Transition metal catalysts for hydrodesulfurization
AssigneeThe Governors of the University of Alberta
InventorsJeffrey Camacho Bunquin, Jeffrey Mark STRYKER
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Abstract
Phosphoranimide-metal catalysts and their role in hydrodesulfurization are disclosed. The catalysts comprise of first row transition metals such as nickel, cobalt and iron. The catalysts have a metal to anionic phosphoranimide ratio of 1:1 and catalyze hydrodesulfurization of a range of sulfur-containing organic compounds under lower temperature and pressure conditions than those commonly used in industrial hydrodesulfurization.
Claims23
A method of catalyzing a hydrodesulfurization reaction comprising:
- reacting an organic substrate having at least one carbon-sulfur bond with a catalyst of general formula:
- [M(NPR3)]n
- where:
- M is a first row transition metal having a +1 oxidation state;
- n is a whole number of at least 2;
- the ratio of M to R3PN− ratio is 1:1;
- R3PN− is a monoanioinic phosphoranimide ligand of structure:
- where:
- R1, R2, R3 can be the same group or different groups;
- R1, R2, R3 are independently alkyl (C1-C18, primary, secondary or tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl or an inert functional group containing at least one heteroatom;
- and
- R1, R2, R3 may be linked to give cyclic systems.
The method of claim 20, wherein X− is F−, Cl−, Br−, I− or OSO2R−, where R=Me, Ph, p-Tol, CF3.
A method of catalyzing the hydrodesulfurization of an organic compound having at least one carbon-sulfur bond comprising:
- reacting the organic substrate with a compound selected from the group consisting of [Fe(NPtBu3)]4, [Co(NPtBu3)]4 and [Ni(NPtBu3)]4.
A method of catalyzing the hydrodesulfurization of an organic substrate comprising:
- reacting the organic substrate with a catalyst of Formula [M(NPR3)]n wherein n is a whole number of at least 2;
- the ratio of M to NPR3is 1:1;
- M is a first row transition metal selected from the group consisting of Fe, Co and Ni;
- NPR3 is:
- where:
- R1, R2, R3 are independently alkyl (C1-C18, primary, secondary or tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl and an inert functional group containing at least one heteroatom selected from the group consisting of a Group 14, Group 15 and Group 16 element, excluding C;
- and
- wherein R1, R2, R3 may also be linked by aliphatic groups to give cyclic systems;
- wherein the reaction is carried out at a temperature range of about 90 to 300° C. in the presence of a reducing agent selected from the group consisting of hydrogen and an organic silyl hydride;
- and
- wherein the reaction is carried out in toluene or tetrahydrofuran.
A process for hydrodesulfurization of an organic substrate having at least carbon-sulfur bond comprising:
- (i) combining the said organic substrate with a transition metal complex of Formula I and a reductant selected from hydrogen and an organic silyl hydride to obtain a reaction medium;
- (ii) allowing the catalyst to catalyze the hydrodesulfurization of the substrate in an organic substrate selected from toluene and tetrahydrofuran;
- (iii) obtaining the desulfurized products derived from the organic substrate;
- wherein the organic substrate is an aromatic or aliphatic compound containing at least one carbon-sulfur bond;
- and wherein the ratio of the catalyst to the organic substrate is less than 1:1, and
- wherein the complex of Formula I is:
- [M(NPR3)]n Formula I
- where
- n is a whole number of at least 2;
- the ratio of M to NPR3 is 1:1;
- M is a first row transition metal selected from the group consisting of Fe, Co and Ni;
- NPR3 is:
- where:
- R1, R2, R3 are independently alkyl (C1-C18, primary, secondary or tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl or an inert functional group containing at least one heteroatom selected from the group consisting of a Group 14, Group 15 and Group 16 element except for C;
- and wherein R1, R2, R3 may also be linked by aliphatic groups to give cyclic systems.
Dependencies are inferred from the claim text.