Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – And additional al or si containing component
Reexamination Certificate
2002-02-14
2003-12-09
Dunn, Tom (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
And additional al or si containing component
C502S064000, C502S073000, C502S074000
Reexamination Certificate
active
06660676
ABSTRACT:
The present invention relates to a catalytic composition which comprises an ERS-10 zeolite, a metal of group VIII, a metal of group VI and optionally one or more oxides as carrier. According to a preferred aspect, the catalytic composition also contains a metal of group II B and/or III A. The catalytic system of the present invention is particularly useful in the upgrading of mixtures of hydrocarbons which boil within the naphtha range containing sulfur impurities, i.e. in hydrodesulfuration with the contemporaneous skeleton isomerization of the olefins contained in these hydrocarbons, the whole process being carried out in a single step. This catalytic system can be used, in particular, for the upgrading of mixtures of hydrocarbons which boil within the naphtha range deriving from cracking processes, preferably mixtures of hydrocarbons having a boiling point within the naphtha range deriving from FCC catalytic cracking (Fluid Catalytic Cracking).
Hydrocarbons which boil within the naphtha range deriving from FCC (i.e. gasoline cut) are used as blending component of gasolines. For this purpose, it is necessary for them to have a high octane number together with a low sulfur content, to conform with the law restrictions which are becoming more and more severe, in order to reduce the emission of pollutants. The sulfur present in gasoline mixtures in fact mainly comes (>90%) from the gasoline cut deriving from FCC.
This cut is also rich in olefins which have a high octane number. Hydrogenation processes used for desulfuration also hydrogenate the olefins present with a consequent considerable reduction in the octane number (RON and MON). The necessity has therefore been felt for finding a catalytic system which decreases the sulfur content in the hydrocarbon mixtures which boil within the naphtha range and, at the same time, minimizes the octane loss (RON and MON), which can be achieved, for example, by the skeleton isomerization of the olefins present.
The use of zeolites with a medium pore dimension as isomerization catalysts and the consequent recovery of octane in the charges already subjected to desulfuration are known (U.S. Pat. Nos. 5,298,150, U.S. 5,320,742, U.S. 5,326,462, U.S. 5,318,690, U.S. 5,360,532, U.S. 5,500,108, U.S. 5,510,016, U.S. 5,554,274, U.S. 599,439). In these known processes, in order to obtain hydrodesulfuration with a reduced octane number, it is necessary to operate in two steps, using in the first step catalysts suitable for desulfuration and in the second step catalysts for recovering the octane number.
U.S. Pat. No. 5,378,352 describes a process in a single step for desulfurating hydrocarbon fractions, with boiling points within the range of gasolines, using a catalyst which comprises a metal of group VIII, a metal of group VI, a zeolite selected from ZSM-5, ZSM-11, -ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, MCM-22 and mordenite, and a metal oxide as ligand, with a process temperature preferably higher than 340° C.
Some catalytic materials containing metals of groups VI and VIII, a refractory carrier and a zeolite selected from ZSM-35, ZSM-5, mordenite and fajasite, are described in EP 442159, EP 437877, EP 434123 for the isomerization and disproportioning of olefins; in U.S. Pat. No. 4,343,692 for hydrodewaxing; in U.S. Pat. No. 4,519,900 for hydrodenitrogenation, in EP 072220 for a process in two steps comprising dewaxing and hydrodesulfuration; in U.S. Pat. No. 4,959,140 for a hydrocracking process in two steps.
We have now surprisingly found a new catalytic system with which it is possible to desulfurate, with high conversion values, mixtures of hydrocarbons that boil within the naphtha range containing sulfur and olefins and contemporaneously obtain the skeleton isomerization of the olefins present. This new catalytic system is also active at temperatures and pressures that are lower than those preferably used in the known art for desulfuration.
Skeleton isomerization enables hydrocarbons to be obtained, which boil within the naphtha range and at the same time with very low RON (research octane number) and MON (motor octane number) losses.
The results obtained do not only relate to the desulfuration of hydrocarbon cuts that boil within the “heavy naphtha” range (130°-250° C.), i.e. cuts poor in olefins, but also feeds of “full range naphtha”, which boil within the range of 35°-250° C., i.e. in the case of cuts rich in olefins. In fact, the catalytic system of the present invention has a high selectivity for desulfuration with respect to hydrogenation, which represents an additional advantage in terms of octane recovery in the end-gasoline.
A first object of the present invention therefore relates to a catalytic composition which comprises an ERS-10 zeolite, a metal of group VIII, a metal of group VI, and optionally one or more oxides as carrier.
According to a particular aspect of the present invention, the catalytic composition also comprises a metal of group II B and/or III A. This metal is preferably deposited on the surface of the zeolite.
ERS-10 zeolite is a porous crystalline material described in EP 796821, having in its calcined and anhydrous form a molar composition of oxides corresponding to the following formula:
m
M
2
O.
z
X
2
O
3
.YO
2
wherein m is a number between 0.01 and 10, M is H
+
and/or a cation of an alkaline or earth-alkaline metal with a valence n, z is a number between 0 and 0.02, X represents one or more elements selected from aluminum, iron, gallium, boron, vanadium, arsenic, antimonium, chromium and manganese and Y represents one or more elements selected from silicon, germanium, titanium, zirconium, characterized by the following X-ray diffraction spectrum from powders (recorded by means of a vertical goniometer equipped with an electronic impulse count system and using CuKa radiation (1=1.54178 A) containing the main reflections indicated in table A:
TABLE A
d (Å)
I/I
0
· 100
11.0 ± 0.1
vs
6.80 ± 0.08
w
5.79 ± 0.06
w
4.59 ± 0.05
m
4.29 ± 0.05
vs
3.96 ± 0.04
m
3.69 ± 0.03
w
3.41 ± 0.03
w
3.33 ± 0.03
w
3.26 ± 0.02
m
3.07 ± 0.02
w
2.68 ± 0.01
w
2.57 ± 0.01
w
2.51 ± 0.01
w
2.38 ± 0.01
w
2.31 ± 0.01
w
2.28 ± 0.01
w
2.11 ± 0.01
w
2.03 ± 0.01
w
1.94 ± 0.01
w
wherein d indicates the interplanar distance, I/I
0
·100 represents the relative intensity calculated by measuring the height of the peaks and percentually relating it to the height of the most intense peak, the symble vs indicates a very strong intensity (60-100), s a strong intensity (40-60), m a medium intensity (20-40) and w a weak intensity (0-20).
M is preferably selected from sodium, potassium, hydrogen or their mixtures. According to a particularly preferred aspect of the present invention the ERS-10 zeolite is in acid form i.e. in the form in which the M cationic sites of the zeolite are prevalently occupied by hydrogen ions. It is especially preferable for at least 80% of the cationic sites to be occupied by hydrogen ions. ERS-10 zeolite based on silicon oxide and aluminum oxide, i.e. an ERS-10 zeolite in which X is aluminum and Y is silicon, is preferably used.
According to an aspect of the present invention, when the catalytic composition comprises ERS-10 zeolite and metals of group VI and VIII, said zeolite is preferably present in a quantity ranging from 70 to 90%; when the catalytic composition also comprises one or more oxides as carrier, said zeolite is preferably present in a quantity ranging from 5 to 30% by weight with respect to the total weight of the catalyst.
The catalysts used in the present invention preferably contain Cobalt or Nickel as metal of group VIII, whereas the metal of group VI is preferably selected from molybdenum or tungsten. According to a particularly preferred aspect, Co and Mo are used. The weight percentage of the metal of group VIII preferably varies from 1 to 10% with respect to the total weight of the catalyst, even more preferably from 2 to 6%; the weigh
Carluccio Luciano Cosimo
Ferrari Marco
Zanibelli Laura
Agip Petroli S.p.A.
Dunn Tom
Ildebrando Christina
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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