Method for catalytically converting residual oils

Abstract

A process for converting residual oil comprising vacuum bottoms in the presence of a cracking catalyst of high surface area and comprising an ultrastable zeolite is described. More particularly, a conversion process particularly contributing to producing cycle oil and gasoline boiling range products with reduced carbon deposition in combination with a relatively high regeneration temperature operation of at least 1350° F. and above, and a short contact time riser hydrocarbon conversion operation contributing to reducing slurry oil product in favor of lower boiling products is described. A fluid cracking catalyst comprising a special ultrastable crystalline zeolite of high silica to alumina ratio provides hydrothermal stability of acceptable tolerance in the environment employed.

We claim: 
     
       1. A method for .[.upgrading.]. .Iadd.increasing conversion to liquid products of .Iaddend.a residual oil portion of crude oil boiling above 600° F. comprising metallo-organic compounds which comprises contacting .Iadd.a feed containing .Iaddend.said residual portion of crude oil boiling above 600° F. .Iadd.said feed having a Conradson carbon content above about 2.5 weight percent .Iaddend.with a catalyst consisting of from 20 to 80 wt. % of an ultrastable faujasite crystalline zeolite dispersed in a .[.silica-clay.]. matrix .[.for a time at a temperature particularly selective for conversion of the residual portion of crude oil to products of gasoline, light cycle oil and gasoline forming gaseous components, and recovering said products comprising gasoline and light cycle oil.]. .Iadd.selected from the group consisting of: silica-clay, silica-alumina, clay, silica, alumina and mixtures thereof,   at a temperature above about 950° F. to provide a ratio of volume percent of light cycle oil to heavy cycle oil of in excess of 1.03 at essentially constant conversion and recover said light cycle oil and heavy cycle oil .Iaddend..   
     
     
       2. The method of claim 1 wherein the .Iadd.light .Iaddend.cycle oil comprises two member rings produced at the expense of producing of cycle oils of higher member rings. 
     
     
       3. The method of claim 1 wherein the ultrastable faujasite zeolite .Iadd.is .Iaddend.of a pv 0.5-3 microns size .[.is distributed in a matrix material selected from; a kaolin clay-silicon oxide binder material; silica-alumina, clay, silica, alumina and a high surface area amorphous material providing active cracking sites.].. 
     
     
       4. The method of claim 1 wherein the catalyst comprises the ultrastable faujasite crystalline zeolite in an amount within the range of 30 to 50 wt. %. 
     
     
       5. The method of claim 1 wherein the ultrastable crystalline zeolite component of the catalyst is prepared under conditions to provide a high surface area material, a silica/alumina ratio of at least 3 and a unit cell size less than 24.65 Angstroms. 
     
     
       6. The method of claim 1 wherein conversion of the residual portion of the crude oil is accomplished for a time less than 3 seconds at an elevated temperature sufficient to achieve substantially instantaneous vaporization of the charged residual oil in atomized condition upon contact with high temperature catalyst particles. 
     
     
       7. The method of claim 6 wherein the temperature of the catalyst is at least equal to the feed pseudo-critical temperature and residual oil feed comprises metalloorganic components boiling above 1025° F. 
     
     
       8. The method of claim .[.7.]. .Iadd.6 .Iaddend.wherein .[.the catalyst elevated.]. .Iadd.said high .Iaddend.temperature .Iadd.of said catalyst particles is .Iaddend.achieved by burning hydrocarbonaceous deposits of said residual oil conversion .Iadd.and .Iaddend.increases in response to the feed Conradson carbon content at catalyst regeneration temperatures in the range of 1350° to 1600° F. 
     
     
       9. The method of claim 1 wherein the ultrastable faujasite crystalline zeolite is prepared to provide high surface area zeolite with a silica/alumina ratio of at least 5 and a unit cell size of about 24.5 Angstroms or less. 
     
     
       10. The method of claim 1 wherein an atomizing diluent material is used with the residual oil feed comprising one or more materials selected from steam, CO 2 , light normally gaseous hydrocarbons comprising C 3  minus materials in cooperation with atomizing spray nozzles. 
     
     
       11. The method of claim 10 wherein the conditions are selected to insure a relatively dilute phase suspension contact between catalyst particles and atomized oil feed for vaporized conversion transfer through a riser conversion zone as a particle concentration in the range of 2 to 10 pounds per cubic foot and a vapor residence time within the range of 0.5 to 3 seconds. 
     
     
       12. The method of claim 1 wherein the residual oil portion of crude oil comprises high boiling Conradson carbon producing materials and metal contaminants. 
     
     
       13. The method of claim 1 wherein the residual oil conversion operation is effected at a temperature in the range of about 950° F. up to about 1400° F. and at a temperature equal to or above the feed pseudo-critical temperature. 
     
     
       14. A method for catalytically converting residual oils comprising vacuum bottoms which comprises, converting said residual oil with a catalyst consisting of about 30-50 wt. % of ultrastable faujasite crystalline zeolite dispersed in a matrix material of clay and silica binder providing active cracking sites,   said catalytic conversion effected at said residual oil pseudo-critical temperature for a time in the range of 0.5 to 3 seconds in a riser reaction zone, and   recovering a product selectively of said catalytic conversion particularly comprising gasoline and light cycle oils comprising largely two member rings separately from catalyst particles comprising hydrocarbonaceous deposits of said conversion.   
     
     
       15. The method of claim 14 wherein the separated catalyst comprising hydrocarbonaceous deposits is regenerated in a sequence of separate catalyst regeneration zones of increasing temperatures in the direction of catalyst flow permitting effecting the residual oil conversion at a temperature in the range of 950° to 1400° F. 
     
     
       16. The method of claim 15 wherein the sequence of catalyst regeneration steps removes residual carbon on the catalyst to below 0.25 wt. %. 
     
     
       17. The method of claim 14 wherein the zeolite comprises less than 0.5 wt. % Na 2  O and a higher surface area than a rare earth exchanged faujasite crystalline zeolite. .Iadd.18. The method of claim 1 wherein said catalyst is regenerated at a temperature above about 1350° F. .Iaddend. .Iadd.19. The method of claim 18 wherein said matrix consists of kaolin clay and silica. .Iaddend. .Iadd.20. The method of claim 1 wherein said contacting time is less than 5 seconds and said temperature for conversion is in the range of 950° F. to about 1400° F. 
     
     
        .Iaddend. .Iadd.21.  The method of claim 1 wherein said matrix has active cracking sites. .Iaddend. .Iadd.22. A method for increasing conversion to liquid products of a residual oil portion of crude oil feed boiling above 600° F. said method comprising: (a) contacting said feed having a Conradson carbon content above about 2.5 weight percent with a catalyst consisting of from 20 to 80 wt. % of an ultrastable Y zeolite dispersed in a matrix said contacting (i) providing an increase in production of light cycle oil relative to heavy cycle oil to provide a ratio of volume percent of said light cycle oil to said heavy cycle oil in excess of 1.03 at essentially constant conversion and (ii) producing carbonaceous deposits on said catalyst; and   (b) regenerating said catalyst by combusting said carbonaceous deposits in the substantial absence of hydrothermal deactivation of said catalyst wherein at least a portion of said regeneration occurs at a temperature of at least about 1350° F. .Iaddend. .Iadd.23. The method of claim 22 wherein said matrix is selected from the group consisting of silica-clay, silica-alumina, clay, silica, alumina, and mixtures thereof. .Iaddend. .Iadd.24. The method of claim 22 wherein said residual oil portion comprises components boiling above 1050° F. .Iaddend. .Iadd.25. The method of claim 24 wherein at least a portion of said regenerating is accomplished at a regenerator temperature of between about 1350° F.   
     
     
        and about 1600° F. .Iaddend. .Iadd.26.  The method of claim 11 wherein said ultrastable Y zeolite has a silica/alumina ratio of at least 3 and a unit cell size less than 24.65 Angstroms. .Iaddend. .Iadd.27. The method of claim 22 wherein a diluent material is used with the residual oil portion said diluent material comprising a material selected from the group consisting of steam, CO 2 , light normally gaseous hydrocarbons comprising C 3  minus materials, and mixtures thereof in cooperation with spray nozzles. .Iaddend. .Iadd.28. The method of claim 22 wherein said regenerating removes said carbonaceous deposits on said catalyst to below about 0.25 weight percent. .Iaddend. .Iadd.29. The method of claim 23 wherein said matrix has active cracking sites. .Iaddend. .Iadd.30. The method of claim 22 wherein said contacting of the residual oil and catalyst is effected at a temperature in the range of about 950° F. to about 1400° F. .Iaddend. .Iadd.31. The method of claim 22, wherein said contacting of the residual oil and catalyst is effected at a temperature equal to or above the crude oil pseudo-critical temperature. .Iaddend. .Iadd.32. In a method for upgrading an oil feed containing residual oil boiling above 600° F. wherein said residual oil is contacted with a cracking catalyst the improvement comprising: providing an increase in production of light cycle oil compared to heavy cycle oil and yield a ratio volume percent of light cycle oil to heavy cycle oil in excess of about 1.03 at essentially constant conversion and an increase in conversion to C 3   and heavier liquid products by contacting said residual oil with a catalyst which maintains an equilibrium surface area in excess of 65 m 2  /gm wherein said catalyst comprises 20 to 80 wt. % ultrastable Y zeolite on a matrix and recovering said light cycle oil and heavy cycle oil. .Iaddend. .Iadd.33. The method of claim 32 wherein carbonaceous deposits are formed on said catalyst by contacting said residual oil and said catalyst containing said deposits is regenerated by combusting said carbonaceous deposits at a temperature of at least about 1350° F. and wherein said equilibrium surface area is at least about 105 m 2  /gm. .Iaddend. .Iadd.34. The method of claim 32 wherein said catalyst is contacted with said residual oil at a temperature of at least about 950° F. .Iaddend. .Iadd.35. The method of claim 32 wherein said matrix is selected from the group consisting of silica-clay, silica-alumina, clay, silica, alumina and mixtures thereof. .Iaddend. .Iadd.36. The method of claim 35 wherein said matrix has active cracking sites. .Iaddend. .Iadd.37. The method of claim 35 wherein carbonaceous deposits found on said catalyst when said catalyst contacts said residual oil are combusted at a temperature of at least about 1350° F. to provide a regenerated catalyst. .Iaddend. .Iadd.38. The method of claim 35 wherein said catalyst is contacted with said residual oil at a temperature equal to or above the pseudo-critical temperature of said crude oil. .Iaddend. .Iadd.39. The method of claim 32 wherein said contacting is effected at a temperature between about 950° F. and 1400° F. and produces carbonaceous deposits on said catalyst, said catalyst containing said deposits being regenerated by combusting said deposits to provide a regeneration temperature in the range of about 1350° F. to 1600° F. .Iaddend. .Iadd.40. The method of claim 39 wherein said regeneration temperature is at least about 1400° F. .Iaddend. .Iadd.41. The method of claim 22 wherein at least a portion of said regeneration occurs at a temperature of at least about 1400° F. .Iaddend.