Mineral oils: processes and products – Chemical conversion of hydrocarbons – Cracking
Reexamination Certificate
1999-06-25
2001-05-15
Yildirim, Bekir L. (Department: 1764)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
Cracking
C208S111010, C208S018000, C208S111300, C502S204000, C502S206000, C502S210000, C502S213000, C502S219000, C502S220000, C502S221000, C502S246000, C502S248000, C502S254000, C502S255000, C502S258000, C502S259000, C502S311000, C502S312000, C502S313000, C502S314000, C502S315000, C502S353000, C502S354000
Reexamination Certificate
active
06231750
ABSTRACT:
The present invention relates to a catalyst for hydrocracking hydrocarbon feeds, said catalyst comprising at least one amorphous or low crystallinity oxide type matrix, at least one element (metal) from group VB (group 5 in the new notation of the periodic table: “Handbook of Chemistry and Physics”, 76
th
edition, 1995-1996, inside front cover), preferably niobium, at least one beta zeolite, at least one promoter element selected from the group formed by boron, phosphorous and silicon, optionally at least one element (metal) selected from group VIB and/or group VIII (group 6 and groups 8, 9 and 10 in the new notation for the periodic table), preferably molybdenum, tungsten, cobalt, nickel or iron. The catalyst also optionally comprises at least one element from group VIIA (group 17 in the new notation for the periodic table), for example fluorine.
The present invention also relates to a catalyst for hydrocracking hydrocarbon feeds, said catalyst comprising at least one beta zeolite, at least one matrix selected from the group formed by mineral matrices, preferably oxide type mineral matrices, preferably amorphous or of low crystallinity and generally porous, at least one mixed sulphide phase comprising sulphur and at least one element from group VB of the periodic table (group 5 in the new notation of the periodic table: “Handbook of Chemistry and Physics”, 76
th
edition, 1995-1996, inside front cover), such as tantalum, niobium or vanadium, preferably niobium, and at least one element from group VIB of the periodic table (group 6) such as chromium, molybdenum or tungsten, more preferably molybdenum. The catalyst can also optionally comprise at least one metal from group VIII of the periodic table (groups 8, 9 and 10), such as iron, cobalt, nickel, ruthenium, osmium, rhodium, iridium, palladium, platinum, and optionally at least one element selected from the group formed by silicon, boron or phosphorous, and optionally at least one element from group VIIA of the periodic table (group 17), such as fluorine, chlorine, bromine or iodine, preferably fluorine.
The present invention also relates to processes for preparing said catalyst, and to its use for hydrocracking hydrocarbon feeds such as petroleum cuts, cuts originating from coal containing aromatic compounds and/or olefinic compounds and/or naphthenic compounds and/or paraffinic compounds, the feeds possibly containing metals and/or nitrogen and/or oxygen and/or sulphur.
Hydrocracking heavy petroleum feeds is a very important refining process which produces lighter fractions such as gasoline, jet fuel and light gas oil from surplus heavy feeds, which lighter fractions are needed by the refiner to enable production to be matched to demand. Some hydrocracking processes can also produce a highly purified residue which can constitute an excellent base for oils. The advantage of catalytic hydrocracking over catalytic cracking is that it can provide very good quality middle distillates, jet fuels and gas oils. The gasoline produced has a much lower octane number than that resulting from catalytic cracking.
All catalysts used for hydrocracking are bifunctional, combining an acid function and a hydrogenating function. The acid function is supplied by large surface area supports (150 to 800 m
2
/g in general) with a superficial acidity, such as halogenated aluminas (in particular fluorinated or chlorinated), combinations of boron and aluminium oxides, amorphous silica-aluminas and clays. The hydrogenating function is supplied either by one or more metals from group VIII of the periodic table, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, or by a combination of at least one metal from group VI of the periodic table, such as molybdenum or tungsten, and at least one group VIII metal.
The equilibrium between the two, acid and hydrogenating, functions is the fundamental parameter which governs the activity and selectivity of the catalyst. A weak acid function and a strong hydrogenating function produces low activity catalysts which generally operate at a high temperature (390° C. or above), and at a low supply space velocity (HSV, expressed as the volume of feed to be treated per unit volume of catalyst per hour, and is generally 2 or less), but have very good selectivity for middle distillates. In contrast, a strong acid function and a weak hydrogenating function produces very active catalysts but selectivities for middle distillates are poor. The search for suitable catalysts thus revolves around the proper selection of each of the functions to adjust the activity/selectivity balance of the catalyst.
Thus one of the great interests of hydrocracking is to have a high degree of flexibility at various levels: flexibility as regards the catalysts used, which provides flexibility in the feeds to be treated and in the products obtained. One parameter which is easily mastered is the acidity of the catalyst support.
The vast majority of conventional hydrocracking catalysts are constituted by low acidity supports such as amorphous silica-aluminas. These systems are more particularly used to produce very high quality middle distillates and again, when their acidity is very low, base oils.
Amorphous silica-aluminas are low acidity supports. Many of the catalysts in the hydrocracking industry are based on silica-alumina associated either with a group VIII metal or, as is preferably when the heteroatomic poison content in the feed to be treated exceeds 0.5% by weight, a combination of sulphides of group VIB and VIII metals. These systems have very good selectivity for middle distillates, and good quality products are formed. The least acid of such catalysts can also produce lubricating bases. The disadvantage of all of such catalytic systems based on an amorphous support is, as has been stated, their low activity; Further, simple sulphides of group VB elements have been described as constituents for catalysts for hydrorefining hydrocarbon feeds, such as by niobium trisulphide in U.S. Pat. No. 5,294,333. Mixtures of simple sulphides comprising at least one group VB element and a group VIB element have also been tested as constituents for catalysts for hydrorefining hydrocarbon feeds as described, for example, in U.S. Pat. No. 4,910,181 or U.S. Pat. No. 5,275,994.
The research carried out by the Applicant on zeolites and on active hydrogenating phases have led the Applicant to the discovery that, surprisingly, catalysts for hydrocracking hydrocarbon feeds comprising:
either at least one amorphous or low crystallinity matrix which is generally porous such as alumina, at least one element from group VB of the periodic table, such as tantalum, niobium or vanadium, preferably niobium, at least one beta zeolite, at least one promoter element selected from the group formed by boron, phosphorous and silicon;
or at least one matrix selected from the group formed by mineral matrices, preferably oxide type mineral matrices, preferably amorphous or of low crystallinity and generally porous such as alumina, at least one beta zeolite, and at least one mixed sulphide phase. This catalyst can also optionally comprise at least one element from group VIII, optionally an element selected from the group formed by silicon, phosphorous and boron, and optionally at least one element selected from group VIIA.
The catalyst of the invention comprises at least one beta zeolite which is preferably at least partially in its hydrogen form. The term “beta zeolite” means zeolites with a BEA structure type as described in the “Atlas of Zeolite Structure Types”, W. M Meier, D. H. Olson and Ch. Baerlocher, 4
th
revised edition, 1996, Elsevier.
The catalyst also comprises at least one element from group VIB of said periodic table such as chromium, molybdenum and tungsten, preferably molybdenum or tungsten, more preferably still molybdenum, optionally a group VIII element i.e., an element selected from the group formed by: Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, preferably iron, cobalt, nickel or ruthenium, and optionally a group VIIA element,
Benazzi Eric
Kasztelan Slavik
Marchal-George Nathalie
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
Yildirim Bekir L.
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