PROCESS FOR THE ALKYLATION OF AROMATIC COMPOUNDS
The present invention relates to a process for the alkylation of aromatic compounds. More specifically, the present invention relates to a process for the alkylation of aromatic compounds, carried out in the presence of a solid catalyst, and a method for increasing the duration of the catalytic activity of said catalyst . The synthesis of alkylaromatic compounds is known in literature. For example, European patent 432,814 describes the synthesis of alkylaromatic compounds, such as cu ene or ethylbenzene, by the reaction between an aromatic hydrocarbon (benzene) and an olefin (propylene or ethylene) in the presence of a Beta zeolite, optionally modified by the partial substitution of the aluminum with other elements such as boron, gallium or iron.
More specifically, according to this patent application, the reagents of the alkylation reaction are put in contact with the catalyst at a temperature ranging from 100
to 300°C, at a pressure ranging from 1 to 5 MPa (10 to 50 atm) and a flow-rate of the reagents which is such as to give a HSV (Weight Hourly Space Velocity) ranging from 0.1 to 200 h"1. Under these operating conditions, the catalyst does not have a long life, referring to the time between two regenerations.
European patent 780,354 describes a method for increasing the life of the alkylation catalysts of- aromatic compounds resorting to particular reagents treatments, in particular of the aromatic compound, suitable for eliminating or significantly reducing the presence of poisons for the catalyst itself. This treatment essentially consists in eliminating the oxygen dissolved in the aromatic hydrocarbon and in percolating the deoxygenated aromatic hydrocar- bon onto a bed of alumina modified with silver.
The Applicant has now found that better results can be obtained than those of the known art, in terms of treatment efficiency and stability of the catalyst with time, by substituting the alumina modified with silver with alumina modified with palladium and contemporaneously treating the aromatic hydrocarbon with hydrogen.
An object of the present invention therefore relates to a process for the alkylation of aromatic compounds which comprises reacting an olefin with an aromatic hydrocarbon in the presence of a zeolite and under conventional operat-
ing conditions, characterized in that the aromatic hydrocarbon, before the alkylation reaction, is passed through a fixed bed, consisting of particles of alumina modified with palladium, in the presence of hydrogen. A further object of the present invention relates to a method for increasing the duration of the catalytic activity of a catalyst for the alkylation reaction of an aromatic hydrocarbon with olefins which comprises treating the aromatic hydrocarbon through a filter, consisting of a fixed bed of particles of alumina modified with palladium, in the presence of hydrogen.
According to the present invention, it is possible, even if not necessary, to effect a pretreatment for the at least partial reduction of the concentration of oxygen in the aromatic hydrocarbon. This treatment can be effected with known techniques such as distillation, also under vacuum, or stripping with inert gases, for example with nitrogen or another inert gas towards the aromatic hydrocarbon. In particular, the possible pretreatment for the re- duction of the oxygen concentration can be effected with a semi-continuous or continuous technique. In the former case, the aromatic hydrocarbon, kept in a closed container is flushed with a stream of nitrogen which bubbles through the liquid mass. In the latter case, the aromatic hydrocar- bon is flushed with gaseous nitrogen in countercurrent us-
ing, for example, filled columns, plate columns, etc. continuously fed at the head with the aromatic hydrocarbon and at the base with nitrogen.
The pretreatment with nitrogen can be effected at room temperature or a high temperature, for example from 50 to
250°C, also depending on the physical state of the aromatic hydrocarbon, and at atmospheric pressure or a value slightly higher than atmospheric pressure or under vacuum.
Either the pretreatment operation with nitrogen be carried out in semi-continuous or continuous, or at room temperature or at a high temperature, it is preferable to operate with nitrogen volume/liquid ratios ranging from 10 to 400.
Any aromatic hydrocarbon which can be used in alkyla- tion reactions with olefins can be adopted in the present invention. In general, aromatic hydrocarbons liquid at room temperature are preferred, such as benzene or benzene substituted with Cι-C4 alkyl radicals. Aromatic hydrocarbons containing from 10 to 25 carbon atoms, or phenols, which are solid at room temperature, can also be used. In this case, the purification treatment described above is effected at a temperature which ensures that the hydrocarbon is in the fluid state.
Analogously, any olefin which can be used in the alky- lation reaction of aromatic hydrocarbons can be adopted in
the present invention, such as, for example, C2-C12 olefins. Preferred olefins are ethylene and propylene.
The passage of the aromatic hydrocarbon through the fixed bed is effected through one or more beds of alumina modified with palladium, in the presence of a stream of hydrogen in equicurrent or countercurrent . In particular, alumina modified with 0.01%-1% by weight of palladium, having a substantially spherical form and with an average particle diameter varying from 3 to 5 mm, can be used. Fur- thermore, the modified alumina has a density ranging from 0.5 to 1 kg/litre and a specific surface ranging from 140 to 180 m2/g.
The alumina modified with palladium according to the present invention can be prepared with the conventional techniques, for example by impregnation of the alumina with palladium chloride and subsequent reduction with hydrogen, after calcination.
The treatment of the aromatic hydrocarbon through the fixed bed preferably takes place in continuous, by passing the aromatic hydrocarbon, in gaseous or liquid phase, on one or more fixed beds, together with a stream of hydrogen. It is preferable to operate with liquid/solid ratios which are such as to give a WHSV ranging from 1 to 30 h"1, with temperatures ranging from 25 to 250°C and with H2/hydrocarbon weight ratios ranging from 10"5 to 10"3.
The alkylation reaction of the aromatic hydrocarbon with olefins takes place with the known methods, for example with the method described in European patent 432,814.
The alkylation reaction can generally be carried out in liquid, gaseous or mixed phase, in batchwise, in continuous or semi-continuous way.
The reaction temperature ranges from 100 to 300°C, preferably from 110 to 250°C, whereas the pressure ranges from 0.5 to 5 MPa (5-50 bars), preferably from 2.5 to 4 MPa (25-40 bars) . The feeding of the reagents, whether operating in continuous or semi-continuous, is such as to give a WHSV space velocity within the range of 0.1 to 200 h"1. The molar ratios aromatic hydrocarbon/olefin range from 2 to 30. Any zeolite capable of providing a catalytic activity in the alkylation reaction of aromatic hydrocarbons can be used in the present invention. Examples are Y and Beta zeolite.
Beta zeolite, described in U.S. patent 3,308,069, is preferred. This zeolite is a synthetic porous crystalline material with the following composition:
[ (x/n) M (1+0.1-x) TEA]A102ySi02wH20 wherein x is a number lower than 1, y ranges from 5 to 100, w is 0 and ranges from 1 to 4, M is a metal belonging to groups IA, IIA, IIIA or a transition metal, TEA is tetra-
ethyl ammonium. This catalyst can also be used in modified form by partial substitution of the aluminum with boron, gallium or iron.
At the end of its catalytic activity, the catalyst can be regenerated by thermal treatment in air at temperatures ranging from 500 to 800°C. The time between two regenerations, thanks to the method object of the present invention, is generally higher than 8000 hours.
Some applicative and non-limiting examples are pro- vided below for a better understanding of the present invention and for its embodiment .
In the examples, a Beta zeolite was used, in the form of pellets, prepared according to the process described in European patent 432,814, having an Si02/Al203 ratio equal to 20 and a sodium content equal to about 200 ppm. EXAMPLE 1
150 cc of extruded catalyst based on beta zeolite are charged into a fixed bed tubular reactor which simulates the first catalytic bed of a multi-bed plant in series. The reactor is maintained at a pressure of 4 MPa and fed in continuous with benzene at a temperature of 220°C and a flow-rate which is such as to give an LHSV of 12 h"1 and with ethylene according to a molar ratio ethylene/benzene equal to 0.05. The alkylated liquid is collected downstream of the
reactor and is subjected to gaschromatographic analysis.
The test is interrupted when traces of non-reacted ethylene are observed in the reactor effluent.
Operating as described above, a productivity of 5,000 Kg of ethylbenzene per Kg of active phase of the catalyst, is obtained. EXAMPLE 2
The same procedure is adopted as in Example -1, except that the benzene before being fed to the reactor is passed on a bed of alumina modified with 0.3% by weight of palladium in the presence of a stream of hydrogen, at a temperature of 80°C and at the pressure necessary for maintaining the benzene in liquid state .
The weight ratio between hydrogen and benzene is equal to 1.5-10"5 and the quantity of alumina is such as to have a WHSV equal to about 8 h"1.
The test is interrupted when traces of non-reacted ethylene are observed in the reactor effluent.
In this way, a productivity of 25,000 Kg of ethylben- zene per Kg of active phase of the catalyst, is obtained.