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Патент USA US2403785

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Patented July 9, 1_946
,UNITED „ STATES Pair151151511"k _„oFFlcE
.. . -' land, Mich., asslgnors to TheY Dow Chemical
Company, „Midland Mich.,Y a' 'corporation of
' kMichigan . *i
' Appxiceaonìocteber 7, 194s, serial No. '505,352v ,
16 claims.- (c1. esci-7.671):
for the-productionpf; alkylated benzene deriva-V
tìlled to separate the products.- The icatalyst layer
of the reaction mixture may bereemployed in the
tives by the reaction between yoleflnes andcertain
alkylationreaction, but after being recycled a
number> of`times, it losesV its activity and is dis
_ >This invention concerns an improvedmethod
aromatic> hydrocarbons or halohydrocarbons in
the presence ¿of aluminum'chloride. n The maro
matic compounds. employed as reactants inthe
process have'the general `formula:
5 . cardedjg'.
_ A. plurality _of alkylatedlaromatic products, e. g.
a mixture ofrmono-ethylbenzene and polyethyl
benzenes', is fòrmedfin the reaction. When a
è ¿,
mono-alkyl aromatic compound is> desired as the
product, vthe varomatic»reactant is used in molec
ular excess overthe oleñnein order that the for
mation of such productmay be favored.. However,
wherein X and Y each represents hydrogen, or a
halogen atom, e. g. chlorine Vor bromine, or an
even when using the aromatic reactant in excess,
polyalkylated products are formed in considerable
amount.' Í For instance, in thev manufacture of
ethylbenzene, althoughy from `2 >to 6 molecular
Veqiii'vaatlents ofjbenzene are usually employed per
alkyl radical. Such reactants,` and also the
alkylated reaction products, are members of the
benzene series and, for convenience, may be re
ferred toas “benzene compounds.”
mole~ of ethylene, the yield of ethylbenzene seldom,
reaction of . oleñnes with benzene com
if> ever, exceeds 65> per cent of theoretical" and
pounds `in the presencer of aluminum chloride is
polyethylbenzenes areV formed Y in considerable
well'k'nown andA is applied industrially in the man-`
amount. Thefpolyethylbenzenes may be “cut
1back,” to'ethylbenzene by being- vreacted with ben- '
u_facture of "ethylben'zene ' Í'.lî'he reaction to pro
ducemethylbenzene is usually carried out at at'
zene _inthe presence of aluminum chloride, but
mospheric pressure or >thereabout and at ’tem
this involves extra operations. It is’desirable that
perature's between r50° and '80°`C. in Íthe'pre'sén'ce 25 the proportionof the products which need be cut
of'aÍmin’or, but appreciable, amount of aluminum „ «back be as small as possible.
„,¿Inabonti'nuous'process for the manufacture
chloride as catalyst.v ' The aluminum chloride is
employed in a concentration corresponding to two
of ethylbeñzene under. the usual operating con
per>` cent or moreV of the weight of thebenzene
ditiohsjust described, Vlarge and expensive re
reactant'i. e. in. amount corresponding to kat 30 actors are requiredlin -order to provide ample time
least 0,01 molecular' equivalent of AlCh per mole
forfftheïalkylation reaction while producing the
of benzene, since smaller proportions areineil’ec
productiin thel amounts Írequired and alsoin order
tual under such usual reaction conditions'. ‘Ai
to ‘Í“cut‘l,back” to ethylbenz'enethe considerable
though other reaction temperatures and pressures
amounts -of polyethylbenzehes which are formed.
have in certain instances been tested, the alumi
num chloride catalyst has, insofar as _'we are
aware, always been used in concentrations as high
Also, although the proportion of catalyst present
in the alkylation mixture at any instant may be
quitefsmalLthe total amount of aluminum chlo
as those just mentioned. Usually. a small amount
ride vconsumed per year is large. For purpose of
of hydrogen chloride,v or a compound capable of
economy, and in order Vto'conserve on aluminum
forming the same in situ in the reaction mixture, 40 chloride which,Y atppresent, is availabler in re
is also added as a catalyst promotor.
` .stricted amountaa method' whereby the reaction
During use in the reaction, the aluminum chlo
ride forms an addition compound with other in
catalyst is desired. `
gredients of the mixture. The addition compound,
_ "Itis v`an object of thisinvention to provide an
may becarried’out with smaller'amounts of the
variously known as a “complex catalyst,” a “cat 45 improved Ymethod’of alkylating hydrocarbons or
alyst complex,”V or as a “catalyst sludge,” possesses
halohydrocarbons of the benzener series with ole
a high catalytic activity, but is only sparingly sol
uble in the reaction mixture. Accordingly, in
usua1 practice, the mixture is stirred or otherwise
flnes, whereby .the- proportion of catalyst required
for the reaction ‘may >be reduced below that here
toiore considered necessary and whereby .the re
agitated during the reaction and'is subsequently 50 actionjmaybe carried' out rapidly and continu
permitted to settle into a lower layer of the com
ouslyin apparatus'Vv of vsimple construction. An
plex catalyst and an upperlayer of the alkylated
other object is to v‘provide such methodwhereby
aromatic products. The upper layer is separated
aîÍPlQfiOalkYljaromatìcicompóund may be pro
and treated to remove the small amount of dis
duced idirectly -inilìlnusually,v high‘ yield, relative
served catalyst, after »fpreçuornally c15- 55 _tajine p'òlyàlkylacec products., _A >further object 1s
in continuous manner using apparatus of simple
220° C., may sometimes be used, but are not rec
„ ommended. Under such preferred conditions,
objects will be apparent from the following de- .
scription of theA invention.
We have found- that byA carrying
. "
actor where it is heated to a reaction tempera
ture of at least 90° C. and preferably from 100 to
200° C. Somewhat higher temperatures, e. g.
to provide such method whereby the alkylation
reaction may be carried out smoothly, rapidly and
construction, e. g. a tubular autoclave.
Él ,'Í
the _vallgylation reaction occurs rapidly and is
usually`> complete' in from 5 to 1`5 minutes. The
rate of now through the reactor is preferably such
tion between an’olenne and a benzene compound,
i. e. a hydrocarbon or nuclear halogenated hy,-
, .,
_as to» permit substantially complete consumption
The reaction is carried
~- 'ofV the o-leñne reactant.
drocarbon of the benzene series, at temperatures-
above 90° C~ and under a pressure suñicientto;
outataipressure of at least 300 pounds per square
inch, gauge, preferably from 600 to 1200 pounds
liquefy the mixture, the proportionof catalyst
required for the reaction may 'bereduced great'- .
ly. We have further foundth'at when a mixture
perïsquarefinçh' yorhiglrier, when using ethylene
las 4areacta'rrtf~y In similar reactions involving the
` use of propyleneror higher oleñnes, instead of
ethylene, lower pressures, in some instances as
matic hydrocarbon is reacted under such condi
tions, a monoalkylated` aromaticv 4compoundï isf lowia's50 `pounds per soluarei inch, may be em
of an oleñne and a molecular excess of an aro?"
formed in higher yield, relative to the, poly- . «
alkylated products, than when the reactio‘ri`is"`
carried out under the hereinbefore Vmentioned
usual reaction
o _
ployed.- In any instance, the pressure should be
sufficient to maintain the reaction mixture large
ly in liqueñed form so that the major part, and
preferably"> all, ~- ofi the olefin> is dissolved in the
aiferriatie~i ïreactant." ' The reactor 'employed is
The reaction between an 'clef-lne and 'a ben
preferablyfconstructed of, or lined with, a sub
zene compound may be carried out'batchwise, but
stance resistant to {corrosion'by acids.> An auto
clave lined WithSni'CReL-astainleSs steel, or glass,
is advantageously carried out in continuous man
ner. Similar reaction temperatures and propor
tions of the reactants and catalyst'are employed
regardless of which procedure is followed'.
The accompanying drawing is -a flow sheet
or 'constructed/of one’ lof ‘said metalsr may be
The mixture flowing from the reaction Zone is
cooled, e. g, to below 5_0? C., and is passed through
which indicates a preferred sequence of 'steps
when applying the invention' .forv the manufac l30 a valve for releasing the pressure. The ethyl
ated benzene products may be distilled directly
ture of ethylbenzene in continuous manner.
from the reacted mixturefand the residual cata
lyst> be Areturned _to >the reaction, or the catalyst
may first bre'removed in'any ofthe usual ways,
ln manufacturing 'ethylbenzene‘ in continuous
manner, ethylene andA benzene` are passed under'
pressure into admixture with one another at rel-l
ative rates of ñcw _such that the mixture con
e. g.. rr'íechanically,'` when a portion of the cata
tains a molecular excess, e.> g; from 2-6 molecular
lyst separates -asa distinct‘layer, or by washing4
equivalents, of benzene per mole of the ethylene.
with water oran -aqueous alkali‘solution, or by
adding ammonia v_toformz a precipitate, etc., and
thel ethylated 'benzeney products may thereafter
Prior to l or after admixing the reactants, alumi
num chloride is added in amount corresponding
to less than 1.2, e_ g. from 0.3 to 1.0 and prefer- ` , be separaterl'byÀ distillation.
benzene reactant. In other words, less than
0.007, e. g. from 0.00175 to 0.00584, and prefer-_
ably from 0.00175 to 0.00437, molecular equiva
lent of aluminum chloride (on la Vbasis of> the
formula AlCla) is employed per mole 'of the aro
matic reactant. The aluminum chloride is ad
vantageously added by passing the benzene re
actant, orv the reaction mixture,` through a bed of
granular aluminum chloride :at the rate necessary
to dissolvethe
required amount
chloride ofis catalyst.'
,usuallyv dis
solved by warming the benzene, e. gyto from 30°
to 50° C., and passing'it through suchbed prio-r
to admixing the ethylene therewithfj'
Usually the prod
ucts‘areurecovered in' somewhat higher yields
ably from 0.3 to 0.7,rper cent ofthe weight of the
`, i
The reactants and the catalyst are preferably
employed in as nearly anhydrous condition as
possible. However, a minor amount of moisture,
e. g. an amount corresponding to one or two- per
cent of .the weight 'of the dissolved aluminum
chloride, may be tolerated. Itshould'be men
tioned that in Friedel-Crafts reactionsI between
olefmes and aromatic hydrocarbons, it has here
tofore been usual practice to add a small amount
when ` the catalyst ‘is >removed before distill
the’products. The distillation is ordinarily
carried -out in such manner as to separate the
ethylbenzene from polyethylbenzenes, e. g. dieth
ylbenzene andtriethylbenzene. By operating as
just fdescribed, "'ethylbenzene may be produced
directly in a yield 'of 80 per cent of theoretical or
higher, based~ on the ethylene employed. Also,
ed molecular'equivalents `orgrnore of ethylene
maybe reacted *per mole> of the aluminum chlo
ride' catalyst. ‘e ‘A
f 'The yield' may be further improved by react
` ingjthe polyethylbenzenes with benzene in the
presenceiof 'aluminum chloride to form an added
amount ofethylbenzene. The procedure for car
ryîligout such dealkylation reaction is well known
and need'not. berg-iven in detail. Instead of car
rying. out .the dealkylation y'reaction separately
from the alkylatiònreaction, the polyethylben
Zenes may be returned to the alkylation reaction
where they serve to suppress the further forma
tion'of polyethylbenzenes and to direct’the re
ac't'ion‘to the formation vof ethylbenzene in in
of hydrogen chloride or an alkyl chloride as a
creased yield. f.
catalyst promotor and such “promotor” may, if
„The ,process may, Vif desired, be modiñed in
desired, be added in practice of this invention.
However, the alkylation reaction occurs satis
minum chloride, the complex catalyst sludge from
factorily under the reaction conditions herein
disclosed in the absence of suchadded promotor
and the latter may be omitted. `
“ "
other-_ways.` For instance, in placeof fresh alu
a¿prior'Eriedel-Crafts reaction may be used as
such, orV _in ‘adrnixture with `fresh aluminum chlo
ride,- to E catalyze the reaction. Such catalyst
The mixture of ethylene, benzene and the -calt
sludge is, of. coursefless active than aluminum
alyst is passed at a liquefying pressure, e. a pres
sure suiîicient to -maintain vthe same in liquid
chloride fitseli` 'and' the _ latter is most conven
iently¿¿employed.A - However, when -operating in
the foregoing continuous manner, the reaction
form, throughv a tubular' autoclave or 'other‘rè- i
liquor winlehotye.A g. atico-200° C.; may 'be
therefrom. AThe 'gasesthus vented naa e volume-of
caused to'floWl from `the tubular reactor through'
a'valve for releasing 'the' pressure and into are
tort, or still, where the benzene and~ethylbenzene
are distilled, preferably in" flash manner. Arcon-. 5
approximately fone liter ' at atmospheric pressure
andcontained little;> if any.' ethylene.' The reac
tion >mixture 'was removed from the »bombl and
Washed successively. with water and -with > a dilute»
siderable portion, e. g. one-half or tWo-thirds,:of.
the residual mixture of polyethylbenzenes and
aqueous sodium‘lhydroxide solution to remove the
the complex catalyst may be admixed with the
tilled, whereby there were. obtained 341 grams of
catalyst. » «The mixture was then fractionally dis
ethylene` and benzene reactants and a minor
unreaoted benzene, 268 grams of ethylbenzene and
amount of added aluminum chloride and be re 10 77 grams of polyethylbenzenes (largely diethyl-1
benzene) .f It was found that 153 molecularA equiv
turned together with sujch starting materials to
the reaction. 'I‘he remaining portion of the still
alents of .ethylene had been reacted per mole of
residue is withdrawn fromn the reaction system, in
aluminum chloride (AlCh) employed. ' The yield
of ethylbenzene Was 80 per cent of theoretical,
order to avoid accumulating spent, i. e. deacti
' vated, catalyst in the reaction zone, and is treated 15 based on the ethylene. '
. to‘free the polyethylbenzenesf-‘of the catalyst as
sociated therewith. The' polyeth‘ylbenze’nes` thusv
Example 2
. >vA ¿solution of. 377.65 >kilograms” (483 moles) .of
benzene v¿and .750 grams.(10.6 moles) vof ethyl
recovered Vvmay be Vadmixed> with lthe' Vbenzene
starting material andbe returnedto the‘re‘ac
tion zones.Y The benzene and ethylbenz'ene mix 20 chloride was pumpedunder pressure through a
heatingV coil, whereit was warmed to between 35°
ture oiltairìledY as the distillate in the >Íìash dis-'
and_.45‘? vC., .and thence through a chamber con
tillation operation is fractionally distilled 'to sep-v
-tainingl granular aluminum chloride. .The rate,V
arate the ethylbenzene product".V "The recovered
of flow through said chamber was such that the.
benzene may be reemployed in“ the process.
liquor dissolved 134 grams of aluminum chloride,
For purpose of clarity, vtheinventìon has 'been
Y an amount corresponding to 0.36 per cent of the
.explained with. special reference - to the prepara'
` tionsof ethylbenzenepbutit maybe applied in
weight ofthe benzene. .Ethylene of 94~per cent
purity was fed, underza pressure of .600*'pounds
per square inch, into admixture with the liquor
ethylene 'to ‘benzene over those hereinbefore rec 30 flowing from the above-mentionedV chamber. A
total of 2886 grams (103 moles)l of ethylene (on
ommended, a polyethylb'enzene, e. g.-~diethylben-
producing other alkylatedíbenzene compounds.
For instance, by increasing the 'molecular ratio of
. a basis of the pure compound) was thus added.
zene or triethylbenzene,-may/-be'producedv as a
Since both the ethylene and the jethyl chloride
are capable of reacting to ethylate benzene, the*
principal product. Also, the method‘may be em
ployed in reacting propylene with ethylbenzene to
form isopropyl-ethylbenzene; in reacting propyl
ethyl chloride may be considered as equivalent
to ethylene. Accordingly, the molecular ratio of
benzene to ethylene plusthe ethyl chloride was
ene with benzene to form isopropylbenzene or a
polyisopropylbenzene; inv reacting .butylene with
Y4.62. The solution of ethylene, benzene, ethyl
chloride andaluminumvchloride was-passed un
benzene to form a butylbenzene or a polybutylben- l
zene; in reacting ethylene ~with chlorobenzene to
form> ethyl-chlorobenzene or diethyl-chloroben
40 dera pressure of about 600 pounds per square
zene; in reacting ~ethylene withbromobenzeneto
zene; or in reacting propylene withchlorobenzene .
inch and at a ratelof approximately 3.6 liters per
hour through a nickel tubular autoclave of %
inch internal diameter vand of 600 cubic centi
to form‘isopropyl-chlorobenzene or di-isopropyl- '
meters capacity while heating the autoclave in
form ethyl-bromobenzene Aor diethyl-_bromoben
chlorobenzene; etc. The method ls particularly
an oil bath at 200° C. The contact time, i. e. the
advantageous ' _when employing ethylene or> pro
time required for an infinitesimal portion of the
lpylene as the oleiine reactant.
The following examples describe certain Ways
Vinwhich the principle of the invention hasbeen
reaction liquor toY travel through the autoclave,
was vapproximately 10 minutes.
As the liquor
flowedv from the autoclave it was cooledto ap
applied, but are not to beconstrued as limiting its 50 proximately _room temperature and then passed
through a valvefor releasing the pressure. Ap
proximately 141 liters of unreaoted gas were
Example-1 Y lr‘*
vented from the reacted mixture. The amount
of gas thus vented corresponded to approximate
A stainless-steelbomb of Y 1.7 liters capacity was
charged with 3.12 grams of granular v.alim'linum 55 ly 6 per cent of the volume of the ethylene of 94
chloride and with a solution of 5_ grams of hy
per cent purity which had been used as a start
drogen chloride in 624 grams of substantially an
ing material; hence it was evident that substan
hydrous benzene. Ethylene of 94 per cent purity Y
was then passed into the bomb» until the pres
tially all of the ethylene, had reacted. There
action mixture was washed successively with
sure inside the bomb was 300 pounds per square 60 water and a dilute aqueous sodium hydroxide so
lution and fractionally distilled. There were ob
inch at 20° C. The bomb was thenclosedand
heated, while rotating the same, so that the tem
tained approximately 27.5 kilograms (352 moles)
perature was increased from 20° tov 115° C. in 25
of unreaoted benzene, 10.34 kilograms (97.5
minutes and from 115° to 200° C. in 55 minutes.
moles) of ethylbenzene, and 1.9 kilograrnsof high
The bomb was maintained at 200 C. for20min 65 er boiling products (largely diethylbenzene-to
utes, hence the total time of heating was approx
gether with some triethylbenzene). The yield of
imately 1 hour 40 minutes. During heating the
ethylbenzene was 85.8 per cent of theoretical,
based on the combined amount of ethylene and
vapor pressure inside the rbomb increased in the
first 25-rninute period fromthe initial pressure
ethyl chloride used as starting materials. A to
of 300 pounds per square-- inch at 20° C. to 580Y 70 tal of. 113.5 molecular equivalents of ethylene
and ethyl chloride were reacted per mole of AlCla.
pounds at 115° C. Thereafter thepressure de
creased> to only 180 pounds per similare-inch- at a
Example 3f ’
temperature of 200° C. at the close ofthe heating
period. The bomb was then, cooled to about room
temperature andV unreactedßgases.. were. , rented
Benzene was ethylatedy in continuous manner
by procedure similar to that vdescribed inEXam
ple 2, except that no ethyl chloride or hydrogenv
gaseousole?lne and aluminum chloride'in amount
not exceeding 0.007 of the molecular equivalent
of the aromatic compound, and heating the mix
chloride was added to the reaction mixture;- in
place of benzene alone, a mixture ofapproxi
mately 90 per cent by weight benzene and 10 per
ture at a reaction` temperature above 90° C.
cent diethylbenzene was used asa starting ma
under a pressure sufficient to maintain it in
liquefied form.
terial; and the amount of aluminum chloride
2. In a method of alkylating an aromatic com
dissolved in the reaction mixture corresponded to
pound having the general formula:
1.1 per cent of the combined weight'of the ben
zene and the dîethylbenzene used as'starting ma
terials. The molecular ratio of benzene to the 10
ethylene consumed was approximately 2:4. The
reaction was carried out at a temperature of
200° C. under a maximum pressure of about 550
pounds per square inch. The products were sep
arated as in Eixample 2. The diethylbenzene re
covered from the mixture was slightly less than
wherein X and Y each represents‘a memberof
the group consisting of hydrogen, halogens, and
alkyl radicals, the steps which consist in forming
that initially employed; hence, no diethylbenzene
was formed in the reaction. The ethylated ben
zene products were obtained in the relative pro
portions of 10 molecular equivalents of ethylben
a mixture of said aromatic compound,` an oleiine
20 having not more than three carbon atoms in the
molecule, and aluminum chloride in amount cor
zene to one molecular equivalent of diethylben
zene to only 0.247 molecular equivalent of high»
er boiling material (calculated as being triethyl
Eœample 4
responding to between 0.00175 and 0.00584 of the
molecular equivalent of the aromatic compound,
and heating the mixture 4to a reaction tempera
ture above 90° C. at a superatmospheric pressure
suflìcient to liquefy the mixture.
3. The method as described in claim 2, wherein
the aromatic reactant- is employed in molecular
A stainless-steel bomb of 1.7 liters capacity
was charged with a mixture of 624 grams (S
excess over the oleñne and the reaction tempera
moles) of benzene, 1.1 grams of ethyl chloride
and 1.6 grams (0.012 mole) of aluminum chloride. 30 ture is between about 90° and about 200° C.
4. In a continuous method for alkylating an
Propylene was fed into the bomb under a pres
aromatic compound >having the general formula:
sure of 60 pounds per square inch, gauge, until
the mixture was saturated therewith. The bomb
was closed and heated gradually, while rotating
the same, to 200° C. and then cooled to room 35
temperature, It wasr noted that the mixture
„ig :î
within the bomb was at approximately atmos
pheric pressure, indicating that practically all of
wherein X and Y each represents a member of
the propylene'had been reacted. The bomb was
opened and discharged. The reacted mixture 40 the group consisting of hydrogen, halogens, and
alkyl radicals, the steps of passing said aromatic
was found to weigh 725 grams, indicating that
compound over solid aluminum chloride at a rate
98.3 grams (2.34 moles) of propylene had been
such that between 0.00175 and 0.007 molecular
consumed. The mixture was Washed successive
’ equivalent of aluminum chloride is dissolved per
ly with water and a dilute aqueous sodium> hy
droxide solution, for purpose of removing the 45 mole of the aromatic compound, admixing with
the resultant solution an oleñne having not more
catalyst, and fractionally distilled. There were
than three carbon atoms in the molecule, the
obtained 490 grams (6.28 moles) of unreacted
mixing being carried out under a pressure suf~
benzene, 172 grams (1.43 moles) of isopropylben
?lcient to liquefy the mixture, and passing the
zene, and 63 grams of higher boiling products,
largely di-isopropylbenzene.
The yield of iso
50 mixture through a reaction Zone where it is heat
propylbenzene was 61 per cent of theoretical,
based 0n the propylene. The molecular ratio’ of
propylene consumed to aluminum chloride em»
ployed was 195.
ed to a reaction temperature above 90° C. while
at a pressure suflicient to maintain the same in
atmospheric pressure as it flows from the reac
liquid form.
5. The method as described in claim 4, where
Other modes of applying the principle of the 55 in the aluminum chloride is employed in a pro
portion corresponding to between 0.00175 and
invention may be employed instead of those ex
0.00584 of the molecular equivalent of the aro
plained, change being made as regards the meth
od herein disclosed, provided the step or steps i matic reactant, the reaction mixture is heated to
a reaction temperature between 90° and 200° C.,
stated by any of the following claims or the
equivalent of such stated step or steps be em 60 the reaction mixture is cooled and brought to
tion zone, and an alkylated aromatic product is
separated from the mixture.
tinctlyclaim as our invention:
6. The method as described in claim 4, where
1. In a method of alkylating an aromatic com
65 in the aluminum chloride is employed in a pro
pound having the general formula:
portion corresponding to between 0.00175 and
0.00437 of the molecular equivalent of the aro
matic reactant, the latter is employed in molecu
lar excess over the oleñne, the reaction mixture
70 is heated to a reaction »temperature between 90°
and 200° C. and is cooled and brought to atmos
pheric pressure as it flows from the heating zone,
wherein X and Y each represents a member of
a mono-alkylated aromatic product is separated
the group consisting of hydrogen, halogens and
We therefore particularly point out and dis
alkyl radicals, the steps of forming a lîqueñed
from the mixture, and polyalkylated aromatic
mixture of the> aromatic compound, a normally 75 products are recycledjto the reaction zone.
7. In a continuous method of alkylating an
aromatic compound having the general formula:
wherein X and Y each represents a member of
benzene, the steps of passing benzene over solid
aluminum chloride at a rate such that aluminum
chloride is dissolved in amount corresponding to
between 0.3 and»1.2 per cent of the weight of
the benzene, passing ethylene into the solution
under- a pressure suflicient to liquefy the mixture
which is formed, passing the mixture through
a heating zone where it is heated to a reaction
the group consisting of hydrogen, halogens and
temperature between 90° and 200° C. while under
alkylfradicals, the steps of passing said aromatic 10 Ypressure suiîicient to maintain the same in
compound, together with between 0.00175 and
liqueñed form, cooling the mixture and bringing
0.007 of its molecular equivalent of aluminum
it to atmospheric pressure as it~ flows Yfrom said
chloride, into admixture with less than 0.5 molec
heating zone, and separating an ethylated ben
ular equivalent of a normallyv gaseous oleflne at
zene compound from the mixture.
a pressure such as to liquefy the resultant mix 15
12. In a continuous methodfor manufactur
ture, passing the latter through a reaction zone
ing ethylbenzene, the steps of passing benzene
where it is heated to a reaction temperature
over solid aluminum chloride at a rate such that f
between 90°.and 200° C. While in liquefied form,
aluminum chloride is dissolved in amount cor
cooling the reaction mixture and vbringing it to '
responding to between 0.3 and 0.7 per cent of
atmospheric pressure as it ñows from said zone,
distilling the lower boiling alkylated- aromatic
the weight of the benzene, admixing ethylene
with the resultant solution Lunder a pressure
suñicient to liquefy the mixture and in amount
portion of the residual mixture of complex cat
such that the mixture contains at least 2 molec
alyst and polyalkylated products to the reaction
ular equivalents of benzene per mole the
zone, and while continuing the foregoing opera 25 ethylene, passing the mixture through a reaction
tions introducing aluminum chloride together
zone where it is heated to a reaction tempera
with the reactants and withdrawing complex cat
ture betewen 90° and 200° C. while at a pressure
alyst from the reaction system at rates such that
sufficient to maintain the same in liquefied form,
product from the reaction mixture, returning a ‘ ’
the mixture in the reaction zone contains be
cooling the mixture and bringing it to atmos- '
Y tween 0.00175 and 0.007 molecular equivalent of
pheric pressure while ñowing from said reac
aluminum chloride in the catalyst per mole of
tion zone, and thereafter separating ethylbenzeneY
the aromatic compounds.
from the mixture.
8. In a method of ethylating an aromatic
13. A method, as described in claim 12, where
compound having the general formula:
in a polyethylbenzene product is admixed with
35 ethylene and benzene and returned to the re
action zone.
14.4 A method, as described in claim 12 where- f
in the polyethylbenzene products are admixed
with ethylene and benzene and returned to the
wherein X and Y each represents amember of 40 reaction zone.
. '
the group consisting of hydrogen,_halogens, and15. In a continuous method of ethylating ben
alkyl radicals, the steps of forming a liqueñed
zene, the steps’oi' admixing ethylene, benzene
mixture of the aromatic compound, ethylene and »
_and aluminum chloride in relative proportions
aluminum chloride in amount not exceeding
0.007 of the molecular equivalent of the aromatic
compound, and heating the mixture at a reac- '
tion temperature above 90° C. under a pressure
sufñcient to maintain the mixture for the most
part in liquefied form.
such that the mixture contains at least two
molecular equivalents of benzene per mole of
the ethylene and contains the aluminum chlo
ride in amount corresponding to between 0.3
and 1.0 per cent of the >weight of the benzene,
applying to the mixture suñìcient pressure to
9. In a method of ethylating , benzene, the 50 liquefy the same, passing the'mixture at such
steps of forming a liquefied mixture of ethylene.
ypressure through a reaction zone where it is
benzene, and aluminum chloride in amount cor
responding to between 0.3 and 1.2 per cent of ~
heatedto a reaction temperature between 100°
and 200° C., Vcooling and releasing the pressure .
the Weight of the benzene, heating the mixture
on'the mixture flowing from the reaction zone,
to a reaction temperature between 90° and'200° 55 distilling ‘ethylbenzene from the reacted mix
C. while at a pressure suiiicient to maintain the
ture, and returning a portion of the residual
same largely in liquefled form, and thereafter
mixture of polyethylbenzenes and complex cata
cooling the mixture, releasing the pressure, and
lyst to the reaction zone together with the ben
separating an ethylated benzene product there
zene and ethylene reactants and sufficient added
60 aluminum chloride so that the mixture within
10. In a method of making ethylbenzene, the
the reaction zone contains between 0.00175 and
steps of forming a, liquefied mixture of benzene, ' 0.00584 molecular equivalent of aluminum chlo
ethylene, and aluminum chloride in amount cor
ride in the catalyst per mole of the aromatic com
responding to between 0.3 and 1.0 per cent of the
weight of the benzene, heating the mixture to
a reaction temperature between 90° and 200° C.
while at a pressure suiiicient to maintain the
same largely in liqueñed form, and thereafter
cooling the- mixture, bringing it to atmospheric
pressure and separating ethylbenzene therefrom. 70
11. In a continuous method of4 ethylatin'g`
16. A method’as described in claim 15, where
in the hot reaction .mixture ñowing from the
reaction mixture is passed into a zone of lower
pressure so asY to distill benzene and ethylbenzene
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