Mineral oils: processes and products – Chemical conversion of hydrocarbons – Cracking
Reexamination Certificate
2000-06-26
2003-03-11
Dunn, Tom (Department: 1725)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
Cracking
C208S111350, C208S21600R, C208S217000, C208S25100H, C208S25400R, C502S064000, C502S066000, C502S074000, C502S079000
Reexamination Certificate
active
06531051
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 VB (group 5 according to the new notation of the periodic table: Handbook of Chemistry and Physics, 76th Edition, 1995-1996), (preferably niobium) and optionally 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 metal of group VIB, advantageously molybdenum and tungsten, and/or at least one metal of group VIII, advantageously cobalt, nickel and iron, and/or at least one metal of group VB, preferably niobium. The catalyst also contains at least one promoter element (phosphorus, boron, silicon).
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 therefore 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+kerosenes) 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 distillate.
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 hydrogenating phase that is present in the oxide matrix, and it is also advantageous to use a large amount of zeolite. A hydrogenating function that is introduced into the zeolite can be ensured by at least one element or element compound of group VB such as niobium, at least one element of group VIB and/or at least one element of group VIII. The element of group VB can advantageously be associated with at least one metal or metal compound of group VIII. It is advantageously possible to use a combination of metals of group VB and optionally 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 element that is located at the matrix (i.e., deposited on the catalyst or contained in the matrix), and selected from the group that is formed by the elements of groups VIB, VIII and VB and at least one promoter element that is selected from the group that is formed by phosphorus, boron, and silicon, whereby the zeolite contains in its porous network at least one element of group VB.
The catalyst of this invention generally contains in % by weight relative to the total mass of the catalyst:
0.1 to 99%, or 0.1-98.8%, 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%, preferably at least 15%, and even at least 20%,
1 to 99.7%, or 1 to 97.9%, preferably 10 to 95% and even more preferably 15 to 95% of at least one amorphous oxide matrix, preferably an alumina, a silica or a silica-alumina,
0.1 to 40%, or 0.1-40%, advantageously 1 to 40%, preferably 1.5 to 35% and even more preferably 2 to 30% of at least one metal of group VB (expressed by weight of oxide),
0 to 40%, advantageously 1 to 40%, preferably 1.5 to 35% and even more preferably 2 to 30% of at least one metal of group VIB (expressed by weight of oxide),
0 to 30%, advantageously 0.1 to 30%, preferably 0.1 to 25% and even more preferably 0.1 to 20% of at least one metal of group VIII (expressed by weight of oxide),
at most 20%, or else 0.1-20%, preferably 0 to 15% and even more preferably 0 to 10% (expressed by weight 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, and the zeolite contains in its porous system (expressed by weight of oxide in the catalyst):
0.1 to 10%, preferably 0.1 to 7%, and even more preferably 0.1 to 5% by weight of oxide of at least one metal of group VB, and optionally,
0 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 and/or at least one metal of group VIB, whereby a content of at least 0.1% is advantageous.
The metal of group VB 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.
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 at the matrix and an element of group VB within the porous network of the zeolite, in combination with the presence of a promoter element.
The hydrogenating function on the matrix is ensured by at least one element of groups VIII, VIB, VB and preferably by at least one element of GVIB or advantageously by an element of GVIII, preferably a non noble element (Co, Ni). A combination of at least one element of GVIII and at least one element of GVIB preferably will be used.
The promoter element is mainly located on the matrix. The silicon promoter e
Cseri Tivadar
Dascotte Philippe
Kasztelan Slavik
Leyrit Pierre
Marchal-George Nathalie
Dunn Tom
Ildebrando Christina
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
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