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US 7,906,447 B2Granted
Regeneration and rejuvenation of supported hydroprocessing catalysts
AssigneeExxonMobil Research and Engineering Company
InventorsStephen J. McCarthy, Chuansheng Bai, William G. Borghard, William E. Lewis
Life of this patent
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Abstract
Methods for rejuvenation of supported metallic catalysts comprised of a Group VIII metal, a Group VIB metal, making use of these metals, an organic complexing agent, and optionally an organic additive, are provided. The rejuvenation includes stripping and regeneration of a spent or partially spent catalyst, followed by impregnation with metals and at least one organic compound. The impregnated, regenerated catalysts are dried, calcined, and sulfided. The catalysts are used for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks.
Claims23
A process for rejuvenating a supported hydroprocessing catalyst, comprising:
- a) providing a supported hydrotreating catalyst that is formed by
- i) impregnating a support with a solution, slurry, or mixture containing at least one Group VIB metal, at least one Group VIII metal, a second organic acid containing a —C(═O)OH functional group and at least one additional functional group selected from carboxylic acid —C(═O)OH, hydroxamic acid —C(═O)N(H)OH, hydroxy —OH, keto >C═O, amino —NH2, amido —C(═O)NH2, imino >C═NH, epoxy —COC, and thio —SH, optionally an additional transition metal, and optionally water or at least one organic additive different from the second organic acid,
- ii) drying the impregnated support at a temperature from 200° C. to 450° C. to produce a partially calcined, impregnated support having a carbon content of at least 5 wt % based on the weight of the partially calcined, impregnated support, the at least one organic additive not being present on the partially calcined, impregnated support, and
- iii) sulfiding the partially calcined, impregnated support that includes at least a portion of the carbon content,
- which supported hydrotreating catalyst is at least partially spent;
- b) stripping the supported hydrotreating catalyst at a temperature less than about 350° C., the supported hydrotreating catalyst including a support, at least one Group VIB metal, and at least one Group VIII metal;
- c) regenerating the stripped catalyst in the presence of an oxygen containing gas at a temperature of about 500° C. or less;
- d) impregnating the regenerated catalyst with a solution, slurry, or mixture consisting essentially of at least one Group VIB metal, at least one Group VIII metal, a first organic acid containing a —C(═O)OH functional group and at least one additional functional group selected from carboxylic acid —C(═O)OH, hydroxamic acid —C(═O)N(H)OH, hydroxy —OH, keto >C═O, amino —NH2, amido —C(═O)—NH2, imino >C═NH, epoxy —COC, and thio —SH, optionally an additional transition metal, and optionally water or at least one organic additive different from the first organic acid;
- e) partially calcining the impregnated, regenerated catalyst at a temperature from about 300 to about 400° C. to produce a partially calcined, impregnated, regenerated catalyst having a carbon content of at least 5 wt % based on the weight of the partially calcined, impregnated, regenerated catalyst, the at least one organic additive not being present on the partially calcined, impregnated support;
- and
- f) sulfiding the partially calcined, impregnated, regenerated catalyst.
8 more elements
A process for making a supported hydroprocessing catalyst from a regenerated catalyst, comprising:
- a) providing a regenerated supported hydrotreating catalyst that was at least partially spent and was regenerated in the presence of an oxygen containing gas at a temperature of about 500° C. or less, the regenerated catalyst corresponding to a fresh catalyst formed by
- i) impregnating a support with a solution, slurry, or mixture containing at least one Group VIB metal, at least one Group VIII metal, a second organic acid containing a —C(═O)OH functional group and at least one additional functional group selected from carboxylic acid —C(═O)OH, hydroxamic acid —C(═O)N(H)OH, hydroxy —OH, keto >C═O, amino —NH2, amido —C(═O)—NH2, imino >C═NH, epoxy —COC, and thio —SH, optionally an additional transition metal, and optionally water or at least one organic additive different from the second organic acid,
- ii) drying the impregnated support at a temperature of from 200 to 450° C. to produce a partially calcined, impregnated support having a carbon content of at least 5 wt % based on the weight of the partially calcined, impregnated support, the at least one organic additive not being present on the partially calcined, impregnated support, and
- iii) sulfiding the partially calcined, impregnated support that includes at least a portion of the carbon content;
- b) impregnating a regenerated catalyst with a solution, slurry, or mixture, the regenerated catalyst including a support, at least one Group VIB metal, and at least one Group VIII metal, and the solution, slurry, or mixture consisting essentially of at least one Group VIB metal, at least one Group VIII metal, a first organic acid containing a —C(═O)OH functional group and at least one additional functional group selected from carboxylic acid —C(═O)OH, hydroxamic acid —C(═O)N(H)OH, hydroxy —OH, keto >C═O, amino —NH2, amido —C(═O)—NH2, imino >C═NH, epoxy —COC, and thio —SH, optionally an additional transition metal, and optionally water or at least one organic additive different from the first organic acid;
- c) partially calcining the impregnated, regenerated catalyst at a temperature from about 300 to about 400° C. to produce a partially calcined, impregnated, regenerated catalyst having a carbon content of at least 5 wt % based on the weight of the partially calcined, impregnated, regenerated catalyst, the at least one organic additive not being present on the partially calcined, impregnated support;
- and
- d) sulfiding the partially calcined, impregnated, regenerated catalyst that includes at least a portion of the carbon content.
5 more elements
Dependencies are inferred from the claim text.