Abstract: There is provided a process for regenerating the activity of used metal catalysts for the hydrogenation of carbon monoxide comprising decreasing the hydrocarbon content thereof, calcining under an oxidant-containing atmosphere, impregnating with a solution of at least one of a metal compound, calcining under an oxidant-containing atmosphere and activating by contacting with a hydrogen-contacting gas at elevated temperatures to form an active catalyst. The process regenerates and enhances both supported and dispersed active metal (DAM) catalysts. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operation thereof. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.

Abstract: There is provided a process for renewing the activity of supported metal catalysts for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons comprising decreasing the hydrocarbon content of the catalyst, preferably by contact with hydrogen-containing gas at elevated temperatures, impregnating under a non-oxidizing atmosphere with a solution of at least one of an ammonium salt and an alkyl ammonium salt, optionally in combination with up to five moles of ammonia per liter of solution to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume; oxidizing the catalyst with a gaseous oxidant in the presence of the impregnating solution and activating the catalyst by reduction with hydrogen at elevated temperatures. Optionally, the catalyst is calcined after the oxidation step, and passivated after the activation step.

Abstract: A process for enhancing metal catalysts for carbon monoxide hydrogenation comprising reducing the catalyst so that at least a portion is in the metallic state, impregnating under a non-oxidative atmosphere with a solution of a salt of at least one metal, optionally in combination with at least one of an ammonium salt, an alkyl ammonium salt, a weak organic acid and ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, and reducing to form an active catalyst. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operations. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.

Abstract: There is provided a process for hydrocarbon synthesis wherein a supported metal catalyst for hydrogenating carbon monoxide to form a mixture of hydrocarbons is regenerated by decreasing its hydrocarbon content, impregnating under a non-oxidative atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally including ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, activating the catalyst by reduction with hydrogen at elevated temperatures and reusing the catalyst. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst has been withdrawn therefrom and returned to at least one reactor. Up to all steps subsequent to decreasing the hydrocarbon content may be effected in a subsequent reactor, or in specialized apparatus.

Abstract: A process for activating a supported metal catalyst or catalyst precursor useful for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons, comprising reducing with a hydrogen-containing gas at elevated temperature so that at least a portion is in the metallic state, impregnating under a non-oxidizing atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally further including ammonia, to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume, oxidizing with a gaseous oxidant in the presence of the impregnating solution and reducing with hydrogen-containing gas at elevated temperatures to form an active catalyst. The steps beginning with the impregnation may be repeated. Optionally, the catalyst may be calcined after the oxidation step and/or passivated after activation.

Abstract: There is provided a process for renewing the activity of used, supported metal catalysts for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons comprising decreasing the hydrocarbon content of the catalyst, impregnating said catalyst under an non-oxidative atmosphere with a solution at least one weak organic acid, preferably a mono- or di-carboxylic acid, to the point where it has absorbed a volume of said solution equal to at least about 10% of its calculated pore volume, oxidizing the catalyst with a gaseous oxidant in the presence of the impregnating solution and activating the catalyst by reduction with hydrogen at elevated temperatures. Optionally, the catalyst is calcined after the oxidation step, and passivated after the activation step. A preferred means of decreasing the hydrocarbon content of the catalyst is contacting it with a hydrogen-containing gas at elevated temperatures.

Abstract: A process of enhancing both the activity and the methane selectivity of a Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein reducible promoter metals comprising one or more of rhenium, ruthenium, palladium, iron and cobalt are added to the DAM. The promoter metals are mixed with the oxidized catalyst precursor as a solution of their reducible salts. The oxidized catalyst precursors are again recovered from the mixture and treated with hydrogen-containing gas to simultaneously form the metals and reactivate the DAM catalyst.

Abstract: A process of enhancing both the activity and the methane selectivity of a Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein reducible promoter metals comprising one or more of rhenium, ruthenium, palladium, iron and cobalt are added to the DAM. The promoter metals are mixed with the oxidized catalyst precursor as a solution of their reducible salts. The oxidized catalyst precursors are again recovered from the mixture and treated with hydrogen-containing gas to simultaneously form the metals and reactivate the DAM catalyst.

Abstract: There is provided an improved system and process for the catalytic hydrogenation of carbon monoxide to form a mixture of hydrocarbons utilizing a plurality of reactors in series. Synthesis gas entering the system under pressure is partially converted in at least one initial stage reactor and the effluent therefrom introduced into a final stage reactor. In the at least one initial stage reactor, a portion of the catalyst is continuously or periodically removed with some hydrocarbons and treated to renew, or renew and enhance it, and returned. The treatment comprises reducing the hydrocarbon context of the withdrawn mixture, heating to a temperature above at least one of the metals in the catalyst thereby forming a melt, removing any slag forming on the melt, cooling the melt and reducing the particle size of the resulting solid to a fine powder of renewed catalyst.

Abstract: A method is disclosed for renewing the activity of a Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst, reducing the hydrocarbon content thereof, heating the mixture above the melting temperature of at least one of the metals of the DAM to form a melt, removing any slag that forms on the melt, cooling the melt to form a solid, reducing the particle size thereof to form a renewed particulate DAM catalyst, which is then returned to the reactor. Wherein the DAM catalyst is a Raney catalyst, a leachable metal is added to the reduced hydrocarbon mixture or the melt under non-oxidizing conditions and, after the solid is reduced to a fine particle size, extracting the leachable metal with caustic.

Abstract: There is provided a process for hydrocarbon synthesis wherein a supported metal catalyst for hydrogenating carbon monoxide to form a mixture of hydrocarbons is regenerated by decreasing its hydrocarbon content, impregnating under a non-oxidative atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally including ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, activating the catalyst by reduction with hydrogen at elevated temperatures and reusing the catalyst. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst has been withdrawn therefrom and returned to at least one reactor. Up to all steps subsequent to decreasing the hydrocarbon content may be effected in a subsequent reactor, or in specialized apparatus.

Abstract: There is provided a process for renewing the activity of used, supported metal catalysts for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons comprising decreasing the hydrocarbon content of the catalyst, impregnating said catalyst under an non-oxidative atmosphere with a solution at least one weak organic acid, preferably a mono- or di-carboxylic acid, to the point where it has absorbed a volume of said solution equal to at least about 10% of its calculated pore volume, oxidizing the catalyst with a gaseous oxidant in the presence of the impregnating solution and activating the catalyst by reduction with hydrogen at elevated temperatures. Optionally, the catalyst is calcined after the oxidation step, and passivated after the activation step. A preferred means of decreasing the hydrocarbon content of the catalyst is contacting it with a hydrogen-containing gas at elevated temperatures.

Abstract: There is provided a process for renewing the activity of supported metal catalysts for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons comprising decreasing the hydrocarbon content of the catalyst, preferably by contact with hydrogen-containing gas at elevated temperatures, impregnating under a non-oxidizing atmosphere with a solution of at least one of an ammonium salt and an alkyl ammonium salt, optionally in combination with up to five moles of ammonia per liter of solution to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume; oxidizing the catalyst with a gaseous oxidant in the presence of the impregnating solution and activating the catalyst by reduction with hydrogen at elevated temperatures. Optionally, the catalyst is calcined after the oxidation step, and passivated after the activation step.

Abstract: There is provided a process for regenerating the activity of used metal catalysts for the hydrogenation of carbon monoxide comprising decreasing the hydrocarbon content thereof, calcining under an oxidant-containing atmosphere, impregnating with a solution of at least one of a metal compound, calcining under an oxidant-containing atmosphere and activating by contacting with a hydrogen-contacting gas at elevated temperatures to form an active catalyst. The process regenerates and enhances both supported and dispersed active metal (DAM) catalysts. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operation thereof. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.

Abstract: A process for enhancing metal catalysts for carbon monoxide hydrogenation comprising reducing the catalyst so that at least a portion is in the metallic state, impregnating under a non-oxidative atmosphere with a solution of a salt of at least one metal, optionally in combination with at least one of an ammonium salt, an alkyl ammonium salt, a weak organic acid and ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, and reducing to form an active catalyst. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operations. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.

Abstract: A process for activating a supported metal catalyst or catalyst precursor useful for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons, comprising reducing with a hydrogen-containing gas at elevated temperature so that at least a portion is in the metallic state, impregnating under a non-oxidizing atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally further including ammonia, to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume, oxidizing with a gaseous oxidant in the presence of the impregnating solution and reducing with hydrogen-containing gas at elevated temperatures to form an active catalyst. The steps beginning with the impregnation may be repeated. Optionally, the catalyst may be calcined after the oxidation step and/or passivated after activation.

Abstract: A method is disclosed for enhancing the activity of a particulate Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst from the reactor, reducing the hydrocarbon content thereof with hydrogen at a temperature above the temperature of the reactor, oxidizing a slurry of the catalyst particles in a suitable fluid at low temperature to form an oxidized precursor, reducing the precursor at elevated temperature to reform the catalyst and returning it to the reactor. The catalyst may be passivated before returning to the reactor.

Abstract: A process of enhancing both the activity and the methane selectivity of a Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein reducible promoter metals comprising one or more of rhenium, ruthenium, palladium, iron and cobalt are added to the DAM. The promoter metals are mixed with the oxidized catalyst precursor as a solution of their reducible salts. The oxidized catalyst precursors are again recovered from the mixture and treated with hydrogen-containing gas to simultaneously form the metals and reactivate the DAM catalyst.

Abstract: A process of enhancing both the activity and the methane selectivity of a particulate Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein one or more promoter metal oxides of chromium, lanthanum and manganese are added to the DAM. Precursors of the promoter metal oxides may be combined with the DAMs prior to or during formation of the initial slurry, during the oxidation step or between recovery of the oxidized catalyst precursor and treatment of it with hydrogen-containing gas to reactivate the catalyst. Conversion of the precursors to the promoter metal oxides is carried out prior to the treatment with hydrogen-containing gas unless said treatment itself produces the conversion.

Abstract: An aqueous low temperature oxidation (ALTO) process wherein a catalyst or catalyst precursor constituted of a solids support, or powder component, and a metal, or metals component, inclusive of cobalt, is oxidized, reduced and rendered catalytically active for conducting carbon monoxide hydrogenation reactions. The cobalt catalyst or cobalt catalyst precursor is thus contacted at low temperature with an oxidant in the presence of water (e.g., water to which an oxidant is added), sufficient to oxidize the cobalt metal, or metals component of the catalyst or catalyst precursor. On reduction, the hydrogenation activity of the cobalt catalyst is increased. All or a portion of the cobalt metal of the catalyst precursor is oxidized to form a Co2+ cationic or oxo-anionic species at least during the initial phase of the reaction.