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A catalyst nominally containing zeolite, clay and silica-alumina gel is disclosed. The zeolite is preferably partially exchanged with high La/Ce ratio solution in a wetting step. The catalyst and processes for its manufacture and use are disclosed. The catalyst is excellent for processing heavy oils

A catalyst nominally containing zeolite, clay and silica-alumina gel is disclosed. The zeolite is preferably partially exchanged with high La/Ce ratio solution in a wetting step. The catalyst and processes for its manufacture and use are disclosed. The catalyst is excellent for processing heavy oils, generally produces higher LCO/slurry oil ratio and has high metals tolerance.

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1. A process for economically converting carbo-metallic oils to lighter product comprising: I. providing a converter feed which has had substantially no hydrotreatment and which comprises at least about 70% by volume of 343° C.+ (650° F.+) of which at least about 10% by volume is of material whic

1. A process for economically converting carbo-metallic oils to lighter product comprising: I. providing a converter feed which has had substantially no hydrotreatment and which comprises at least about 70% by volume of 343° C.+ (650° F.+) of which at least about 10% by volume is of material which will not boil below about 552° C. (about 1025° F.), said material being characterized by a carbon residue on pyrolysis of at least about 2 and by containing at least about 5.5 ppm of nickel equivalents of heavy metals; II. bringing said converter feed together with a low coke, high octane, high activity, high selectivity, metal tolerant, hydrothermally and thermally stable, low slurry oil producing cracking catalyst for the conversion of hydrocarbons contaminated with pyrolysis carbon precursors and metals to produce lower molecular weight products, said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size in spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt.% alumina; (d) from about 0.5 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) and wherein the catalyst is characterized in that the zeolite is partially exchanged with said rare earths from a solution and a portion of said rare earths is also precipitated onto said matrix of said catalyst; having an equilibrium MAT conversion activity level of at least about 40 volume percent and bearing an accumulation of at least about 2000 ppm by weight of nickel equivalents of heavy metals expressed as metals on regenerated equilibrium catalyst, and with additional gaseous material including steam to form a stream comprising a suspension of said catalyst in said feed and gaseous material wherein the ratio of the partial pressure of the added gaseous material relative to the partial pressure of the feed is in the range of about 0.25 to about 4, and causing the resultant stream to flow at a velocity of at least about 25 feet per second through a progressive flow type reactor having an elongated reaction chamber which is at least in part vertical or inclined for a vapor residence time in the range of about 0.5 to about 3 seconds at a temperature of about 482° C. to about 760° C. (about 900° F. to about 1400° F.) and under a total pressure to about 10 to about 50 pounds per square inch absolute sufficient for causing a conversion per pass in the range of about 60% to about 90%, while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.3 to about 3% by weight; III. separating said catalyst from the resultant cracking products; IV. stripping hydrocarbons from said separated catalyst; V. regenerating the metals-bearing, coked catalyst in one or more stages with oxygen-containing combustion-supporting gas under conditions of time, temperature and atmosphere sufficient to reduce the carbon on the catalyst to about 0.25% by weight or less, while forming combustion product gases comprising CO and/or CO 2 ; and VI. recycling the regenerated catalyst to the reactor for contact with fresh feed. 2. A process for economically converting carbo-metallic oils to lighter products, comprising: I. providing a converter feed containing 343° C.+ (650° F.+) material, said converter feed having had substantially no prior hydrotreatment and being composed of at least about 70% by volume of said 343° C.+ (650° F.+) material and of at least about 10% by volume of material which will not boil below about 552° C. (about 1025° F.), at least about 85% by volume of said converter feed not having been previously exposed to cracking catalyst under cracking conditions, said converter feed being further characterized by a carbon residue on pyrolysis of at least about 4 and by containing more than about 5.5 parts per million of Nickel Equivalents of heavy metals; II. bringing said converter feed together with a low coke, high octane, high activity, high selectivity, metal tolerant, hydrothermally and thermally stable, low slurry oil producing cracking catalyst for the conversion of hydrocarbons contaminated with pyrolysis carbon precursors and metals to produce lower molecular weight products, said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt. % of a clay comprising kaolin, having a size in spherical equivalents of from 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt.% alumina; (d) from about 0.5 to about 3 wt.% of rare earths, comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in said acidic matrix and wherein a portion of said rare earths has also been precipitated into said matrix; having an equilibrium MAT conversion activity level of at least about 40 and bearing a heavy metals accumulation of about 2000 to about 30,000 Nickel Equivalents by weight expressed as metals on regenerated equilibrium catalyst in a catalyst to converter feed weight ratio of at least about 6, and with H 2 O in a weight ratio relative to the converter feed of about 0.04 to about 0.3 to form a stream comprising a suspension of said catalyst in a mixture of said converter feed and steam and causing the resultant stream to flow at a linear velocity of at least about 35 feet per second through a progressive flow type reactor having an elongated riser reaction chamber which is at least in part vertical or inclined for a vapor residence time in the range of about 0.5 to about 3 seconds at a reaction chamber outlet temperature of about 496° C. to about 649° C. (about 925° F. to about 1200° F.) and under a partial pressure of feed of about 15 to about 35 pounds per square inch absolute sufficient for causing a conversion per pass in the range of about 60% to about 90%, while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.3 to about 3% by weight; III. at at least one location along the elongated reaction chamber, including an outlet means at the downstream end of the elongated reaction chamber or an extension thereof, ballistically separating said catalyst from at least a substantial portion of the stream comprising said catalyst, steam and resultant cracking products formed in the elongated reaction chamber by projecting catalyst particles in a direction established by said elongated reaction chamber or said extension thereof, diverting vapors in said stream, including said steam and said products, in an abrupt change of direction relative to the direction in which said catalyst particles are projected; IV. stripping hydrocarbons from said separated catalyst; V. regenerating said catalyst in one or more regeneration stages with oxygen-containing combustion-supporting gas under conditions of time, temperature and atmosphere sufficient to reduce the carbon on the catalyst to about 0.25 by weight or less, while forming gaseous combustion product gases comprising CO and/or CO 2 ; and VI. recycling the regenerated catalyst to the reactor for contact with fresh feed. 3. A process for economically converting carbo-metallic oils to lighter products, comprising: I. providing a converter feed containing at least about 70% by volume of 343° C.+ (650° F.+) material and at least about 10% by volume of material which will not boil below about 552° C. (about 1025° F.), said converter feed being characterized by a carbon residue on pyrolysis of at least about 2 and by containing at least about 5.5 parts per million of Nickel Equivalents of heavy metals; II. bringing said converter feed together with liquid water in a weight ratio relative to converter feed in the range of about 0.04 to about 0.15; III. bringing said converter feed together with a low coke, high octane, high activity, high selectivity, metal tolerant, hydrothermally and thermally stable, low slurry oil producing cracking catalyst for the conversion of hydrocarbons contaminated with carbon and metals to produce lower molecular weight products, said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size in spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt.% alumina; (d) from about 0.5 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in said acidic matrix and wherein a portion of said rare earths has also been precipitated into said matrix; said cracking catalyst having an equilibrium MAT conversion activity level of at least about 50 volume percent and bearing an accumulation of more than about 2000 ppm by weight of Nickel Equivalents of heavy metals expressed as metals on regenerated equilibrium catalyst; IV. forming a stream containing fine droplets of said converter feed, said catalyst and steam resulting from the vaporization of said liquid water and causing the resultant stream to flow through a progressive flow type reactor having an elongated riser reaction chamber which is at least in part vertical or inclined at a linear velocity of at least about 35 feet per second for a vapor residence time in the range of about 0.5 to about 3 seconds at a reaction chamber outlet temperature of about 502° C. to about 649° C. (about 935° F. to about 1200° F.) and under a pressure of about 15 to about 35 pounds per square inch gauge sufficient for causing a conversion per pass in the range of about 60% to about 90% to products comprising C 3 olefins, C 4 olefins, C 5 -430° F. gasoline while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.3 to about 3% by weight, but insufficient for fully vaporizing the converter feed; V. at least one location along the elongated reaction chamber, including an outlet means at the downstream end of the elongated reaction chamber or an extension thereof, ballistically separating said catalyst from at least a substantial portion of the stream comprising said catalyst, steam and resultant cracking products formed in the elongated reaction chamber, by projecting catalyst particles in a direction established by said elongated reaction chamber or said extension thereof, diverting vapors in said stream, including said steam and said products, in an abrupt change of direction relative to the direction in which said catalyst particles are projected and separating the thus projected catalyst from the diverted steam and products, by collecting the catalyst thus separated into a catalyst collection chamber, and preventing at least about 80% by volume of the total feed and product vapors which have passed through said elongated reaction chamber from having further contact with the thus separated catalyst in said catalyst collection chamber; VI. stripping hydrocarbons from said separated catalyst; VII. regenerating said separated catalyst by burning the coke in at least one or more regeneration zones at temperatures as high as 871° C. (1600° F.), with oxygen-containing combustion-supporting gas while forming combustion product gases comprising CO and CO 2, maintaining the CO:CO 2 molar ratio of the combustion product gases formed from the burning of at least the major weight portion of the coke at a level of at least about 0.3 while such gases are in heat exchange contact with the separated catalyst; and burning sufficient coke to reduce the weight of carbon on catalyst to about 0.1% or less, and; VIII. recycling the regenerated catalyst to the reactor for contact with fresh feed. 4. A process for economically converting carbo-metallic oils to lighter products, comprising: I. providing a converter feed containing 343° C.+ (650° F.+) material, said 343° C.+ (650° F.+) material being characterized by a carbon residue on pyrolysis of at least about 1 and by containing at least about 4 parts per million of Nickel Equivalents of heavy metals; II. bringing said converter feed together with a low coke, high octane, high activity, high selectivity, metal tolerant, hydrothermally and thermally stable, low slurry oil producing cracking catalyst for the conversion of hydrocarbons contaminated with carbon and metals to produce lower molecular weight products, said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size in spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt.% alumina; (d) from about 0.5 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in said acidic matrix and wherein a portion of said rare earths has also been precipitated into said matrix, said cracking catalyst bearing substantially more than 600 ppm Nickel Equivalents of heavy metal to form a stream comprising a suspension of said catalyst in said feed and causing the resultant stream to flow through a progressive flow 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 482° C. to about 760° C. (about 900° F. to about 1400° F.) 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 on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.3 to about 3% by weight; III. separating said catalyst from the resultant cracking products; IV. stripping adsorbed hydrocarbons from said separated catalyst; V. regenerating said metals-bearing, coked catalyst by burning the coke in at least one regeneration zone with oxygen-containing combustion supporting gas while forming combustion product gases comprising CO and CO 2, maintaining the CO:CO 2 molar ratio of the combustion product gases formed from the burning of at least the major weight portion of the coke at a level of at least about 0.25 while such gases are in heat exchange contact with the catalyst, burning sufficient coke to reduce the weight of carbon on catalyst to about 0.1% or less while limiting the amount of combustion-supporting gas supplied to the regeneration operation as a whole to less than the stoichiometric amount which would be required to burn all of the carbon in the coke to CO 2, to burn all of the H 2 in the coke to H 2 O, and to burn any other combustibles which may be present in the coke to their respective combustion products, and restricting the combined free oxygen mole% of all gases resulting from the entire, completed combustion of coke in said regeneration zone or zones to an amount substantially less than 2%; and VI. recycling the regenerated catalyst to the reactor for contact with fresh feed. 5. A process for economically converting carbo-metallic oils to lighter products, comprising: I. providing a converter feed that has had substantially no prior hydrotreatment and contains at least about 70% by volume of 343° C.+ (650° F.+) material and at least about 10% by volume of material which will not boil below about 552° C. (about 1025° F.), said converter feed being characterized by a carbon residue on pyrolysis of at least about 2 and by containing at least about 5.5 parts per million of Nickel Equivalents of heavy metals; II. bringing said converter feed together with liquid water in a weight ratio relative to converter feed in the range of about 0.04 to about 0.15; III. at a catalyst to fresh converter feed weight ratio of at least about 6, bringing said converter feed together with a low coke, high octane, high activity, high selectivity, metal tolerant, hydrothermally and thermally stable, low slurry oil producing cracking catalyst for the conversion of hydrocarbons contaminated with carbon and metals to produce lower molecular weight products, said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt.% alumina; (d) from about 0.5 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in said acidic matrix and wherein a portion of said rare earths has also been precipitated into said matrix, said catalyst having an equilibrium MAT conversion activity level of at least about 50 volume percent and bearing an accumulation of more than about 3000 ppm by weight of Nickel Equivalents of heavy metals expressed as metals on regenerated equilibrium catalyst; IV. forming a stream containing fine droplets of said converter feed, said catalyst and steam resulting from the vaporization of said liquid water and causing the resultant stream to flow through a progressive flow type reactor having an elongated riser reaction chamber which is at least in part vertical or inclined at a linear velocity of at least about 35 feet per second for a vapor residence time in the range of about 0.5 to about 10 seconds at a reaction chamber outlet temperature of about 496° C. (about 925° F.) to about 649° C. (about 1200° F.) and under a pressure of about 15 to about 35 pounds per square inch gauge sufficient for causing a conversion per pass in the range of about 60% to about 90% while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.3 to about 3% by weight, but insufficient for fully vaporizing the converter feed; V. separating said catalyst from at least a substantial portion of the stream comprising said catalyst, steam and resultant cracking products formed in the elongated reaction chamber; VI. stripping said separated catalyst; VII. regenerating said catalyst in one or more regeneration stages; and VIII. recycling the regenerated catalyst to the reactor for contact with fresh feed. 6. A process for converting a hydrocarbon stream contaminated with carbon and metals, to lower molecular weight products, utilizing a low coke, high octane, high activity, high selectivity, metal tolerant, thermally and hydrothermally stable, low slurry oil producing catalyst, said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size in spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt.% alumina; (d) from about 0.1 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of from about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in an acidic matrix and wherein a portion of said rare earths has been precipitated into said matrix. 7. A process as claimed in claims 1, 2, 3, 4, 5, or 6 wherein the catalyst has a pore volume greater than 0.4 cc per gram as determined by water titration. 8. A process as claimed in claims 1, 2, 3, 4, 5, or 6 wherein said catalyst has from about 40 to 70% of all pores in the 100-1000 .ANG. diameter range and less than 35% of all pores between 20-100 .ANG. as measured by mercury porousimitry. 9. A process as claimed in claims 1, 2, 3, 4, 5, or 6 wherein said catalyst has at least 10% of all pores greater than 100 .ANG.. 10. A process as claimed in claims 1, 2, 3, 4, 5, or 6 wherein said catalyst contains from about a ratio of 0.5 to 1.5 acidity in the matrix relative to the acidity in the zeolite. 11. A process for catalytically cracking a metal-contaminated residual oil feedstock containing components that do not boil below about 1025° F., and having greater than 15 ppm Nickel+Vanadium and at least 200 ppm basic nitrogen, which comprises: I. contacting said feedstock at a temperature in the range of about 350° to 650° F. in a riser cracking zone in the presence of about 5-20 wt% water based on feed with a regenerated cracking catalyst at a temperature in the range of 1300° F. to 1500° F. characterized by a metals content greater than 5,000 ppm Nickel plus Vanadium and having a Ramsbottom carbon value greater than about 2 to form cracked products; Ii. said catalyst comprising in combination: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size in spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt. % alumina; (d) from about 0.5 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in said acidic matrix and wherein a portion of said rare earths has also been precipitated into said matrix; III. said catalyst being deactivated in step I with an accumulation of at least about 2,000 ppm by weight of nickel equivalents of heavy metals expressed as metals on regenerated equilibrium catalyst; IV. separating said deactivated catalyst from said cracked products; V. recovering said cracked products comprising gasoline and higher boiling liquid products, passing said separated, deactivated catalyst to a regeneration zone; VI. contacting said deactivated catalyst comprising hydrocarbonaceous deposits and metal contaminants in a 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° to 1500° F., and VII. recycling said regenerated catalyst to said cracking zone. 12. A process of claim 11 wherein said cracked products comprise a C 5 -430° F. endpoint fraction having a Research Octane Number of above 90 as measured without octane-enhancing additives. 13. A process for catalytically cracking a carbo-metallic containing residual feedstock containing components boiling above 1025° F., greater than 15 ppm Nickel+Vanadium and at least 200 ppm basic nitrogen, which comprises: I. contacting said feed stock at a temperature in the range of 350° to 650° F. in a riser cracking zone in the presence of 5-20 wt% water based on feed and in the absence of added molecular hydrogen with a fluidized, regenerated cracking catalyst characterized by a metal content greater than 5,000 ppm Nickel equivalents and having a Ramsbottom carbon value greater than about 2, thereby forming cracked products and coked catalyst; II. said catalyst comprising: (a) from about 8 to about 25% by weight of a zeolite comprising an HY zeolite, having a silica-alumina mole ratio of at least about 5, and having a cell dimension of about 24.30 to about 24.70 angstroms; (b) from about 20 to about 70 wt.% of a clay comprising kaolin, having a size in spherical equivalents of from about 0.5 to about 2 microns; (c) from about 35 to about 70% by weight of an acidic silica-alumina co-gel matrix comprising at least about 13 wt. % alumina; (d) from about 0.5 to about 3 wt.% of rare earths comprising lanthanum and cerium in a ratio of about 1 to about 6; (e) wherein said zeolite is partially exchanged with said rare earths from a solution and wherein said zeolite is contained in said acidic matrix and wherein a portion of said rare earths has also been precipitated into said matrix; III. said cracked products containing gasoline being characterized by an octane value greater than 90 neat and containing oxygenated compounds; IV. 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 section; V. passing said separated coked catalyst to a two-stage regeneration zone; VI. contacting said coked catalyst in said two-stage regeneration zone with an oxygen containing gas at 1400° F. 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 minimize hydrothermal degradation and to form a regenerated catalyst with more than 0.1 wt% residual carbon to produce a flue gas containing a CO 2 /CO ratio below 2/1, and having an oxygen content which does not support combustion at the temperature, pressure, and composition of the flue gas; VII. 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 of the two-stage regenerator, thereby selectively forming liquid cracked products.