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. 17, 1946.
W. N. AXE
2,412,595
PROCESS FOR REACTION OF AROMATIC HYDROCARBONS WITH
NORMALLY GASEOUS UNSATURATED HYDROCARBONS
Filed March 3, 1942l
Patented Dee. 17, rais
42,412,595 A
UNITED STATES v'ln'ßl'rala'l‘ ol-'Flclzf
PROCESS FOR REÁCTIGN 0F AROMATIC HY
DROCARBONS WITH NORMALLY GASEOUS
UNSATURATED HYDROCARBON S
y’
william N. Axe, Bartlesville, om., „signor to
Phillips Petroleum Company, a
Delaware
corporation of
Application March 3, 1942, Serial No. 433,191
9 calma (cl. 26o-611)
l
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2
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have heretofore produced substantial proportions
of the polyalkylated compounds under .conditions
The. present invention relates to a process for
the alkylation of aromatic hydrocarbons. More
speciilcally, it relates to the alkylation of aro
matic hydrocarbons with lowfboiling aliphatic
necessary to produce alkylation.
_
It is an object of this‘inven'tion to provide a
process for the alkylation of aromatic hydro
oleiins. Still more speciilcally, this invention
relates to a process for the alkylation of aromatic
hydrocarbons wherein new and valuable im
provements are made possible through the use
of a novel alkylation catalyst composition.
' carbons with olefins employing a more
selective
catalyst than- has heretofore been known. It is
a further object of this invention to provide an
alkylation process operable at such mild condi- '
The alkylation of aromatic hydrocarbons 10 tions of temperature and pressure that extraordi
nary economy in operation is realized. It is a
' still further object offthis invention to provide
wherein an alkyl, cycloalkyl-„or aralkyl group is
introduced into the aromatic nucleus has long
been 'known and has been practiced under‘a
variety of conditions. Classical alkylation procedures involved the action of alkyl halides or al
cohols on aromatic hydrocarbons in the presence
'
a process' for the alkylation of. aromatic hydro
carbons wherein yields ci' mono-alkylated prod
is "ucts are higher than have previously been ob
of so-called li‘riedel-Crafts catalysts 'including
such materials as- aluminum chloride and.
bromide, ferrie chloride,v and the like. More re
cently, direct use .of olefins instead of the cor
responding alcohols and/or alkyl halides has been
proposed as the said oleiins become more avail
able from sources such as the petroleum industry.
In the alkylatlon of aromatic hydrocarbons
with oleflns, the classical catalysts' have been
employed, often with' so-called activators, to
modify reaction conditions.v Other suggested cat
tainable without anysacriilce ofïconversion ef
ficiency. These and‘other objects and advan
tages will be apparent from _the following `dis
closure.
l
-
"
.~
.
’
.
.
I have now discovered thatl the alkylation of
aromatic compounds such' as benzene audits
homologues
with Y olennic
hydrocarbons
is
smoothly and completely.. catalyzed by~ an ad
dition compound of boron iluoride and ortho
phosphoric acid with such eñlciency that-the
yield of mono-alkylated products may closely ap
proach theoretical proportions at the point .of
complete olefin conversion. While
alysts include analogous salts such as zinc, stannic Y substantiallyutilizing
this reaction may be oper
f
the
process
and titanium chlorides, boron halides, and sul 30
ated
under
a
rather
wide range of mild condi- '
furic acid. Since all these materials are ca
tions and with a variety of both aromatic,’olepable of oleñn polymerization, it has been nec- .
iìnic, and in some cases dioleñnic, compounds
essary to carefully regulate reaction conditions
without
seriously. affecting the yield and/or effl
»in order to maintain alkylation as the predom
ciency, it often comprises the contacting of con
inant reaction. Even with precautions, poor
trolled proportions of aromatic hydrocarbon and
yields based on both oleilns and aromatics, exces
alkylating agent with a liquid boron ñuoride
sive sludge formation, high catalyst consump
ortho-phosphoric .acid catalyst in a manner that
tion, and uncontrolled alkylation have usually
resulted since catalysts active enough to initiate ~ produces substantially complete reactions. The '
alkylation have heretofore lcaused concurrent ' hydrocarbon reaction mixture is either intermit
40 tently or continuously 'separated from the cat
polymerization and poly-alkylation.
alyst, and the alkylate recovered by distillation
For example, with" aluminum chloride, the>
from the excess of aromatic hydrocarbon. Sub
quantities of catalyst required so far exceed nor
sequent fractionation o! the alkylate may be uti
mal catalytic proportions that the catalyst costs
lized to remove minor amounts of polyalkylated
and aluminum chloride sludge formation have
products from the mono-alkylated compound,
been excessive. Also, in the use of sulfuric acid,
and unconverted aromatic compound may be re
only the less' reactive oleñns such as ethylene or
turned to the reaction zone with additional q_uan
propylene can be employed, since polymeriza
tities of alkylating agent;
.
tion is appreciable with high homologues.
A
speciñc
embodiment
of
the
process
is illus
thermor'e, a great part of the4 diihculty in pre
trated
in
the
ilow
diagram
of
the
drawing
which
50
paring mono-alkylated aromatics has resulted
shows an arrangement of process equipment for
from~the diii'erence in the rate and/or ease of
the continuous or semi-continuous alkylation of
alkylation of the original aromatic and the mono-_
an aromatic hydrocarbon with an olefin hydro
alkylated derivative. The latter is apparently so
carbon. „ For the purpose of simplifying the de
much more reactive toward the olefin that con- .
55 tailed description of the flow diagram, it will be
ventional alkylation catalysts and techniques
»ananas
.
Y
-
3
.
assumed that benzene is being alkylated with a
tion to periodically or continuously withdraw
normally = gaseous olefin such as ethylene or
portions of the catalyst in the reaction vessel
propylene, although such simpliñcation- should
'
and to reactivate or replace the withdrawn mate->
-rial with fresh catalyst. This Withdrawal is indi-v
In the drawing, the benzene feed from vessel
cated by line 20 which leads to the supply vessel
not be construed as limitation.
- i
_ I is charged by pump 2 through line 3 to reaction
vessel I.v This reaction vessel is equipped with a »
I 'mechanical means. of agitation -to provide in-~
9.
This latter vessel may also serve ' for the
preparation 'of the catalyst with boron fluoride _
admitted' to prepare and/or .reactivate the cata-' lyst from source 2i and line 22. Also. in some
cases when ~alkylating with ethylene or pro-v
amate contact between the liquid catalyst phase.
» contained therein and the substantially im-.
miscible hydrocarbon phase circulated there
through.- The benzene feed is added inadmixl
pylene containing. Aunreactive diluents. it may
even> be desirable to admit minor amounts of'
ture with controlled’mol proportions of olefin boron -iluoride continuously through line 2_3 to
theroleiin feed stream. Higher oleiins are not
from supply vessel 5. 'I'his latter supply vessel is
illustrated as va pressure tank from which the 15 ordinarily adapted to such a procedure. Instead
olefin may be taken as a gas through- line 6A or
of adding minor> amounts of boron fluoride as
as a liquid through line 6B, and. thence through
such; frequently I ilnd it desirable to pass _the
normallyg'aseous oleiin 'feed entering via line
line] for admixture with the benzene in_line 3.
Alternately, the olefin -may be introduced sep
8 through a body .of-spent catalyst contained in
spent catalyst ,liberates free
arately to the reaction vessel through line 8.
v20
unit
boron8Aiiuoride'there~
whereby
.
The alkylation reaction occurring in vessel 4 is
>When phosphoric acid is used to scrub'boron
timed for suitable conversion of the oleñn during
iiuoride- from" gases issuing-from the reaction
contact with catalyst supplied from vessel 9, pump I0 (or the equivalent). and line II. A partial
vessel, this scrubbing liquid may be recirculated .
gravity separation between hydrocarbon and
repeatedly. as through line ISA. until conslder- A «
catalyst may thus be obtained in the upper por
able amounts'` of boron iiuoride are absorbed.
hydrocarbon phase is withdrawn through/a take
vThis partially prepared .catalyst may then be ’
placed in the catalyst preparation vessel and ~
oil' line I2. _ 'I'his line which may embody a liquid
boron fluorideadded to vcomplete thev catalyst
_" level control device is located along the vertical
preparation according to the following ‘descrip
tion. -To this end. the phosphoric acid which
' -tion of vessel 4 after the agitation period and the
axis of the reactor in accordance with the iiow --
passes from scrubber >IB through line I8 may be
passed through line ISB to supply vessel 8.
rate of hydrocarbons and the time required for
reaction. - The liquid withdrawn through line
The . boron fluoride-orthof-phosphoric acid
I2 passes to separator I3 for separation and re
moval of .suspended catalyst through line Il to 35 .catalyst of this -invention is prepared by adding
supply vessel 9. Any'gas issuing from vessel 4, _
gaseous boron ñuoride to the acid; or aqueous
lsolutions thereof. The-resulting reaction is ex
such as unreacted components of the oleñn feed,
as where a normally gaseous oleiin such as
othermic, and the` rate of BF: addition is usually
controlled, together with externalcooling of the ' l
ethylene or butadiene is the alkylating oleñn.
addition product, to lavoid temperatures much
' 4passes through line I5 to scrubber I8 wherein the
gas is scrubbed with a selective solvent for boron
ñuoride which may be present in minor amounts:
above about 200° F. which may 4prolong -the
preparation. Saturation of the acid and comple
therein due to mechanical loss, decomposition of
tion of the preparation is denoted by escaping .
catalyst complex by saturated components of
the oleiln feed. etc. This solvent is conveniently
phosphoric acid similar to that used in prepar
` The exact mechanism of the addition reaction
and/o1` the formulas of the _compounds formed
in the preparation ofthe catalyst are not always
ing the original catalyst, and-may iiowas shown
known, but it is fairly'well established that two-`
a through line I'I, scrubber I6, and line I9 to be
used as described hereinafter. ' The scrubbed gas
reactions occur. One is the formation of boron
then is vented through pressure control valve I8 50 fluoride hydrate with any water -present with the
ortho-phosphoric acid: the other is the formation
which lmaintains the desired pressure inÍ the
òf an addition compound of boron fluoride and
system. '
ortho-phosphoric acid containing approximately
The alkylate, substantially free of suspended'
equi-molecular proportions of each. For ex
catalyst, is next washed in vessel 24 with a
reagent which removes any dissolved boron 65 ample, when using 85 per cent acid. the amount
of boron fluoride absorbed corresponds to forma-'iiuoride _Water is most satisfactory for this pur
pose and may iiow as shown through line 25 into
tion of the BF'3.II3PO4 addition compound'plus
e
suihcient boron fluoride -to form a hydrate with
15 weight per cent of water present. At satura
the scrubber and out through line 26. Entrained
washing liquid and tracesl of acidic components
in the alkylate leaving vessel 25 may be removed
by percolation over an alkaline coagulating
hydrate represents an HzOzBF: mol ratio of ì '
and/or dehydrating material in vessel 21. The
washed liquid is then fractionated in column
I The ortho-_phosphoric acid employed may be
tion under the above-mentioned conditions, this
slightly over 1:1.
«
‘
'
f
_
the concentrated acid ranging from the 85 per
' 28, wherein unalkylated benzene is taken -over
head and returned by line 29 to storage vessel I.; 65 cent acid of commercial grade up to about 100
per cent H;¢PO4l Or, aqueous solutions contain
The total allwlate is removed by line 30 and may
ing as little as 20’to 40 per cent `HsPOi may be
be utilized as the~ ilnal product when taken
` employed.` For most applications, a moderately
through line 3| to storage vessel 32. Alternately,
concentrated to concentrated acid (i. e. from
' _ substantially pure mono-alkylate may be obtained
by fractionation of the total alkylate in column
33, with the mono-alkylate being taken overhead
through line 34 vto storage 35, and the bottoms
comprising `poly-alkylated products vbeing re
moved through line 36 to storage 31.
It may be desirable, also, in this type of opera- -
7.o
about '10% to about 100% H3P04) is preferred
since such preparations show greater activity
` over longer periods than those containihg larger
proportions of boron 'ñuoride hydrate and
'smaller proportions of the' HzPO4 addition com
u.
pound.
.
,
»
.
6
5
In .the preparation of mono-alkylated com-‘_
tive ingredient ofthe catalyst, although it may
pounds, it is desirable to operate with an excess
1 promote and/or cooperate in the activity of he
of the aromatic feedin'order to reduce the olefin- '
BFa.HaPO4 complex >in some obscure fashion. l
concentrationl and the probability of reaction’ of
volefin withmono-alkylate." Thus inthe prior art,
in order to obtain fair yields of mono-alkylate,
Thus, boron ñuoride hydrate te which _phosphoric
acid has been added (regardless of the propor- .
tions) -is relatively inactive and does not exhibit
the qualities of the catalyst prepared accord> .g
huge excesses of the aromatic -compound have
10 been employed in the reaction mixture and thus
to this invention. Similarly,lwhen an active cat
handled'through the entireA system of process
alyst of my preferred composition loses appreci
able 'quantities of boron ñuoride during use, it
equipment. 'With the catalyst'vof the present in
vention' high yields of mono-alkylate are ob
`
tained withonly a moderate excess of aromatic
compound in the reaction vessel. Thus, it is
The addition of a slight excess of phosphoric
acid to a. normally active catalyst results in a con
dition approximating spent catalyst.
On
usually preferred to maintain minimum benzene
the -
propyleneA ratios of at about 1.5:1 in order to ob
other hand, -addition of boron fluoride hydrate to
_tain maximum yields offisopropylbenzene. With '
an' active catalystdoes not-materially impair its
lower ratios in th'e‘neighborhood of 1:-1, the yield
activity. From this evidence it may be deduced
20 of monoalkylate may be somewhat decreased
that decompositionof the phosphoric acid com
plex- (BFs.H3PO4) is the primary reaction con
while higher ratios above about 4:1 are of littlebenefit since the results are no better and operat
trolling catalyst life; and this complex is there
fore the essential ingredient of the catalyst com
position;
;
»
,
,
.
ing costs are greatly increased.
The temperature in the reaction zone is also l
chosen in conformity with the nature of the re
actants and the desired products. In order to
control the rate of alkylation and maintain high
yield of mono-alkylate, temperatures are usually
employed withinthe range of from about'40‘? to
about 200° F. with a narrower range of about 80°..
to about 120° F. often preferred for reactions em-l
.
Asa consequence, my preferred ,catalysts do not
reach maximum activity until lthephosphoric acid
solution is saturated with b'oron fluoride. "I'hus,
it will be apparent that >from the standpoint of
both the catalyst cost and activity, it is more eili
cient to employ concentrated acid solutions to de
crease~ the ~quantity of the> boron fluoride con- ,
sumed in hydrate formation. -On the other hand,
95 to A100 lper cent phosphoric acid is relatively
expensive and tends to solidify lat moderately low
temperatures so that 70 to 90 per cent concentra
ploying ethylene and propylene as the alkylating
agents. Since the alkylationisan exothermic re
action, means are ordinarily provided to' removel
35 any excess heat of reaction.
tions are often preferred. - However, after addition
,
~
.
Such means may
-include water >cooling-of the reaction' vessel-or
equivalent heat transfer methods. In many cases,
it is convenient to carefully regulate the rate of
.of boron fluoride, the finished catalyst is a heavy
liquid vwhich shows no tendency to solidify at
temperatures as low-as _40° F.
considera-_ -
tions.
tablished thatthe hydrate is not the principal ac
becomes less active,
.
determined by the following general
In this connection, ithas been definitely es
cooling so that the heat of reaction at kanyde- _
~
.It has also been established that a mineral aci
40
is not in itself responsible for the peculiar alkyiat
ing activityof the catalyst compositicmsince sub
sired rate .of reactant feed is suil‘lcient to main
' tain the temperature of the rreaction zone-within .
a preferred range.y
,
, Y
„ A,
`
Pressures are chosen in accordance with reac
stitution of other mineral acids produces catalysts Y
tion requirements involving the relative ease and'
of greatly different characteristics. This is par-- 45 rate of alkylation, and are usually about atmos
ticularly true of sulfuric acid which, although pre
pheric or low superatmospheric pressure between
viously employed alone as an alkylation catalyst,
zero and 100 pounds gage, With the catalyst com- ‘ '
vwhen saturated with boron fluoride or mixed with
boron fluoride hydrate does not produce a catalyst'
comparable to my preferred composition. This.
latter circumstance is apparently due to the fact
positions of the present invention, high pressures
' are not required.
The only function served by
elevated pressures is the increased concentration
of olefin in the reaction zone.
Even ethylene, '
that sulfuric acid does not form a boron fluoride
which is the most refractory of -oleiins, has been
addition complex as does phosphoric acid, and the
catalysts, therefore, do not have analogous com
positions or properties. The sulfuric`acid-boron
fluoride hydrate catalyst thus exhibits only a
somewhat modified composite of the properties of
the two ingredients, whereas the catalysts of the
present invention exhibit entirely new properties
used to alkylate benzene with a satisfactory reac
tion velocity at atmospheric pressure in the pres
ence of my preferred catalyst. In most cases,
since- the unrestricted passage of vapors through
the reaction zone is eventually detrimental to the
catalyst, gaseous oleiins such as ethylene or‘pro
resulting from the new chemical compositions
formed from the ingredients.
-
‘v
The reaction conditions most favorable for the
process of this invention depend to a large extent
on the nature of the reactants and the- desired
product.
The conditions of flow rate, tempera- -
ture, -and mol proportions of reactants may be
somewhat different‘when using ethylene or pro
pylene than when using higher oleñns such as
. butylenes, pentenes or the cyclic oleñns winch may
exhibit appreciable differences in reactivity. Also, -
more careful control of contact time and olefin
concentration must be exercised when preparing
mono-alkyiates of the more reactive aromatic`
compounds. Therefore, the specific conditions for
each particular application will be influenced or
pylene are added at such a rate thatsubstan
tially complete reaction of the olefin occurs, or the
pressure may be regulated to -provide maximum
olefin concentrations as dictated by the chosen
aromatic-olefin mol ratio.
_
The alkylating agents which may be employed
in the present invention include the aliphatic
and cyclo-aliphatic oleiins such as ethylene, pro
pylene, butylenes, pentenes, etc., and cyclopro-l
p‘ene, cyclobutene, cyclopentene. cyclohexene> and
other alkyl-substituted cyclo-oleñns. These com
pounds may be employed in substantially pure
form or in mixtures with corresponding paraflins
or substantially inert fluids. Mixtures of two or
more oleiins may be used if the alkylated prod-`
ucts are~to be utilized as the corresponding mix
tures and/or segregated by fractionation. A1
2,412,595
7
8
.
difference in specific gravity of the two liquid
kylation may also be performed with dioleñns
such as butadiene, to produce the corresponding
alkenyl benzene. However, since these products
phases.
'
The catalyst of this invention may be employed
over extremely long periods to alkylate large‘vol
urnes of aromatic compounds without appreciable
loss of activity, particularly when employing eth
are unsaturated, diolefins are ordinarily removed
from olefin feed stocks prior to their use in the
manufacture of alkyl benzenes.
ylene or propylene as the alkylating agent. ' With
` When. the olefin feed contains appreciable
higher olefìns which gradually form alkyl deriva
amounts of unreactive components such as ethane
tives of the catalyst or polymers. there is a slow
less but substantially inert gases, the passage of 10 loss of activity which may eventually require re
placement of the catalyst after .treatment of
the gas through the catalyst hydrocarbon mix
' in ethylene, propane in propylene or other harm
about 50 to 200 or more volumes of hydrocarbon
ture may result in the evolution of minor amounts
of boron fluoride from the catalyst. These gases,
however, may be scrubbed free of boron fluoride
per volume of catalyst. With ethylene gas as the
alkylating agent, or with propylene or butylene
containing unreactive components, the pre
with phosphoric acid, or evenwith portions of 15 gases
viously mentioned devices for replacement of
the catalyst composition from which the boron
minor losses of boron fluoride are substantially
fluoride was evolved and loss from the system
the
sole measures necessary to obtain extremely
thus prevented._ Usually this removal of boron
long catalyst life. This feature is in direct con
fluoride is so gradual that the loss of catalyst
trast to the behavior of such4 catalysts as alumi
activity is negligible over long periods of opera'
num halides, sulfuric acid, and the; like which
tions, and the recovery and regeneration meth
must be used in relatively large quantities and
ods illustrated previously adequately'provide for
which rapidly deteriorate into inactive sludges
retention of substantially all boron fluoride with
with consequent losses of both catalyst and re-the exception of traces dissolved in the outgoing
stream of liquid hydrocarbons.
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25
actant.
-
Under the most favorable conditions for mono
For the preparation of the preferred mono
alkylate production, the present process is capa
valkylated aromatics, benzene or a similarly un
ble of producing very high yields of mono-alkyl
substituted aromatic compound is,A of course, a
ated
aromatics. Thus, mono-alkylate yields
necessary starting material. Derivatives of sub
based on the total alkylate produced may _range
Astituted benzenes, for example, may also be pre 30 from about 80 to 98 per cent. Even without elab
pared when poly-alkylated compounds are~ de
sired.~ _In the latter case, the selectivity of the
catalyst in restricting the extent of alkylation
is somewhat decreased due to the effect of the
alkyl substituent already present but the reaction
is still highly efficient.
orate contro1 methods, poly-alkylated products
35
As indicated above, the alkylation may be car
. ried out with the liquid aromatic hydrocarbon
serving as the reaction medium since the con
seldom amount to morethan 15 to 20 per cent of
the total alkylate when employing the lower ali
phatic oleñns as alkylating agents. This feature
is again in direct contrast to processes using sul
furie -acid and other less selective catalysts which
may produce alkylate mixtures containing _no
more than 30 to 50 per cent of mono-alkylate
along with large amounts of compounds repre
centration of olefin alkylating agent is effectively 40 senting the maximum extent of substitution in
controlled ahead of the reaction zone. ' -Alter-'
nately, the aromatic hydrocarbon may be mixed
with and/or dissolved in a suitable inert liquid
solvent such as the paraffin or cycloparaflin hy
drocarbons of five to eight or more carbon atoms.
Thisarrangement is of _particular importance
when operating at temperatures-such that the
aromatic~ hydrocarbon is a solid, since it allows `
the aromatic nucleus.
_
-
'
.»
_ However, the above-mentionedspecial quali
ties of the boron ñuorlde-ortho-phosphoric acid
catalyst do not preclude poly-alkylate formation
when the production of poly-'substituted aromat
ics is desired. With proper adjustment of the
aromatic-oleñn mol ratio, and corresponding ob
vious _revision of reaction conditions, high yields
dispersion and satisfactory alkylation of the solid 50 of di- and tri-alkylated aromatics may be ob
compound in a solvent which simultaneouslyl
servesas a solvent for the olefin alkylating agent.
The quantity of catalyst required to promote
the alkylation reaction under the conditions out
tained with efficient operation and excellent
lined is dependent on such factors as the -efii
the process of this invention and the improved
results obtainable thereby. However, since the
examples and the possible modiñcations could be
multiplied indefinitely, no limitation is intended.
ciency of agitating or- contacting devices and
the reactivity of the olefin alkylating agent. In
some instances, as little as one volume of catalyst
in 10. to 20 or more volumes of the hydrocarbon
catalyst life. y
The following-exemplary operations will serve '
to illustrate specific procedures in carrying out
Example 1
phase may be satisfactory, while in other reac~
tions this volume ratio may be as high as 1:1.
In a batch-type operation, a _reaction flask
With extremely large volumes of catalyst present
fitted with a mechanical stirrer was charged with.
in the reaction zone, oleñns such as butenes, pen-four mols of benzene and 50 ml. of catalyst pre
tenes, and the higher homologues may be dis
pared by saturating 85 per cent ortho-phosphoric
solved in the catalyst to a limited extent and con 65 acid with boron fluoride. While the mixture was
sumed in side reactions such as polymerization.
agitated to maintain the catalyst in suspension,
gaseous propylene was introduced at substantially
esterification, and the- like, so that such mixture
proportions are usually avoided. The boron flu
atmospheric pressure and a rate of about 0.4 mol `
_ oride-phosphoric acid catalysts exhibit very slight
per hour. The reaction flask was maintained at
mutual solubility with hydrocarbons, and sep 70 a temperature of 80 to 85° F. and the propylene
aratlo? of the catalyst at any stage of the proc
was almost completely reacted. After about 3.5
ess out of the zone of mixing or agitation is con
mols of propylene were added, the reaction was
veniently effected by gravity separation from
stopped, and the hydrocarbons separated from
the lighter hydrocarbon phase. The rapidity of
the catalyst. On distillation, slightly over 0.5 mol
such separation is greatly promoted by the great 75 of unreacted benzene w-as recovered, and the
2,412,595
9
benzene.
~
‘
with Vethylene was carried out at 85 to 95° F. and
‘
substantially atmospheric pressure. The average
Inv similar experiments under substantially
identical conditions,.catalysts prepared from 60,
mol ratio of» benzene to ethylene was 2:1 and
ethylene 'conversion was over 80 per cent per
92, and 98 per cent H3PO4 were utilized. The first
produced a totalralkylate containing 85 per cent
pass. The catalyst withdrawn in suspension in
~ the eñluent liquid was re-saturated with boron
isopropylbenzene. _The second and third catalysts
produced alkylate containing 82 per cent vot the
mono-alkylate.
-
>fluoride prior to- its return to the reaction zone
so that there Was no appreciable loss of activity.
»
Fractionation of the total alkylate produced over
90 per cent of ethyl benzene.
When 85 per cent sulfuric acid was used instead
of phosphoric acid under identical conditions,
the yield of isopropylbenzene was only about 60
’V Example 6
per cent of the total alkylate, and a large pro
portion of the propylene passed through the re
action .zone unreacted.
-
'Example 2
'
Benzene was alkylated with propylene in a
continuous. operation wherein a mixture of _
benzene and propylene in a mol ratio about 4:1 20
was passed through a reaction zone containing
The hydrocarbon effluent
The
-
catalyst -activity.
rated and fractionated. The yield of monobutyl
benzenes '(iso- and tertiary) was 50 per cent of
the alkylate, indicating a more rapidproduction
30 of higher alkylate with the more reactive isq
-The hydrocarbon eiiiuent was fractionated to
recover unreacted benzene, and the alkylate was
'- then fractionated to separate mono-,and di-iso--
butylene and/or di-isobutylene. No ‘isobutylene
polymers were formed.
propylbenzene. The niono-alliylate` was about
95/per- cent and the di-alkylate about ñve per 35
~ cent of the total.
Inga similarv experiment with a benzene
-propylene ratio of 1.511, the yield of isopropyl
Y.
n
v
,
y
Example
A mixture of 4.5 mols of benzene and 100 ml.
l of BFa-HaPOi catalyst made’from 85 per cent
acid was stirred in a reaction vessel while about
four mols of ethylene were passed in at a pres-`
' sure about one pound gage.
The reaction tem
perature ranged from about 85 to about 100° F.
varying with the ethylene absorption rate. The
`
'
of benzene and BFa-HaPO4 catalyst. Two mols of
producing an alkylate containing 80 percent of
40
3
`
Example 8
Benzene was alkylated with pentene-2 by "add
ing the liquid.v oleñn dropwise to a stirred mixture
- pentene were thus added to three mols of benzene,
, ì benzene was 92 per cent of the alkylated products.
_
Example 7 .
was halted and the alkylated products'were sepa
was settled free of entrained catalyst, and the
latter was returned to the reaction zone.
total alkylate.
to 84° Rand atmospheric pressure. After four
mols of isobutylene had been added.’ the reaction
substantially-_ completely reacted at a tempera
- reaction proceeded for 32 hours with no loss of
Butene-2 vapor was passed into a mixture of
two mols of benzene with 50ml. of BFa-HsPOr
catalyst until one mol of olefin had been ab
sorbed. The temperature was 85 to 90° F. The
yield of sec-butyl benzene was 85 per cent of the
Isobutylene was passed into 'a mixture of four
mols of benzene and 50 ml. of catalyst prepared
from 85 per cent H-sPOi at a temperature of 80
50 ml. of catalyst prepared from 85 per cent
H3PO4 and BFa. The flow rate was about two
mols of mixture perhour, and the propylene was
' ture of` 80 to 90° F.
l0
vscribed in Example 2, the alkylation of benzene
total alkylate contained 88 per cent of isopropyl
Z-phenylpentane.
'
`
v
,Y
n
f
Example
'
I
9
Naphthalene was dissolved in cyclohexane and
stirred with BFa-HsPO4 catalyst while propylene
was passed into the mixture at 85 to 90° F.
Almost theoretical conversion to isopropylnaph
thalene was obtained;
'
Example 10
reaction was halted when sufficient ethylene had
been absorbed to convert over` ’10 per cent of the 50
Two mols of butadiene vapor were passed at 'a
benzene. The liquid products were withdrawn,
moderate flow rate into a mixture of four mols
washed andv fractionated to remove unreacted
of benzene and 50 ml. of BF3-HaPO4 catalyst at
benzene, and the alkylated products were frac
85 to 88° F. The benzene-alkylate solution
'. tionated to separate ethylbenzene from the poly
yielded over 80 per cent of phenylbutenes boiling
alkylated benzenes. The ethylbenzene was 85
between 355 and 365° F. No butadiene polymers
per cent of the total alkylate, and the remainder
were identiñed in the products.
The small amount of gas escaping from the
reaction flask was scrubbed with- 85 per cent
While the foregoing descriptive matter and
examples have been relatively speciñc for the
purpose of illustrating the novelty and important
- was di-ethylbenzene.
phosphoric acid, and several grams of boron
. improvements of the present invention, numerous
fluoride were recovered. The catalyst was again
saturated with boron ñuoride andrestored to its
modiiications and alternative operations will be
original activity.
scope of my disclosure.
'
Example 4
apparent and, therefore, are considered within the
No limitations are im
plied except as recited in the following claims.
I claim:
'
The operation to Example 3 was repeated 65
l. A process for the alkylation of 'benzene with
'under identical conditions except that the pres
ethylene which comprises passing a major pro
sure was raised to 100 pounds gage. Three mols
portion of benzene and a minor proportion of
of ethylene were added to the benzene-catalyst
ethylene at a temperature in the range of about
mixture, at a rate corresponding to substantially
complete reaction.v The total alkylate contained 70 80° F. to about 120° F. and at a pressure in the
range of zero to about 100 pounds gage into inti
about '15 per cent of ethylbenzene and over 20
mate contact with a catalyst comprising essen
per cent of di-ethylbenzene.
tially the addition compound of boron fluoride
Example 5
and ortho-phosphoric acid and prepared by sat
In a continuous operation similar to that de .75 urating concentrated ortho-phosphoric acid with
2,412,595
11
12
boron fluoride, whereby alkylation occurs to form
‘
6. The process of claim 4 wherein said normally
Pthylbenzenes, continuously withdrawing liquid
gaseous unsaturated hydrocarbon is propylene.
and gaseous eiiiuents from the reaction zone,
'1. The process of claim 4 wherein said normally
gaseous unsaturated hydrocarbon is butadiene.
8. A process for reacting a low-boiling aromatic
hydrocarbon with a low-boiling unsaturated hy
drocarbon, which comprises contacting in a reac
scrubbing the gaseous eñiuent with phosphoric
acid to recover boron fluoride, separating en
trained catalyst from the liquid eiiiuent for re
' turn to the reaction zone, fractionating the liquid
hydrocarbons to separate unreacted benzene
tion zone a mixture comprising such hydrocar
which is returned to the reaction zone with fur
bons, and containing a molar excess of said aro
ther amounts of ethylene, and iinally fraction
ating- the ethyibenzenes to recover a major pro
portion of mono-_ethylbenzeneand a minor pro-'
portion of di-ethylbenzene.
10 matic hydrocarbon, under reaction conditions
with a liquid catalyst comprising essentially an
addition compound of boron fluoride and ortho
‘ phosphoric acid, intimately admixinghydrocar
2. A process as in claim 1 wherein the catalyst
is re-saturated with boron iiuoride _prior to re
cycling to the reaction zone.
bons effluent from said reaction zone with ortho
phosphoric acid to remove minor quantities of
boron iiuoride associated therewith, separating
3. A process as in claim 1 wherein an amount
of boron iiuoride substantially equivalent to that
withdrawn with the gaseous eiiiuent is added with
the ethylene feed.
4. A process for the reaction of aromatic hydro
carbons with normally gaseous unsaturated hy
drocarbons which comprises the simultaneous
contacting of said hydrocarbons with a catalyst
comprising the addition compound of boron fluo- -
ride with ortho-phosphoric acid, in a reaction
zone, removing from said reaction zone a gaseous
from said admixing a material comprising ortho
phosphoric acid and a resulting complex of
ortho-phosphoric acid and boron fluoride and
adding thereto .additional quantities of boron ~
iiuoride to effect substantially complete satura
tion, and passing the resulting material‘to said
reaction zone as catalyst.
9. A process for the alkylation of benzene with
ethylene which comprises passing a major pro
portion of benzene and a minor proportion of
ethylene at a temperature in the range of about
mixture comprising unreacted normally' gaseous
80° F. to about 120° F. and at a pressure in the
unsaturated hydrocarbon and minor'amounts of
range of zero to about 100 poundsgage into inti
boron fluoride, scrubbing said gaseous mixture 30 mate contact with a catalyst comprising essen
with ortho-phosphoric acid to remove said. boron
tially the additioncompound of boron iiuoride
iiuoride therefrom and convert said ortho-phos
and orthophosphoric acid and prepared by sat
phoric acid to an addition compound with said
urating concentrated orthophosphoric acid with
boron iiuoride, adding boron ñuoride thereto as
boron iiuoride, whereby alkylation occurs to form _
necessary to saturation therewith, and using the 35 ethylbenzenes, continuously withdrawing liquidresultingmaterial as catalyst in said contacting " and gaseous eiiiuents from the reaction zone, and
scrubbing said gaseous eiiiuents with orthophos
5. The process of claim 4 wherein said normally
phoric acid to recover boron ñuoride.
, gaseous unsaturated hydrocarbon is ethylene.
WILLIAM N. AXE.
step.
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