Carbo-metallic oil conversion process and catalysts
First Claim
1. A continuous process for cracking of a residual hydrocarbon feedstock into lower molecular weight hydrocarbon transportation fuels, said cracking being carried out in the presence of a catalyst having catalyst parameters comprising porosity, metals content, rare earth content, and zeolite content, said residual hydrocarbon feedstock comprising metal contaminants, fractions boiling above 1025°
- F. comprising asphaltenes, polynuclear aromatics, naphthenes and prophyrins, which process comprises in combination the steps of;
A. providing an aqueous slurry of a colloidal matrix material selected from the group consisting of silica colloid, alumina colloid, and mixtures thereof at a pH in the range selected from the group of ranges consisting of (1) about 3.5 to about 5.5 and (2) about 7 to about 13, said pH being selected to retard gelation of said colloidal matrix material;
B. providing an aqueous slurry of fluidizable clay particles adjusted to a pH substantially the same as that of said colloidal matrix material;
C. providing an aqueous slurry comprising calcined crystalline zeolite;
D. preparing each of said aqueous slurries from ingredients including water, wherein total sodium content of a spray dried composite comprising said slurries is less than about 0.25 percent by weight sodium oxide;
E. thoroughly mixing said slurries to provide a mixture of slurries;
F. feeding said mixture into a spray drier to provide a fluidizable catalyst suitable for fluid catalyst cracking having less than 0.25 wt.% sodium oxide, said catalyst being prepared at the same site where said conversion process is being conducted, and said catalyst being adapted to optimize said catalyst parameters comprising porosity, metals content comprising rare earth metals and zeolite content with respect to composition of said feedstock; and
G. contacting said catalyst in a riser cracking zone with said hydrocarbon feedstock under hydrocarbon cracking conditions comprising a catalyst-to-oil ratio in the range of about 5;
1 to 20;
1, a product recovery temperature within the range of 950°
F. to 1150°
F., and a reactant residence time of less than 3 seconds to produce hydrocarbon transportation fuels.
0 Assignments
0 Petitions
Accused Products
Abstract
Commercial catalysts are prepared combining the various ingredients into a catalytic binder system which has been freed of sodium so that the catalyst ingredients can be preferably spray dried and used in Fluid Catalytic Cracking or Reduced Crude Conversion hydrocarbon conversion operations without subsequent washing or drying. Catalysts can even be prepared on site, e.g., in spray drier operations performed in the FCC/RCC refenerator. Low-sodium slurries of any or all of the following ingredients can be employed in the manufacture: zeolites, clays, sols, carbon blacks, sacrificial sieves, acid matrix substances, and getters.
-
Citations
15 Claims
-
1. A continuous process for cracking of a residual hydrocarbon feedstock into lower molecular weight hydrocarbon transportation fuels, said cracking being carried out in the presence of a catalyst having catalyst parameters comprising porosity, metals content, rare earth content, and zeolite content, said residual hydrocarbon feedstock comprising metal contaminants, fractions boiling above 1025°
- F. comprising asphaltenes, polynuclear aromatics, naphthenes and prophyrins, which process comprises in combination the steps of;
A. providing an aqueous slurry of a colloidal matrix material selected from the group consisting of silica colloid, alumina colloid, and mixtures thereof at a pH in the range selected from the group of ranges consisting of (1) about 3.5 to about 5.5 and (2) about 7 to about 13, said pH being selected to retard gelation of said colloidal matrix material; B. providing an aqueous slurry of fluidizable clay particles adjusted to a pH substantially the same as that of said colloidal matrix material; C. providing an aqueous slurry comprising calcined crystalline zeolite; D. preparing each of said aqueous slurries from ingredients including water, wherein total sodium content of a spray dried composite comprising said slurries is less than about 0.25 percent by weight sodium oxide; E. thoroughly mixing said slurries to provide a mixture of slurries; F. feeding said mixture into a spray drier to provide a fluidizable catalyst suitable for fluid catalyst cracking having less than 0.25 wt.% sodium oxide, said catalyst being prepared at the same site where said conversion process is being conducted, and said catalyst being adapted to optimize said catalyst parameters comprising porosity, metals content comprising rare earth metals and zeolite content with respect to composition of said feedstock; and G. contacting said catalyst in a riser cracking zone with said hydrocarbon feedstock under hydrocarbon cracking conditions comprising a catalyst-to-oil ratio in the range of about 5;
1 to 20;
1, a product recovery temperature within the range of 950°
F. to 1150°
F., and a reactant residence time of less than 3 seconds to produce hydrocarbon transportation fuels.
- F. comprising asphaltenes, polynuclear aromatics, naphthenes and prophyrins, which process comprises in combination the steps of;
-
2. In a process for effecting catalytic cracking wherein a spray dried cracking catalyst particle is contacted with an oil feed boiling above gasoline boiling range to form gasoline, light and heavy cycle oils wherein said catalytic cracking is conducted in a riser cracking zone under hydrocarbon cracking conditions and in the presence of the cracking catalyst comprising fluidizable catalyst particles, the improvement which comprises:
-
A. maintaining at the site of said process separate slurries, said slurries comprising;
a slurry of fluidizable clay particles;
a faujasite slurry of catalytically activated Y faujasite zeolite particles of less than 5 microns containing at least one of hydrogen and exchanged rare earth metals comprising lanthanum (La) and cerium (Ce) wherein a La/Ce ratio is at least 1;
a carbon particle slurry comprising suspended particles selected from the group consisting of a carbon black, and thermal furnace black;
a sieve slurry comprising fluidizable particles of a sieve that are selected from the group consisting of zeolite A, ZSM-4, mordenite, gmelinites, chabazite and a co-gelled SiO matrix slurry of colloidal particles of an acidic matrix substance selected from the group consisting of ground silica-alumina gel, and titania-silica gel;
a slurry of powder of a binder substance selected from the group consisting of acid leached bentonite, acid leached halloysite, pseudoboehmite, silicic acid and montmorillonite; and
a slurry of powders selected from the group consisting of titania, alumina, zirconia, indium oxide, manganese dioxide and lanthanum oxide;B. maintaining the sodium content of each of the slurries sufficiently low so that at the time of mixing three or more of such slurries in a homogenizing zone at said site to form a mixture of slurries, the sodium content of the mixture is less than 0.2 wt%, said three or more of such slurries comprising at least said slurry of clay particles said faujasite slurry, and said matrix slurry; C. charging said slurries to said homogenizing zone in amounts determined to provide spray dried catalyst particles suitable for effecting optimum catalytic cracking of said oil feed in said riser cracking zone said catalyst composition having been optimized to said oil feed; D. mixing said slurries in said homogenizing zone to form said mixture of slurries; E. spray drying at said site said mixture of slurries to form said spray dried catalyst particles; and F. introducing said spray dried catalyst particles into said riser cracking zone for contact with said oil feed therein. - View Dependent Claims (3, 4, 5, 6, 7, 8, 9, 10, 11, 12)
-
-
13. A continuous process for cracking of a residual hydrocarbon feedstock into lower molecular weight hydrocarbon transportation fuels in a conversion system comprising a riser cracking zone and a regeneration system, wherein said conversion is conducted in the presence of a catalyst having catalyst parameters comprising porosity, metals content, rare earth metal content, and zeolite content, said feedstock comprises metal contaminants, fractions boiling above 1025°
- F., asphaltenes, polynuclear aromatics, polar molecules, naphthenes, and porphyrins, which process comprises;
A. providing at the site of said process separate aqueous slurries of catalyst ingredients, each of said slurries having been prepared from low-sodium content ingredients and low-sodium content water so that the total sodium content of a spray-dried composite of any combination of said slurries is less than about 0.25 percent by weight sodium oxide, said slurries comprising; (a) an aqueous slurry of the hydroxy form of a colloidal matrix material selected from the group consisting of silica colloid, alumina colloid, and mixtures thereof having a pH within the range selected from the group of ranges consisting of; (1) about 3.5 to about 5.5; and (2) about 7 to about 13, said pH being selected to retard gelation of said colloidal matrix material, (b) an aqueous slurry of fluidizable clay particles adjusted to a pH substantially the same as that of said colloidal matrix material, (c) an aqueous slurry comprising catalytically activated Y faujasite zeolite particles having a silica-to-alumina ratio greater than 5;
1, a lanthanum-to-cerium ratio greater than 3;
1, and a rare earth oxide content greater than 5 wt%,(d) an aqueous slurry of particles of a carbon black, or thermal furnace black, (e) an aqueous slurry of fluidizable particles of a sacrificial sieve selected from the group consisting of zeolite A, ZSM-5, mordenite, chabazite, and co-gelled silica-alumina, (f) an aqueous slurry of a powder of a binder substance selected from the group consisting of acid-leached bentonite, acid-leached halloysite, pseudoboehmite, silicic acid, and montmorillonite, (g) an aqueous slurry of an acidic matrix substance selecte from the group consisting of acid-activated clay, silica-alumina, silica-titania, and silica-zirconia, and (h) an aqueous slurry of powders of metal getters selected from the group consisting of titania, alumina, zirconia, indium oxide, manganese dioxide, and lanthanum oxide; B. thoroughly mixing said selected slurries having the above low-sodium content to provide a mixture of slurries, the ratios of said selected slurries being varied to optimize said catalyst parameters for optimum conversion of the hydrocarbon feedstock; C. injecting said mixture into the dilute catalyst phase of said regeneration system in order to spray dry said mixture and form a low-sodium fluidizable catalyst suitable for fluid catalyst cracking, said catalyst being adapted to optimize said catalyst parameters with respect to composition of said feedstock; D. contacting said catalyst in said riser cracking zone with said feedstock under hydrocarbon cracking conditions comprising a catalyst-to-oil ratio within the range of about 5;
1 to about 20;
1, a reactant residence time of less than 3 seconds, and a product recovery temperature within the range of 950°
F. to 1150°
F. to produce said lower molecular weight hydrocarbon transportation fuels and a spent catalyst; andE. regenerating said spent catalyst in said regeneration system. - View Dependent Claims (14, 15)
- F., asphaltenes, polynuclear aromatics, polar molecules, naphthenes, and porphyrins, which process comprises;
Specification