Mineral oils: processes and products – Chemical conversion of hydrocarbons – Cracking
Reexamination Certificate
2000-10-16
2004-03-30
Elve, M. Alexandra (Department: 1725)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
Cracking
C208S111300, C208S111350, C502S064000, C502S066000, C502S074000, C502S079000
Reexamination Certificate
active
06712953
ABSTRACT:
This invention relates to a catalyst that can be used for hydrorefining and hydrocracking of hydrocarbon feedstocks under hydrogen pressure, whereby said catalyst comprises at least one zeolite, preferably a Y or beta zeolite, and at least one oxide matrix, whereby the zeolite contains in its porous network at least one metal of group VIB (group 6 according to the new notation of the periodic table: Handbook of Chemistry and Physics, 76th Edition, 1995-1996), preferably molybdenum and tungsten, and/or at least one noble or non-noble metal of group VIII (groups 8, 9 and 10) of said classification, preferably cobalt, nickel and iron. The oxide matrix contains at least one hydro-dehydrogenating metal, preferably of group VIB, advantageously molybdenum and tungsten, and/or at least one metal of group VIII, advantageously cobalt, nickel and iron. At least one promoter element (phosphorus, boron, silicon) is present.
This invention also relates to the processes for preparation of said catalyst, as well as its use for the hydrocracking of hydrocarbon feedstocks, such as the petroleum fractions and the fractions that are obtained from carbon containing sulfur and nitrogen in the form of organic compounds, whereby said feedstocks optionally contain metals and/or oxygen.
Conventional hydrocracking of petroleum fractions is a very important refining process that makes it possible to produce, starting from excess heavy hydrocarbon feedstocks, lighter fractions such as gasolines, kerosenes and light gasoils that the refiner seeks to adapt his production to the structure of the demand. Relative to the catalytic cracking, the advantage of catalytic hydrocracking is to provide more selectively middle distillates, kerosenes and gasoils of very good quality.
The catalysts that are used in conventional hydrocracking are all of bifunctional type that link an acid function to a hydrogenating function. The acid function is generally provided by crystallized aluminosilicate-type substrates that are called zeolites. The hydrogenating function is provided either by one or several metals of group VIII of the periodic table, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by a combination of at least one metal of group VI of the periodic table, such as chromium, molybdenum and tungsten, and at least one metal of group VIII, in general a non-noble metal such as Co, Ni and Fe.
The pure or dealuminified zeolite-type substrates that are, for example, of Y type or else beta type have a very strong acidity. These substrates therefore ensure the acid function of the hydrocracking catalysts. These systems are active, and the products that are formed are of good quality. The drawback of these zeolite-based catalytic systems is a degradation of the selectivity of middle distillates (gasoil+kerosene) when the amount of zeolite is increased. This therefore limits the amount of zeolite that can be used in the catalyst and therefore the level of activity that can be achieved while maintaining a good selectivity of middle distillates.
The applicant discovered that to obtain a hydrocracking catalyst that has strong activity and good selectivity of middle distillates, it is advantageous to provide a promoter element and to introduce into the porous network of the zeolite a hydrogenating phase that thus comes to reinforce the hydro-dehydrogenating phase that is present in the oxide matrix, and it is also advantageous to use a large amount of zeolite. The hydrogenating function that is introduced into the zeolite is ensured by at least one metal or metal compound of group VI and/or at least one metal or metal compound of group VIII. It is advantageously possible to use a combination of metals of group VI and/or a combination of metals of group VIII.
More specifically, the invention relates to a catalyst that contains at least one matrix, at least one zeolite and at least one hydro-dehydrogenating element that is located at the matrix (i.e., deposited on the catalyst or contained in the matrix), catalyst in which the zeolite contains in its porous network at least one element of group VIB and/or group VIII, whereby the catalyst also contains at least one promoter element that is selected from the group that is formed by boron, silicon and phosphorus.
The catalyst of this invention generally contains in % by weight relative to the total mass of the catalyst:
0.1 to 99%, or 0.1-98.7%, or else 0.1 to 95% and preferably 0.1-90% and even 0.1-85%, of at least one zeolite, preferably a Y zeolite or a beta zeolite, advantageously the zeolite content is at least 5% by weight, preferably at least 15%, and even at least 20%,
1 to 99.7%, or 1 to 98.8%, preferably 10 to 98% and even more preferably is to 95% of at least one amorphous oxide matrix, preferably an alumina, a silica or a silica-alumina,
at least one of the elements of groups VIB and/or VIII at a ratio of:
0.1 to 40%, preferably 3 to 45% and even more preferably 5 to 30% of metals of group VIB (expressed in % of oxide),
0.1 to 30%, preferably 0.1 to 25% and even more preferably 0.1 to 20% of metals of group VIII (expressed in % of oxide),
at most 20%, or else 0.1-20%, preferably 0 to 15% and even more preferably 0 to 10% (expressed in % of oxide), of at least one promoter element that is selected from the group that is formed by boron, phosphorus, silicon (not including the silicon that is contained in the zeolite),
and optionally 0-20%, preferably 0.1-15%, or else 0.1-10% of at least one element that is selected from group VII A, preferably fluorine,
catalyst in which the zeolite contains in its porous system at least one of the elements of groups VIB and VIII at a ratio of (in % by weight in the catalyst):
0.1 to 10%, preferably 0.1 to 5% and even more preferably 0.1 to 3% by weight of oxide of at least one metal of group VIB,
0.1 to 10%, preferably 0 to 7% and even more preferably 0 to 5% by weight of oxide of at least one metal of group VIII.
The metal of group VIB that is contained in the porous network of the zeolite can be the same or different from the one that is contained in the matrix. In the same way, the metal of group VIII that is contained in the zeolite can be the same or different from the one that is contained in the matrix.
The demonstration of the presence of the hydrogenating phase in the porous network of the zeolite can be carried out by various methods that are known to one skilled in the art such as, for example, the electronic microprobe and the electronic transmission microscopy equipped with an X energy dispersion spectrometer with a detector that allows the identification and the quantification of elements that are present in the crystals of the zeolite and in the oxide matrix.
A preferred catalyst comprises at least one element of GVIB in the zeolite, at least one element of GVIII at the matrix and at least one promoter element (i.e., located mainly at the matrix and deposited on the matrix).
The catalyst of this invention has a very high hydrocracking activity of the hydrocarbon fractions and a greater selectivity than the catalytic formulas that are known in the prior art. Without subscribing to any particular theory, it seems that this particularly high activity of the catalysts of this invention is due to the joint presence of a hydrogenating function on the matrix and a particular hydrogenating function within the porous network of the zeolite, in combination with the presence of a promoter element.
More specifically, a preparation method comprises the following stages:
a) Introduction into the zeolite of at least one element of group VIB and/or group VIII;
b) mixing with the matrix and shaping to obtain the substrate;
c) introduction of at least one promoter element by impregnation and introduction of at least one hydro-dehydrogenating element into the matrix or in the substrate by at least one of the following methods:
addition of at least one compound of said element during the shaping to introduce at least a portion of said element,
impregnation of the substrate with at least one comp
Cseri Tivadar
Dascotte Philippe
Kasztelan Slavik
Leyrit Pierre
Marchal-George Nathalie
Elve M. Alexandra
Ildebrando Christina
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
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