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Patente Dec. 1%,
'. I
_ era
2,412,229
smmon or snom'rrc
,- soc
1
hr
ns
_Raymond E. Scaad, Chicago, 111.,
Universal Oil
:,-
or to
nets ilompany, Chicago,
a corporation of
.,
were
Application May 31, 1941,
erlal No. scale:
20 Claims. (6i. zoos-s11)
2
,butadiene and isoprene, also non-conjugated
This invention relates to the treatment of
,diole?ns, and other poly-ole?ns. Oleilnic hydro
aromatic hydrocarbons to produce alkylated are?
carbons utilizable as alkylating agents are obtain
able from any source and are present in products
of thermal and catalytic cracking of oils, in those
matic hydrocarbons. More‘ speci?cally it is con
cerned with the production of mono-alkylated
and poly-alkylated aromatic hydrocarbons in the
presence of a catalyst.
obtained by dehydrogenating paramnic and
It is recognized that in general the catalytic
alkylation- of aromatic hydrocarbons has been
ole?nic hydrocarbons or in the products resulting
from dehydrating alcohols.
Alkylation of aromatic compounds may also be
known for some time. However, the present in
vention di?erentiates from the prior art on this
subject in the use of a particular catalytic mate
rial comprising as its active ingredients. pyro=
phosphate of a metal selected from members of
the right-hand column of group I of the periodic
e?ected in the presence of catalysts hereinafter
described by charging with'the aromatic hydro~
carbon a substance capable of producing ole?nic
hydrocarbons under the operating conditions
chosen for the reaction. Such ole?n-producing
15 substances, include alcohols, ethers, esters, and
table.
alkyl halides which are capable of undergoing ole
In one speci?c embodiment the present inven
hydration or splitting to olefinic hydrocarbons,
tion comprises a process for producing alkylated
containing at least 2 carbon atoms per molecule,
aromatic hydrocarbons which comprises subject
which may be considered as present in the re~
ing an aromatic hydrocarbon and an ole?nic
hydrocarbon to contact under alkylating condi
20 action mixture even though possibly only as
‘transient intermediate compounds which react
tions in the presence of a catalyst comprising as
its active ingredient a pyrophosphate oi‘ a metal
. further with aromatic hydrocarbons to produce
desired reaction products.
selected from members of the right-hand column
of group I of the periodic table, and preferably of
Aromatic
hydrocarbons,
Catalysts suitable for use in effecting the proc
25 ess of the present invention comprise preferably
' copper-and silver.
such as benzene,
toluene, other almzlated benzenes, napththalene,
alkylated naphthalenes, other poly=nuclear aro- -
matics, etc., which are alkylated ‘by olefl'nic hydro
carbons as hereinafter set forth, may be obtained
copper and silverv salts of pyrophcsphoric acid as
well as the materials formed by mildly treating
these pyrophosphates at elevated temperatures
with hydrocarbons, hydrogen, or other reducing
gases prior to use as alhylating catalysts. The
metal pyrophosphates utilized as alkylating
catalysts may be formed by adding an aqueous
solution of an’alltall metal pyrophosphate to
by the distillation of coal, by the dehydrogenation
of naphthenic hydrocarbons, by the dehydrogena~
tion and cyclization of aliphatic hydrocarbons,
an aqueous solution oi’ a water=soluble copper
alkylated aromatic hydrocarbons, and allrylated
naphthenic hydrocarbons, and by other means.
35 or silver salt to e?‘ect precipitation of the desired
metal pyrophosphate which may be separated by ;
Oleflnic hydrocarbons utilizable' as alkylating
filtration from the‘ precipitation mixture, then
agents in the present instance comprise mono
washed, dried, and formed into particles suitable
ole?ns and poly-oleflns. Oleflns which are em
for use as a reactor ?lling material.
ployed in the present process are either noally
gaseous or normally liquid and comprise ethylene 410 Pyrophosphates of copper, "silver, or, mixtures
thereof may be used as such or mixed with or de
and its higher homologs, both gaseous and liquid,
posited upon carriers or supporting materials such
the latter including various polymers of normally
as silica, diatomaceous earth, alumina, magnesia,
gaseous ole?ns, but these di?erent clefinic hydro
silica-alumina composites, crushed porcelain, "
carbons and those mentioned hereinafter are not
necessarilyequivalent in their action as alkyleting 45 pumice, ?rebrick, etc. A composite of a group
I metal pyrophosphate, metal acid pyrophosphate,
agents. Cyclic ole?ns- may also serve in alkyl
and 'a ‘selected carrier in ?nely powdered form
ating aromatic hydrocarbons but generally under
after thorough ‘mechanical mixing, is subjected ,
conditions of operation different from those
employed when alkylating aromatic hydrocarbons
to drying, pelleting, and heating operations, the
by non-cylic ole?ns, and this reaction may in 50 latter carried out in a stream of air, nitrogen,
hydrogen, or hydrocarbon gases to produce formed
volve intermediate formation of ole?ns vfrom
particles of catalyst suitable for use as packing
cyclopara?ins in they presence of the catalyst.
Other ole?nic hydrocarbons which may be inter
material in a reactor employed for effecting alkyl
atlon of aromatic by ole?nic hydrocarbons, or
acted with the above indicated aromatic hydro
carbons include conjugated diolenns such as - 55 the metal pyrophosphate itself may be similarly
2,412,229
3
.'
~
~
4
.
formed into pellets or granules usually by com
pressing a mixture of the powdered metal pyro
phosphate and a suitable pelleting lubricant such
as hydrogenated cocoanut oil, starch, etc. The
activity of supported metal pyrophosphate
suspension by some method of agitation,
catalysts is also controlledto a substantial extent,
choice of operating procedure is dependent upon
by varying the proportions of active metal pyro- '
the circumstances such as the temperature, pres- .
also be effected in a closed vessel in which some
of the reacting, constituents are‘in liquid phase
and in which the catalyst is preferably in finely
divided form and is maintained in dispersion or .
The
phosphate and carrier. Accordingly, catalytic
material of appropriate activity is thus available
sure, and activity of catalyst found to‘be most ef
fective ‘for producing the desired reaction be-v
for use with both substantially straight chain 10 tween particular aromatic and ole?nic hydrocar
ole?ns and with the more reactive ole?ns such
as those containing a tertiarycarbon atom as is
bons.
.
'
. Metal pyrophosphates as herein described are
present in isobutene, tri-methyl ethylene, etc..
preferred catalysts as they permit continuous re-'
The di?erentalkylating catalysts which may thus
action of aromatic and ole?nichydrocarbons in
be prepared and employed in the present process
the presence of a ?xed bed of catalyst and thus
are not necessarily equivalent in their action.
make it possible to avoid mechanical problems as
In effecting reaction between aromatic hydro
well as oxidation and corrosion di?loulties en
carbons and anvalkylating agent, as an ole?nic
countered when this reaction is carried out in I
hydrocarbon, according to the process of the pres
the presence of sulfuric acid which is sometimes
ent invention, the exact method of procedure 20 used as an alkylating catalyst. Further, a, pyro
phosphate of copper or silver also has the advan
varies with the nature of the reacting constitu
ents. A simple procedure, utilizable in the case ,
tage over aluminum chloride utilized as catalyst
of an aromatic hydrocarbon which is normally -for alkylating aromatic compounds with ole?nic ,
liquid, or if solid is readily soluble or easily dis
hydrocarbons in that the metal pyrophosphate
persible in a substantially inert liquid, and a
.forms substantially no addition compounds or
normally gaseous or liquid ole?nic hydrocarbon,
complexes with aromatic and/or ole?nic hydro-‘
consists in contacting the aromatic and ole?nic - carbons while such formation of addition com
hydrocarbons with a catalyst containing a pyro
pounds 'is characteristic of catalysts containing.
phosphate of a metal selected from the members
aluminum chloride.
of the right-hand column of group I of ‘the peri 30 Reactions between aromatic and ole?nic hy-,
odic table at a temperature of from about 100°
_ drocarbons inthe presence of a pyrophosphate of
to about 450° C. and preferably between about
a‘ non-alkaline metal of ‘group I of the periodic
250° and about 400° C. under a pressure of from
table are apparently of a relatively simple char
substantially atmospheric to approximately 100
acteralthough they may be accompanied by cer
atmospheres. Intimate contact of the reacting
tain amounts of polymerization and decomposi
components with the catalyst is effected bypass
tion, the latter being particularly in evidence
ing the reaction mixture through a ?xed bed of
when the reaction is carried out at a temperature
in the neighborhood of 450° C. While not under
granular or pelleted catalyst or the reacting com
ponents may be mixed with ?nely divided cat-v.
stood completely, a typical alkylation of an arc
alyst and reacted in either a batch or continuous 40 matic hydrocarbon by an ole?n apparently in
. type of operation. The hydrocarbons subjected
volves the addition of the aromatic hydrocarbon
to reaction are preferably in the proportion of 1
to a double bondelof an ole?nic hydrocarbon'to ,
molecular proportion of ole?nic hydrocarbon to ~ produce a higher-boiling alkylated aromatic hy
‘between about 2 and about 20 molecular propor
drocarbon which may in turn undergo further
tions of aromatic hydrocarbon in order to di
reaction with one or more molecular proportions
minish polymerization of ole?nic hydrocarbons
of ole?nic hydrocarbon to ,form' dialkylatedand '
and to favor interaction of oleflnlchydrocarbons
more-highly alkylated aromatic hydrocarbons.
with the aromatic hydrocarbon or m'ixture of aro-~
In case the alkylating ole?nic hydrocarbon is, a
matic hydrocarbons in the hydrocarbon fraction,
diole?n or other poly-ole?n, the interaction with
undergoing treatment. The addition of a hy
‘an aromatic hydrocarbon may involve. not only
drogen-containing gas to the alkylation mixture
the combination of aromatic‘ and ole?nic hydro
frequently has a. bene?cial effect upon the re
carbons but possibly the polymerization of a high
action.
‘
er boiling unsaturated aromatic hydrocarbon re
'Thus a hydrocarbon mixture “comprising es- ,
sentially normally liquid aromatic hydrocarbons
and a fraction containing ole?nic hydrocarbons
are commingled and passed‘through a reactor
containing a pyrophosphate of copper and/or sil
sulting from the primary reaction. ‘ Thus benzene
55 and butadiene give among other products a sub
stantial yield of phenyl butenes which polymerize
to' form dimers of phenyl butene.- Within cer
tain limits it is possible to produce mainly mono-,
ver, or at least a portion of thearomatic hydro
' alkylated aromatic hydrocarbons by proper ad
carbon is charged to such a reactor while the 60 justment of catalyst activity, ratio of the aromatic
fraction containing ole?nic hydrocarbons, as such
to ‘the ole?nic hydrocarbons charged, operating '
or preferably diluted. by anotherportion of the
aromatic hydrocarbon being treated, is intro
duced at various points between the inlet and the
outlet of the reaction zone in such a way that
conditions such as temperature, pressure, and rate
of feed of the reacting'components, etc.
The reaction between an aromatic hydrocar
,, bon and a hexene or other normally liquid ole?n
the reaction mixture being contacted with the
of higher molecular weight may involve not only
catalyst will at all 'times contain a relatively low
addition of aromatic and ole?nic hydrocarbons
but also a depolymerization or splitting of the
proportion of the ole?nic hydrocarbon and thus
ole?nic hydrocarbon into ole?nic fragments .of
favor interaction of aromatic and ole?nic hydro
carbons rather than ‘polmerization of the latter. 70 lower molecular weights which react with the _'
aromatic hydrocarbons to ‘produce alkylated aro-'
While the method of passing the aromatic and
matic hydrocarbons. Thus benzene and di-iso
ole?nic hydrocarbons, either together-or counter
currently, through a suitable reactor containing
butene or_tri-isobutene react and yield tertiary
butyl benzene and poly-tertiary butyl benzenes,
the granular catalyst, is generally customary pro
cedure, the interaction of these hydrocarbons may 75 while nonene and benzene yield both butyl and
garages
amyl benzenes as well as other products by so
called depoly-alkylation.
weight of mono-isopropyl benzene, and 5 parts by
weight of more highly propylated benzenes.
Example II‘
I
In general, the products formed by interac
tion of an ole?nic hydrocarbon with a molal ex
cess of an aromatic hydrocarbon are separated
A solution consisting of 28 parts by weight (0.07 ,
from the unreacted aromatic hydrocarbon by
molecular proportion) of potassium pyrophos
phate trihydrate dissolved in 600 parts by weight
suitable means as by distillation, and the unre
acted portion of the aromatic hydrocarbon orig
of water was added gradually with stirring over
inally charged and generally the poly-alkylated
a period of 15 minutes to a solution containing 45 '
hydrocarbons formed are returned to the process 10 parts by weight (0.26 molecular proportion) of
and mixed with additional quantities of the ole=
silver nitrate dissolved in 1250 parts by weight of
?nic and aromatic hydrocarbons being charged
water. The precipitated material was washed by
to contact with the catalyst. This recycling of v decantation three times using 1000 parts by
polyalkylated aromatic hydrocarbons sometimes
weight of water in each wash after which the
aids in the production of mainly mono-alkylated 1% precipitate was collected on a ?lter and washed
aromatic hydrocarbons and depresses the forma=
with 1000 parts by weight of water. The washed
tion of more-highly alkylated derivatives. The
precipitate after drying for 16 hours at 140° C.
total alkylated product thus freed from the ex
yielded 37 parts ‘by weight of yellowish‘ brown
cess of the orignally charged aromatic hydrocar
granules of silver pyrophosphate thus equivalent
bon is separated into desired fractions by distilla 20 to 93% of the'theoretical based upon the quan
tion at ordinary or reduced pressure or by other
suitable means.
'
tity of potassium pyrophosphate employed.
‘
The excess silver nitrate remaining in the
1
While the process of this invention is particu
larly applicable to the production of alkylated
mother liquor after precipitation and separation
flnic hydrocarbons, it may be utilized also ‘in al
ditional quantity of silver pyrophosphate.
of the silver pyrophosphate could be treated with
aromatic hydrocarbons from aromatic and ole» 25 more potassium, pyrophosphate to produce an ad
. kylating other aromatic compounds as in con
10 parts by weight of the silver'pyrophosphate
obtained as above described, 80 parts by weight of
verting phenols and ole?nic hydrocarbons into
alkylated phenols using a catalyst containing a
benzene, and 20 parts icy-weight of propane were
pyrophosphate of a group I metal hereinabove 30 charged to the rotating autoclave used in Exam
set forth and generally operating within the
ple I, which was then placed under 50 atmos
ranges of temperature and pressure hereinabove
pheres pressure of- nitrogen and heated 4 hours * I
set forth.
,
'
at 300° C. After cooling the autoclave, the reac
The following examples are given to illustrate
tion product removed therefrom was found to
the character of results obtainable by thepuse of 35 contain 34 parts by weight of mono-lsopropyl
the present process, although the examples
benzene and 7 parts by weight of more highly
givenv are not introduced with the intention of
propylated benzenes.
'
unduly restricting the generally broad scope of
The nature of the present invention and its
the invention.
_
‘
.
commercial utility can be seen from the speci?
Emmple I
40 cation and examples given, valthough neither sec
tion is intended to limit its generally broad scope.
A solution of 53 partsby weight (0.14 molecular
I claim as my invention:
. .
proportions) of potassium pyrophosphate trihy
1. A process for producing aromatic compounds
drate in 600 parts by weight of water‘ was added
having a higher number or carbon atoms per
gradually with stirring over a period of 15 min
utes to a second solution containing 63 parts by
weight (0.25 molecular proportion). of copper sul
fate, pentahydrate dissolved in 1250 parts by
weight of water. The precipitate so formed was
45 molecule than the aromatic compound from
which they are derived which comprises subject
ing an aromatic compound and an _o1e?nic hy
droearbon to contact under alkylating conditions
in the presence of an alkylating catalyst whose
washed by decantation three times using 1000 50 alkylating components consist essentially of a
parts by weight of water in each wash. iThejpre~
pyrophosphate of a metal selected from the mem
cipitated material was then collected on a ?lter,
bers of‘ the right-hand column of group I of the
washed again with 1000 parts by weight of water, ' periodic table.
and afterward dried for 16 hours at 140° to 145° C._
2. A process for producing alkylated aromatic
Thus 38 parts by weight of light blue powdery 55 hydrocarbons
which comprises‘ subjecting an aro-'
copper pyrophosphate was obtained which repre-i
matic hydrocarbon and an ole?nic hydrocarbon
sented 90% of the theoretical yield based upon
contact under alkylating conditions in the pres
the quantity of potassium pyrophosphate used in / to
ence of‘ an allrylating catalyst whose alkylatlng '
the precipitation.
The excess copper sulfate remaining in the ’
> components consist essentially of a pyrophos
mother liquor after precipitation of the copper, 00 phate of a metal selected from the members of
zhglrlght-hand column of group I of the periodic
pyrophosphate could be treated with more potas
a e.
sium pyrophosphate to produce an additional
3'. A; process for producing alkylated aromatic
quantity of copper pyrophosphate.
hydrocarbons which comprises subjecting an aro
10 parts by weight of the copper pyrophosphate 05 matic hydrocarbon and an ole?nic hydrocarbon
prepared as hereinabove indicated, 80 parts by
to contact at a temperature of from about 100°
weight of benzene, and 20 parts by weight ofpro»
to about 450° C. in the presence of an alkylating
,pene were charged to a steel autoclave which was
catalyst whose alkylating components consist es
then placed under 50 atmospheres initial nitro
sentially 01’ a pyrophosphate of a metal selected
gen pressure and heated for 4 hours at 300° C.
70 irom the members oi’- the right-hand column of
The resulting reaction mixture yielded 10 parts
by weight of mono-isopropyl benzene and 2 parts
group I of the periodic table.
>
i
4. A process for producing alkylated aromatic
by weight .of higher boiling, alkylated benzenes.
hydrocarbons which comprises subjecting an aro
A likereaction mixture after being heated for 4
matic hydrocarbon and an "ole?nic hydrocarbon
hours at 350° C. was found to contain 35 parts by 70 to contact at a temperature of irom about 100°.
‘2,412,329
"
a
catalyst whose alkylating' components consist es
to about450° C. under a pressure of from sub
sentially of copper pyrophosphate._
stantially atmospheric to approximately 100 at
‘
'
-
12. .A process for producing alkylated benzenes
mospheres in the presence of an alkylating cata
which comprises subjecting benzene and an ole
lyst whose alkylating components consist essen
tially of a pyrophosphate of a metal selected from ' 5» ?nic hydrocarbon to contact at a temperature of
from about 100° to about 450° C. under a pres
the members of the right-hand column of group
sure of from substantially atmospheric to ap
_
I
~
100 atmospheres in the presence of
i 5. A process-for producing alkylated aromatic . proximately
an alky-lating catalyst consisting essentially of a
hydrocarbons which comprises subjecting an aro
of a metal selected from the mem
matic hydrocarbon and an’ole?nic hydrocarbon lo pyrophospha‘te
bers of the right hand column of group I of the
to contact at a temperature of from about 100°
periodic table.
to about 450° C. under a pressure of from sub
13. A‘process for producing alkylated benzenes.
stantially atmospheric to approximately 100 at
' . which comprises subjecting benzene and propene
mospheres in the presence of a hydrogen-contain
is to contact at a temperature of from about 100°
II of the periodic‘table.
ing gas and of an alkylating catalyst whose a1
to about 450° C. under a pressure of from sub
kylating components consist essentially of a pyro
phosphate of a‘ metal selected from the members
of the right-hand column of. group I or the pe
riodic table.‘
stantially atmospheric to approximately 100 at
mospheres in the presence of an alkylating cata
lyst consisting essentially of copper pyrophos
-_
>
6. A process for producing alkylated aromatic 20 phate.
14. A process for producing alkylated benzene
hydrocarbons which comprises subjecting an aro
‘ which comprises subjecting benzene and propene
matic hydrocarbon and a, normally gaseous ole
to contact at a temperature of from about 100°
finic hydrocarbon to contact at a temperature of
to about 450° C. under a pressure of from. sub
from about 100° to about 450° C. under‘a pressurev
or from substantially atmospheric to approxi 25 stantially atmospheric-to approximately 100 at
mospheres in the presence of an alkylating cata
mately 100 atmospheres in the presence of an al
lyst consisting essentially of silver pyrophosphate.
kylating catalyst whose alkylating components
15. A process for producing alkylated aromatic
consist essentially of a pyrophosphate of a metal
hydrocarbons
which comprises subjecting an arc
selected from the members of the right-hand
30 matic hydrocarbon and an oleflnic hydrocarbon
column of group I of the periodic table.‘
to contact at a temperature of from about 100° to
'7. A process for producing alkylated aromatic
about 450° C. under a pressure of from substan
hydrocarbons which comprises subjecting an ar0—
tially atmospheric to approximately 100 atmos
matic hydrocarbon and a normally liquid- ole?nic
pheres in the presence of a substantially inert
hydrocarbon to contact at a temperature of from
carrier supporting an alkylating catalyst consist
C.
under
a
pressure
of
‘
about 100° to about 450°
ing essentially ‘of a pyrophosphate of a metal se
from substantially atmospheric to approximately
lected from‘ the members of the right hand col
100 atmospheres in the presence of an alkylating
catalyst containing a pyrophosphate of a metal
selected from the members of the right-hand col
umn of group. I of the periodic table.
.
umn of group I of the periodic table.
‘
16. An alkylation process which comprises re
40 acting an aromatic compound with an ole?n in
the presence of an alkylating catalyst consisting
8. A process. for producing alkylated aromatic
hydrocarbons which comprises subjecting an aro
matic hydrocarbon and an ole?nic hydrocarbon
essentially of a pyrophosphate of a metal ‘from
‘ I$31551right-hand column of group I of the periodic
to contact at a temperature of from about 100°
to about 450° C. under a pressure of from sub 45
stantially atmospheric to approximately 100 at
mospheres in the presence of an alkylating cata
lyst containing copper pyrophosphate.
e.
-
-
17. The process as de?ned in claim l?iurther -
characterized in that said catalyst is composited
with a relatively inert supporting material.
18. An alkylation process which comprises re
acting an aromatic compound with an ole?n in
9. A process for producing alkylated aromatic
hydrocarbons which comprises subjecting an aro 50 the presence of a sulfuric acid-free alkylating cat- ‘
alyst comprising a pyrophosphate of a metal from
‘ matic hydrocarbon and an ole?nic hydrocarbon to,
the-right-hand column of group I of the periodic contact‘ at a temperature of from about 100° to
table.
.
about 450° C. under a pressure of from substan
19. A method for alkylating aromatic hydro
tially atmospheric to approximately 100 atmos 55 carbons
which comprises ‘contacting an aromatic
pheres in the presence of an alkylating catalyst
hydrocarbon with an ole?n hydrocarbon at ele
whose alkylating- components consist essentially
vated temperature in the presence of catalytic
. of silver pyrophosphate. _
material comprising as an essential ingredient
10. A process for producing alkylated aromatic
copper pyrophosphate.
\
/
‘
hydrocarbons which comprises subjecting an aro
matic hydrocarbon and a normally gaseous ole 60 .20. A process for producing a mono-alkylated
vhydrocarbon which comprises alkylating an arc
?nic hydrocarbon to contact at a temperature of
matic hydrocarbon with an ole?n in the presence .
from about 110° to about 450° C. under a pressure
of from substantially atmospheric to approxi
mately 100 atmospheres in the presence of an
of a sulfuric acid-free alkylating catalyst com
_
prising a pyrophosphate of a metal‘ from the
alkylating catalyst whose alkylating components 65 right-hand column vof group I of the periodic
table, thereby forming mono-alkylated'and poly
alkylated aromatic hydrocarbons, separating the
mono-alkylated from the poly-alkylated hydro
consist essentially of copper pyrophosphate.
11. A process for producing alkylated aromatic
hydrocarbons which comprises subjecting an arc
matic hydrocarbon and a normally liquid ole?nic
carbons, and returning at least a portion of the _ >
hydrocarbon to contact at a temperature of from 70 poly-alkylated aromatic hydrocarbons to the al
about 100° to about 450° C. under a pressure of
from substantially atmospheric to approximately
100 atmospheres in the presence of an alkylating
kylating step. .
‘
RAYMOND E. SCHAAD.
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