Carbo-metallic oil conversion process and catalysts

• US 4,877,514 A
• Filed: 11/10/1988
• Issued: 10/31/1989
• Est. Priority Date: 12/07/1981
• Status: Expired due to Fees

• Current Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Original Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Inventors: Beck, H. Wayne, Hettinger, William P.
• Primary Examiner(s): McFarlane, Anthony
• Application Number:
  US07/271,414
• Time in Patent Office: 355 Days
• Field of Search: 208/120, 208/121, 208/113, 208/251 R, 502/64, 502/65, 502/67, 502/68, 502/69
• US Class Current: 208/120.05
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/084 Y-type faujasite
• CPC Class Codes: C10G 11/05 Crystalline alumino-silicates, e.g. molecular sieves

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.

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.

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.

3. The process of claim 2 wherein the crystalline faujasite zeolite comprises a silica to alumina ratio greater than 5/1, a La/Ce ratio greater than 3/1 and a rare earth oxide content greater than 5 wt.% rare earths.

4. The process of claim 2 wherein a formed matrix composition slurry is provided by one or more components which provide pore size openings in the spray dried particles of at least 500 Angstroms in an amount of 40 or more percent with at least 25% thereof being greater than 1000 Angstroms.

5. The process of claim 4 wherein the formed matrix composition of the catalyst particle is an acidic material wherein said acidity is supplemented by the addition of one or more materials selected from sulfonates, phosphates a halogen contributing material, phosphoric acid, boric acid, acid activated clay, silica alumina, silica titania and silica zirconia.

6. The process of claim 5 wherein the spray dried slurry is provided with a metal sorbent material and a vanadia immobilization agent by the addition thereto of a material selected from alumina, pillared interlayered clay material and a metal additive which complexes with vanadia to effect collection and immobilization thereof, said metal additive being selected from the group consisting of titania, zirconia, indium oxide, manganese dioxide, and lanthanum oxide.

7. The process of claim 2 wherein two or more colloidal suspensions of the same or different average particle size and composition are used in the slurry, whereby the spray dried catalyst particle porosity, acidity and attrition, resistance of the catalyst particle are changed by varying the proportions of the respective suspensions so as to modify the composition of the resulting catalyst.

8. The process of claim 2 wherein the matrix forming inorganic oxide colloid slurry is maintained during storage at a pH outside the range of 5.5 to 7.

9. The process of claim 2 wherein the spray dried catalyst particle compositions are formed from a slurry comprising a material selected from the group consisting of a silica sol coated with one or more of TiO₂, ZrO₂, Re₂ O₃, Fe₂ O₃ and Al₂ O₃ or alumina sol coated with one or more of TiO₂, ZrO₂, Re₂ O₃, and Fe₂ O₃.

10. The process of claim 2, wherein said separate slurries are used to form catalyst particles comprising:

a zeolite content of 10 to 60 weight percent;

a clay particle content of 10 to 60 weight percent;

a matrix forming sol content of from 10 to 40 weight percent;

a pore forming additive of up to 25 weight percent;

a sieve selected from the group consisting of zeolite A, ZSM-4, mordenite, gmelinites, chabazite;

a co-gelled SiO matrix slurry of colloidal particles of an acidic matrix substance selected from the group consisting of ground silica-alumina gels, and titania-silica of up to 20 weight percent;

an acid matrix substance of up to 50 weight percent;

a binder material of up to 60 weight percent; and

a material capable of forming high melting reaction products with vanadium in a regenerator to thereby immobilize it by not melting at temperatures found in the regenerator, said material being present in up to 20 weight percent of the spray dried catalyst particle.

11. The process of claim 2, wherein a spray dried catalyst composition suitable for the catalytic cracking of a reduced crude and used in said cracking process is prepared by:

A. forming a kaolinite clay of fluidizable particles in demineralized water of about 4.0 pH;

B. forming fluidizable particles of faujasite crystalline zeolite with a lanthanum to cerium ratio greater than 1;

1 in 4.0 pH dimeneralized water;

C. charging the kaolinite slurry of (A) and said zeolite slurry of (B) to a homogenizing mixer with a slurry of a colloidal silica wherein total sodium content of both slurries is sufficiently low so that sodium content of the spray dried catalyst is less than 0.25 weight percent;

D. thoroughly mixing the slurries of (C) to obtain a slurry mixture of about 4.0 pH with a viscosity of 900 cps at 100°

F.; and

E. spray drying said slurry mixture comprising silica colloid, clay and crystalline zeolite in a catalyst regenerator to obtain microspherical fluidizable catalyst particles comprising a lanthanum rich crystalline zeolite.

12. The process of claim 11, wherein an alumina powder is added to the kaolinite slurry prior to mixing with the zeolite slurry, the pH of the slurry comprising alumina powder without zeolite component is adjusted to a pH of 10 by addition of ammonium hydroxide and thereafter adding the faujasite zeolite particles as a powder to the slurry comprising alumina and adjusting the viscosity of the slurry mixtures with water to form a slurry suitable for said spray drying.

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; and

E. regenerating said spent catalyst in said regeneration system.

14. The process of claim 13, wherein said slurry of matrix material contains one or more components which provides spray dried particles having at least 40% of their pore openings greater than 500 Angstroms and at least 25% of their pore openings greater than 1,000 Angstroms.

15. The process of claim 13, wherein said slurry of colloidal matrix material is provided with added acidity by the addition thereto of a member selected from the group consisting of inorganic nitrates, inorganic sulfates, organic sulfonates, inorganic phosphates, a halogen contributing material, phosphoric acid, boric acid, acid-activated clay, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, and mixtures thereof.