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Patented Nov. 12, 1946
2,411,047
. {UNITED v STATES
PATENT
OFFICE
2,411,047
ALKYLATION OF AROMATICS
Carl 31mm, Riverside, and Vladimir N. Ipatieff,
Chicago, 111., assignors to Universal Oil Prod
ucts Company, Chicago, 111., a~corporation of
Delaware
1
No Drawing. Application December 20, 1944,
Serial No. 569,098
14 Claims. (Cl. 260——67 1)
2
The present invention relates to the interac
tion of alkylatable aromatic hydrocarbons with
ole?nic hydrocarbons in the presence of a novel
alkylation catalyst. It is more particularly con
catalytic dehydrogenation of naphthenic or cyclic
ole?ns having a ring structure comprising at
least 6 carbon atoms. The ole?ns may be ob
tained in large quantities in the gaseous products
‘ cemed with the production of alkylatable hydro 5 from cracking and other hydrocarbon conversion
carbons which can be used as intermediates in
operations or by the dehydrogenation of such
the manufacture of synthetic rubber or can be
compounds as ethyl alcohol. Although the cata
incorporated into gasolines to form premium
lysts of the present invention are particularly ap
fuels. This application is a continuation-in-part
plicable when ethylene is employed as the alkyl—
of our earlier application Serial No. 470,223, filed 10 ating agent, our invention is broader in scope and
December 26, 1942, now Patent No. 2,366,736,
the catalyst may be used generally for reacting
granted’January 6, 1945.
.
i
The alkylation of aromatics, particularly ben
zene with ethylene, has become very important
aromatic hydrocarbons or aromatic compounds
such as halogenated aromatics, phenols, etc., with
either normally gaseous or normally liquid ole
at the present time. . The primary product of the
?nic hydrocarbons, particularly ole?ns contain
reaction, ethyl benzene, upon dehydrogenation
ing from 2 to about 12 carbon atoms per mole
cule or compounds capable of forming ole?ns
under the particular set of conditions selected for
the operation. In certain instances, polymers of
zene and similar compounds have been found to 20 the lower boiling ole?ns may be employed, al
have excellent antiknock properties and are val
though not necessarily under the same operating .
uable as addition agents to gasolines.
conditions. For example, when ole?nic polymers
In one embodiment the present invention com
are reacted with the aromatic, it is generally de
prises a process for the alkylation of an alkylat
, sirable to employ a somewhat higher ratio of aro
able aromatic compound with an ole?n, partic
matic to ole?n in the hydrocarbon charging stock
ularly ethylene, in the presence of boron tri?uo
than would ordinarily be used when monomeric
ride and an acid ?uoride.
ole?nic reactants are employed.
The two components which, when combined,
As previously stated, boron tri?uoride or the
form our novel alkylation catalyst when used ‘in
acid ?uorides alone are not, alkylating catalysts.
dividually do not catalyze the interaction of an 30 However, when employing the two together, an
aromatic with an ole?n to any great extent. We
active catalyst is obtained. While the catalyst
have found that upon combination these mate
has been found to possess some activity regard
rials produce a very effective catalyst as is borne
less of_ the proportions of boron tri?uoride and
out by the experimental data presented herein
acid ?uoride, the best results are obtained when
after in this speci?cation. These catalysts pos 35 a de?nite molal excess of BF: over ‘the acid ?uo
yields substantial quantities of styrene which is
now extensively employed in the manufacture of
synthetic rubber. Ethyl benzene, isopropyl ben
sess qualities which make their use on commer
cial operation particularly attractive. Perhaps
ride is maintained.
‘
The alkylation reaction in the presence of the’
the most important characteristic of these cata
lysts is their ability to catalyze the interaction
boron trifluoride alkali metal acid ?uoride cata
lyst may be carried out at a temperature from
of benzene with ethylene, as well as with higher 40 about -l0° C. to about 400° C., although a more
boiling ole?ns. With most of the prior art al
preferable operating range is from about —10° C.
,kylation' catalysts, for example, sulfuric acid, it
to about 100° C. It is highly desirable that the
has been found that while these catalysts are
reaction be carried out under su?icient pressure
e?ective in causing the interaction of benzene
to maintain a substantial portion of the reactant '
with propylene, butylene, etc., they do not pos
sess the ability to e?ect interaction of benzene
45 in the liquid phase, for example, from about 10
to about 200 atmospheres, depending‘ upon the
amount of boron tri?uoride present, the tempera
Benzene and other aromatics may be readily
ture of the reaction and other factors. In order
obtained by the distillation of coal tar products
to minimize polymerization‘of the ole?nic re
or may be found in substantial quantities in 50 actants, a hydrocarbon feed to the alkylation zone
straight-run gasolines from various crude oils,
should contain a substantial excess of aromatic
particularly the coastal crude oils. These aro
hydrocarbons over the ole?nic hydrocarbons, for
matics may also be produced by the catalytic de
example, a molal ratio of‘ aromatics to ole?ns of
hydrocyclization of normal para?ins having at
about 2:1 to about
20:1 or higher. If desired the _
‘ ‘
' least 6 carbon atoms to the molecule or by the '— ole?nic reactants-may be introduced at spaced '
and ethylene.
2,411,047
3
I
'
aromatic compound with an alkylating agent
points throughout the alkylation zone in order to
maintain the desired high aromatic to ole?n ratio.
under alkylating conditions in the presence of
boron tri?uoride and an acid ?uoride.
In the case of the preferred operation wherein
potassium or sodium acid ?uoride is maintained
2. A process for the synthesis of hydrocarbons
which comprises reacting an alkylatable aromatic
hydrocarbon with an ole?nic hydrocarbon under
alkylating conditions in the presence of boron tri
as a ?xed bed, the e?luent material from the al
kylation zone is introduced into a separation step
_ wherein hydrocarbon reaction products are sepa
?uoride and an acid ?uoride.
rated from boron tri?uoride which can then be
recycled to the alkylation stage .asihereinbefore
described. The hydrocarbon reaction products
are ‘fractionated to separate desired alkylation
10
products from unconverted aromatics. The lat
ter are recycled to the alkylation zone in order to
maintain the desired high aromatic to ole?n ratio
3. A process for the alkylation of aromatic hy
drocarbons with ole?nic hydrocarbons which
comprises contacting aromatics and ole?ns at a
temperature of from about —10° C. to about 400°
C. in the presence of boron tri?uoride and an acid
?uoride.
in the hydrocarbon feed stock. lLight hydrocar 15
bon contaminants in the charging stock to the
process may also be removedinithe fractionation
step in order to prevent their accumulation in the
alkylation system. For example, if appreciable
}
4. A process of claim -1 further characterized
in that said acid ?uoride ‘comprises an acid
?uoride of an alkali metal.
'
5. A process for the synthesis of organic com
pounds‘ which comprises reacting an aromatic
amounts of ethane, propane, or normal butane 20 compound with an alkylating agent under al
kylating conditions in the presence of boron tri
are introduced with the fresh hydrocarbon feed it
?uoride and an acid ?uoride of potassium. .
will be desirable to remove ‘these constituents
6. A process for the synthesis of hydrocarbons ,
during the fractionation operation. In general
which comprises reacting an aromatic hydrocar
it is not intended to limit the broad scope of the
present invention to any particular method of - bon with an ole?nic hydrocarbon under alkylat
ing conditions in the presence of boron tri?uoride
contacting the catalyst and the reactants.
'
and an acid ?uoride of potassium. '
The following examples are introduced in order
7. A process for the synthesis of organic com
to illustrate the nature of the present invention
pounds whichcomprises reacting an. aromatic "
as it is applied to the alkylation of benzene with
compound with an alkylating agent under. al
30
kylating conditions in the presence of boron tri
In these examples a rotating autoclave of about
?uoride and an acid ?uoride of sodium.
850 cc. capacity was employed as a reaction zone.
8. A process for the synthesis of hydrocarbons The autoclave was rotated at the specified tem
which comprises reacting an aromatic hydrocare
perature for about 4 to 6 hours, then cooled to
bon with an ole?nic hydrocarbon under alkylat
room temperature and the pressure released‘
ing conditions in the presence of boron tri?uoride
through bubblers containing caustic solution.
ethylene.
‘
a
\
meter and subsequently analyzed.‘ The auto
clave was then opened and the liquid reaction
andvan acid ?uoride‘of sodium.
9. A process for the synthesis of hydrocarbons
which comprises alkylating benzene with ethyl
when alkylating benzene and ethylene in the
propylene in the presence of boron tri?uoride and
The non-condensible gas was measured in a gas
product removed therefrom, washed, dried and 40 ene in the presence of boron tri?uoride and an ~
alkali metal acid ?uoride.
distilled.
'.
10. A process for the synthesis of hydrocar
The following table presents the operating
bons
which comprises alkylating benzene with
conditions employed and, the results obtained '
presence of boron tri?uoride.
‘
an alkali metal acid ?uoride.
‘
11. A process for the synthesis of hydrocar
_Experiments 1 and 2 indicate that the indi
bons‘ which comprises aikylating benzene with
vidual materials do not possess‘ any activity as
alkylation catalysts, but it is only when used in - ethylene in the presence of boron tri?uoride and
' an" alkali metal acid ?uoride.
conjunction with one another that. an active
112;“ A process for the synthesis of hydrocarbons
whlch'comprises passing aromatic hydrocarbons,
alkylating catalyst is obtained.
ole?nic hydrocarbons and boron tri?uoride
Experiment number
1
Conditions:
emperature, ° C ____________ __
Hrs rotated at tem
Charge, g.:
p
u
léF F1 _____________ _B
a __________ __
1345332155.
_.
Recovery, g.: __________ n
Eth
ene __________________ __
3
4
5
25
25
300
6
6
' 4
6
0
15
40
15
18
55
43
60
160
160
160
24
24
38
30
0
6
3
24
Benzene ______________________ __‘___..
Ethylbenzene __________ __
2
160
160 60
zone and fractionating said hydrocarbon reac
tion products to recover desired alkylation prod
ucts.
'
13. The process of claim 12 wherein said solid
contact material consists essentially of potas
sium acid ?uoride as its active ingredient.
52
14. A process of claim 12 wherein said solid
15
contact material consists essentially of sodium
9
-65
acid ?uoride as its active ingredient.
________ __ __.‘_
_ ________ __
52
78
Diethylbenzenes ____________________________ __
Higher ethylated benzene ___________________ __
16
4
26
14
We claim as our invention:
120
through an alkylating zone containing therein a
?xed bed Of solid contact material comprising an
alkali‘ metal acid ?uoride, separating boron tri
?uoride from the hydrocarbon reaction products,
recycling said boron tri?uoride to the alkylating
\
1. A process for the synthesis of organic com
pounds which comprises reacting an allgvlatable
CARL B. LINN.
'
VLADIMIR N. IPA'I'IEFF.
.
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