IPC분류정보
국가/구분 |
United States(US) Patent
등록
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국제특허분류(IPC7판) |
|
출원번호 |
US-0384407
(2009-04-03)
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등록번호 |
US-8128811
(2012-03-06)
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발명자
/ 주소 |
- McCarthy, Stephen J.
- Bai, Chuansheng
- Borghard, William G.
- Lewis, William E.
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출원인 / 주소 |
- ExxonMobil Research and Engineering Company
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대리인 / 주소 |
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인용정보 |
피인용 횟수 :
8 인용 특허 :
4 |
초록
▼
Methods for hydroprocessing of hydrocarbon feedstocks, including hydrodesulfurization and hydrodenitrogenation, using rejuvenated supported metallic catalysts are provided. The supported metallic catalysts comprised of a Group VIII metal, a Group VIB metal, are rejuvenated by a process making use of
Methods for hydroprocessing of hydrocarbon feedstocks, including hydrodesulfurization and hydrodenitrogenation, using rejuvenated supported metallic catalysts are provided. The supported metallic catalysts comprised of a Group VIII metal, a Group VIB metal, are rejuvenated by a process making use of these metals, an organic complexing agent, and optionally an organic additive. 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.
대표청구항
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1. A method for hydroprocessing a hydrocarbon feedstock using a rejuvenated supported hydroprocessing catalyst, comprising exposing the hydrocarbon feedstock to the rejuvenated supported hydroprocessing catalyst under effective hydroprocessing conditions, wherein the rejuvenated supported hydroproce
1. A method for hydroprocessing a hydrocarbon feedstock using a rejuvenated supported hydroprocessing catalyst, comprising exposing the hydrocarbon feedstock to the rejuvenated supported hydroprocessing catalyst under effective hydroprocessing conditions, wherein the rejuvenated supported hydroprocessing catalyst is prepared by a process comprising:a) preparing a solution, slurry, or other mixture containing at least one Group VIB metal, at least one Group VIII metal, and a first organic complexing agent;b) stripping a supported hydrotreating catalyst, 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 the solution, slurry, or mixture;e) drying the impregnated, regenerated catalyst at a temperature of from 200 to 450° 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 organic solvent not being present on the partially calcined, impregnated support; andf) sulfiding the partially calcined, impregnated, regenerated catalyst. 2. The method of claim 1, wherein the dried, impregnated, regenerated catalyst is subjected to at least one further cycle of steps (c) and (d) until an impregnated, regenerated support having a total Group VIB and Group VIII metals content of at least about 35 wt % is produced. 3. The method of claim 1, wherein the solution, slurry, or other mixture further comprises at least one organic additive different from the organic complexing agent. 4. The method of claim 1, wherein the first organic complexing agent is an organic acid that contains 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. 5. The method of claim 1, wherein the first organic complexing agent is glyoxylic acid, pyruvic acid, or citric acid. 6. The method of claim 1, wherein the supported hydrotreating catalyst is formed by i) preparing a solution, slurry, or other mixture containing at least one Group VIB metal, at least one Group VIII metal, and a second organic complexing agent;ii) impregnating a support with the solution, slurry, or mixture;iii) 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 organic solvent not being present on the partially calcined, impregnated support; andiv) sulfiding the partially calcined, impregnated support that includes at least a portion of the carbon content. 7. The method of claim 6, wherein the second organic complexing agent is an organic acid that contains 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. 8. The method of claim 6, wherein the second organic complexing agent is glyoxylic acid, pyruvic acid, or citric acid. 9. The method of claim 6, wherein the first complexing agent is different from the second complexing agent. 10. The method of claim 1, wherein the impregnated, regenerated catalyst is partially calcined at a temperature from about 200 to 150° C. 11. The method of claim 1, wherein the impregnated, regenerated catalyst is partially calcined at a temperature from about 300 to about 400° C. 12. The method of claim 1, wherein stripping the supported hydrotreating catalyst comprises stripping the supported hydrotreating catalyst with a flowing gas stream at a temperature of about 350° C. or less. 13. The method of claim 12, wherein the supported hydrotreating catalyst is stripped with a flowing inert gas. 14. The method of claim 1, wherein the supported hydrotreating catalyst is stripped using a solvent stripping sequence. 15. The method of claim 1, wherein the supported hydrotreating catalyst is a spent or partially spent catalyst having about 20 wt % or less of coke. 16. The method of claim 1, wherein at least one of the Group VIB metal and the Group VIII metal is provided as a metal salt, the anion of the metal salt being a conjugate base of the solvent. 17. The method of claim 1, wherein the solution, slurry, or mixture comprises at least one additional transition metal. 18. The method of claim 17, wherein the at least one additional transition metal comprises Co, Mo, Ni, W, Zn, Fe, Cu, or Mn. 19. The method of claim 1, wherein impregnating a regenerated catalyst with the solution, slurry, or mixture comprises impregnating the regenerated catalyst with a volume of solution per volume of support that is between about 0.9-1.05 times the pore volume of the support per volume of support. 20. The method of claim 1, wherein impregnating a regenerated catalyst with the solution, slurry, or mixture comprises impregnating the regenerated catalyst with a volume of solution per volume of catalyst that is between about 0.9-1.05 times the pore volume of the support per volume of catalyst. 21. A method for hydroprocessing a hydrocarbon feedstock using a rejuvenated supported hydroprocessing catalyst, comprising exposing the hydrocarbon feedstock to the rejuvenated supported hydroprocessing catalyst under effective hydroprocessing conditions, wherein the rejuvenated supported hydroprocessing catalyst is prepared by a process comprising:a) preparing a solution, slurry, or other mixture containing at least one Group VIB metal, at least one Group VIII metal, and a first organic complexing agent;b) impregnating a regenerated catalyst with the solution, slurry, or mixture, the regenerated catalyst including a support, at least one Group VIB metal, and at least one Group VIII metal;c) drying the impregnated, regenerated catalyst at a temperature of from 200 to 450° 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 organic solvent not being present on the partially calcined, impregnated support; andd) sulfiding the partially calcined, impregnated, regenerated catalyst that includes at least a portion of the carbon content. 22. The method of claim 21 wherein the regenerated catalyst corresponds to a fresh catalyst formed by i) preparing a solution, slurry, or other mixture containing at least one Group VIB metal, at least one Group VIII metal, and a second organic complexing agent;ii) impregnating a support with the solution, slurry, or mixture;iii) 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 organic solvent not being present on the partially calcined, impregnated support; andiv) sulfiding the partially calcined, impregnated support that includes at least a portion of the carbon content. 23. The method of claim 21, wherein at least one of the Group VIB metal and the Group VIII metal is provided as a metal salt, the anion of the metal salt being a conjugate base of the solvent. 24. The method of claim 21, wherein the solution, slurry, or mixture comprises at least one additional transition metal. 25. The method of claim 24, wherein the at least one additional transition metal comprises Co, Mo, Ni, NV, Zn, Fe, Cu, or Mn. 26. The method of claim 21, wherein impregnating a regenerated catalyst with the solution, slurry, or mixture comprises impregnating the regenerated catalyst with a volume of solution per volume of support that is between about 0.9-1.05 times the pore volume of the support per volume of support. 27. The method of claim 21, wherein impregnating a regenerated catalyst with the solution, slurry, or mixture comprises impregnating the regenerated catalyst with a volume of solution per volume of catalyst that is between about 0.9-1.05 times the pore volume of the support per volume of catalyst.
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