Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
1998-10-30
2001-09-25
Killos, Paul J. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C568S880000, C502S170000, C502S325000
Reexamination Certificate
active
06294696
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to concurrently filed applications entitled: Process for Preparing Catalysts for Use in Organic Compound Transformation Reactions (Attorney Docket No. PET 1702), based on French Application No. 97/13.684 filed Oct. 31, 1997, by Jean-Marie BASSET et al.; Process for Dehydrogenating Saturated Aliphatic Hydrocarbons to Olefinic Hydrocarbons (Attorney Docket No. PET 1703), based on French Application No. 97/13.685 filed Oct. 31, 1997, by Fabienne LE PELTIER et al.; Process for Selective Hydrogenation of Unsaturated Compounds (Attorney Docket No. PET 1706), based on French Application No. 97/13.687 filed Oct. 31, 1997, by Blaise DIDILLON et al.; and Catalytic Hydroreforming Process (Attorney Docket No. PET 1707), based on French Application No. 97/13.686 filed Oct. 31, 1997, by Fabienne LE PELTIER et al.
The present invention relates to a novel process for hydrogenating organic functions and/or an aromatic group in the presence of a catalyst comprising at least one support and at least one metal from group VIII of the periodic table. The catalyst comprises at least one additional element selected from germanium, tin, lead, rhenium gallium, indium, gold, silver and thallium. The catalyst can also contain a further 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 halogen-containing compound.
Patents and publications demonstrating that the addition of promoters to a base metal improves the quality of catalysts exist in large numbers. Such elements are added in different forms such as salts or organometallic compounds. In general, catalysts which are more active or more selective and sometimes more stable than the corresponding monometallic catalyst are obtained. The manner in which such modifying agents are introduced is not inconsequential as it dictates the properties of the catalyst to a great extent.
Thus catalyst formulations used in processes for converting hydrocarbons have been the subject of a very large number of studies.
In the chemical field, the use of catalysts constituted by a plurality of metallic elements prepared by methods involving the use of an organometallic compound have also been widely described. Such catalysts are particularly suitable for selective hydrogenation of acid, ester, aldehyde, nitrogen-containing or olefinic functions. They have, for example, been described for the hydrogenation of aromatic ketones (French patent FR-A-2 964 286), of nitrogen-containing compounds (FR-A-2 671 347), and for the hydrogenation of aldehydes (FR-A-2 653 118).
The processes cited above describe the production of a catalyst using at least one organometallic compound of a metal M. The metal M is introduced in the form of at least one organometallic compound selected from the group formed by complexes, in particular carbonyl or polyketone complexes of metal M, and metal hydrocarbyls of metal M, such as alkyls, cycloalkyls, aryls, metal alkylaryls and metal arylalkyls.
Introducing the additional element M in the form of an organometallic compound leads to more effective catalysts but necessitates the use of an organic solvent. The impregnating solvent described in U.S. Pat. No. 4,548,918 is selected from the group formed by oxygen-containing organic solvents containing 2 to 8 carbon atoms per molecule, paraffin, naphthene or aromatic hydrocarbons essentially containing 6 to 15 carbon atoms per molecule, and halogen-containing oxygen-containing organic compounds containing 1 to 15 carbon atoms per molecule. Such solvents can be used alone or mixed together.
In the present invention we have discovered that particularly effective catalysts can be prepared by introducing metal M in the form of an organometallic complex which is soluble in an aqueous solvent. This represents a considerable advance as regards ease of use during production of the catalyst. Using large quantities of organic solvents has many disadvantages as regards safety (flammability, toxicity) and as regards costs.
In the present invention, the hydrocarbon conversion processes are operated at a temperature in the range 10° C. to 800° C., a pressure in the range 0.1 to 10 MPa, with an hourly space velocity in the range 0.1 to 100 volumes of liquid feed per hour per volume of catalyst.
The present invention thus provides a novel process for hydrogenating organic functions such as aldehyde, ketone, ester, acid, nitro or aromatic functions. The conditions used are conditions which are known to the skilled person, in particular an average temperature in the range 10° C. to 500° C., a pressure in the range 0.1 to 10 MPa and a space velocity in the range 0.5 to 50 volumes of liquid feed per hour per volume of catalyst.
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, IIIB, IVA or IVB of the periodic table such as oxides of magnesium, aluminium, silicon, titanium, zirconium or thorium, used alone or mixed together or mixed with oxides of other elements from the periodic table. Charcoal can also be used. X, Y, mordenite, faujasite, ZSM-5, ZSM-4 or ZSM-8 type zeolites or molecular sieves can also be used, as well as mixtures of oxides of group IIA, IIIA, IIIB, IVA or IVB metals with a zeolitic material.
For hydrocarbon transformation reactions, alumina constitutes the preferred support, the specific surface area of which is advantageously in the range 5 to 400 m
2
per gram, preferably in the range 50 to 350 m
2
per gram.
Silica, charcoal and alumina constitute preferred supports for use in transforming organic functions.
In addition to a support, the catalyst of the invention includes:
a) at least one group VIII metal selected from iridium, nickel, palladium, platinum, rhodium and ruthenium. Platinum, palladium, ruthenium and rhodium are preferred metals. The percentage by weight is in the range 0.1% to 10%, preferably in the range 0.1% to 5%.
b) at least one additional element M selected from the group formed by germanium, tin, lead, rhenium, gallium, indium, gold, silver and thallium. Tin and germanium are preferred elements. The percentage by weight is in the range 0.01% to 10%, preferably in the range 0.02% to 5%. In some cases, at least two of the metals from this group can advantageously be used at once.
Depending on the application, the catalyst can also contain 0.2% to 3% by weight of a halogen or halogen-containing compound. It can also contain 0.2% to 3% by weight of an alkali or alkaline-earth metal.
The catalyst can be prepared using different procedures for impregnating the support and the invention is not limited to any specific impregnation procedure. When several solutions are used, intermediate drying and/or calcining steps can be carried out.
The additional element M can be introduced during production of the support. One method, for example, consists of blending the moist powdered support with catalyst precursors and then forming and drying. The group VIII metal, additional metal M, optional halogen or halogen-containing compound, optional alkali or alkaline-earth metal, and optional metalloid, can be introduced simultaneously or successively, in any order. In accordance with the invention, the characteristic feature of contact with the organometallic element M is that it is introduced in an aqueous solvent.
The precursor of element M can be selected from the group formed by halogen-containing compounds, hydroxides, oxides, carbonates and carboxylates of organometallic compounds of element M, this list not being limiting in nature. These compounds comprise at least one carbon-M bond. The precursor for element M can also be selected from compounds with general formula (R
1
)
x
M(R
2
)
y
where x+y=the valency of metal M and where R
1
is selected from the group formed by alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl functions, and R
2
is a function with formula C
a
H
b
R′
c
, where R′ represents a hydroxi
Didillon Blaise
Le Peltier Fabienne
Institut Francais du Pe'trole
Killos Paul J.
Millen White Zelano & Branigan P.C.
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