Claims
- 1. A process of catalytic hydroconversion of a heavy hydrocarbon oil containing a substantial portion of components having am atmospheric boiling point above about 565.degree. C. (1059.degree. F.) to give a product hydrocarbon oil containing a substantial portion of components having a boiling point below about 565.degree. C. (1050.degree. F.), the process comprising:
- mixing the heavy hydrocarbon oil with an oil soluble molybdenum compound, wherein the molybdenum compound has a first decomposition temperature of at least 222.degree. C. (431.degree. F.), to give a mixture having from about 0.005 to about 0.050 weight percent molybdenum compound, wherein said mixture consists essentially of the heavy hydrocarbon oil and the oil soluble molybdenum compound;
- introducing the mixture into a hydroconversion zone, the hydroconversion zone being at a temperature from about 343.degree. C. (650.degree. F.) to about 454.degree. C. (850.degree. F.) and a total pressure from about 6996 kPa (1000 psig) to about 24,233 kPa (3500 psig) and containing heterogeneous catalyst, the catalyst including a Group VIII non-noble metal oxide, and a Group VI-B metal oxide on an alumia or silica-alumina support;
- introducing a reactor feed gas into The hydroconversion zone, the reactor feed gas including a majority of hydrogen gas, the introducing being conducted at a rate from 356.2 liters (H.sub.2) / liters(oil) (2000 standard cubic feet (H.sub.2) / Barrel (oil)) to about 1781.2 liters (H.sub.2) / liters(oil) (10,000 standard cubic feet (H.sub.2) / Barrel (oil)); and,
- recovering the product hydrocarbon oil from the hydroconversion zone.
- 2. The process of claim 1 wherein the Group VIII non-noble metal oxide is nickel oxide and the Group VI-B metal oxide is molybdenum oxide.
- 3. The process of claim 1 wherein the alumina or silica-alumina has a Total Surface Area from about 150 to 240 m.sup.2 /g, a Total Pore Volume (TPV) from 0.7 to 0.98 and a pore diameter distribution such that no more than 20% of the TPV is present as primary micropores having diameters no greater than 100 .ANG., at least about 34% of the TPV is present as secondary micropores having diameters from about 100 to 200 .ANG., and from about 26% to 46% of the TPV is present as macropores having diameters of at least 200 .ANG..
- 4. The process of claim 1 wherein the reactor feed gas contains at least 93% by volume of hydrogen and is substantially free of hydrogen sulfide.
- 5. The process of claim 4 wherein the reactor feed gas is introduced at a rate from about 356.2 liters (H.sub.2) / liters(oil) (2000 standard cubic feet (H.sub.2) / Barrel (oil)) to about 712.5 liters (H.sub.2) /liters(oil) (4,000 standard cubic feet (H.sub.2) / Barrel (oil)).
- 6. The process of claim 1 wherein the temperature of the hydroconversion zone is from about 371.degree. C. (700.degree. F.) to about 441.degree. C. (825.degree. F.) and the total pressure is from about 9065 kPa (1300 psig) to about 11,822 kPa (1700 psig).
- 7. The process of claim 1 wherein the mixing of the heavy hydrocarbon oil with an oil soluble molybdenum compound includes mixing a first portion of the heavy hydrocarbon oil with the soluble molybdenum compound to give a pre-feed mixture in which the concentration of molybdenum compound is from about 0.02 to about 0.42 weight percent, and mixing said pre-feed mixture with additional heavy hydrocarbon oil to give a reactor feed mixture having a concentration of molybdenum compound from about 0.005 to about 0.050 weight percent.
- 8. The process of claim 1 wherein the recovered product hydrocarbon oil has an API gravity uplift of greater than 10 over the API gravity of the heavy hydrocarbon oil feed.
- 9. The process of claim 1 wherein the hydroconversion zone is an ebullated bed reactor and the introducing of the mixture into the hydroconversion zone is conducted at a rate from about 0.08 to 1.5 m.sup.3 (oil) / m.sup.3 (reactor void volume)/hour.
- 10. A method of hydrocracking a heavy whole petroleum crude oil having at least 40 weight percent components boiling above about 565.degree. C. (1050.degree. F.) to give a processed crude oil containing a majority of components boiling below about 565.degree. C. (1050.degree. F.), the process comprising:
- mixing the heavy whole petroleum crude with a oil soluble Group VI-B metal compound, the metal compound having a first decomposition temperature of at least 222.degree. C. (431.degree. F.), to give a reactor feed mixture having from about 0.005 to about 0.050 weight percent metal, wherein said reactor feed mixture consists essentially of the heavy whole petroleum crude and the oil soluble group VI-B metal compound;
- reacting the mixture and a hydrogen containing feed gas in an ebullated-bed reactor, the reactor being at a temperature from about 343.degree. C. (650.degree. F.) to about 454.degree. C. (850.degree. F.) and at a total pressure of no greater than about 13,201 kPa (1900 psig) and wherein the ebullated bed includes a supported heterogeneous catalyst the supported heterogeneous catalyst comprising a Group VIII non-noble metal oxide, a Group VI-B metal oxides no more than 2 weight percent phosphorous oxide and an alumina or silica-alumina support; and,
- recovering the processed crude oil from the reactor.
- 11. The method of claim 10 wherein the Group VI-B metal compound in the reactor feed mixture is a molybdenum containing.
- 12. The method of claim 11 wherein the hydrogen containing feed gas includes a majority of hydrogen gas and is substantially free of hydrogen sulfide, and wherein the gas introduction is conducted at a rate from 356.2 liters (H.sub.2) / liters(oil) (2000 standard cubic feet (H.sub.2) / Barrel (oil)) to about 1781.2 liters (H.sub.2) / liters(oil) (10,000 standard cubic feet (H.sub.2) / Barrel (oil)).
- 13. The method of claim 12 wherein the mixing of the heavy whole petroleum crude oil with an oil soluble molybdenum compound comprises combining a first portion of the heavy whole petroleum crude oil with the oil soluble molybdenum compound to give a pre-feed mixture in which the concentration of molybdenum compound is from about 0.020 to about 0.420 weight percent, and mixing said pre-feed mixture with additional heavy whole petroleum crude oil to give a reactor feed mixture having a concentration of molybdenum compound from about 0.005 to about 0.050 weight percent.
- 14. The method of claim 13 wherein the reactor feed mixture and the hydrogen containing feed gas are introduced into the ebullated-bed reactor at a rate from about 0.08 to about 1.5 m.sup.3 (oil)m.sup.3 (reactor void volume)/hour.
- 15. The method of claim 14 wherein the temperature of the reactor is from about 371.degree. C. (700.degree. F.) to about 441.degree. C. (825.degree. F.) and the total pressure is from about 9065 kPa (1300 psig) to about 11,822 kPa (1700 psig).
- 16. The method of claim 15 wherein the alumina or silica-alumina support has a Total Surface Area (TSA) of about 150 to 240 m.sup.2 /g, and Total Pore Volume (TPV) from about 0.7 to 0.98 and a pore diameter distribution such that no more than 20% of the TPV is present as primary micropores having diameters no greater than 100 .ANG., at least about 34% of the TPV is present as secondary micropores having diameters from about 100 .ANG. to about 200 .ANG., and from about 26% to about 46% of the TPV is present as macropores having diameters of at least 200 .ANG..
- 17. The method of claim 16 further comprising combining the reactor feed mixture with hydrogen containing feed gas at a pressure no more than about 205 kPa (15 psig) above the reactor pressure, pre-heating the pressurized reactor feed mixture in a reactor feed heater to a temperature no greater than 11.degree. C. (20.degree. F.) above the reactor temperature immediately before introducing the preheated, pressurized reactor feed into the reactor.
- 18. The method of claim 17 wherein the recovered processed crude oil has an API gravity uplift of greater than 10 over the API gravity of the heavy whole petroleum crude oil.
- 19. The method of claim 10 wherein the processed crude oil has a decreased amount of sediment in the portion of the processed heavy crude oil having a boiling point above about 343.degree. C. (650.degree. F.) as compared with the same product resulting from the process conducted without the molybdenum compound in the reactor feed mixture.
Parent Case Info
This application claims the benefit of U.S. Provisional Application No. 60/011,652, filed on Feb. 14, 1996.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
PCT/US97/02409 |
2/14/1997 |
|
|
6/19/1998 |
6/19/1998 |
Publishing Document |
Publishing Date |
Country |
Kind |
WO97/29841 |
8/21/1997 |
|
|
US Referenced Citations (15)