PROCESS FOR ALKYLATING AROMATIC HYDROCARBONS AND CATALYST THEREFOR

PROCEDE ET CATALYSEUR POUR L'ALKYLATION DES HYDROCARBURES AROMATIQUES

English Abstract

ABSTRACT OF THE DISCLOSURE
Alkylatable aromatic hydrocarbons are alkylated with olefins
and alkylhalides under anhydrous alkylating conditions in the presence
of a metallic cation exchanged trioctahedral 2:1 layer-lattice smectit-
type catalyst in which the metallic cation has a Pauling electronegativity
greater than 1Ø In a specific embodiment, 1-dodecene is reacted with
benzene by contacting the dodecene and benzene under anhydrous conditions
in the liquid phase at the boiling point of the mixture with a catalyst
comprising a metallic cation such as A13+, In3+ and Cr3+ exchanged onto
the surface of hectorite clay.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. In a process for alkylating in the liquid phase an
alkylatable aromatic hydrocarbon with an olefin-acting
compound selected from the group consisting of mono-
olefins, alkyl bromides, alkyl chlorides, and mixtures
thereof, the improvement which comprises contacting said
hydrocarbon and said compound under anhydrous alkylating
conditions with a catalyst comprising a trioctahedral 2:1
layer-lattice smectite-type mineral selected from
hectorite, stevensite and saponite containing a metallic
cation having a Pauling electronegativity greater than 1.0
in cation exchange positions on the surface of said
mineral.
2. The process of claim 1 wherein said catalyst is
selected from the group consisting of:
(a) hectorite-type clays having the following
structural formula:
[ (Mg??x Li? )VI Si8 O20(OH)4-yFy ]? Mz
where 0.33 ? x <1
0 ? y ?4
and M is at least one metallic cation having a Pauling
electronegativity greater than 1.0 of valence z;
(b) stevensite-type clays having the following
structural formula:
[ (Mg6-x)VI Si8 O20(OH)4-y Fy ]<IMG> Mz
where 0.16 ?x ? 0.5
0 ? y ? 4
and M is at least one metallic cation having a Pauling
electronegativity greater than 1.0 of valence z; and
(c) saponite-type clays having the following
structural formula:
21

[ (Mg?+ )VI (Si8-xA1?+ )IV O20(OH)4-y
Fy ] ? Mz
where 0.33 ? x ? 1
0 ? y ? 4
and M is at least one metallic cation having a Pauling
electronegativity greater than 1.0 of valence z.
3. The process of claim 2 wherein 0 ? y ? 2 in all of
said clays.
4. The process of claim 3 wherein said aromatic
hydrocarbon is benzene and wherein said olefin-acting
compound is a mono-olefin.
5. The process of claim 4 wherein said mono-olefin is
dodecene.
6. The process of claim 3 wherein said cation is
selected from the group consisting of A13+, Cr3+,
Ga3+, In3+, Mn2+, Fe3+, Co3+, Co2+, Ni2+,
Cu2+, Ag+, Be2+, Mg2+, La3+ Ce3+, Pd2+, and
mixtures thereof.
7. The process of claim 3 wherein said cation is
selected from the group consisting of A13+. Cr3+,
In3+, the rare earths and mixtures thereof.
8. The process of claim 7 wherein said hydrocarbon is
benzene and said compound is a mono-olefin.
9. The process of claim 7 wherein said mineral is
said hectorite-type clay.
10. The process of claim 9 wherein said hydrocarbon
is benzene and wherein said compound is a mono-olefin.
11. A process for alkylating aromatic hydrocarbons
which comprises contacting in the liquid phase an
alkylatable aromatic hydrocarbon with an olefin-acting
compound selected from the group consisting of
mono-olefins, alkyl bromides, alkyl chlorides, and
22

mixtures thereof, under aklylating conditions in a
reaction zone which is substantially free of water and in
the presence of an effective amount of a catalyst, said
catalyst comprising a metallic cation exchanged tri-
octahedral 2:1 layer-lattice smectite-type mineral
selected from the group consisting of hectorite, steven-
site, and saponite, wherein said metallic cation has a
Pauling electronegativity greater than 1Ø
12. The process of claim 11 wherein said cation is
selected from the group consisting of Al3+, Cr3+,
In3+, the rare earths, and mixtures thereof.
13. The process of claim 12 wherein said hydrocarbon
is benzene and wherein said compound is a mono-olefin.
14. The process of claim 13 wherein said mono-olefin
is dodecene.
15. A process for alkylating benzene with a
mono-olefin which comprises contacting in the liquid phase
said benzene and said olefin in a reaction zone under
anhydrous alkylating conditions in the presence of an
effective amount of a catalyst, said catalyst comprising a
metallic cation-exchanged trioctahedral 2:1 layer-lattice
smectite-type mineral selected from the group consisting
of hectorite, stevensitel and saponite, wherein said
metallic cation has a Pauling electronegativity greater
than 1Ø
16. The process of claim 15 wherein the pressure is
atmospheric, the temperature is the boiling point of
benzene, the molar ratio of benzene to o]efin is from
about 5:1 to 10:1, and the weight ratio of olefin to said
catalyst is from ahout 2:1 to 20:1.
23

17. The process of claim 16 wherein said cation i5
selected from the group consisting of A13+, Cr3+,
In3+, the rare earths, and mixtures thereof.
18. The process of claim 17 wherein said olefin is
dodecene.
19. The process of claim 18 wherein water is removed
from said catalyst by azeotropic distillation from a
catalyst-benzene mixture before addition of said dodecene.
20. A catalyst for the alkylation of aromatic hydro-
carbons with a mono-olefin which comprises a trioctahedral
2:1 layer-lattice smectite-type mineral selected from the
group consisting of hectorite, stevensite, and saponite
containing a metallic cation having a Pauling electro-
negativity greater than 1.0 in cation exchange positions
on the surface of said mineral.
21. The catalyst of claim 20 wherein said smectite-
type mineral is selected from the group consisting of:
(a) hectorite-type clays having the following
structural formula:
[ (Mg6?? Li? )VI Si8 O20(OH)4-yFy ]? Mz
where 0.33 ? x ? 1
0 ? y ? 2
and wherein M is at least one of said metallic cations
having a Pauling electronegativity greater than 1.0 of
valence z;
(b) Stevensite-type clays havlng the following
structural formula:
[ (Mg6-x)VI Si8 O20(OH)4-yFy ] ? Mz
where 0.16 ? x ? 0.5
0 ? y ? 2
24

and wherein M is at least one of said metallic cations
having a Pauling electronegativity greater than 1.0 of
valence z; and
(c) saponite-type clays having the following
structural formula:
[ (Mg6)VI (Si8-xAlx)VI O20(OH)4-yFy] ? Mz
where 0.33 ? x ? 1.0
0 ? y ? 2
and wherein M is at least one of said metallic cations
having a Pauling eleactronegativity greater than 1.0 of
valence z.
22. The catalyst of claim 21 wherein said metallic
cation is selected from the group consisting of A13+,
Cr3+, Ga3+, In3+, Mn2+, Fe3+, Co3+, Co2+,
Ni2+ CU2+, Ag+, Be2+, Mg2+, La3+, Ce3+,
Pd2+, and mixtures thereof.
23. The catalyst of claim 21 wherein said metallic
cation is selected from the group consisting of A13+,
Cr3+, In3+, the rare earths and mixtures thereof.
24. The catalyst of claim 21 wherein said
smectite-type mineral is hectorite and wherein said
metallic cation is selected from the group consisting of
Al3+1 Cr3+, In3+, the rare earths, and mixtures
thereof.

Description

This invention relates to a process for the liquid
phase alkylation of aromatiC hydrocarbons in which the
catalyst comprises certain cation-exchanged trioctahedral
2:1 layer lattice smectite-type clays. More parti~ularly,
the present invention is concerned with a method wherein
an aromatic hydrocarbon, e . g. benzene, and an alkylating
agent, e.g. an olefin, are reacted in the liquid phase
in the presence of a catalyst which comprises a trioctahedral
2:1 layer-lattice smectite-type mineral which has a metal
cation having a Pauling electronegativity greater than 1.0
in ion-exchange positions on the surface of the clay particles.
- It has been reported that various materials
containing acidic catalytic sites are useful in catalyzing
the reaction between aromatic hydrocarbons and various
alkylating agents such as olefins and alkyl halides. See
for example: the Kirk-Othmer Encyclopedia of Chemical
Technology, 2nd Edition, Vol. 1, pp. 882-901 (1963);
"Alkylation of Benzene with Dodecene-l Catalyzed by Supported
Silicotungstic Acid", R.T. Sebulsky and A.M. Henke, Ind.
Eng. Chem. Process Res. Develop., Vol. 10, No. 2, 1971,
pp. 272-279; "Organic Molecule and Zeolite Crystal:
At the Interface", P.B. Venuto, Chem. Tech., April, 1971,
pp. 215-224; "Catalysis by Metal Halides. IV. Relative
Efficiencies of Friedel-Crafts Catalysts in Cyclohexane-
Methylcyclopentane Isomerization, Alkylation of Benzene
and Polymerization of Styrene", G.A. Russell, J. Am. Chem.
Soc., Vol. 81, 1959, pp. 4834-4838.
It has also been proposed to use various modified
clays as catalysts in various acid catalyzed reactions
such as alkylation, isomerization, and the like. Se0
for example the following U.S Patents: 3,665,778;
-2-
, '" ' '
,:,

- 3,665,780; 3,365,347; 2,39~,945; 2,555,370; 2,582,956;
2,930,820; 3,360,573; 2,945,072; 3,074,983. The latter
patent is the only patent known to me which discloses the
use of hectorite clay as a catalyst. Other references which
disclose -the use of clays as catalysts are as follows:
"Acid Activation of Some Bentonite Clays", G.A. Mills, J.
Holmes and E.B. Cornelius, J. Phy. & Coll. Chem., Vol. 54,
pp. 1170-1185 (1950); "H-Ion Catalysis by Clays", N. T.
Coleman and C. McAuliffe, Clays and Clay Minerals, Vol. 4,
pp. 282-289 (1955); "Clay Minerals as Catalysts", R.H. S.
Robertson, Clay Minerals sull., Vol. 1, No. 2, pp. 47-54
(1948); `'Catalytic Decomposition of Glycerol by Layer
Silicates", G.F. Walker, Clay Minerals, Vol~ 7, pp. 111-112
(1967); "Styrene Polymerization with Cation-Exchanged
Aluminosilicates", T.A. Kusnitsyna and V.M. Brmolko,
Vysokomol. Soedin., Ser. B1968, Vol. 10, No. 10, pp. 776-9-
see Chem. Abstracts 70:20373x (1963); "Reactions Catalyzed
by Minerals. Part I. Polymerization of Styrene", D.H.
Solomon and M.J. Rosser, J. Applied Polymer Science, Vol.9,
1261-1271 (1965).
I have now Eound that trioctahedral- 2:1 layer-
lattice smectite-type minerals, par-ticularly hectorite,
which have had their exchangeable cations replaced with
a metallic cation having a Pauling electronegativity
greater than 1.0 are effective catalysts for the alkylation
of an alkylatable aromatic hydrocarbon, e.g. benzene,
with an olefin or alkyl halide under anhydrous alkylating
conditions in the liquid phase.
Accordingly, it is an object of this invention
to provide a process for alkylating in the liquid phase
an alkylatable aromatic hydrocarbon with an olefin or
' . : ~ - .

¢~
alkyl halide under anhydrous alkyla-ting conditions in -the
presence o~ a trioctahedral 2:1 layer-lattice smectite-
type catalyst whleh has in its cation exchange positions
a metallie eation having a Pauling eleetronegativity greater
than 1Ø It is another object of this invention to provide
a method of alkylating aromatic hydrocarbons which comprises
contacting in the liquid phase on alkylatable aromatic
hydroearbon with an olefin or alkyl halide in a reaction
zone which is substantially free of water and in the presence
of an effective amount of a catalyst, said catalyst
comprising a metallie eation exehanged trioetahedral 2:1
layer-lattiee smeetite-type mineral wherein the metallie
cation has a Pauling electronegativity greater than 1Ø
Other objeets and advantages of th.is invention will become
apparent to those skilled in the art upon reading the
disclosure and the appended claims.
-3a-
.
- ' '" ''''"` " " :,

The catalyst o~ this invention comprises (11 a
metallic cation which has a Pauling electronegativity
~ greater than 1.0 exchanged onto the surface of (2) a
trioctahedral 2:1 layer-lattice smectite-type mineral.
Representative metallic cations which are useful in
this invention may be derived from the following metals,
the Pauling electronegativity of which is given in paren-
theses (See "The Nature of the Chemical Bond", L. Pauling,
1960, 3rd Edition):Be (1.5), Mg (1.2), Al (1.5), Ga (1.6~,
In (1.7), Cu (1.9), Ag (1.9), La (1.1), Hf (1.3),
Cr (1.6), Mo (1.8) Mn (1.5), Fe (1.8), Ru (2.2~, Os (2.2),
Co (1.8), Rh (2.2), Ir (2~2), Ni (1.8), Pd (2.2),
Pt (2.2), and Ce (1.1). Preferred metallic cations are
A13+, In3+, Cr3~, and the rare earth cations,
particularly La3+ and Ce3+. Mixtures of two or more
metallic cations having a Pauling electonegativity greater
than 1.0 may be present in the catalyst in cation exchange
positions on the surface of the trioctahedral 2:1 layer-
lattice smectite-type mineral.
Representative trioctahedral 21 layer-lattice
smectite-type minerals which are useful in this invention
are naturally-occurring hectorite, stevensite, and
saponite, and their synthetic structural analogs.
The structure of trioctahedral 2:1 layer~lattice
smectite minerals is well known. See for example the
ollowing publications. "The Chemistry of Clay Minerals",
C.E. Weaver and L.D. Pollard, 77 86 (1973). Elsevier
Scientific Publishing Co.; "Clay Mineralogy", R.E. Grim,
77-92, 2nd Edition (1968). McGraw-Hill Book Co.;
"Silicate Science. Vol. I. Silicate Structure", W. Eitel,
234-247 (1964). Academic Press: "Rock-Forming Minerals.
Vol. 3 Sheet Silicates", W.A. Deer, R.A. ~owie, and
~r~ ~
; !) . - 4 -
, , ,,, -,,, : : ,
,

J. Zussman, 226-245 (1962), John Wiley and Sons, Inc.
The smectite-type minerals useful in this invention
can be synthesiæed hydrothermally~ In general a gel
containing the required molar ratios of silica, alumina,
magnesia and fluoride and having a pH at least 8 is
hydrothermally treated at a temperature within the range
from 100C. - 325C., preferably 250C. - 300C., and
preferably at the autogeneous water vapor pressure for a
period of time sufficient to crystallize the desired
smectite, generally 12 - 72 hours depending on the temp-
erature of reaction. In general as the reaction
temperature decreases the reaction time increases for well
crystallized smectite-type minerals. Many of thë
smectite-type minerals can be crystallized from melts of
the oxides at very high temperatures, generally greater
than 950C.
The following references describe processes for the
hydrothermal synthesis of smectite-type minerals: "A Study
of the Synthesis of Hectorite", W.T. Granquist and S.S.
Pollack. Clays and Clay Minerals, Proc. Nat'l. Conf.
Clays Clay Minerals. 8, 150-169 (1960); "Synthesis of a
Nickel-Containing Montmorillonite", B. Siffert and F.
Dennifeld. C.R. Acad. Sci., Paris, Ser. D~ 1968, 267(20),
1545-8 (Reference Chemical Abstracts, Vol. 70; 43448q);
"Synthesis of Clay Minerals", S. Caillere, S. Henin, and
J~ Esquevin. Bull. Groups franc-argiles. 9, No. 4, 67-76
~1957) (Reference Chemical Abstracts 55L8190e); U.S.
Patent 3,586,478; UOS. Patent 3,666,407; U.S. Patent
3,671,190.
Hectorite type clays can be represented by the
structural formula:

[ (M96~ LiX ) VI Si8 20 (OH) ~_y Fyl
where O . 3 3 ~ x ~ 1
O ~ y < 4
and where M is at least one charge-balancing cation of
valence z. Preferably 0 < y < 2
2 0
'
- Sa -
, .. ' . ' ' ' ' '

Stevensite-type clays can be represen-ted by the
structural formula:
[ g 6-x) si8 20(OH) ~ 2x MZ
where 0.16 < x < 0.5
0 < y < 4
and where M is at least one charge balancing cation of
valence z. Preferably 0 < y < 2.
Saponite-type clays can be represented by ~he
structural formula:
~ Mg 6~VI (Si8 XAl 3X)Iv 020)0H)4 y F~ z M
where 0.33 < x < 1
0 < y < 4
and where M is at least one charge-balancing cation of
valence z. Preferably 0 < y < 2.
In the catalyst of the present invention M is
at least one metallic cation which has a Pauling electro-
negativity greater than 1Ø However, before preparing
the catalyst by an ion-exchange process, the charge-
balancing cation present on the surface of the layer
lattices must be a cation capable of being exchanged,
preferably Na , Li , or NH4 , unless it is a metallic
cation which has a Pauling electronegativity greater than
' 1Ø
The minerals can contain minor amounts of other
metals substituted isomorphously in the layer-lattices
for the metals indicated in the above formulas, such as
Fe2+, and A13+ in the octahedral layer and Fe3+ in the
tetrahedral layers. Metals having an ionic radius not
greater than 0.75 A can be present in the octahedral layer.
Metals having an ionic radius not greater than 0.64 A

r~Lt~
can be present in -the tetrahedral layers. Such minor
inclusions are common in naturally occurring minerals.
Generally the sum of such extraneous isomorphously substituted
metals will amount to no more than 5 mole percent based
on the metals present in the layer in which the substitution
occurs.
The preferred trioctahedral 2:1 layer-lattice
smectite-type mineral is hectorite.
The catalyst of th~ present invention can be
prepared by any ion-exchange process wherein a metallic
cation having a Pauling electronegativity greater than 1.0
- can be made to replace the exchangeable cation of the
smectite-type clay. Preferably an aqueous solution of
a soluble salt of the desired metallic cation is admixed
with the desired smectite-type clay for a period o~ time
sufficient to effect the desired exchange. Preferably
an amount of metallic cation will be used which is from
100% to 500~ of the exchange capacity of the smectite-
type clay, more preferably 100% to 300~. It is preferred
to exchange at least 50~ of the exchangeable cations of
the smectite with the metallic cations of this invention.
It is also preferred to remove excess metallic cation salt
and the soluble salt by-products of the exchange from
the catalyst such as by filtration and washing prior to
drying the catalyst. Alternatively the excess metallic
cation salt and soluble salt by-product can be removed
from the dried catalyst by slurrying the catalyst in an
appropriate solvent, such as water or methanol, followed
by filtration and re-drying. The exchange can also be
conducted using a solution of the metallic cation salt
in an appropriate organic solvent, such as methanol.

~.~3~
Alterna-tively, the process disclosed in U.S. Patent No.
3, 725, 528 can be used to prepa~e the cat~lyst.
The eatalyst o~ this invention has been ~ound
to be active in cataly~ing the reaction between alkylatable
aromatic hydrocarbons and ole~in-acting compounds under
anh~drous alkylating conditions in the liquid phase.
Alkylatable aromatic hydrocarbons which can be
used in thé inventive process include benzene, toluene,
xylene, the naphthalene series of hydrocarbons, etc. Any
aromatic hydrocarbon ean be alkylated if it has an
unsubstituted earbon as long as steric hindrance does not
prevent alkylation with the particular olefin-acting
compound chosen or use in the pxocess, and as long as
the alkyl side chains on the aromatic ring do not prevent
the aromatic compound from being adsorbed onto the
layer-lattice surfaces of the catalyst. senzene is the
preferred aromatic hydrocarbon.
The ole~in-acting eompounds may be selected from
the group eonsisting of mono-olefins, alkyl bromides,
alkyl chlorides, and mixtures thereof. Representative
olefins include ethylene, propylene, l-butene, 2-butene,
l-pentene, 2-pentene, l-hexene, propylene tetramer,
l-octadecene, etc. Representative alkyl halides include
n-butyl bromide, n-butyl chloride, n-dodecyl bromide,
n-dodecyl chloride/ ete.
The process is carried out in the liquid phase
utilizing a catalytically effective amount of the eatalyst
hereinbefore described. The catalyst can be used in
amounts ~rom 1% to 100% by weight based on the olefin-
acting compound depending on the particular metalliccation-exchanged smectite-type ca-talyst chosen for
-8-
.,
. . . . . .
. , :. : :
'. . ~ '

6~D
r the reac-tion, the temperature o~ the reaction, and the
length of time the catalyst has been in service. Preferably
a concentration of catalyst from 2~ -to 50~ by weight is
used since thls gives a relatively fast alkylation, still
more preferably 2% to 10~,.
The pressure can be elevated and is not critical
as long as some of the olefin-acting compound can be kept
dissolved in the liquid aromatic phase. Thus the pressure
should be correlated with the temperature at which the
reaction is being carried out in order to maintain the
aromatic hydrocarbon in the liquid phase and to maintain
a sufficient amount of olefin-acting compound dissolved
therein to allow the alkylation reaction to pxoceed.
Atmospheric pressure is preferred because of the simplicity
of operations under atmospheric conditions.
The process is conducted at an elevated temperature
since the rate of alkylation is undesirably low at room
temperature. Preferably the temperature is in the range
from 40C to 20QC, more preferably 70C to 150C. It
is desirable to conduct the process at the boiling point
(reflux temperature) of the alkylatable aromatic hydrocarbon
provided that it is in the above noted range. A non-
alkylatable solvent, such as cyclohexane, can be used
to provide the liquid alkylating medium and the temperature
can conveniently be maintained at the boiling point
of the solvent.
The molar ratio of alkylatable aromatic hydrocarbon
to alkylating agent, i.e., the olefin-acting compound,
can vary widely depending on the product desired. Thus
at higher ratios such as 10 or above ess,entially only
mono-alkylated product is obtained whereas at lower ratios
_g_
' ' ' ' '
.

the amount o~ polyalkylated product is increased. Preferably
a molar ratio wlthin -the range from 3:1 to 20:1 will be
used, more preferably 5:1 to 10:1.
It lS important to maintain the reaction system
free of water since water has a deactivating effect on
the catalyst. Thus the catalyst must be dried before use.
This may conveniently be done by removing the water from
the catalyst at a low temperature, i.e., less than about
200C. Alternatively the water may be removed by azeotropic
distillation from a mixture of the catalyst in the alkylatable
aromatic hydrocarbon or the solvent to be used in the
reaction. This method will also remove any water present
in these organic systems and is preferred. The term
"anhydrous" as used in this specification and in the claims
is intended to mean that any free water which is present
in the catalyst or the organic components present in the
reaction mix is removed from the reaction system.
- The following non-limiting examples are given in
order to illustrate the invention.
~XAMPLES 1 - 27
Various cation exchanged forms of the natural
mineral hectorite were prepared as follows: The exchange
cation salt was dissolved in 500 to 750 ml. of methanol.
Hectorite clay which had been previously dispersed in
water, centrifuged, and spray dried in order to obtain
the purified clay, was mixed in this salt solution at
a concentration of 300 milliequivalents of cation per 100
grams of clay. This mixture was allowed to stand for
approximately 20 hours before it was filtered. The
filter cake was re-dispersed in 500 - 750 ml. of methanol
followed by filtration for a total of 3 successive washings.
--10--
.
.

The cation exchanged hec-torite was -then air dried for 20
hours at room temperature followe~ by oven drying at
105~C for 2 hours. The clay obtained by this process was
very fine and needed no grinding. In the case of Ag -
hectorite, 10 ml. of concentrated nitric acid was added to
the methanol solution before adding the clay to the solution,
in order to prevent oxide formation or hydrolysis of the
Ag .
These cation exchanged hectorite clays were
evaluated as catalysts for the alkylation of benzene using
the following procedure: 10 grams o the cation exchanged
hectorite and 200 - 250 ml. of benzene are refluxed in
a round bottom flask equipped with a Dean-Stark tube
attached to remove, azeotropically, sorbed water from
the clay. After 2 - 4 hours the tube was removed and the
reflux condenser rinsed with methanol and air dried to
remove any residual moisture trapped in the condenser.
10 grams of the alkylating agent were added to the flask
and the mixture refluxed with stirring for 24 hours. The
clay was removed by filtration and washed with 100 ml.
of benzenè. The benzene was removed from the filtrate
by vacuum evaporati;on leaving a product of unreacted
alkylating agent and/or alkylbenzené. This product was
then weighed!and analyzed by either infrared spectrophoto-
metry, refractometry, or gas chromatography to determine
the amount of alkylbenzene formed. The cation exchanged
hectorites evaluated and the data obtained are given
in Table 1.
The data indicate that the natural hectorite
clay containing exchanged metallic cations having a
Pauling electronegativity less than or equal to 1.0 were
. .
.' , .

~¢~ 3~
ineffective as catalysts for the alkyla-tion of benzene.
Metallic ca-tions having a Pauling electronegativity greater
than 1.0 were effective catalysts when exchanged onto
hectorite. These include se2 and Mg (Group IIA), A13
and In3 (Group IIIA), La tGroup IIIs)~ Cr3 (Group VIA),
Mn2+ (Group VIIB), Fe3+, Co2+, Ni2 and Pd2+ (Group VIII),
cu2 and Ag (Group IB), and Ce3 (rare earths). The
effect of moisture within the reaction zone on the activity
of certain of the catalysts can be ascertained by reference
to the data for Examples 1, 4 and 6. The small amount of
water which remained in the reflux condenser (Examples 1,6)
! or in the atmosphere (Example 4) was sufficient to decrease
the activity of A13+-exchanged hectorite approximately 50%,
whereas In3 -exchanged hectorite was very active in the
presence of such small quantities of water.

p~
TABLE 1
Alk~lation of senzene
Alkylating Agent: Catalyst Weight Ratio = 1:1
Benzene: Alkylating Agent Mole Ratio = 10:1
Temperature = 80.1C (B.P. of Benzene)
Duration of Re~ction = 24 Hours
Catalyst = Various Cation Exchanged Forms of Hectorite
Example Exchangeable Pauling
Cation on Electro-
Hectorite negativity Alkylating % Yield of
of Cation Agent Alkylbenzene
1 Al + 1.5 n-Butyl Bromide ~0 (36)
2 I~3 1.7 n-Butyl Bromide 86
3 H 2.1 n-Butyl Bromide 10
3+ b
4 A13+ 1.5 n-Butyl Chloride 18 (40)
In 1.7 n-Butyl Chloride 94
6 A13+ 1.5 Lauryl Bromide 89 a48)
7 In3+ 1.7 Lauryl Bromide (86)a
8 Fe 1.8 Lauryl Bromide (31)
9 A133++ 1.5 l-Octadecene93Cd
ln 1.7 l-Octadecene93
11 A13+ 1.5 1-Dodecene 88
12 Fe3+ 1.8 l-Dodecene 88
13 Cr3+ 1.6 l-Dodecene100
14 La3+ 1.1 l-Dodecene100
Ce2+ 1.1 l-Dodecene 99
16 Be2+ 1.5 l-Dodecene 96
17 Mg 1.2 l-Dodecene 96
18 ~n22-+~ 1.5 l-Dodecene 92
19 Co 1.8 l-Dodecene 91
Ni2+ 1.8 l-Dodecene 93
21 Cu 1.9 l-Dodecene 99
22 Pd2+ 2.2 l-Dodecene 71
23 ~g2+ 1.9 1 Dodecene100
24 Ca2+ 1.0 l-Dodecene 52
Ba+ 0.9 l-Dodecene 5
26 Li+ 1.0 l-Dodecene 5
27 Na 0.9 l-DodeceneTrace
a Methanol Rinse of Reflux Condenser Omitted
b Nitrogen Circulated through the Reaction Flask
c Small Amount of n-Butyl Bromide Added to Promote the Reaction
d Small Amount of Lauryl Bromide added to promote the reaction
e Clay without Exchange Treatment - Primarily Na Form.
-13-

EXAMPLES 28 - 43
Several cation exchanged hectorites were prepared
by at least one of the following procedures as indicated
in Table 2: Process A - exchange in methanol solution
as in Examples 1 - 27; Process s - exchange in aqueous
solution substituting water for methanol in Process A
except in the last washing step; Process C - exchange in
aqueous solution, no washing. These catalysts were evaluated
for the alkylation of benzene by l-dodecene at a l-dodecene:
catalyst weight ratio of 10:1 using the same process as
in Examples 1-27. The percent conversion of the olefin
~ after one hour is given in Table 2. The catalysts used
in Examples 33, 34, 37 and 38 were the same catalysts used
in Examples 32, 33, 36 and 37 respectfully, after rinsin~
them with benzene.
The data indicate that water is the preferred
solvent for the metallic cation salt, i.e., for the exchange
solution, and that the catalyst should be washed to remove
soluble salts from the catalyst. The catalyst can be
re-used after rinsing with benzene to remove adsorbed
products from the catalyst.
. . --1~--
. . .

TABI,E 2
Alkylation of Benzene with l-Dodecene
Benzene: l-Dodecene Mole Ratio = 10:1
l-Dodecene: Catalyst Welght Ratio: = 10:1
Temperature = 80.1C (B.P. of Benzene)
Duration of Run = One Hour
Example Exchangeable l-Dodecene Catalyst %
Cation onto Catio Preparation Conversion
Hectorite Ratio Process of Olefin
28 A13-~ 1,000/1 A 53
29 A1 1,000/1 B 95
Al 1,000/1 C 1~2
_ 31 Al 1,000/1 C 4.4
32 A1 1,000/1 ~ B 97
33 Al 1,000/1 B 77(a)
34 Al 1,000/1 B 37(b)
cr 526~1 A 90
36 Cr3 526/1 B 99+
37 Cr 526/1 B 82(c)
38 Cr3+ 526/1 B 5~(d)
39 In 263/1 A 3
In 263/1 B 99
41 ~ Mg 833/1 A 29
42 Fe3 357/1 B 84
43 ~g 256/1 A 21
. .
(a) The catalyst from the previous experiment, after X hours
reaction time and Y~ conversion of dodecene, was re-used
after it was rinsed with benzene, where X = 4 hours and
Y = 99.3%.
(b) As la), except X = 7 hours and Y = 99.1
(c) As (a), except X = 1 hour and Y = 99~%
(d) As (a), except X - 3 hours and Y = 93.4%
-15-

Y7~
Example 44
A sample of synthetic hectorite, commercially
available from NL INDUSTRIES, II~C. as BARASYMR LIH, was
exchanged with AlC13 using the process of Examples 1-27
to the A13+-exchanged form. This sample was used to
catalyze the reaction between n-butyl bromide and benzene
using the same process and conditions as i~ Examples 1-27~
62~ of this alkylating agent were converted to alkylbenzene.
Example 45
A sample of synthetic Na+-stevensite was exchanged
to the A13 form with AlC13 using the aqueous exchange
~ process B of Examples 28 - 43. This Al -stevenslte was
characterized by the structural formula:
~Mg5 83 Sig O20(OH)4] 0.11 Al
This sample was evaluated as a catalyst for the conversion
of l-dodecene and benzene to dodecylbenzene as in Examples
28 - 43. 44% of the dodecene was converted to dodecyl-
benzene after one hour.
- Examples 46 - 47
A13 -exchanged hectorite was used to catalyze
the alkylation of anthracene with l-octadecene by refluxing
anthracene and l-octadecene in a molar ratio of 10:1 and
an octadecene:catalyst ratio of 1:1 in cyclohexane. No
octadecene was detectable after 24 hours. Similar results
were obtained when biphenyl was substituted for the
anthracene.
Example 48
A sample of synthetic Na -saponite containing
occluded MgO was exchanged with ~lC13 using the process
of Exarnple 44. The A13 -saponite is characterized by
the structural formula:
-16-
. .
,

[ g6 S17,25 Alo.75 O20(OH)4]0.25 Al ~ 1.5 ~gO
This sample was evaluated as in Examples 28 ~ 43. 74~
of the dodecene was converted to dodec~lbenzene after one
hour.
Examples 49 - 59
An Al3~-exchanged hectorite and a Cr3~-exchanged
hectorite (purified natural clay as in Examples l - 27)
were prepared by the aqueous exchange process B of Examples
28 - 4'3. These,clays were evaluated as catalysts for the
alkylation of benzene by l-dodecene at various mole ratios -
of benzene to dodecene and/or various weight ratios oi
dodecene to catalyst as indicated in Table 3. The percent
conversion of dodecene after l hour and, in some cases,
24 hours using the same process as in Examples l - 27 was
determined. The data obtained are given in Table 3.
The data indicate that these exchanged clays
were excellent catalysts at concentrations of exchanged
clay greater than about 2%, based on the weighk of dodecene,
` although concentrations as low as 1~ converted most of
the dodecene in 24 hours.
17-

Table 3
Alkylation of Benzene with l-Dodecene
Benzene: l-dodecene Mole Ratio: as indicated
l-dodecene: Catalyst Weight Ratio: as indicated
Temperature: 80.1C (B.P. of Benzene)
Duration of Run: l,24 hours
Catalyst: A13 - and Cr3~-exchanged Hectorite as
indicated
Exchangeable l-dodecene Benzene -to % Conversion
Cation on to Catalyst l-dodecene of l-dodecene
E ~mple HectoriteWt. Ratio Mole Ratio l Hr._24 Hr.
49 Cr3+ 10:1 lO:l 99.6 --
Cr3+ 20:1 10:1 98.4 --
51 Cr3+ 40:1 10:1 70.1 --
52 Cr3+ 100:1 10:1 43.7 83.8
53 A13 lO:l 10:1 97.0 --
54 Al 20:1 10:1 98.2 --
Al3 40:1 10:1 82.1 99.0
56 Al3 50:1 5:1 55.2 90.2
57 Al3+ 100:1 lO:l 34.2 78.0
58 Al lO0:1 5:1 18.9 71.6
59 Al lO0:1 20:1 29.6 67.1
-17a-
.
. :. .
.

Example_60
A sample of synthetic hectorite-type clay commerially
available as LAPONITE B ~ was exchanged with AlC13
using process B of Examples 28 - 43 to the A13+-
exchanged form. This sample was used to catalyze the
reaction between l-dodecene and benzene as in Examples 28
- 43. 88% of the dodecene was converted to dodecylbenzene
after 1 hour.
.

As indicated, the trioctahedral 2:1 layer-lattice
smectite-type clay minerals useful in preparing the catalysts
for the catalytic processes descrlbed and hereinafter
claimed can be prepared synthetically by either a hydro-
thermal process or a pneumatolytic process. Such smectite-
type clays can be synthesized having one or more metallic
cations having an ionic radius not greater than 0.75 A in
the central octahedral layer and having one or more metallic
cations having an ionic radius not greater than 0.64 A
in:ithe two outer tetrahedral layers. Thus such synthetic
trioctahedral 2:1 layer~lattice smectite-type clays have
the following general structural formula:
[ bM + cM ) (dD+3 + e D+4 +fD+5)IV O (O )
z
where 11 < a+2b+3c < 12 0 < a < 1
31 < 3d+4e+5f < 32 5 < b < 6
43 < a+2b+3c+3d+4e+5f< 43.67 0 < c < 0.3
x = 44-(a+2b+3c+3d+4e+5f3 0 < d < 1
o < y < 4 7 < e < 8
0 ~ f < 0.4
and where the metallic cations M are in the octahedral
layer and have an ionic radius not greater than 0.75 A,
the metallic cations D are in the two outer tetrahedral
layars and have an ionic radlus not greater than 0.64 A,
and R is at least one exchangeable charge-balancing cation
of valence z.
Preferably the cation M is selected from the
group consisting of Li+ M 2-~ Ni2-~ C 2~ z 2-~ C 2-
~
Mn2+, A13 , and mixtures thereof, the cation D is selected
- from the group consistiny of ~13+, Cr3 , Fe3~, Si ~, Ge 4,
-19-
.. . . . .

and mi~tures thereof, and the cation R is selected from the
group consisting of Li , Na , NH4 , and mixture thereof.
Such synthetic hectorite-type clays can be repre-
sented by the structural formula:
_
(M6 x LiX) (D8 ) 20(OH)4_yFy~ Z R
where 0.33 x < 1 and 0 < y < 4.
Such synthetic saponite-type clays can be
represented by the structural formula:
[(M6 ) ~D8 x Dx ) O20(H)4 yFy~ x RZ
where 0.33 ~ x ~ 1 and 0 < y < 4.
It will be understood that while I have explained
-
the invention with the aid of specific examples, nevertheless
considerable variation is possible in choice o~ raw materials,
proportions, processing conditions and the like, within
the broad scope of the invention as set forth in the claims
which follow. Thus, for example, my inventive catalyst
may be used simultaneously with other catalytic materials
so as to suit,particular conditions and circumstances.
-20-
. .