Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2001-07-12
2003-05-20
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S150000, C502S170000, C502S313000, C502S314000, C502S315000, C502S316000
Reexamination Certificate
active
06566296
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a process for preparing a catalyst composition, the catalyst composition thus obtained and the use of the composition in hydroprocessing applications.
2. Discussion of the Prior Art
Catalysts comprising at least one Group VIII non-noble metal component and at least two Group VIB metal components, the Group VIII and Group VIB metal components making up at least 50 wt. % of the catalyst composition, calculated as oxides, are known in the art.
U.S. Pat. No. 4,596,785 describes a catalyst composition comprising the disulfides of at least one Group VIII non-noble metal and at least one Group VIB metal. U.S. Pat. No. 4,820,677 describes a catalyst comprising an amorphous sulfide comprising iron as the Group VIII non-noble metal and a metal selected from molybdenum, tungsten or mixtures thereof as the Group VIB metal, as well as a polydentate ligand such as ethylene diamine. In both references the catalyst is prepared via the co-precipitation of water-soluble sources of one Group VIII non-noble metal and two Group VIB metals in the presence of sulfides. The precipitate is isolated, dried, and calcined in an inert atmosphere, which means that sophisticated techniques are required to carry out these processes.
U.S. Pat. No. 3,678,124 discloses oxidic catalysts to be used in the oxidative dehydrogenation of paraffin hydrocarbons. The catalysts are prepared by co-precipitating water-soluble components of the Group VIB metals and Group VIII non-noble metals.
In WO 9903578 catalysts are prepared by co-precipitating specified amounts of a nickel, molybdenum, and tungsten source in the absence of sulfides.
Non-prepublished international patent application PCT/EP00/00354 (corresponds to U.S. patent application Ser. No. 09/482,811, filed Jan. 13, 2000, incorporated herein by reference thereto) describes the preparation of sulfided catalyst compositions by coprecipitation of at least one Group VIII non-noble metal component and at least two Group VIB metal components to form an oxygen-stable precipitate, which is subsequently sulfided. Non-prepublished international patent application PCT/EP00/00355 (corresponds to U.S. patent application Ser. No. 09/231,118, filed Jan. 15, 1999, incorporated herein by reference thereto) describes the preparation of a catalyst composition by contacting at least one Group VIII non-noble metal component and at least two Group VIB metal components in the presence of a protic liquid, wherein at least one of the metal components is at least partly in the solid state during contacting.
Although the catalysts of some of these references, in particular those of Non-prepublished international patent applications PCT/EP00/00354 and PCT/EP00/00355 show a high activity, there is still need for improvement thereof.
SUMMARY OF THE INVENTION
Accordingly, the present invention, in one embodiment, pertains to a process for preparing a catalyst composition wherein at least one Group VIII non-noble metal component and at least two Group VIB metal components are combined and reacted in the presence of a protic liquid, after which the resulting composition is isolated and dried, the total of the Group VIII and Group VIB metal components, calculated as oxides, making up at least about 50 wt. % of the catalyst composition, calculated on dry weight. The process requires that an organic oxygen-containing additive is added prior to, during, or subsequent to the combining and reacting of the metal components in such an amount that the molar ratio of the total amount of additive added to the total amount of Group VIII and Group VIB metal components is at least about 0.01.
In a second embodiment, the present invention comprises a catalyst composition comprising at least one Group VIII non-noble metal component and at least two Group VIB metal components. The catalyst composition further comprises at least about 0.01 mole of an organic oxygen-containing additive per mole of the total of Group VIB metals and Group VIII non-noble metals present in the catalyst composition. The total of the Group VIII and Group VIB metal components, calculated as oxides, make up at least about 50 wt. % of the catalyst composition, calculated on dry weight.
In a third embodiment, the present invention comprises the use of the above catalyst composition for the hydroprocessing of hydrocarbon feedstocks by contacting the feedstocks with the catalyst composition at hydroprocessing conditions. Optionally, the catalyst composition may first be sulfided.
Other objectives and embodiments of the present invention encompass details about catalyst compositions, reactants and organic oxygen-containing additive all of which are hereinafter disclosed in the following discussion of each of the facets of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
It has been found that the performance of catalysts comprising at least one Group VIII non-noble metal component and at least two Group VIB metal components, the total of the Group VIII and Group VIB metal components, calculated as oxides, making up at least about 50 wt. % of the catalyst composition, calculated on dry weight, can be further improved by adding certain additives in such an amount that the molar ratio of the total of all additives to the total of the Group VIB metals and Group VIII non-noble metals employed in the process is at least about 0.01.
The preparation process according to the invention comprises two specific embodiments, namely a first embodiment wherein the catalyst is dried under such conditions that at least part of the additive is maintained in the catalyst composition, and a second less preferred, embodiment, wherein the catalyst composition is subjected to a calcination step at such conditions that the additive is removed from the catalyst.
It is noted that additive-containing catalysts and the preparation thereof are known in the art. Reference is made to EP 0601722, JP 04-166231, JP 04-166233, JP 06-339635, JP 06-210182 and WO 96/41848. However, these references are directed to conventional carrier based hydrotreating catalysts, which comprise up to about about 25 wt. % of molybdenum, calculated as trioxide, and up to about 10 wt. % of a Group VIII metal component, in particular nickel or cobalt, calculated as oxide on catalyst carrier which is generally alumina. The reason behind the increase in activity obtained in these references was believed to reside in the influence of the additive on the interaction between the metals-components and the alumina. There is nothing in these references which suggests to apply an additive in non-alumina-carrier based catalyst compositions. Additionally, none of these references deals with catalysts containing two Group VIB metal compounds.
In the context of the present specification, the wording “metal component” refers to a salt, oxide, sulfide, or any intermediate form between oxide and sulfide of the metal in question. As will be evident to the skilled person, the wording “at least two Group VIB metal components” is intended to refer to components of at least two Group VIB metals, e.g., the combination of molybdenum and tungsten.
The indications Group VIB and Group VIII used in the present specification correspond to the Periodic Table of Elements applied by Chemical Abstract Services (CAS system).
Suitable Group VIB metals include chromium, molybdenum, tungsten, or mixtures thereof, with a combination of molybdenum and tungsten being preferred. Suitable Group VIII non-noble metals include iron, cobalt, nickel, or mixtures thereof, preferably cobalt and/or nickel. Preferably, a combination of metal components comprising nickel, molybdenum, and tungsten or nickel, cobalt, molybdenum, and tungsten, or cobalt, molybdenum, and tungsten is employed in the process of the invention.
It is preferred that nickel and/or cobalt make up at least about 50 wt % of the total of Group VIII non-noble metals, more preferably at least about 70 wt %, still more preferably at least about 90 wt %. It may be especially preferred for the G
Cerfontain Marinus Bruce
Eijsbouts Sonja
Plantenga Frans Lodewijk
Akzo Nobel N.V.
Bell Mark L.
Hailey Patricia L.
Morris Louis A.
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