Zeolite Y catalyst containing silicon useful for hydrocracking

Details Zeolite Y catalyst containing silicon useful for hydrocracking Zeolite Y catalyst containing silicon useful for hydrocracking

1999-05-05

2001-01-09

Dunn, Tom (Department: 1754)

Mineral oils: processes and products

Chemical conversion of hydrocarbons

Cracking

C208S111200, C208S111300, C208S111350, C202S098000, C202S098000, C202S098000, C202S098000, C202S098000

Reexamination Certificate

active

06171474

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a catalyst comprising a matrix, at least one particular Y zeolite, at least one hydro-dehydrogenating metal, and silicon deposited on the catalyst.
The present invention also relates to processes for preparing said catalyst, and to its use in converting hydrocarbon-containing feeds such as petroleum cuts, cuts from coal, or hydrocarbons produced from natural gas. The hydrocarbon-containing feeds contain aromatic and/or olefinic and/or naphthenic and/or paraffinic compounds, and possibly metals and/or nitrogen and/or oxygen and/or sulphur.
BACKGROUND OF THE INVENTION
Hydrocracking is gaining in importance in refining as the need to convert heavy fractions into lighter fractions which can be upgraded as fuels increases. This results from the increasing demand for fuels. Such upgrading involves a relatively large reduction in the molecular weight of the heavy constituents which can, for example, be achieved through cracking reactions.
The catalytic hydrocracking process uses catalysts containing a hydrogenating, desulphurising and denitrogenating function provided by the active phase based on transition metals, and an acidic function, generally provided by the amorphous matrix or a zeolite, or a mixture thereof. A good hydrocracking catalyst will be constituted by a properly adjusted hydrogenating function and acidic function. Hydrocracking is used to treat feeds such as vacuum gas oils, and atmospheric or vacuum residues, which may or may not be deasphalted. Hydrocracking can produce highly purified lighter cuts, i.e., with a low sulphur, nitrogen and metals content.
Increasing the activity and selectivity of hydrocracking catalysts is thus important. One means consists of acidifying the matrix without poisoning the activity of either the transition-metal based hydrogenating phase or the cracking activity of the zeolite-based acidic phase.
SUMMARY OF THE INVENTION
The invention relates to a catalyst suitable for use in hydrocracking hydrocarbon-containing feeds. The catalyst contains at least one hydro-dehydrogenating metal, preferably selected from group VIB and group VIII of the periodic table. The catalyst comprises at least one Y zeolite with a faujasite structure which is at least partially in its hydrogen form, and an amorphous or low crystallinity matrix acting as a binder. The catalyst is characterized in that it also comprises silicon as a promoter element, and optionally phosphorous and/or boron, optionally a group VIIA element (halogen), preferably fluorine, and optionally a group VIIB element (preferably manganese, and rhenium may also be advantageous).
The catalyst of the invention has a higher hydrocracking activity and selectivity than those of prior art catalytic formulae based on dealuminated Y zeolite. Without wishing to be bound to a particular theory, it appears that this particularly high activity of the catalysts of the present invention is due to the acidity of the catalyst being reinforced by the joint presence of boron and silicon on the matrix which causes a very substantial improvement in the hydrocracking properties compared with catalysts in routine use.
The catalyst of the present invention generally comprises, in weight % with respect to the total catalyst weight, at least one metal selected from the following groups and with the following amounts:
0.1% to 60%, preferably 0.1% to 50%, more preferably 0.1% to 40%, of at least one hydro-dehydrogenating metal selected from group VIB and group VIII (% of oxide);
0.1% to 99.7%, preferably 1% to 99%, of at least one amorphous or low crystallinity oxide type porous mineral matrix;
0.1% to 90%, preferably 0.1% to 80%, more preferably 0.1% to 70%, of at least one Y zeolite with a lattice parameter in the range 2.424 to 2.455 nm, preferably in the range 2.426 to 2.438 nm and which shows particular characteristics hereafter described;
0.1% to 20%, preferably 0.1% to 15%, more preferably 0.1% to 10%, of silicon deposited on the support (matrix + zeolite) and principally located on the matrix (% of oxide);
and optionally:
0 to 20%, preferably 0.1% to 15%, more preferably 0.1% to 10%, of boron, advantageously deposited on the catalyst;
0 to 20%, preferably 0. 1% to 15%, more preferably 0.1% to 10%, of phosphorous (% of oxide), advantageously deposited on the catalyst;
0 to 20%, preferably 0.1% to 15%, more preferably 0.1% to 10%, of at least one element selected from group VIIA, preferably fluorine;
0 to 20%, preferably 0.1% to 15%, more preferably 0.1% to 10%, of at least one element selected from group VIIB (% of oxide).
The used dealuminated Y zeolite is characterized by different specifications:
a lattice parameter in the range 2.424 to 2.455 nm, preferably in the range 2.426 to 2.438 nm;
a global SiO
2
/Al
2
O
3
mole ratio of more than 8;
a framework SiO
2
/Al
2
O
3
mole ratio which is higher than or equal to the global SiO
2
/Al
2
O
3
mole ratio;
a quantity of cations of alkaline-earth metals or alkali metals and/or rare earth cations (atomic number 57 to 71 inclusive) such that the atomic ratio [n×M
n+
]/Al (n being the charge of cation M) is less than 0.8, preferably less than 0.5 and more preferably less than 0.1;
a specific surface area, determined by the BET method, of more than about 400 m
2
/g, preferably more than 550 m
2
/g;
a water adsorption capacity for P/P
0 =
0.2 of more than about 6% by weight at 25° C.
The group VIB, group VIII and group VIIB metals in the catalyst of the present invention can be completely or partially present in the form of the metal and/or oxide and/or sulphide.
The catalysts of the invention can be prepared using any suitable method. Preferably, the silicon and/or boron are introduced into the catalyst already containing the support and the group VIB and optional group VIII metal or metals. Preferably, a conventional NiMo or NiMoP type hydrocracking catalyst on a support comprising a mixture of alumina and Y zeolite is impregnated with an aqueous boron solution or with an aqueous silicon solution or it is impregnated with an aqueous solution containing both boron and silicon.
The silicon introduced onto the support of the invention is principally located on the matrix of the support and can be characterized by techniques such as a Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with X ray analysis of the catalyst components, or by producing a distribution map of the elements present in the catalyst by electronic microprobe. These local analyses can furnish the location of the various elements, in particular that of the promoter element, more particularly that of the amorphous silica, on the support matrix due to introduction of the silicon in accordance with the invention. The location of the silicon on the framework of the zeolite contained in the support is also revealed. Further, a quantitative estimate of the local silicon contents or other promoter elements can be carried out.
In addition,
29
Si NMR with magic angle spinning is a technique which can detect the presence of the amorphous silica introduced into the catalyst using the procedure described in the present invention.
More particularly, a process for preparing the catalyst of the present invention comprises the following steps:
a) preparing a mixture hereinafter termed the precursor, comprising at least the following compounds: a matrix (amorphous and/or low crystallinity), at least one Y zeolite (preferably dealuminated), at least one element (hydro-dehydrogenating, from group VIB and/or VIII), optionally phosphorous, the whole preferably being formed and dried;
b) impregnating the precursor defined in step a) with a solution (preferably aqueous) containing silicon, optionally phosphorous and/or boron, and optionally at least one group VIIA element, preferably fluorine;
c) advantageously, leaving the moist solid in a moist atmosphere at a temperature in the range 10° C. to 80° C.;
d) drying the moist solid obtained in step b) at a temperature in the rang

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