Chemistry of hydrocarbon compounds – Saturated compound synthesis – By condensation of a paraffin molecule with an olefin-acting...
Reexamination Certificate
1999-12-07
2001-05-01
Bell, Mark L. (Department: 1755)
Chemistry of hydrocarbon compounds
Saturated compound synthesis
By condensation of a paraffin molecule with an olefin-acting...
C585S721000
Reexamination Certificate
active
06225517
ABSTRACT:
This invention relates to a new alkylation catalyst, its preparation process, and its use in alkylation processes, notably in the alkylation of isobutene by light olefins. It is to this particular application of this catalyst that we will refer to more specifically, because of its economic importance, but this invention is, of course, not limited to this application.
It is known that isobutene alkylation by light olefins—that have between three and five atoms (referred to as C
3
to C
5
)—yields an alkylate which possesses a high octane level and minimal amounts of unsaturated or aromatic compounds. This interesting property allows the use of the alkylate in important gasoline formulation, which is currently being researched by the petroleum industry.
This type of reaction can be achieved only with acid or very acid catalysts, and not without a reduction of peripheral reactions such as polymerization, which produce unsaturated hydrocarbons. Among these catalysts, we should mention sulfuric acid and fluoric acid types, which are, during the alkylation process, placed in contact as liquids with the isoparrafin-olefin mix to form an emulsion. However, such processes pose serious security, corrosion, and environmental problems. Since several national legal bodies are adopting stricter restrictions in this area, specialists have had to turn toward the development of catalysts prepared with a base of solid acids.
Among these solid-acid catalysts, we should mention those of Lewis and/or of Bronsted, which have been set on various inorganic platforms, as described in patents U.S. Pat. Nos. 3,975,299, 3,852,371, 3,979,476, and 4,613,723. We can also mention solid-acid catalysts based on aluminia chloride, described in the patents U.S. Pat. Nos. 3,240,840, 3,523,142, 4,066,716, 4,083,800, 4,066,716, 4,113,657, 4,138,444, and 2,999,074. We can see, however, that these catalysts have an insufficient activity, a minor alkylation selectivity, and that they do not really provide the stability generally required of catalysts. Furthermore, certain catalysts require operating temperatures that are lower than the ambient temperature, and this increases operating costs.
SUMMARY OF THE INVENTION
While the Applicant was performing research, it was discovered, by a surprising method, that adding metals from groups IA and IIA of the Periodic Table of Elements to the solid-acid alumina chloride-based catalyst increases performance.
These are the objectives of this invention:
to augment the selectivity and/or stability of this type of catalyst, while maintaining a sufficient activity level in the alkylation of isobutene by light olefins, and
to be able to perform the alkylation of the isobutene in a wide range of temperatures, especially near ambient temperature, thus making operation easier.
To this effect, the invention first aims to be an alkylation catalyst containing a porous alumina support, which has at least one halogen on its surface, and which between 0.005 and 1% of its weight is made up of at least one metal from the IA or IIA group of the Periodic Table of Elements.
The alumina, as the support surface, will have a porous density between 5 and 400 m
2
/g as determined by the B.E.T. method. The halogen on the support surface may be chloride, and its weight amount should be between 2 and 10%, preferably between 3 and 8%. The weight amount of the group IA or IIA (Periodic Table of Elements) metals will be best between 0.05 and 0.5%.
The catalyst, according to the invention, may eventually contain a metal from group VIII of the Periodic Table of Elements, in order to facilitate its regeneration (platinum for example).
The catalyst described in the invention may be prepared according to the preceding instructions, by usual manufacturing methods well known to professionals in this field. One of the preparation methods may consist, first, of laying the metal (or metals) from group IA or IIA of the Periodic Table of Elements by impregnation of the alumina support into a water-based solution which contains the salt of at least one of these metals. This water-based solution may be nitrate, chloride, or sulfate-based, but since, as described later, the catalyst must undergo a chlorinating, the Applicant therefore prefers to use a water-chlorine solution and one of the metals mentioned above. Of these metals, the Applicant has successfully tested lithium, sodium, potassium, cesium, magnesium, and barium.
The impregnation phase in the water-based metal-salt solution is then followed by a drying of the solution in an evaporation centrifuge.
After these two steps, the catalyst is dried at 120° C. then calcined in an oven at 500° C.
The catalyst support may also be impregnated by the so called dry impregnation method, well known from a previous technique, or by any other means of impregnation.
The second step is to chloride the impregnated support, using, for example, nitrogen or hydrogen-maintained anhydrous chlorhydric acid, at temperatures equal to or greater than 650°, or by any other chlorination method.
A second element of the invention is thus the manufacturing process of this catalyst, outlined in the following steps:
pre-impregnation of a porous alumina support by at least one salt of a metal from groups IA and/or IIA of the Periodic Table of Elements, dry or in a water-based solution,
drying of the impregnated support,
calcination of the support, and
finally, chlorinating of the support.
The prepared catalyst is now ready to be used in the alkylation process, especially for the alkylation of isobutenes by light olefins, notably by butenes.
The following uses of the catalyst constitute other parts of the invention.
In the case of the alkylation of isobutenes by light olefins, the process can be realized under the following conditions:
temperature: between −20° and 100° C., preferably between −5° and 35° C.,
pressure: sufficient to maintain the elements in a liquid form within the reactor,
hourly spatial speed: expressed in p.p.h. (weight of olefins passing on the catalyst by weight unit of the catalyst and by hour), between 0.001 and 10 h
−1
, preferably between 0.05 and 3 h
−1
,
molar ratio of isobutene to olefins: between 1 and 100.
The reactor within which the alkylation occurs may uses the catalyst as a solid bed, a mobile bed, a fluid bed, or even in suspension in the efficiently agitated liquid phase of the reagents.
The Applicant has successfully used a reactor which uses the catalyst as a solid bed, which is then filled with isobutene prior to the beginning of the alkylation process, that is to say before the injection of the isobutene-olefins mix into the reactor. Working with an excess of isobutene in relation to olefins (molar relation between 1 and 100) restricts secondary reactions.
The activity of the catalyst is measured by the conversion of olefins.
The conversion of the olefins is calculated according to this formula:
Conversion
=
rate
of
olefin
mass
input
-
rate
of
olefin
mass
output
rate
of
olefin
mass
input
Furthermore, we know that the alkylate obtained from the alkylation of isobutene by light olefins contain different elements, such as and in particular, hydrocarbons C
5
to C
7
, heavier hydrocarbons C
8
, among which trimethylpentane (TMP) and dimethylhexanes (DMH), and finally of hydrocarbons heavy in C
9+
.
The selectivity of the catalyst for alkylation is measured by:
the selectivity of the obtained alkylates, represented by the selectivity in C
9+
compounds.
the composition of the resulting alkylate, represented by:
the rate of C
5
-C
7
in the C
5+
;
the rate of C
6
in the C
5+
;
the rate of C
9+
in the C
5+
.
According to the following formulas:
C
5
+
selectivity
=
Rate
of
C
5
+
mass
input
Rate
of
&emsp
Milan Alain
Nascimento Pedro
Szabo Georges
Bell Mark L.
Hailey Patricia L.
Sughrue Mion Zinn Macpeak & Seas, PLLC
Total Raffinage Distribution , S.A.
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