Claims
- 1. A process for the catalytic reforming of a contaminated feedstock comprising a combination of:
- (a) contacting the contaminated feedstock in a sorbent pretreating step with a nickel sorbent at a pressure of from atmospheric to 50 atmospheres, a temperature of from about 70.degree. to 200.degree. C., and a liquid hourly space velocity of from about 2 to 50 hr.sup.-1 to produce a low-sulfur hydrocarbon feedstock;
- (b) contacting a combined feed comprising the hydrocarbon feedstock and free hydrogen in the absence of added halogen in a first reforming zone at first reforming conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 260.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 40 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a first reforming catalyst comprising platinum and alumina to convert sulfur compounds in the hydrocarbon feedstock to hydrogen sulfide and produce a halogen-free first effluent;
- (c) contacting the first effluent in a sulfur-removal zone at sulfur-removal conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 260.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 40 hr.sup.-1, and a hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a solid sulfur sorbent comprising a manganese component to remove hydrogen sulfide and produce a halogen-free second effluent containing less than 20 parts per billion sulfur; and,
- (d) contacting the second effluent in a second reforming zone in the presence of free hydrogen and in the absence of added halogen at second reforming conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 425.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 10 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a second reforming catalyst comprising a non-acidic L-zeolite, an alkali-metal component and a platinum-group metal component to produce a halogen-free aromaticsrich effluent.
- 2. The process of claim 1 wherein the hydrocarbon feedstock comprises a naphtha with a final boiling point of from about 100.degree. to 160.degree. C.
- 3. The process of claim 1 wherein the hydrocarbon feedstock comprises a raffinate from aromatics extraction.
- 4. The process of claim 1 wherein the sulfur content of the second effluent is less than about 14 parts per billion.
- 5. The process of claim 1 wherein the first reforming zone and the sulfur-removal zone are contained within a single reactor vessel.
- 6. The process of claim 1 wherein the sulfur-removal zone and the second reforming zone are contained within a single reactor vessel.
- 7. The process of claim 1 wherein the first reforming conditions comprise a pressure of below 10 atmospheres.
- 8. The process of claim 1 wherein the sulfur-removal conditions comprise a temperature of from about 310.degree. to 420.degree. C.
- 9. The process of claim 1 wherein the second reforming conditions comprise a pressure of below 10 atmospheres.
- 10. The process of claim 1 wherein the first reforming catalyst comprises potassium-form L-zeolite.
- 11. The process of claim 1 wherein the manganese component comprises one or more manganese oxides.
- 12. The process of claim 1 wherein the manganese component consists essentially of one or more manganese oxides.
- 13. The process of claim 12 wherein the manganese component consists essentially of MnO.
- 14. The process of claim 1 wherein the platinum-group metal component of the second reforming catalyst comprises a platinum component.
- 15. The process of claim 1 wherein the non-acidic L-zeolite comprises potassium-form L-zeolite.
- 16. The process of claim 1 wherein step (a) comprises hydrotreating the contaminated feedstock at a pressure of from about atmospheric to 100 atmospheres, a temperature of from 200.degree. to 450.degree. C., a liquid hourly space velocity of from about 1 to 20 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a catalyst comprising a refractory inorganic oxide support containing one or more metal components selected from the Group VI B (6) and VIII (8-10) metals prior to sorbent pretreating.
- 17. A process for the catalytic reforming of a contaminated feedstock comprising a combination of:
- (a) hydrotreating the contaminated feedstock at a pressure of from about atmospheric to 100 atmospheres, a temperature of from 200.degree. to 450.degree. C., a liquid hourly space velocity of from about 1 to 20 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a catalyst comprising a refractory inorganic oxide support containing one or more metal components selected from the Group VI B (6) and VIII (8-10) metals to obtain hydrotreated hydrocarbons;
- (b) contacting the hydrotreated hydrocarbons in a sorbent pretreating step with a nickel sorbent at a pressure of from atmospheric to 50 atmospheres, a temperature of from about 70.degree. to 200.degree. C., and a liquid hourly space velocity of from about 2 to 50 hr.sup.-1 to produce a low-sulfur hydrocarbon feedstock;
- (c) contacting a combined feed comprising the hydrocarbon feedstock and free hydrogen in the absence of added halogen in a first reforming zone at first reforming conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 260.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 40 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a first reforming catalyst comprising platinum and alumina to convert sulfur compounds in the hydrocarbon feedstock to hydrogen sulfide and produce a halogen-free first effluent;
- (d) contacting the first effluent in a sulfur-removal zone at sulfur-removal conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 260.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 40 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a solid sulfur sorbent comprising a manganese component to remove hydrogen sulfide and produce a halogen-free second effluent containing less than 20 parts per billion sulfur; and,
- (e) contacting the second effluent in a second reforming zone in the presence of free hydrogen and in the absence of added halogen at second reforming conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 425.degree. C. to 560.degree. C., a liquid hourly space velocity of from about 1 to 10 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a second reforming catalyst comprising a non-acidic L-zeolite, an alkali-metal component and a platinum-group metal component to produce a halogen-free aromatics-rich effluent.
- 18. The process of claim 17 wherein the manganese component comprises one or more manganese oxides.
- 19. The process of claim 1 wherein the platinum-group metal component of the second reforming catalyst comprises a platinum component.
- 20. A process for the catalytic reforming of a contaminated feedstock comprising a combination of:
- (a) hydrotreating the contaminated feedstock at a pressure of from about atmospheric to 100 atmospheres, a temperature of from 200.degree. to 450.degree. C., a liquid hourly space velocity of from about 1 to 20 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a catalyst comprising a refractory inorganic oxide support containing one or more metal components selected from the Group VI B (6) and VII (8-10) metals to obtain hydrotreated hydrocarbons;
- (b) contacting the hydrotreated hydrocarbons in a sorbent pretreating step with a nickel sorbent at a pressure of from atmospheric to 50 atmospheres, a temperature of from about 70.degree. to 200.degree. C., and a liquid hourly space velocity of from about 2 to 50 hr.sup.-1 to produce a low-sulfur hydrocarbon feedstock;
- (c) contacting a combined feed comprising the hydrocarbon feedstock and free hydrogen in the absence of added halogen in a first reforming zone at first reforming conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 260.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 40 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a first reforming catalyst comprising platinum and alumina to convert sulfur compounds in the hydrocarbon feedstock to hydrogen sulfide and produce a halogen-free first effluent;
- (d) contacting the first effluent in a sulfur-removal zone at sulfur-removal conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 260.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 40 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a solid sulfur sorbent consisting essentially of one or more manganese oxides to remove hydrogen sulfide and produce a halogen-free second effluent containing less than 20 ppb sulfur; and,
- (e) contacting the second effluent in a second reforming zone in the presence of free hydrogen and in the absence of added halogen at second reforming conditions comprising a pressure of from atmospheric to 20 atmospheres, a temperature of from 425.degree. to 560.degree. C., a liquid hourly space velocity of from about 1 to 10 hr.sup.-1, and a hydrogen to hydrocarbon ratio of from about 0.1 to 10 moles of hydrogen per mole of hydrocarbon with a second reforming catalyst comprising a non-acidic L-zeolite and a platinum-group metal component to produce a halogen-free aromatics-rich effluent.
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of prior copending application Ser. No. 842,835, filed Feb. 27, 1992, now U.S. Pat. No. 5,211,837, which is a continuation-in-part of Ser. No. 555,962, filed Jul. 20, 1990, abandoned, which is a continuation-in-part of Ser. No. 408,577, filed Sep. 18, 1989, abandoned, the contents of all of which are incorporated herein by reference thereto.
US Referenced Citations (17)
Continuation in Parts (3)
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Number |
Date |
Country |
Parent |
842835 |
Feb 1992 |
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Parent |
555962 |
Jul 1990 |
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Parent |
408577 |
Sep 1989 |
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