Claims
- 1. A process for economically converting carbometallic oils to lighter products, comprising:
- a. providing a converter feed containing 650.degree. F.+ (343.degree. C.) material, said 650.degree. F.+ (343.degree. C.) material being characterized by a carbon residue on pyrolysis of at least about 1 and by containing at least about 4 parts per million Nickel Equivalents of heavy metal;
- b. simultaneously contacting said converter feed with H.sub.2 and a hot cracking catalyst bearing substantially more than 600 parts per million of heavy metals contaminants which are capable of activating hydrogen to form a stream comprising a suspension of said catalyst and said H.sub.2 in said feed and causing the resulting stream to flow through a progressive flow type reactor having an elongated reaction chamber which is at least in part vertical or inclined for a vapor riser residence time in the range of about 0.5 to about 10 seconds at a temperature of about 900.degree. F. (482.degree. C.) to about 1400.degree. F. (760.degree. C.) and under a pressure of about 10 to about 50 pounds per square inch absolute sufficient for causing a conversion per pass in the range of about 50% to about 90% while producing coke in amounts in the range of about 6% to about 14% by weight based upon fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.3% to about 3% by weight to produce cracking products and coked catalyst;
- c. separating said coked catalyst from said cracking product;
- d. stripping absorbed hydrocarbons from said coked catalyst;
- e. regenerating said coked catalyst by burning said coke in at least one regeneration zone with an oxygen-containing combustion-supporting gas while forming combustion products comprising CO and/or CO.sub.2 ;
- f. stripping said regenerated catalyst with an inert gas; and
- g. recycling said stripped catalyst for contact with fresh feed.
- 2. The process of claim 1 wherein the concentration of said hydrogen gas is in the range of 10 to 500 SCF/BBL.
- 3. The process of claim 1 wherein the concentration of said hydrogen gas is in the range of 50 to 350 SCF/BBL.
- 4. The process of claim 1 wherein said H.sub.2 is provided from a gas stream containing 80% or more H.sub.2.
- 5. The process of claim 1 wherein said H.sub.2 is provided from a gas stream containing at least about 60% H.sub.2 in said source.
- 6. The process of claim 1, 2, 3, or 4 wherein H.sub.2 is brought together with said catalyst prior to contact of said catalyst with said converter feed.
- 7. The process of claim 1 in which said catalyst is regenerated to contain less than 0.25% coke.
- 8. The process of claim 1 wherein said catalyst is regenerated to contain less than 0.05% coke.
- 9. The process of claim 1 wherein said coked catalyst is regenerated with a resulting gas containing a CO/CO.sub.2 ratio in the range of about 0.20 to 0.25.
- 10. The process of claim 9 wherein said CO/CO.sub.2 ratio is greater than 0.25.
- 11. The process of claim 9 wherein the CO/CO.sub.2 ratio is greater than 0.3.
- 12. The process of claim 1, 2, 3, 4, or 5 in which a two stage regenerator is employed.
- 13. A process according to claim 1, 2, 3, 4, or 5 wherein said feed comprises a Ramsbottom carbon value is in the range of about 2 to about 12.
- 14. A process according to claim 1, 2, 3, 4, or 5 wherein the feed as a whole contains at least about 5.5 parts per million Nickel Equivalents of heavy metal(s), of which at least about 2 parts per million is nickel (as metal by weight).
- 15. A process according to claim 1, 2, 3, 4, or 5 wherein said feed comprises about 15% or less by volume of recycled oil.
- 16. A process according to claim 1, 2, 3, 4, or 5 wherein said feed is processed in a substantially once-through or single pass mode with no substantial amount of recycled oil in the feed.
- 17. A process according to claim 1, 2, 3, 4, or 5 wherein said catalyst is maintained in contact with said feed in said reaction zone in a weight ratio of catalyst to feed in the range of about 3 to about 18.
- 18. A process according to claim 1, 2, 3, 4, or 5 wherein said process being conducted in a plant wherein the ratio between the number of barrels per day of plant throughput and the total number of tons of catalyst undergoing circulation throughout all phases of said process is in the range of about 2 to about 30 tons of catalyst per thousand barrels of daily plant throughput.
- 19. A process according to claim 1, 2, 3, 4, or 5 wherein said process being conducted in a plant wherein the ratio between the number of barrels per day of plant throughput and the total number of tons of catalyst undergoing circulation throughout all phases of the process is about 2 tons of catalyst or less per thousand barrels of daily plant throughput.
- 20. A process according to claim 1, 2, 3, 4, or 5 wherein said catalyst is added to said process at a rate in the range of about 0.1 to about 3 pounds per barrel of feed.
- 21. A process according to claim 1, 2, 3, 4, or 5 wherein there is an accumulation of heavy metals on said catalyst in the range of about 3500 ppm to about 70,000 ppm Nickel Equivalents, by weight measured on regenerated equilibrium catalyst.
- 22. The process of claim 1, 2, 3, 4, or 5 wherein said H.sub.2 is injected into said converter feed prior to contacting said converter feed with said catalyst.
- 23. The process of claim 1, 2, 3, 4, or 5 wherein said H.sub.2 is injected into said feed prior to contact of said feed with said cracking catalyst.
- 24. The process of claim 1, 2, 3, 4, or 5 wherein said H.sub.2 is injected into said feed prior to contact with said cracking catalyst.
- 25. The process of claim 1, 2, 3, 4, or 5 wherein said H.sub.2 is brought together simultaneously with said feed and said cracking catalyst.
- 26. The process of claim 1, 2, 3, 4, or 5 in which said cracking catalyst contains more than 800 ppm of heavy metal.
- 27. The process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst contains greater than 2000 ppm of nickel plus vanadium.
- 28. The process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst contains between about 800 and 50,000 parts per million of heavy metal.
- 29. The process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst contains greater than 5,000 ppm nickel plus vanadium.
- 30. The process according to claim 1, 2, 3, 4, or 5 wherein said cracking catalyst contains greater than 10,000 ppm Nickel plus Vanadia.
- 31. The process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst contains greater than 15,000 ppm Nickel plus Vanadia.
- 32. Process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst has a MAT activity greater than 10.
- 33. The process of claim 1, 2, 3, 4, or 5 in which said cracking catalyst has a MAT greater than 50.
- 34. The process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst has a MAT greater than 60.
- 35. The process of claim 1, 2, 3, 4, or 5 wherein said cracking catalyst has a MAT in the range of 10 to about 60.
- 36. The process of claim 1, 2, 3, 4, or 5 wherein the amount of said H.sub.2 added to said reactor is greater than twice the stoichiometric oxygen content as oxides of nickel, vanadium, iron and copper on said regenerated catalyst.
- 37. The process according to claim 1 in which said 650.degree. F.+ (343.degree. C.) material represents at least about 70% by weight of said feed.
- 38. A process according to claim 1 or 10 wherein the 650.degree. F.+ (343.degree. C.) material includes at least about 10% by volume of material which will not boil below 1000.degree. F. (538.degree. C.).
- 39. The process according to claim 1, 2, 3, 4, 5, or 10 in which the 650.degree. F.+ (343.degree. C.) material includes at least about 10% by volume of material which will not boil below 1025.degree. F. (552.degree. C.).
- 40. The process according to claim 1, 2, 3, 4, 5, or 10 wherein said carbon residue on pyrolysis corresponds to a Ramsbottom carbon value in the range of about 2 to about 12.
- 41. The process according to claim 1, 2, 3, 4, 5, 9, or 10 wherein said carbon residue on pyrolysis of said feed as a whole corresponds to a Ramsbottom carbon value of at least about 1.
- 42. The process according to claim 1, 2, 3, 4, 9, or 10 wherein said metal in said feed is greater than 5 ppm nickel plus vanadium plus iron plus copper.
- 43. The process according to claim 1, 2, 3, 4, 9, or 10 wherein the metals in said feed are greater than 10 ppm, nickel plus vanadium plus iron plus copper.
- 44. The process according to claim 1, 2, 3, 4, 9, or 10 wherein the metals in said feed are greater than 20 ppm, nickel plus vanadium plus iron plus copper.
- 45. The process according to claim 1, 2, 3, 4, 9, or 10 wherein the metals in said feed are greater than 50 ppm, nickel plus vanadium plus iron plus copper.
- 46. The process according to claim 1, 2, 3, 4, 9, or 10 wherein the metals in said feed are greater than 100 ppm, nickel plus vanadium plus iron plus copper.
- 47. The process according to claim 2, 3, 4, 9, or 10 wherein said feed comprises about 15% or less by volume of recycled oil.
- 48. The process according to claim 1, 2, 3, 4, 9, or 10 wherein said catalyst is maintained in contact with said feed in said reactor zone in a weight ratio of catalyst to feed in the range of about 3 to about 18.
- 49. A process for catalytically cracking a metal-contaminated residual oil feedstock containing components that do not boil below about 1025.degree. F. (552.degree. C.), greater than 15 ppm Nickel+Vanadium and at least 200 ppm basic nitrogen, which comprises: contacting said feedstock in a riser cracking zone in the presence of about 5-20 wt % water based on feed with hydrogen gas and a regenerated cracking catalyst, at a temperature in the range of 1300.degree. F. (704.degree. C.) to 1500.degree. F. (816.degree. C.), said catalyst being characterized by a metals content greater than 5,000 ppm, Nickel plus Vanadium and having a carbon content less than about 0.10 wt %, to form cracked products and deactivating said catalyst while said catalyst accumulates metal contaminants and hydrocarbonaceous deposits; separating said deactivated catalyst from said cracked products; recovering said cracked products; regenerating said separated, deactivated catalyst in said regeneration zone under conditions to produce a CO rich flue gas and provide a regenerated cracking catalyst having less than about 0.10 wt % residual carbon, at a temperature in the range of 1300.degree. F. (704.degree. C.) to 1500.degree. F. (816.degree. C.), and recycling said regenerated catalyst to said cracking zone.
- 50. A process of claim 49 wherein said cracked products comprises a C.sub.5 -430.degree. F. endpoint fraction having a Research Octane Number above 90 as measured without octane-enhancing additives.
- 51. A process for catalytically cracking a carbometallic containing residual feedstock containing components boiling above 1025.degree. F. (552.degree. C.), greater than 15 ppm Nickel+Vanadium and at least 200 ppm basic nitrogen, which comprises: contacting said feedstock in a riser cracking zone in the presence of 5-10 wt % water based on feed with hydrogen gas and a fluidized, regenerated cracking catalyst characterized by a metal content greater than 5,000 ppm Nickel equivalents and having a carbon content less than 0.1 wt %, thereby forming cracked products and coked catalyst; said cracked products containing gasoline being characterized by an octane value greater than 90 neat and containing oxygenated compounds; separating said coked catalyst from said cracked products by separation means such that less than 1% of the coked catalyst is carried over to a product separation means; passing said separated coked catalyst to a two-stage regeneration zone; regenerating said coked catalyst in a two-stage regeneration zone with an oxygen-containing gas at 1400.degree. F. (760.degree. C.) or higher such that 75% or more of the coke is removed in the first or upper stage and the contact time in the second or lower stage is less than one-half of that in the upper stage to form said regenerated catalyst with less than 0.1 wt % residual carbon, while producing a flue gas containing a low CO.sub.2 /CO ratio, preferably below 2/1, with the oxygen content in said second or lower stage being below combustion supporting levels; recycling said regenerated catalyst to said riser cracking zone with the unit in complete heat balance by the combination of water addition to the riser, low feed preheat, low oxygen utilization, and low thermal output per pound of coke, thereby selectively forming liquid cracked products.
- 52. A process for catalytically cracking a metal-contaminated residual oil feedstock containing components that do not boil below about 1025.degree. F. (552.degree. C.), greater than 15 ppm Nickel+Vanadium and at least 200 ppm basic nitrogen, which comprises: contacting said feedstock in a riser cracking zone in the presence of about 5-15 wt % water based on feed, hydrogen gas, and a regenerated cracking catalyst characterized by a metals content greater than 5,000 ppm Nickel plus Vanadium and having a carbon content less than about 0.10 wt % at a temperature in the range of 1300.degree. F. (704.degree. C.) to 1500.degree. F. (816.degree. C.) to form cracked products and deactivating said catalyst with metal contaminants and hydrocarbonaceous deposits; separating said deactivated catalyst from said cracked products; recovering said cracked products; passing said separated, deactivated catalyst to a regeneration zone; contacting said deactivated catalyst in said regeneration zone under conditions to produce a CO rich flue gas and provide a regenerated cracking catalyst having less than about 0.10 wt % residual carbon at a temperature in the range of 1300.degree. F. (704.degree. C.) to 1500.degree. F. (816.degree. C.), and recycling said regenerated catalyst to said cracking zone.
- 53. A process for catalytically cracking a carbometallic containing residual feedstock containing components boiling above 1025.degree. F. (552.degree. C.), greater than 15 ppm nickel+vanadium and at least 200 ppm basic nitrogen, which comprises: contacting said feedstock in a riser cracking zone in the presence of 5-20 wt % water based on feed with hydrogen gas and a fluidized, regenerated cracking catalyst characterized by a metal content greater than 5,000 ppm Nickel Equivalents and having a carbon content less than about 0.1 wt %, thereby forming cracked products containing gasoline being characterized by an octane value greater than 90 neat and by containing oxygenated compounds; separating said coked catalyst from said cracked products by separation means such that less than 1% of the coked catalyst is carried over to the product separation means passing said separated coked catalyst to a two-stage regeneration zone; contacting said coked catalyst in said two-stage regeneration zone with an oxygen-containing gas at 1400.degree. F. (760.degree. C.) or higher such that about 75% or more of the coke is removed in the first or upper stage and the contact time in the second or lower stage is less than one-half of that in the upper stage to form a regenerated catalyst with less than 0.1 wt % residual carbon with the production of a flue gas containing a low CO.sub.2 /CO ratio, preferably below 2/1, and wherein said oxygen content in said oxygen-containing gas is below combustion supporting levels; recycling said regenerated catalyst to said riser cracking zone with the unit in complete heat balance by the combination of water addition to the riser, low feed preheat, oxygen utilization, and low thermal output per pound of coke from the two-stage regenerator, thereby selectively forming liquid cracked products.
- 54. A process according to claim 49, 50, 51, 52 or 53 wherein said water additionally comprises hydrogen sulfide.
- 55. A process according to claim 53 wherein the concentration of said hydrogen sulfide is in the range of about 500 to about 5000 ppm.
- 56. A process according to claim 53 wherein the ratio of said hydrogen sulfide in said feed as a whole is in the range of about 0.05 to about 0.4.
CROSS REFERENCE TO RELATED APPLICATIONS/PATENTS
The present application is a continuation-in-part of copending U.S. patent application Ser. No. 094,227, (now U.S. Pat. No. 4,354,923) filed Nov. 14, 1979.
Patent application U.S. Pat. Nos. 094,092, 094,216, 094,217, (now U.S. Pat. Nos. 4,332,673; 4,341,624; and 4,347,122 respectively) all filed Nov. 14, 1979, and 246,791 filed Mar. 23, 1981 (now U.S. Pat. No. 4,376,038) are related applications.
U.S. Pat. No. 4,299,687 issued Nov. 10, 1981 is also related.
US Referenced Citations (18)
Non-Patent Literature Citations (1)
Entry |
Shankland and Schmitkons "Determination of Activity and Selectivity of Cracking Catalyst", Proc. API 27 (III) 1947, pp. 57-77. |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
94227 |
Nov 1979 |
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