Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
1998-08-28
2001-03-06
Dunn, Tom (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
C502S327000, C502S328000, C502S330000, C502S332000, C502S333000, C502S334000, C502S335000, C502S337000, C502S338000, C502S339000, C585S260000
Reexamination Certificate
active
06197721
ABSTRACT:
The present invention relates to a novel catalyst comprising at least one support and at least one metal from group VIII of the periodic table. This catalyst can also contain another metal selected from the group formed by alkali metals and/or a metalloid such as sulphur and/or any other chemical element such as a halogen or a halogenated compound.
Control of the textural characteristics of metal particles deposited on a support has been the subject of numerous studies in the literature and continues to be the centre of interest in recent research. Particle size, for example, is a determining factor when a catalyst is used in a reaction qualified as “structure sensitive” as defined by Boudart. A chemical transformation is termed “structure sensitive” if the reaction rate (or turn over frequency
1
) is dependent on metal crystallite size, in the case of monometallic catalysts, or on the surface composition for bimetallic catalysts. Similarly, the electronic state of the metal constituting the active surface site will set the adsorption energy of the reactants and as a result, the catalytic performances (activity, selectivity and stability). The literature contains many examples of studies aimed at establishing the structure sensitivity or insensitivity of a given reaction: hydrogenation of linear or cyclic alkenes
2 3
on Pt or Pd based catalysts (insensitive reaction), hydrogenation of alkynes and diolefins
4
(sensitive reactions), hydrogenolysis of C—C bonds in paraffin or naphthene compounds
5 6
.
1
The turn over frequency is defined as the rate of reaction reduced to the number of surface metal atoms.
2
J. C. Schlatter, M. Boudart, J. Catal., 24, 1972, 482.
3
M. Boudart, W. C. Cheng, J. Catal., 106, 1987, 134.
4
S. Hub, L. Hilaire, R. Touroude, Appl. Catal. 36, 1992, 307.
5
J. Barbier, P. Marecot, Nouv. J. Chim. 5, 1981, 393.
6
J. R. Anderson, Y. Shymoyama, Proc 5
th
Int. Cong. Catal., Palm Beach, 1972, North Holland Publ. Co/Amer. Elsevier, Vol 1, 1973, 55.
The formulation of catalysts used in hydrocarbon conversion processes has formed the subject of a large number of studies. Supported metal catalysts containing a metal phase based on palladium or nickel supported on a refractory oxide type support such as alumina are currently used in gasoline hydrogenation reactions, for example.
For reactions termed structure sensitive reactions, the protocol for preparing the catalysts is particularly important and aimed at obtaining an optimum size for the metal particles corresponding to the maximum reaction rate. Thus in the case of the selective hydrogenation of butadiene, the most active catalyst must contain particles of about 40 Å.
However, the “structure sensitive” nature of a reaction imposing a set particle size which is in general relatively large (several tens of Angströms) substantially limits the metal surface exposed per unit mass of metal, limiting the catalytic activity as a result.
The present invention shows that it is possible to prepare catalysts containing at least one metal from group VII of the periodic table of the elements which perform particularly well. The size of the metal particles is generally below 10 Å, which means that the majority of the metal atoms deposited on the support are exposed to the reactants. These catalysts are characterized by volumes of chemisorbed CO of at least 180 cm
3
per gram of metal, corresponding to a dispersion
7
of 80% or more. Characterization by programmed temperature reduction (PTR) of this type of catalyst produces a single hydrogen consumption peak centred on a range of temperature of 50° C. to 300° C. (preferably 100° C. to 200° C.). Hydrogen salting-out is not observed at low temperatures (about 70° C.), salting-out generally being associated with the formation of metal hydrides and characterized in PTR by an intense hydrogen production signal at about T=70° C.
7
Metallic dispersion is defined as the ratio of the number of metal atoms exposed on the surface to the total number of metal atoms.
The volume of chemisorbed carbon monoxide is generauy measured using the following procedure: after treatment at 200° C. in a stream of hydrogen for 2 hours, then in helium for 2 hours, it is allowed to cool down to ambient temperature, keeping it in helium, before injecting a known volume of CO. The CO consumption is followed by gas phase chromatography.
The PTR analysis procedure is based on measuring the quantity of hydrogen consumed by reduction of the metallic phase as a function of temperature. The PTR profile obtained thus shows the intensity of reduction as a function of temperature. Integrating the reduction peaks gives the quantity of hydrogen consumed. The procedure includes in-situ re-oxidation, generally by prior calcining at 200° C. for two hours with a temperature rise of 5° C./min. After re-oxidation, the samples are reduced, from ambient temperature up to 900° C., by increasing the temperature at 5° C./min in a gas stream constituted by 5% hydrogen and 95% argon, injected at a flow rate of 20 cm
3
/min.
Another characterization technique for characterizing the nature of the interactions between the metal and the support consists in EXAFS (for “Extended X-ray Absorption Fine Structure). In fact, this spectroscopic technique enables the direct determination (in terms of nature and number) of the elements located in the vicinity of a given element. It is thus possible to know the environment of the metal deposited by any preparation method.
The hydrocarbon conversion processes for which the catalysts of the invention are applicable operate at a temperature in the range 10° C. to 800° C. and at a pressure in the range 0.1 to 10 HPa.
More particularly, the catalysts of the present invention are applicable:
to catalytic purification of olefin cuts by selective hydrogenation. The conditions generally used for this type of transformation are an average temperature in the range from 25° C. to 200° C., a pressure in the range 0.1 to 10 MPa and a molar ratio of hydrogen to hydrocarbons in the range 1 to 150. The feed is generally a steam cracking, cut containing 5 to 12 carbon atoms per molecule;
to catalytic hydrogenolysis processes carried out in the range 400° C. to 800° C., at a pressure in the range 0.1 to 2 MPa and with a molar ratio of hydrogen to hydrocarbons of 0 to 20;
to hydrogenation processes for hydrocarbons containing alkyne, diene or olefin functions, or aromatic functions, under conditions which are known to the skilled person, more particularly an average temperature in the range 10° C. to 400° C. and at a pressure in the range 0.1 to 10 MPa; and
to processes for hydrogenation of organic functions such as aldehyde, ketone, ester, acid or nitro functions, under conditions which are known to the skilled person, more particularly an average temperature in the range 10° C. to 500° C. and at a pressure in the range 0.1 to 10 MPa.
The support for the catalyst of the invention comprises at least one refractory oxide which is generally selected from oxides of metals from groups IIA, IIIA, IVB and IVA of the periodic table of the elements, such as magnesium, aluminum, silicon, titanium, zirconium or thorium oxides, used alone or as a mixture or mixed with oxides of other metals from the periodic table. Activated carbon can also be used. Type X, Y, mordenite, faujasite, ZSM-5, ZSM-4, ZSM-8, etc. type zeolites or molecular sieves, also mixtures of metal oxides from groups IIA, IIIA, IVB and/or IVA with a zeolitic material can also be used.
For hydrocarbon transformation reactions, the preferred support is alumina, with a specific surface area which is advantageously in the range 5 to 400 m
2
/gram, preferably in the range 5 to 150 m
2
/gram.
Preferred supports used for transforming organic functions are silica, carbon and alumina.
In the catalyst of the invention, the group VIII metal is usually selected from iridium, nickel, palladium, platinum, rhodium and ruthenium. Platinum and palladium are the preferred metals for the hydrocarbon conversion reactions. Rhodium and ruthenium
Delage Maryline
Didillon Blaise
Uzio Denis
Dunn Tom
Institute Francais du Petrole
Millen White Zelano & Branigan P.C.
Nguyen Cam N.
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