Ashland Oil, Inc.

Stephen M Kovach

William P Hettinger, Jr

Edward B Cornelius

James Donald Carruthers

H Wayne Beck

Oliver J Zandona

James L Palmer

Hubert W Beck

Ronald A Kmecak

James F Hoffman

George D Wilson

George D Myers, Deceased

Charles B Miller

A process is disclosed for the conversion of a hydrocarbon oil feed having a significant content of vanadium to lighter oil products by contacting the feed under conversion conditions in a conversion zone with a catalyst containing a metal additive to immobilize vanadium compounds. Conversion conditions are such that coke and vanadium are deposited on the catalyst in the conversion zone. Coked catalyst is regenerated in the presence of an oxygen containing gas at a temperature sufficient to remove the coke and regenerated catalyst is recycled to the conversion zone for contact with fresh feed. The metal additive is present on the catalyst in an amount sufficient to immobilize the vanadium compounds in the presence of oxygen containing gas at the catalyst regeneration temperature. A catalyst composition comprises a crystalline alumino-silicate zeolite dispersed in an amorphous inert solid matrix containing the metal additive, which may be introduced into the catalyst during the conversion process or during catalyst manufacture. Metal additives include water soluble inorganic metal salts and hydrocarbon soluble inorganic metal salts and hydrocarbon soluble organometallic compounds of select metals.

Immobilization of vanadia deposited on catalytic materials during

A three stage catalytic cracking process capable of converting high molecular weight hydrocarbons containing catalyst poisons into products of lower molecular weight by cascading catalyst from a fluid catalytic cracking unit to a reduced crude conversion unit to a metals removal unit is disclosed. Efficiencies in conversion operations are made possible.

Cascading of fluid cracking catalysts

A catalyst nominally containing zeolite, clay and silica-alumina gel. The zeolite is preferably partially exchanged with high La/Ce ratio solution in a wetting step. The catayst 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.

High performance catalysts for carbometallic oil conversion and their

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.

Carbometallic oil conversion with zeolite y containing catalyst

A process for economically converting carbo-metallic oils to lighter products. The carbo-metallic oils contain 650.degree. F.+ material which is characterized by containing material which will not boil below about 1025.degree. F., a carbon residue on pyrolysis of at least about 2, and a nickel plus vanadium content of at least about 4 parts per million. This process comprises adding an additive to the feedstock consisting of a compound containing titanium, zirconium, or aluminum so as to restore cracking activity of high metal contaminated and deactivated, zeolite containing catalysts, resulting from processing of these carbo-metallic oils.

Process for cracking high-boiling hydrocarbons using continuous addition

Contaminating metals including nickel, vanadium, iron and copper are deposited on a fluid cracking catalyst during the processing of carbo-metallic containing oils such as residual oils, reduced crudes or topped crudes. These contaminating metals lead to undesirous side reactions such as dehydrogenation, coking and methyl group removal which adversely affect conversion and gasoline selectively. Furthermore vanadia deactivates the crystalline zeolite component of the catalyst in addition to causing catalyst agglomeration because of its pentoxide melting point by treatment with a reducing gas such as ammonia. The ammonia is added as ammonia or in the presence of diluents such as nitrogen, carbon dioxide, flue gas, fuel gas and steam. The reaction of ammonia with vanadium produces vanadium nitride which is water insoluble and facilitates the disposal of high vanadium containing spent of deactivated catalyst by landfill techniques.

Ammonia contacting to passivate metals deposited on a cracking catalyst

A process is disclosed for the treatment of a hydrocarbon oil feed having a significant content of vanadium to provide a higher grade of oil products by contacting the feed under treatment conditions in a treatment zone with sorbent material containing a metal additive to immobilize vanadium compounds. Treatment conditions are such that coke and vanadium are deposited on the sorbent in the treatment zone. Coked sorbent is regenerated in the presence of an oxygen containing gas at a temperature sufficient to remove the coke, and regenerated sorbent is recycled to the treatment zone for contact with fresh feed. The metal additive is present on the sorbent in an amount sufficient to immobilize the vanadium compounds in the presence of oxygen containing gas at the sorbent regeneration temperature. A sorbent composition disclosed comprises a kaolin clay containing the metal additive, which may be introduced into the clay during the treatment process or during sorbent manufacture. Metal additives include water soluble inorganic metal salts and hydrocarbon soluble organo-metallic compounds of select metals.

Immobilization of vanadia deposited on sorbent materials during

An improved process and catalyst for economically converting carbo-metallic oils to lighter products. This process is practiced in accordance with effective metals management, carbon management and catalyst activity management combined with feed atomization-vaporization, efficient stripping of carbonaceous material from the coked catalyst, exothermic and endothermic removal of hydrocarbonaceous material to effectively maintain the RCC unit in heat balance. This reduced crude cracking process is practiced with a new and improved catalyst composition identified as RCCC-1 Special that is characterized by the following composition; at least 30 wt % rare earth exchanged 'Y' faujasite crystalline zeolite with a silica to alumina ratio of at least 5 of a high lanthanum to cerium ratio and residual sodium content less than 0.30 wt %, is provided with a pore volume greater than 0.35 cc/gm. and comprises a clay matrix material that may or may not be acidic with pore size openings in the range of 500 to 2,000 angstroms. The RCCC-1 Special can contain metal promoters to catalyze the endothermic removal of coke and the partial removal of hydrogen present in the carbonaceous material with carbon dioxide. In addition, metal additives to passivate and immobilize vanadium are contemplated.

Catalyst for the conversion of carbo-metallic containing oils

Mixtures of aromatic and olefinic hydrocarbons are contacted in the presence of a catalyst under appropriate pressure, temperature and space velocity to effect alkylation of the aromatic hydrocarbon. The catalyst is alumina containing boria and an oxide of a metal from Group IVA (tin and lead) or Group VIIB (manganese).

Alumina catalyst for alkylating aromatics with olefins

A process is disclosed for the treatment of a hydrocarbon oil feed having a significant content of metals to lighter oil products by contacting the feed under conversion conditions in a conversion zone with a catalyst containing a sacrificial trap material sufficient to immobilize Ni-V-Na compounds. Conversion conditions are such that carbonaceous material and metals are deposited on the catalyst in the conversion zone. The catalyst is regenerated in the presence of an oxygen containing gas at a temperature sufficient to remove the carbonaceous deposits, and regenerated catalyst is recycled to the conversion zone for a contact with fresh feed. The sacrificial trap material is present on the catalyst in an amount sufficient to substantially immobilize the metal compounds in the presence of oxygen containing gas at the catalyst regeneration temperature. A catalyst composition for the above conversion comprises a catalytically active alumino-silicate zeolite dispersed in an amorphous inert solid matrix material containing the sacrificial trap material with or without one or more selected metal additives. The sacrificial trap material preferable includes inexpensive naturally occurring or synthetic zeolites which can be ion exchanged with water soluble metal additives.

Trapping of metals deposited on catalytic materials during carbometallic

A catalyst nominally containing zeolite, preferably HY zeolite and/or ultrastable HY zeolite, clay, alumina and an acidic silica-alumina co-gel matrix. The zeolite is preferably partially exchanged with high La/Ce ratio solution in a wetting step, and rare earths are precipitated onto the matrix. The catalyst has high metals tolerance and is capable of cracking heavy reduced crude oils, producing higher LCO/slurry oil ratio.

An improved process and catalyst for economically converting carbo-metallic oils to lighter products. This process is practiced in accordance with effective metals management, carbon management and catalyst activity management combined with feed atomization-vaporization, efficient stripping of carbonaceous material from the coked catalyst, exothermic and endothermic removal of hydrocarbonaceous material to effectively maintain the RCC unit in heat balance. This reduced crude cracking process is practiced with a new and improved catalyst composition identified as RCCC-1 Special that is characterized by the following composition; at least 30 wt % rare earth exchanged 'Y' faujasite crystalline zeolite with a silica to alumina ratio of at least 5 of a high lanthanum to cerium ratio and residual sodium content less than 0.30 wt %, is provided with a pore volume greater than 0.35 cc/gm. and comprises a clay matrix material that may or may not be acidic with pore size openings in the range of 500 to 2,000 angstroms. The RCCC-1 Special can contain metal promoters to catalyze the endothermic removal of coke and the partial removal of hydrogen present in the carbonaceous material with carbon dioxide. In addition, metal additives to passivate and immobilize vanadium are contemplted.

Process and catalyst for the conversion of carbo-metallic containing oils

A process is disclosed for the conversion of high boiling oil feeds having a significant level of Conradson carbon components and metals to form lighter oil products by contacting the feed under catalytic conversion conditions with a catalyst containing one of a select group of metal additives to catalyze the endothermic removal of carbon with CO.sub.2. Conversion conditions are such that hydrocarbonaceous material and metals are deposited to deactivate the catalyst in the conversion zone. Deactivated catalyst is partially regenerated in the presence of carbon dioxide containing gas before or after oxygen regeneration at a temperature below 1600.degree. F. to provide a regenerated catalyst which is recycled to the conversion zone for further contact with fresh feed. The metal additive is present on the catalyst in an amount sufficient to catalyze the endothermic removal of carbonaceous material in the presence of a carbon dioxide rich gas at regeneration temperature below 1500.degree. F. The catalyst composition comprises a crystalline alumino-silicate dispersed in a solid matrix material and containing one or more of the metal additives. Metal additive may be introduced into the catalyst during the conversion process or during catalyst manufacture. Metal additives include water soluble inorganic metal salts, hydrocarbon soluble organo-metallic compounds of the select group of metals, and metal contaminants found in a high boiling residual oil feed.

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Ashland, KY, United States of America

Stephen M Kovach