin injection with immediate refrigera
tion ofthe reaction mix in a heat exéhangetype
poses of illustration and that any number from
one to ten or more may be provided depending on
the length of the tank and the construction of
the agitator. Also mounted within tank Ilis a
refrigeration coil comprising a plurality of ver
tically arranged pipes 28 closely surrounding the
of reactor having multiple concentric pipes.
In accordance with the present invention, the
olefin or other alkylatinmllent -is dispersed in
very finew divided formthroughout an extensive l0 periphery of'the agitating and dispersion mem
bers 2l and spaced .from the wall of the tank.
zone, so as to avoid local accumulation, by cen'-A
While any suitable construction of heat exchange Ä
ltrifugal force, with or without added pressure,
coil can be employed, the one illustrated is de
signed for serial flow` from refrigeration inlet 2l
iiciently removed from the axis of rotation to I6 'to outlet ll, alternate pairs of vertical pipes 28
being equipped with return bends indicated at II
provide high linear velocity of the said opening
at top >and bottom for serial flow. Preferably,
in a circular path of substantial diameter through
two semi-cylindrical coils are provided to forni
the reaction mix. Atthe same time-the disper
the
complete enclosing cylinder of . refrigeration .
sion member also functions as an efllcient agita
tor to produce high speed agitation and local re 20 coils about the dispersion members 25, each coil
being equipped with its separate refrigeration in
circulation of reaction mix past the zone of dis
let and outlet 2’ and 3l respectively to give more
persion. -The zone of dispersion is closely sur
emcient and uniform refrigeration.
'
rounded by refrigeration means. so that the mix
Y from a small opening or openings in a rotary dis
persion member, wherein the Jet opening is suf-h
containing the highly dispersed olefin, immedi
Each or the agitating and distributing mem- .
ately after the latter has been introduced, is sub 25' bers 25 may be constructed as shown in Fig. 2.
jected to heat exchange or chilling to remove the ,. A solid metal disc 3l is pinned or otherwise se
heat of reaction as fast as it is liberated.
More
cured to shaft Il in nxedlocation so that a plu- ‘
rality of small drill holes 34 extending throughv
over, this is accomplished by an improved alkyla
the annular metal wall of shaft I8 communicate
tion reactor of simple and inexpensive construc
tion, and which is readily controlled in operation. 30 with radial bores 35 drilled completely through
disc 33 from the outer periphery to the central
In the drawing, which illustrates preferred ern-,
opening which snugly nts about shaft I8. Welded
bodiments of the present invention:
or otherwise secured to the periphery of disc II
Fig. 1 is a diagrammatic view with the reactor
in vertical section, of a single stage alkylation sysf _ are a plurality of curved agitating blades ß,
tem embodyingv the features of the present in 35 shown as six in number. The direction of rota
tion is indicated by the arrow 31. Each blade
vention.
‘
has a leading face 38 ` hich is curved in the form ’
Fig. 2 is a plan view of the combined agitator
of a scoop and is .als tapered off on the upper
and dispersion member employed in the reactor
side, so that rotation imparts both an outward
of Fig. l;
Figs. 3 to 6 inclusive are plan views, similar to 40 and upward thrust to the- liquid contents within
reaction zone 26, thereby producing a` local re
Fig. 2,-illustrating various modifications of the
= circulation indicated by the arrows 39 in Fig. 1.
combined agitator and dispersion member; and
The trailing wall of each blade 30 is drilled com
Fig. 'l is a _diagrammatic view of a multi-stage
alkylation system involving separate reactors and ' pletely through from the tip to the inner surface
which rests on the periphery 'of the disc, thereby
refrigeration heat exchangers, and representing
forming a bore 40 which constitutes a continu
a further modiilcation of the present invention.
~
ation of the cooperating radial bore t! in the
Referring to Fig. 1, the isoparamn feed from
disc. The interconnected bores through the
line III is forced by pump II through either or
shaft, disc and blade thus form a continuous uni
both of valve controlled lines I2 and I3. Valve
directional radial passage from the hollow space
controlled line I2 is joined by line Il through 50 4I
within shaft I8 to the very tip of the blade Il.
which a mixture of isoparaf?n recycle and cata
If desired, the outer end _of bore 40 can be
lyst, obtained as hereinafter described, is intro
to receive a small nozzle or'jet, which „
duced into the system. As shown, line I2 enters _ threaded
preferably has its outer tip substantially flush
the lower end of a vertical tank I5 constituting
with the tip of the blade. However, this is not
the alkylation reactor.
.
,
essential, since the 4bore lo can be drilled of de
Mounted in suitable bearings I6 and Il carried
sired size to function as the jet. While each
at opposite ends of tank I5 is an _axially positioned
blade 3-6 is shown as equipped with a dispersing
hollow shaft I8, the lower end of which is directly
jet, it will be understood that only one blade may
connected to variable speed driving motor I-il.
be so provided, or alternate blades equipped with
60
Olefln feed from line 2li is forced by pump 2l, to
jets, etc. whereby from one to six iets are af
gether with any isoparaflin from line I3, through
forded for the particular agitator and dispersing
line 22. The ,latterl communicates by conven
member shown.A The construction shown, in
tional floating connection 23 with the upper end
which there is a jet. for each blade, with the jet
of shaft I8, wherebyA the olefin or mixed isopar-_ ~ located at the tip of -the blade, constitutes a
añln and olefin feed is introduced into the space
preferred arrangement.
.
within the hollow shaft. Preferably, the bulk of
The-size of each jet depends upon the diameter
, the isoparafiin fresh feed and >recycle is intro
and speed of rotation of the agitator and con
duced along with the alkylation catalyst through
sequently upon. the centrifugal force produced
line I2 _;, although a suflicient amount of isoparaf- e
duringA its operation. However, the iet should
70
fin may be added by line I3 to forin a premixed
be less than one-fourth inch. in diameter in any
feed in line 22 wherein the isoparailln is at least
about equal in molar ratio tolthe olefin content. ' event, and preferably is .about one-«sixteenth to
one-eighth of an inch, vwith the communicating
Mounted at spaced intervals along the length
bores of somewhat larger size to avoid plugging
of shaft I8 are a plurality of agitating and dis
75 and facilitate cleaning. The distance of the iet
persion members indicated generally by'the nu
I. "» accuse' - ì'
.
from the axis of rotation. and the speed of rota
6
‘
tank, and again as» it is diverted inwardly toward
the center. Moreover, 'the relatively rapid local
recirculation
increases the ' contact of the mix
v
tion, are selected to give a linear velocityof the
„ .iet through the reaction mix of about 5-60 feet
per second and preferably about 10-20 feet «per
'
with the coil, further improving the cooling enact. .
second. \ Ordinarily, the _agitator will have a
minimum= diameter of about six inches for a
small diameter tank Iii of about twelve inches;
and this may vary up to an agitator diameter of
about eight feet for a twelve foot diameter tank. `
'I‘he reaction products discharged by line 44
are allowed to stratify in settler 45 into an upper
hydrocarbon layer and a lower catalyst layer.
'I'he former is withdrawn by line 48 to conven
tional neutralizing and- washing zones', and the
With the smaller diameter agitators, a variable
neutralized hydrocarbon is then passed to con- `
speed motor I9 may be directly connected to
ventional stabilizing and. fractionating equip
shaft I8 to drive that shaft over a speed range of
ment,
where the desired aviationor motor fuel- , ’
about 1800-3600 R. P. M. On the other hand,
alkylate, consisting essentially of branched chain ,
with the larger diameter agitators. the motor
paramn hydrocarbons
may be connected to a speed reducing gearing 15 is recovered. Also, the of high antiknock value,
excess isoparamn or iso-A
to drive the agitator at about 50 R. P. M. for the
butane is recovered as an isobutane-rich frac
largest size speciiìed above. up to about 1800
tion for recycling in the system.I The isoparaflln '
R. P. M. for the intermediate size, to produce
recycle line is indicated at 41. >A stream of the
linear velocities of the jets Within the vrange
specified.
`
,
v
j
»
4
settled acid is withdrawn by line 48, ' and the
~
major proportion recycled by line 49 which Joins
In 'the customary alkylation operation of a
_ low-boiling isoparañln, such as isobutane, with a
normally gaseous olefin, such as a butylene, the -,
,line i4. A minor proportion of the catalyst may
be discharged 'to recovery by line 50, and makeup
ycatalyst introduced by line 5|. Preferably, the
tank is maintained under a pressure ofabout
recycle isoparailln 41 is first mixed and emulsiiled
50-75 pounds per square inch tomaintain the 25 with
the recycle and fresh feed catalyst as shown,
hydrocarbons in' liquid phase. Generally, the
and
this
mixture or emulsion then introduced
centrifugal force produced at the ,iet -willucon
together with the fresh isoparamn feed from line
slderably over-balance the maintained pressure- 'i0
into the reaction zone.
within the tank. A regulating valve 43 is there
The
invention is applicable to the al
fore -provided in feed line' 22 _to permit desired 30 kylationpresent
ofl any low-boiling isoparailln with any
control of the rate of feed of the olefin to the _ normally gaseous or normally liquid olefin. Thus,
dispersion -iets _or oriñces. ’.
"
i
'
.
A_discharge line 44 leads from the upper por
tion of the tank to a settler 45. A progressive
movement of the reaction mix takes -placethrough the reaction zone 26 fromv the inlet to
the outlet, depending on the rate of feed. The
high linear velocity of the Jets carried by the
rotary agitators' produces a very ñne dispersion '
the is‘oparafiln may -be isobutane, isopentane -or
isohexane.
The oleiln may be ethylene, pro
pylene, butylenes,l pentylenes, hexylenes„other
as' higher
boiling monomeric oleilns or certain se- '
lected fractions of cracked naphthas, oleiln poly
ì mers, such as diisobutylene,
triisobu'tylene, cross
polymers of isobutylene and normal butylenes,
and various mixed or non-selective polymers. In
ofthe oleñn feed into the reaction mix from the 40 place of oleñns as the alkylating agent, various
blade tips. At the same time, the blades 36
alkyl esters, such as the sulfates, chlorides,- ilu
produce a violent agitation in the form of a local
orides, etc. of- the corresponding oleiins may be
recirculation of reaction mix outwardly and- up
used. Moreover, various aliphatic alcohols and `
wardly against the wall ofv tank I5, from where
ethers, such as tertiary butyl alcohol, isopropyl
it i's diverted inwardly toward the center as 45 alcohol, butyl ether, etc., may be employed as the
shown. A similar local recirculation is created
alkylating agent, particularly with catalysts
for each dispersion zone; and the opposing forces
which have tolerance for water liberated in the
and currents in the region between two adjacent
reaction, such as BFs-water complex. The ex
zones further contribute to the agitating effect.
pression “alkylatingl agent” is' used herein
-Fl-om the center, the reaction mix is again-drawn 50 throughout the‘description and claims to denote'
outwardly to the periphery oi.' the agitator, where
any of the above compounds which react with an
it is picked up by the rotating blades and the
isoparailln or_other organic compound having a
cycle repeated.
replaceable hydrogen atom in _this alkylation re
, In those cases where the centrifugal force may
' action to produce alkylated compounds. In place
not be suilìcient to overcome the high pressure- 55 of the pure hydrocarbons or other alkylating
within the tank plus the pressure drop in the
agents, itis of course to be .understood that vari
dispersion system, then the oleiìn feed pump 2i
ous reñnery fractions, such as C4, Ca-C4, C4--Cs,
is designed to supply the feed in liquid phase .~ Ca-Cs, Cs, etc. may be employed.
under an excess pressure, and valve 43 usedto
The present invention is applicable to the use
regulate the rate of olefin feed in a similar
of any of the well-known- alkylation catalysts,
manner. In any event, it is desired to~have at
.such as sulfuric acid, hydroñuoric acid, aluminum
least two pounds per square inch pressure drop
chloride-hydrocarbon complex, BFa.H20, chloro
across the orifices and preferably about 5-15
sulfonic acid, iluorosulfonle acid, and the like.
pounds per square inch or more.
In thisy man
ner, the oleñn is 'jetted into the reaction mix
The variousconditions for the reactions employ
ing these catalysts are well-known; and >conven
with substantial force, providing the high dis
tional conditions coupled with the features of
persion described above. The mix containing
the present invention as set forth above may be
dispersed oleñn immediately contacts the re
used. By way of example, the invention is more
frigeration coil 28 just after the olefin has been`
particularly described herein in connection with
added, so that refrigeration is present at sub 70 the use of strong'> sulfuric acid as the catalyst; but
stantially the instant of initial reaction. By'
it is to be understood that this is by way of illus
spacing the refrigeration coil from the wall, it
tration and not limitation.
will be noted that the local recirculationprovides The conventional conditions for this sulfuric
double contact of the mix with the coil, once as
acid alkylation include an isoparafdn-oleñn feed
it is proceeding outwardly toward the wall of the 76 ratio of about 3:1 to 8:1 or higher, an acid
'
f
.9,459,036 ._
~
strength'jm the reacuón zone or about aia-96%
` with mak eup acid of 'about 98-100% strength, a
temperature of about -20-80°,F. and preferably
` about`35-60° F., suifieient pressure to maintain
> 4thehydrocarbon reactants
in -the liquid phase,
an acid to hydrocarbon volume ratio in the vre
action zone, of _about 0.5:1-to about 2:1 and pref-
erably about 0.8:1 to 13:1, and'a contact time
of about 15-60 minutes. A high isoparaifin con
centration of around Gil-70% by" volumel in the
hydrocarbon phase in the reacted mix can be
employed, although the present invention en
ables much> lower isoparamn concentrations of
about 40-50% to be used with greatly improved
economiesand Iincreased capacity, , while stili
_
8
_
.
~
.
periphery of the'disc assembly are a plurality of
blades Oli. One .or more, and' preferably all. of
l
the blades aredrilled to provide passages il in"
alignment with- cooperating drill holes through
the outer concentric ring 51, whereby the olefin
_is fed by centrifugal force through the passage
_ ways 0I and out of the blade tips. As shown, each
blade has a'leading edge 82 whichextends sub- stantially >radially and is comparatively fiat and
generally parallel to a vertical plane through the
raxis oi` rotation. while the rear or trailing edge
I3 is curved.` Moreover, the blades are elongated
' somewhat with respect to the „diameter of the
discs Il, Iin comparison to the construction shown
. in Fig. 2. This form provides more o_f 44a, churning
effect, and _gives »local recirculationboth above
maintaining good quality of product. Also, while
and below the- agitator.
' the longer conventional times of contact may be
«
F18. 4 discloses a further modification wherein
the agitator and dispersing member is of-the pro
peller type, having a plurality of elongated fan
blades 65 attached ~to a-central collarv 66, the lat
ter being fastened to the hollow shaft. Each
fan blade 85 is formed of two opposing vsheet metal
used together with conventional emulsion orhy
drocarbon recycle, it will be noted from Flg.,1
that emulsion or' hydrocarbon recycle need not
. be employed and in fact is desirably omitted,
and once-through now used. The contact time
may be reduced to as low as 1-5 minutes with
plates which arestampedfor otherwise, pressed
further increase in capacity. This enables small
. into the usual curved shape._'and .whicnare'weld
er size reactors to be used for >an equivalent out
ed together at their inner surfaces'indicated at 61 _
pense
put, with
andresulting
lowering decrease
of powerinrequirements
installation ex-`
for- - and also about the remainingperipliery, thereby
the reactor.
.
forming an interior hollow chamber 68 which com
municates with aligned bores 89 drilled through
the collar 66 and shaft. The outer tip of each
`
While the invention has been described above
as particularly applied to the alkylation of an
isoparaflln with an alkyl'ating agent, it is to be
understood that the invention is applicable to
the alkylation of any organic compound having a
readily replaceable hydrogen atom with a suit
nl
bladeis drilled or otherwise provided with a plu
rality of iets indicated _at 10 .and shown Ato be six
in Depending
number. . on the
pitch and
^
mounting
‘. „ . of the
blades,V either a central downward. or upward
able alkylating agent. For example, the-method ;
and apparatus described herein can be employed
circulation of the reaction mix is imparted-by the
. rotation of the propeller. With this agitator, tank
- I5 is preferably provided with interior -bai'iies in
forthe alkylation of a normal paraffin with an
olefin or other alkylating ' agent, employing a
the form of plates which are located intermediate
catalyst effective for this normal parailin alkyla'-V
tion, such as HIL-EP3, aluminum- chloride with
hydrogen chloride,` and the like. Likewise, the
invention isapplicable to the alkylation of aro
matics and hydroxy-aromatics, such as benzene,
.gli
the various agitators, said plates being lformed
with openings at the periphery thereof which pro
vide communicating passages along the wall of
tank II for progressive movement of the reaction
mixture from the inlet to the outlet. ._ These
>`toluene, xylene, phenol, cresol, etc., with an al- y
kylating agent such as an olefin, an alcohol, an .- bai'iies thus provide contact surfaces for the local
By way of specific examples,
there is mentioned the alkylation of benzene with
ethylene to produce ethyl benzene, an interme
diate in the manufacture of styrene; thevalkyla
recirculation. For example, assuming 4tirelire-g
' alkyl halide, etc.
- tion of chlorinated kerosine with benzene to pro
. duce so-called “keryl’benzene” for the detergents
peller is set to cause an upward circulation, the
mixture will contact the superposed baille-.and be
deflected outwardly'and downwardly to the, wall
v
ofy tank l5, and thence be returned to thecenter .
for recirculation by `'the propeller. In this form,
and wetting agents; and the preparation of al
kylated phenols as special >solvents or chemicals.
the bafiles can be provided with openings receiv
The conditions for these various reactions are -
periphery of the bailles can terminate just within ,
known, and conventional conditions can be uti
lized in conjunction with‘the principles of the
present invention. The expression “organic com
.pound having a readily replaceable` hydrogen
atom" is used for convenience throughout the de
scription and claims to designate the various ma
terials described above which can be alkylated l
with the mentioned alkylating agents in the pres
l ence of suitable alkylation catalysts as described.
Referring to Fig. 3, a modified form of agitator
and dispersion member is illustrated. This com
prises two flat sheet metal discs indicated at Sli,
which are attached by welding or in other suitable
manner on opposite sides of inner and outer con
centric metal rings indicated at 56 and 51 re
spectively. The disc assembly is in turn pinned
to shaft i8 so that one or more ‘drill holesl through
the annular shaft are in alignment with drill holes
ing the pipes 28 of the heat exchange coil, or<the
the coil, and be fastened 1n place by suitable. lugs
extending inwardly from thewall of tank- I5. The
rapid rotation of the propeller disperses the alkyl
- ating agent by centrifugal force-through the jets
10 outwardly toward the refrigerating zone of coil
28; and the reaction mixture containing dispersed
alkylating agent is then drawn toward the center
and forced by the propeller in the recirculating
path previously described, whence it is again
brought into contact with the refrigera-tlng coil.
A further modification of the bladed impeller
of the disc type is shown in Fig. 5. This comprises
a single metal disc 12 having affixed to its pe
riphery a plurality of curved blades 13. Mounted
immediately above 'the discs 12 and preferably at
` tached thereto in the form of strengthening ribs
are a plurality of radially extending hollow spokes
1I extending outwardly ~-from a central collar 15
and terminating approximately "at'the- periphery
I8 through the inner ring 56, whereby the olefin
of disc 12. One or more, and preferably all;l of
feed is supplied to an inner annular chamber 59
75
thehollow
spokes are equipped-:with iets-indi
4 formed between the discs lit. Attached to the
cated at 1I' at substantially the- periphery of the
-
disc an'd immediately in advance of a cooperatingj _
. blade 1‘3 in the direction _of rotation of the im- > peller.
Each blade has a curved portion 'oi' in- -
creasedwidth extending. outwardly to overlap and
, impact the dispersed alkylatingïagent immediate
Ole?n or other alkylating agent is introduced f
byline 22'. and is then split 'between the various,
reactors by the _valve controlled branch lines 83. -
Each of the _branch lines 88 communicates by a
floating connection with the hollow shaft 86 of
the reactor, whereby the alkylating agent is fed
ly after it is discharged from the cooperating jet
through lthe hollow shaft and thence through
18. Dispersion is thus effected by the combined'
communicating
passages in the agitator 81 to be
.letting action ofthe rotary dispersion member
discharged from the rotating‘iets in the manner
'and >by impact of the blades on the reaction mix
described. - It will be understocdthat
containing the dispersed alkylating agent imme~ _ previously
the rate of feed of alkylatlng agent can be varied
diately after the latter has been injected. The
throughout the _various stages of the plural stage
inner ends of the hollow spokes communicate with ` unit, and preferably is reduced in the direction of
1 aligned drilled bores 11 ~in the collar 15 and shaft.
`flow in accordance with the isoparaflln concen
It will be understood that, in all ofthese various
tration of the hydrocarbon phase of the reacted
modifications, the refrigerating coil 28 closely sur
rounds the zone of dispersion. Thus, in Fig. 5, the
Reaction products from theiinal stagewheat _
alkylatingagent is‘ilrst jetted into the'reaction .
mix
mix, is then immediately'impacted by the blades '
’
`
‘
exchanger pass by line 84 to valve controlled line .
85, and thenceV to settler 45', from where the hy
to further promote dispersion, and -isîthen cir 20 drocarbon and catalyst streams are removed by
culated into immediate .contact with the refrig- t lines 46' and 48' in the, manner previously de.
erating coil.
j
Y
.
scribed. It 'will be understood that primed ref
’ Fig. 6 discloses a further modification> of the ' erence numerals are employed in Fig. '1 to desig
propeller type of agitator, similar to Fig. 4, except . nate` similar elements as described above for
that in this case the‘blades 8l) are of the _circular -25 F18’. 1.
or wider oval type and overlap each other. Here
While once-through iiow, with the reactionv
again, each blade is formed of two opposed plates - products from the last stage passing directly by
which are. fastened together to form an interior .t line 85 to settler 45', constitutes the preferred
`hollow chamberY receiving alkylating agent
operation, the present invention can be employed _
through communicating bores in the supporting 30 with emulsion recycle if desired. As shown, a
collar 8| and the hollow shaft. In this form,_each
valve controlled branch line 81 containing an
blade is provided with a plurality of jets 82,
_ emulsion recirculating pump- 88 communicates _
shown as three in number, formed on the leading
lwith line .84 and discharges into feed line I2'.
edge rearwardly Yfrom .theztip; and the trailing
Consequently, by suitable regulation of the valves
side of each blade is curved upwardly so as to 35 in 85 and 81-respectively, any desired portion of
provide immediate impact of the mixture con
taining dispersed alkylating- agent by the blade
the reaction mix- from line 84 can be recycled in
~the system, the balance being-discharged to re
in its rotation. It will be understood that, With.
covery.l
the propeller of‘Fig; 6, bailles can be mounted in
It will be understood that reactors of the type
tank I5 to provide for the local recirculation in 40 disclosed in Figs. 1-5 can alsobe connected in ‘
the manner described _for Fig. 4.
series for multi-stage operation. . Also, reactor
While the alkylatlon apparatus comprising ro
’85 of Fig. 7 can be equipped with an interior re
tary agitating and dispersion members closely
surrounded by va. refrigerating coil constitutes a
preferred form of the invention, whereby sub
stantially immediate refrigeration in the zone or
zones of dispersion is secured, this can be modi
ñed while still retaining features and advantages
of the present invention.
_
-
_ _
Fig, 7 illustrates such a modification- involving
a multi-stage system, including alternately con
y frigeration coil -in >place of the exterior heat ex-_ changer shown.
Further, any combination of
agitators of the types shown in Figs. 2~-6 can be
used in one reactor, for example, acombination
of impeller and propeller agitators.
The following is listed as a speclñc example of
'the present invention. A twelve inch diameter
cylindrical tank equipped with an eight inch di
ameter multi-bladed impeller of the type dis
nected reactors and refrigerated heat exchang
closed in Fig. 2, with the latter surrounded by a `
ers. As shown, each reactor comprises a tank v85
one inch external diameter heat exchange coil
of comparatively small volume and equipped with spaced one-half inch from the tank wall and also
a central hollow shaft 88 carrying a rotary agita .: one-half inch from the blade
_ tips, is utilized for
tor and dispersion 4member 81, preferably of the
multi-bladed disc type of Fig. 2, 3 or 5. The
mixed isoparaiiin or other organic compound and
isobutane-butylene alkylation
with strong s111- '
furie acid. A 1:1 by volume mixture of isobutane
and
sulfuric acid of about 93% system acidity is
’ alkylation catalyst are introduced‘by line I2'
continuously fed into the tank, while the'butylen'e
into the lower portion of tank 85, and reaction
feed is jetted into the mixture through jets having
products discharge from the upper portion there- ,
a
diameter of one-sixteenth inch and carried by
'of by line 88>in accordance with the feed rate.
the impeller rotating at 180GB.- P. M. The tem
These products then flow through heat exchanger
perature is maintained at about 35° F., and the
88 supplied with refrigerant by line 80 and dis
reaction
mix discharging from the reactor has a
charged by line 8i. While there is local recircula 65 volume -ratlo
of acid to total hydrocarbons of
tion within tank 85 as produced by the agitator
about 0,8:1, and an isobutane concentration lin
81, due to the relatively small volume of tank 85
the hydrocarbon phase of- the reaction mix of
in comparison to the fresh. feed rate, the time of
about 50%. Under these conditions, a rate of
contact within tank 85 -is of the order of several
feed of olefin equivalent to about 0.5 volume per
minutes or less. Consequently, the mixture is 70 volume
of catalyst per hour produces an alkylate
promptly introduced by line 88 into the heat ex
of
substantially
ceiling lquality from a total C4
changer 88, where the heat of reaction is removed
refinery gas _fraction containing substantial
and the temperature controlled. 'I'he products
then iiow- by line 88' into the next reaction tank
85 and` so throughout the system in series i’iow.
amounts of-both isobutylen'e and normal butyl
enes. A yield of total liquid alkylate of approxi
mately 194 %l by Weight on the. basis of the olefin
Y
11
'
iz
1
charged is secured, of which about 96% boils
is immediately removed to prevent local overheat
aviation fraction having a cleafr CFRM octane of
having a replaceable hydrogen atom with an
alkylating agent in the presence of a liquid aliryl~>
of any increment ofthe mixture.
.
within the aviation fraction below 311° F., the _ c _ ing
'4. In the alkylation oi' an organic compound
95.
'
Obviously many modiilcations and variations of
the invention, as hereinbefore set forth,-may be
made without departing from the spirit and scope
thereof, but only such limitations should be im
posed as are indicated in the appended claims. 10
I claim:
ation catalyst, the improvement which comprises
dispersing the alkylating agent in liquid Phase
in a small jet into a reaction mix of organic coin
pound and alkylation catalyst in a reaction zone.
while moving the iet through the reaction. zone in
a cylindrical path of substantial diameter and
_
~ at high linear velocity, subjecting the .1 et through
1_. »Continuous alkylation apparatus _of the
character described. comprisinga tank adapted
out its entire path of movement to violent impact
immediately» after it is discharged into the re
. end of said tank adaptedlor introducing liquid 15 action zone, and immediately subjecting the re
action mix containing dispersed alkylating agent _
organic compound and liquid alkylation catalyst
to indirect refrigerative chilling in a zone closely
into said reaction zone, a discharge line at the
to confine a reaction zone, a supply line at one
surrounding the zone of alkylating agent dis
opposite end of said tank adapted for the dis
charge-of reaction products, a central hollow
rotary shaft mounted within said tank, an agi-.
tator having an impact blade carried by said shaft
persion and impact to remove the heat-of re
action and prevent local overheating of any in
crement of the reaction mix. ' '
5. In an alkylation reactor of the character
described, having a tank providing a reaction
space. a hollow rotary shaft mounted therein, and
` ~ within said tank, a dispersmg jet carried by said
agitator and having a small opening positioned»
at a substantial distance from the axis of rota
tion of said shaft and immediately in advance 25 means for supplying alkylating agent in _liquid
phase to said hollow shaft: a rotary agitator
of an impact portion of said blade in the directie-i
of rotation of said agitator, said shaft and agi
and alkylating agent dispersion member carried
tator having communicating passages between
by -said shaft comprising a disc carrying a plu
rality of agitating blades about the periphery
the space~within said hollow shaft and said jet
opening, a supply line for liquid alkylating agent,
a floating connection between said supply line
ao thereof, a Jet mounted adjacent the periphery
~ and one end of said hollow‘shaft, power means
. said bladesin the direction of rotation thereof,
of said disc immediately in advance of one of
and said parts having a passage providing com
connected to the other end of said shaft for
rotating the same, whereby liquid alkylating
munication between said hollow shaft and said
agent is supplied to saidhollow shaft and thence 35 jet, whereby a >liquid stream of alkylating agent
is discharged from said iet during rotation of said
- to said jet and is discharged from the latter in
a manner toy be immediately impacted by said
member and the said liquid stream is immediately
blade, and a refrigeration coil mounted within
said tank- and closely surrounding said agitator
impacted by said one blade.
liquid alkylation catalyst, the improvement which
comprises introducing the liquid alkylation eat
alyst and organic compound adjacent _one end
propeller blades of substantial curvature carried
by said shaft, a jet mounted at the leading edge
of one of said blades and directed to discharge
across the path of movement of a curved trailing
side of said blade, said parts having a passage
-
'
-
.
6. In an aikylation reactor of the character
so as to be positioned between the circular path 40 described, havingv a tank providing a reaction
of said Jet and t-he wall of said tank, said re
space, >a hollow rotary shaft mounted therein,
frigeration coil being spaced from the tank wall.
and means for supplying alkylating _agent in
2. In the alkylation of an organic compound
liquid phase to said hollow shaft; a rotary agi
having a. replaceable hydrogen atom with an
tator and alkylating agent dispersion member
orga'nic alkylating agent in the presence of a ' carried by said shaft comprising a plurality of
of a long closed reaction zone, progressively ilow
ing the reaction mix at a relatively slow rate
through said reaction zone from said one end to
the opposite end thereof and discharging reaction
providing communication between said hollow
shaft and said jet, whereby said jet discharges
products from adjacent said opposite end, dispers
ing the alkylating agent by multipoint addition
on rotation of 'said member a liquid stream of
alkylating agent which is immediatelyvimpacted
by the curved trailing side of saidfbIade.
from a large number of >orifices spaced along the
greater part of the length of said reaction zone
7. In an alkylation reactor of the character
described, having a tank providing a reaction
space, a hollow rotary shaft mounted therein,
in circular paths of substantial diameterextend
and means for supplying alkylating agent in liquid
ing generally across the direction of progressive
flow of reaction mix along the _length of said 60 phase to said hollow shaft; a rotary agitator and
alkylating agent dispersion member carried by
reaction zone, subjecting the alkylating agent to
saidshaft, a jet carried by said member at a
mechanical impact immediately after dispersion
substantial distance from the axis `of rotation
from said oriiìces and throughout the entire range
thereof, said parts having a passage providing
of rotative movement of said orifices and simul
communication between said hollow shaft and
taneously agitating the reaction mix by internally
said jet, and an impact surface carried by said
recirculating a plural number of different local
member in a position to immediately impact thc
ized portions oi the reaction mix at a relatively
liquid stream of allwlating agent as it is dis
high rate while maintaining the relatively slower ,
liâîziarged from said jet on rotation of said mem
progressive ilow of reaction mix along the length
while moving said orifices at high peripheral speed _
y of said reaction zone.
70
3. The method according to claim 2, -wherein
'the reaction mix containing dispersed alkylating
agent is subjected to indirect refrigerative chilling
closely surrounding the zones of dispersion and
mechanical impact, whereby the heat of reaction 75
r.
8. Continuous alkylation apparatus of the char
acter described, comprising a tank adapted to
confine a reaction zone, a supply line at one end
of said tank 4adapted for introducing liquid or
ganic compound and liquid alkylation catalyst
2,459,636
into said reaction zone, a discharge line at the
opposite end of said tank for the discharge of
reaction products, a central hollow rotary shaft
mounted within said tank, an agitator carried
by said shaft within said tank comprising a disc '
carrying a plurality of agitating-blades about the
~ periphery thereof, together with a plurality of jets
positioned at a substantial distance from the
axis of rotation of said shaft, said shaft and agi~
said hollow shaft; a rotary agitator and alkyi- f
ating agentv dispersion member carried by said
shaft comprising'a disc carrying a plurality of
agitating blades fspaced about the periphery
thereof, a plurality of hollow radial spokes ex
tending outwardly from said‘central hollow shaft
to the periphery of said disc on one side of the
latter, together` with a plurality of jets carried
the outer ends of said hollow spokes adjacent
tator having communicating passages between 10 _ at
the periphery of said disc and immediately in
the space within said hollow shaft and said jets.
Í each said jet being mounted adjacent the pe
riphery of said disc immediately in advance of a
cooperating blade in the direction of rotation of
Said agitator whereby each cooperating blade is
adapted to impact liquid as it is discharged from 15
said jet, means for supplying lliquid alkylating
agent to said hollow shaft, and a refrigeration
coil mounted within said tank and closely sur
. rounding said agitator so as to be positioned be
advance of said .blades in the direction of ro
tation of said agitator and adapted to provide
impact of jetted'liquid by said blades immediately
after discharge from- the said jets.
'
WILLIAM N. FENNEY.
Y REFERENCES >CITED
The following references are of record in the
ñle of this patent: .
tween the circular path' of each said jet and the 20>
UNI/TED STATES PATENTS
wall of said tank, said refrigeration coil being
Number
Name
Date
spaced from the tank wall.
Altshulal‘ et al ____ __ Api'. 15,l 1941
9. In an alkylation reactor ofthe character de- ` ‘ 2,238,802
scribed, having a tank providing a reaction space, 25 2,246,703 ‘ Thiele et al _______ __ June 24, 1941
2,357,607
Ocon et al. _______ _- Sept. 5, 1944
a hollow rotary 'shaft mounted therein, and means
for supplying alkylating agent in liquid phase to
2,379,368
2.419,09? ,
Matuszak _____ -..___ June 26,- 1945
Stratford et al _____ __ Apr. 15, 1947
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