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Патент USA US2404536

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Patented July 23, 1946
Louis Schmerling and Vladimir N._ Ipatieff, Chi
cago, Ill., a'ss‘ignors‘to Universal Oil Products
Company, Chicago, 111., a corporation of Dela
‘ No'Drawing. Application June 13,1942,
Serial No.446,930
6Claims. (01. 260-6717 W
I weight 7from that of acetic ‘acid up to those
This invention relates to catalytic processes
having the molecular weight of stearic acid or
involving the addition of alkyl substituent groups
to hydrocarbons. The invention is speci?cally ,even higher; Among the metal halides the most
generally utilizable compound is aluminum
concerned with the use of new types of cata
chloride althoughthe other halides of aluminum
lysts for increasing the rates of reaction between
aromatic hydrocarbons which are to be alkylated ~ and particularly the bromide are usable and also
the halides and particularly the'chlorides of zinc,
' and the compounds servingas thesource of the
iron, and'zirconium. fWhile the inventiongen
alkyl groups.
erally contemplates the .use of catalysts produced.
It is recognized that the alkylation of aromatic
by interacting one acid or its anhydride with a
single metal halide, catalysts may be produced
and para?inic hydrocarbons has already been
accomplished by the useof various types of catad
lysts such as‘, for example, mineral acids in
cluding sulfuric and phosphoric acids and 'metal
halide catalysts of the Friedel-Crafts' type.
Both mono- and poly-nuclear aromatics have 15
been alkylated directly with ole?ns or with com-- ‘
by reacting more than one acid with one metal
halide “or one acid with more than one metal
halide. The composite catalysts thus produced
have'been found to possess generally high activ
ity in processes involving the selective alkylation
of aromatics with ole?ns with reduced tendencies
in the direction of ole?n polymerization and'in
and esters. The catalysts which form the essen
tial subject matter of the present invention are > ' the direction of forming “metal halide-‘hydro
capable of being applied to substantially all of ‘20 carbon complexes‘the' ‘presence "of which has a
these'types' of alkylation reactions although ob—. " ‘tendency "to lower the catalytic activity below
that of- the ‘original ‘catalyst. It is generally
viously the diiferentcaitalysts will have different
‘ preferable in ‘conducting alkylation reactions in
, degrees of effectiveness in a given alkylation re
accordance with the present invention to vem
action " involving, on the one hand, particular
aromatics and mixtures of such hydrocarbons .25 ploy molar excesses of'aromatic hydrocarbon at
all times and to conduct‘ the reactions in the
and, on the ‘other hand, the different compounds
presence of minor amounts of a hydrogen halide.
which ‘serve as sources of the alkyl groups. The
When an aliphatic acid is reacted with a
present invention is concerned with processes‘ in
metal halide catalyst of the Friedel-Crafts type,
which aromatic hydrocarbons are alkylatedj' in
the presence of modi?ed catalysts of ‘the Friedel 30 a series of reactions apparently takes place 'de
pending upon the molal equivalents of the metal
Crafts type which possesses the general‘ advan
halide ‘employed in respect to the acid. In the
tage of having a lower tendency toward the
case .of the interaction, of acetic anhydride, for
formation of hydrocarbon-metal halide ' com
example, with aluminum chloride, the ?rst mole
plexes of generally inferior catalytic activity. ‘
of aluminum chloride evidently forms acetyl
In one speci?c embodiment the ‘present- in
. chloride and a complex according to the follow
vention comprises a process for the introduction
ing equation:
of alkyl substituent groups into the nucleus of
pounds which yield alkyl groups such as alcohols
aromatic hydrocarbons which consists in con
tacting aromatic hydrocarbons and compounds
serving as a source of said alkyl groups in the
0 + A101; 2 omc0o1+ omooolucig '
presence of catalyst composites formed by inter
acting aliphatic carboxylic acids-or their cor
responding anhydrides with metal halide cata
Acetic anhygdride
Acetyl chloride “ Complex lysts of the Friedel-C'rafts type.
We have found that catalysts having activity 45'. When another mole of aluminum chloride is
in promoting the alkylation of aromatic hydro
added, there is a formation of'a'complex with
carbons may be formed by interacting different
the acetyl'chlo'ride which apparently ‘proceeds
aliphatic carboxylic acids ; andv certain metal
according to the following equation:
halide catalysts of' the Friedel-C'rafts type. By
choosing different acids of the broad class men
tioned and interacting them with different‘ rep
_ CHaOQCl + A1015
resentatives of the metal halide group, a large
number of alternatively utilizable catalysts can
when a third mole of aluminum chloride is added
the primary complex shown in the ?rst equation
be manufactured although their > activity in
di?erent alkylation reactions will vary‘ over a
. is converted into an acylating complex.‘
considerable range. - While the catalysts may be
analogous interactions between other acids
55 “orBy
anhydrides'of aliphatic acids and other Fried
el-Crafts" metal halides, similar'reaction prod
formed by interacting either the acids them
selves or their anhydrides, advantages arelfre
ucts are formed which have been found to have
quently gained by using the anhydrides‘rather
than the acids, which may vary in molecular
applicability to increasing the rate of the alkyla
tion of aromatic hydrocarbons ‘with olefins and
other compounds capable of supplying alkylsglo
trchlloridea ‘Thus, 65 parts‘ by weight git-?nely di
vided isubstanti‘ally anhydrous
stituent “groups.” The activity of the'ccimposites
ride was prepared and to the powdered material
increases generally as the amount of metal halide
'50 parts by weight of acetic anhydride were
increases but, if this increase goes beyond a o'er-,1v
tain de?nite point, the compositesvbeglm?tg £14519; V '5 added andlthe mass thoroughly mixed. The evo
y'l chloride was noted and mixing
tion as the metal halides themselves and beyond 7,
this the advantages inherent in “the ‘use of ‘*tli'e -
"continued while the tempera- < V
complex may be lost.
The present types of‘cataly'st‘s are ‘isr‘iér‘ér‘iibit‘
ed to 60° C.
The composite ma
‘te‘rialthiis produced was readily reduced to a
made by thoroughly and quicklyllmixingtan acid 10 {?‘nelydivided powder by grinding in the absence
anhydride and a metal halide‘siichias all'?iii'
L'2‘Djparts by Weight of the catalyst powder thus
chloride at a, relatively low temperature at wqhrch
the reaction (which is?usually vigorous) "can ‘be
prepared was suspended-in 100 parts by weight
of benzene, and propylene 'was gradually intro
a controlled and the composites are recovered in
powdered form; in which *eé?ditibnwnéy i'daii "be 15 ‘ducé'd ‘to the‘siispéhs'ipih Eat [a ‘temperature of
uectiyferjiil'the iform'ofHaréér particles
y 'pelletiri’fg “or- ’~'otIie'rWi'se farming i‘the
w..CoutingImusu operations inieiyithe jéiiatcie'd “15y .
“well-known ;pro.cedures.l..1li'or exampleL a Sus
cxiensionmtpowderedcatalystdn ‘an aromatic
, hydrocarbon ‘may. be passed‘ through‘a're'actor of
Va tubular variety Vwhich"is"provided ‘With’ ba?ies
j tolinsurexiturbulence, and an ‘ialkylating'pom- v,
‘pound introduced atwarious points along ‘the line
of ?ow' after which the productsfare"sub'jected
‘ to fractionation for recovery of desired alkylated
products and unreacted hydrocarbons whichlat
' and
ter may be returned to further reaction Mi‘n‘the
‘metal capable o'fr‘formfng" a me’tal’halifde
primary‘alkylatiiig?one“int‘thei presence of fresh
catalyst or separated and recirculated catalyst if
it has retained suf?cient catalytic activity. Con
tinuous operations may also be‘conducte'd by such
llll ~AL
;_ l
in the presence ‘pita catalystrcpmprismg a‘ cat
alytic compoundvha'ving‘ the formula
lalwlormetthe ,lisuisltzarloineiie “to
iI?QW awe-rarely or ‘(snared Lgraeular qatalxst
Wm 93 5 9: E<4 . .lQ3
s qealrgwacliioyapor ehaseiis
‘ passed 'up‘wardlykgcounter-currentuto the descend
ing streamofr aromatic hydrocarbon.
The folllowirigj'illustrative?atafare"introduced
nstance of_ the manufacture of a
‘ F‘iZ‘HsCOUAlXz
;: Vii-An“ a1kylation<nrossss wbirzhucomprisesxre
70 -etcting. angarpma?c _'99_m.p0un91 :with'ani vole?n
int-the :presencsi of. a; catalyst. comprisinaa sat
elytisacompound, having ‘thefqrmulai ‘RCOOAHQ
A'lcataly'st “assorted
proportions of‘acetic _. anhydride
and'aluminum ‘15
wherein R; is an alkyulggriou and
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